Materials Selection Guidelines

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The document discusses guidelines for selecting materials for geothermal power systems based on fluid properties and power cycles.

The document provides guidelines for selecting materials for geothermal power systems based on the properties of geothermal fluids and different power cycles.

The document covers geothermal power cycles, the effect of fluid properties on power cycles and applicability, corrosion considerations, and materials selection guidelines.

ALO-3904-1

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MATERIALS SELECTION GUIDELINES FOR


GEOTHERMAL POWER SYSTEMS
First Edition

BY
David W. DeBerry
Peter.F. Ellis
Colin C. Thomas

LL
-J

September 1978

Work Performed Under Contract No. EG-77-GO43904

I.

Radian Corporation
Austin, Texas

i
.
1
I
1
1
1

U a

DEPARTMENT OF ENERGY
Geothermal Energy
..

DISCLAIMER
This report was prepared as an account of work sponsored by an
agency of the United States Government. Neither the United States
Government nor any agency Thereof, nor any of their employees,
makes any warranty, express or implied, or assumes any legal
liability or responsibility for the accuracy, completeness, or
usefulness of any information, apparatus, product, or process
disclosed, or represents that its use would not infringe privately
owned rights. Reference herein to any specific commercial product,
process, or service by trade name, trademark, manufacturer, or
otherwise does not necessarily constitute or imply its endorsement,
recommendation, or favoring by the United States Government or any
agency thereof. The views and opinions of authors expressed herein
do not necessarily state or reflect those of the United States
Government or any agency thereof.

DISCLAIMER
Portions of this document may be illegible in
electronic image products. Images are produced
from the best available original document.

NOTICE
This report was prepared as an account of work sponsored by the United States
Government. Neither the United States nor the United States Department of Energy, nor
any of their employees, nor any of their contractors, subcontractors, or their employees,
makes any warranty,express or implied, o r assumes any legal liability o r responsibility for
the accuracy, completeness or usefulness of any information, apparatus, product or process
disclosed, o r represents that its use would not infringe privately owned rights.

This report has been reproduced directly from the best available copy.
Available from the National Technical Information Service, U. S. Department of
Commerce, Springfield, Virginia 22161.
Price: Paper Copy $1 1.75
Microfiche $3.00

ALO-3904-1
Distribution Category UC66d

DCN# 78- 200-181-

FIRST EDITION
MATERIALS SELECTION GUIDELINES
FOR GEOTHERMAL POWER SYSTEM

By :
David W. DeBerry
Peter F. E l l i s
Colin C. Thomas
Radian Program Manager:

Marshall F. Conover

September, 1978

Radian Corporation
8500 Shoal Creek
Austin, Texas 78766

Contract No. EG-77-C-04-3904


DOE Program Manager: D r . Robert R. Reeber
Division of Geothermal Energy

Prepared For:
United S t a t e s Department of Energy

Energy Technology
Washington, D.C.

20545

TABLE OF CONTENTS

1.0

2.0

INTRODUCTION.....................................
1.1 Background and Purpose......................
1 . 2 Scope.......................................
1 . 3 Summary and Overview........................

Page
1-1
1-1
1-3
1-4

GEOTHERMAL POWER CYCLES.......................... 2 - 1


2 . 1 Description of Nine Power Cycles............ 2 - 1
2 . 2 Effect of Geothermal Fluid Properties on the
Applicability of Power Cycles............... 2 - 4
2.3 Effect of Fluid Properties on Materials
'Performancein Specific Process Streams..... 2 - 2 4
2 . 3 . 1 Dual Flashed Steam Cycle
2-25
Direct Binary Cycle .................. 2-28
2.3.2
2.3.3
Flashed Steam Binary Cycle ........... 2-29

.............

3.0

4.0

CHEMICAL COMPOSITION OF GEOTHERMAL FLUIDS FROM A


CORROSION STANDPOINT.............................
3-1
3 . 1 Key Corrosive Chemical Species.............. 3 - 1
3 . 2 Key Corrosive Chemical Species in Selected
3-5
KGRA's ......................................
RESULTS OF CORROSION TESTS IN GEOTHERMAL FLUIDS..
4 . 1 Corrosion Tests at U.S. Liquid-Dominated
KGRA's ......................................
4.1.1 Most Corrosive: Salton Sea
4.1.2
Moderately Corrosive: Baca. East
Mesa. Heber. Mono-Long Valley. Raft
River
Least Corrosive: Beowawe
4.1.3
4.2 Results of Corrosion Tests at Baca (Valles
Caldera) New Mexico KGRA
4.2.1
Test Conditions
4.2.2
Results

4-1
4-2

.......... 4 - 3

................................
............
....................
......................
..............................
ii

4-3
4-5
4-11
4-11
4-15

TABLE
.
OF CONTENTS (Continued)

4.3

Results of Corrosion Tests at East Mesa.


California KGRA .............................
4.3.1
Description of Test Streams
4.3.2
Laboratory Tests.....................
4.3.3
Field Tests..........................
Results of Corrosion Tests at Heber.
California KGRA .............................
4.4.1 Test Conditions......................
4.4.2
Results
Results of Corrosion Tests at Raft River.
Idaho KGRA ..................................
4 . 5 . 1 Results of Coupon Tests..............

..........

4.4

..............................

4.5

4.5.2

4.6

Results of Tests of Potential Heat


Exchanger Materials ..................
Results of Corrosion Tests in Salton Sea.
California KGRA .............................
4 . 6 . 1 Results of Laboratory Tests Using
Synthetic Fluids
4.6.2
Results of Field Tests at Well
Magmamax No . 1.......................

.....................

5.0

4-20
4-20
4-27
4-30
4-38
4-38
4-38
4-43
4-43
4-51
4-52
4-52
4-72

CORROSION MODES FOR METALS IN GEOTHERMAL SYSTEMS. 5 - 1


5 . 1 Mild and Low Alloy Steels................... 5-5
5 . 1 . 1 General Guidelines for Using Mild
Steels ...............................
5-5
Uniform and Localized Corrosion of
5.1.2
5-9
Mild Steels ..........................
Stres Corrosion Cracking of Low Alloy
5.1.3
5.1.4

...

5-24
5-24

Hydrogen Blistering of Mild Steels


5-32
Stainless Steels
5-33
5.2.1 General Guidelines for Use of Stainless Steels
5-33
5.1.5

5.2

..............................
Sulfide Stress Cracking of Low and
Middle Alloy Steels..................

............................
..........................

iii

TABLE OF CONTENTS (Continued)


Pa=
Corrosion Resistance of Major
Classes of Stainless Steels.......... 5-35
5.2.3 Pitting and Crevice Corrosion of
Stainless Steels.....................
5-36
5.2.4 Stress Corrosion Cracking of Stainless Steels..........................
5-44
5.2..5 Intergranular Corrosion of Stainless
Steels. ..............................
5-49
5.2.6 Sulfide Stress Cracking of Stainless
Steels...............................
5-51
Titanium and Titanium Alloys ................ 5-51
5.3.1 Uniform Corrosion of Titanium........
5-52
5.3.2 Pitting and Crevice Corrosion of
Titani. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-52
5.3.3 Galvanic Coupling and Other Precautions.............................
5-56
5.3.4 Stress Corrosion Cracking of TitaniumBased Alloys .........................
5-57
Nickel-Based Alloys .........................
5-59
5.4.1 General Corrosion Resistance of NiCr-Mo Alloys .........................
5-59
5.4.2 Stress Corrosion Cracking of NickelBased Alloys .........................
5-59
5.4.3 Sulfide Stress Cracking and Hydrogen
Embrittlement........................
5-60
5.4.4 Intergranular Corrosion of NickelBased Alloys .........................
5-60
Copper-Based Alloys .........................
5-61
Applicability of Other Metallic Materials ... 5-62
5.6.1 Cobalt Alloys ........................
5-62
5-63
5.6.2 Zirconium and Tantalurn...............
5-63
5.6.3 Aluminum Alloys ......................
Condensate..................................
5-64
Steam from Liquid-Dominated Geothermal
Sources......... ............................
5-65
5.2.2

5.3

5.4

5.5
5.6

5.7
5.8

iv

TABLE OF CONTENTS (Continued)


Page

5.8.1
5.8.2
5.8.3

General Corrosion in Geothermal


Steam................................
Corrosion Fatigue....................
Exfoliation..........................

5-66
5-66
5-71

6.0

NONMETALLIC MATERIALS ............................


6.1 Concrete Polymer Composites.................
6.2 Cements .....................................
6.3 Elastomers ..................................
6.4 Fiber Reinforced Laminates..................
6.5 FRP and Coated Pipe .........................
6.6 Thermoplastics..............................

6-1
6-2
6-4
6-6
6-8
6-8
6-10

7.0

REFERENCES .......................................

7-1

APPENDIX A

Corrosion Experience at Operating United States


and Foreign Geothermal Power Plants ............ A-1

APPENDIX B

Corrosion in Seawater Desalination Plants ...... B-1

APPENDIX C Preliminary Comparison of Geothermal Fossil


Fuel Generating Plant Availability ............. C-1
APPENDIX D Geothermal Elastomeric Materials ............... D-1
APPENDIX E Comparative Alloy Costs ........................

Ecl

APPENDIX F Preliminary List of Available Geothermal Power


Equipment.......................................
F-1

LIST OF TABLES

. . . . . . .

2-1

P o t e n t i a l Geothermal Power Cycles

2-2

Equipment L i s t f o r Direct Cycle Using Steam


Dominated Geothermal Resource . . . . . . .

2-3

2-4

2-5

2-6

2-7

2-8
2-9

2-10

3-1
3-2

. .

Equipment L i s t f o r Single Flashed Steam Cycle


Using Natural Pressure Liquid Dominated
Geothermal Resource . . . . . . . . . . . . .

Page
2-2
2-6

2-8

Equipment f o r Dual Flashed Steam Cycle Using


Natural Pressurized, Liquid Dominated Geotherm a l Resource . . . . . . . . . . . . . . . . .

2-10

Equipment L i s t f o r Direct Binary Cycle Using


Natural Pressure, Liquid Dominated Geothermal
Resource . . . . . . . . . . . . . . . . . .

2-12

Equipment L i s t f o r Flashed Steam Binary Cycle


Using Natural Pressure, Liquid Dominated
Geothermal Resource . . . . . . . . . . . . .

2-14

. .

2-16

Equipment L i s t f o r Direct Binary Cycle Using


Pumped, Liquid Dominated Geothermal Resource

2-18

Equipment L i s t f o r Flashed Steam Binary Cycle


Using Pumped, Liquid Dominated Geathermal
Resource . . . . . . . . . . . . . . . . . .

2-20

. .

2-22

Equipment L i s t f o r Two Phase Expander Cycle


Using Natural Pressure, Liquid Dominated
Geothermal Resource . . . . . . . . . . . .

Equipment L i s t f o r Two Phase Expander Cycle


Using Pumped, Liquid Dominated Geothermal
Resource . . . . . . . . . . . . . . . . .

Typical Concentrations of Key Corrosive Chemic a l Species i n Fluid from Seven KGRA's . . . .

3-7

Typical Composition of Noncondensable Gases i n


. . . . . . . . . . . . . . . . .
Seven KGRA's

3-8

.
.

4-1

Ferrous Materials Tested a t Geothermal S i t e s

4-2

Nonferrous Materials Tested a t Geothermal S i t e s

4- 7

4- 3

Compositions of Brand Name Alloys

. . . . . . .

4-8

vi

4-6

U
LIST OF TABLES (CONT'D)

Page

4-4

Corrosion Screening Results f o r Baca (Valles


Caldera) Flashed Wellhead Fluids . . . . . .

. .

4-12

4-5

Corrosion Screening Results f o r Baca (Valles


Caldera) Steam A f t e r Flashing . . . . . . .

. .

4-13

W e l l N o . 11 Used i n Corrosion Tests a t Baca,


New Mexico KGRA (TO-089) . . . . . . . . . .

. .

4-14

Results of Corrosion Tests of Heat Exchanger


M a t e r i a l s a t Baca, New Mexico KGRA . . . . .

. .

4-16

Corrosion T e s t Results f o r Turbine Materials


i n Flashed Steam a t Baca (Valles Caldera) .

. .

4-17

4-6

4-7
4-8

Composition of Flashed Steam and Fluid from

4-9

E a s t Mesa Corrosion Screening Results f o r


Wellhead Fluid . . . . . . . . . . . . . .

. . .

4-21

4-10

E a s t Mesa Corrosion Screening Results f o r


Liquid Stream A f t e r F i r s t Flash . . . . .

. . .

4-22

4-11

East Mesa Corrosion Screening Results f o r


Liquid S t r e a m A f t e r Second Flash . . . . .

. . .

4-23

4-12

East Mesa Corrosion Screening Results f o r


S t e a m from F i r s t Flash . . . . . . . . . .

. . .

4-24

4-13

East Mesa Corrosi


Screening Results f o r
Steam from Second Flash . . . . . . . . .

. . .

4-25

4-14

Comparison of Mesa 6-1 and Cerro P r i e t o Geothermal Fluids . . . . . . . . . . . . . . .

4-15

Composition of Test Streams from Well Mesa 6-1


a t East Mesa S i t e

4-16

Results of Laboratory and F i e l d Corrosion T e s t s


i n East Mesa Wellhead Fluid . . . . . . . . . . 4-29

4-17

F i e l d Corrosion Results i n E a s t Mesa Wellhead


Fluid . . . .
. . . . . . . . . . . .

4-18

Corrosion T e s t Results i n F i r s t and Second


Flashed F l u i d a t East Mesa . . . . . . . .

. .

. . . . . . . . . . . . . . .

. .

vii

4-26
4-27

4-32

. . .

4-33

LIST OF TABLES (CONT'D)

Page
4- 19

Corrosion T e s t Results i n F i r s t and Second


Flashed Steam a t E a s t Mesa . . . . . . . .

. . . 4-34

4-20

E f f e c t of Temperature and A c i d i f i c a t i o n on
General Corrosion a t E a s t Mesa . . . . . .

. . .

4-37

4-21

Heber Corrosion Screening Results f o r Wellhead


Fluid . . . . . . . . . . . . . . . . . . . . .

4-39

4-22

Composition of Geothermal Fluid from Two Wells


a t Heber, C a l i f o r n i a KGRA . . . . . . . . . .

. 4-40

4-23

Corrosion T e s t Results f o r Wellhead F l u i d a t


Heber, C a l i f o r n i a . . . . . . . . . . . . .

. .

4-41

4-24

R a f t River Corrosion Screening Results f o r


Wellhead F l u i d

4-25

Composition of Wellhead Fluid from Three Wells


i n t h e Raft River, Idaho KGRA . . . . . . . .

. 4-45

4-26

Rates of Uniform, P i t t i n g , and Crevice Corros i o n f o r Metals Exposed t o Raft River Wellhead
Fluid..

4-47

. . . . . . . . . . . . . . . . . 4-44

...................

4-27

C l a s s i f i c a t i o n of M e t a l l i c Construction
Materials by Corrosion Resistance Using Results
of Coupon T e s t s a t Raft River, Idaho KGRA . . . 4-48

4-28

Tube t o Tubesheet Combinations Tested a t Raft


River . . . . . . . . . . . . . . . . . . . . .

4-29

Salton Sea Corrosion Screening Results f o r


Wellhead Fluid . . . . . . . . . . . . . .

. . . 4-53

4-30

Salton Sea Corrosion Screening Results f o r


F l u i d (Liquid Stream) A f t e r F i r s t Flash .

. . . 4-54

4-31

Salton Sea Corrosion Screening Results f o r


Steam from F i r s t Flash

4- 32

Salton Sea Corrosion Screening Results f o r


Scrubbed Steam from F i r s t Flash . . . . .

4-33

Salton Seal Corrosion Screening Results f o r


Fluid (Liquid Stream) A f t e r Second Flash . .

4-51

. . . . . . . . . . . . . 4-55

viii

. . . 4-56
. . 4-57

LIST OF TABLES (CONT'D)

Page

4- 34
4- 35

Salton Sea Corrosion Screening Results f o r


Steam from Second Flash

4-58

Salton Sea Corrosion Screeing Results f o r


Scrubbed Steam from Second Flash

4-59

............

.......

4- 36

Salton Sea Corrosion Screening Results f o r


Concentrated Gas-Flue Fluid a t 105C . . .

4-37

Composition of Synthetic Salton Sea Fluid Used


i n Laboratory T e s t s

4-61

4-38

Tests Using Deaerated and Oxygenated Synthetic


Salton Sea Fluid

4-63

4- 39

Corrosion Rates Measured i n F i f t e e n Day Autoclave Tests Using Synthetic Salton Sea Fluid
with Addition of COn and CHs

4-64

. .

. . . . . . . . . . . . . .

...............

.........

4-60

4-40

Results of Laboratory T e s t s of t h e E f f e c t of
Welding on Uniform Corrosion R a t e i n Synthetic
Salton Sea F l u i d . . . . . . . . . . . . . . . 4-65

4-41

Corrosion Rates Measured i n Laboratory Tests


Using Deaerated and .Aerated S y n t h e t i c Salton
Seal Fluids

4-70

4- 42

C h a r a c t e r i s t i c s of Geothermal Fluids from


Three Wells i n t h e Salton Sea KGRA

4-74

4- 43

F l u i d C h a r a c t e r i s t i c s of Seven GLEF Process


Streams i n T e s t s of Corrosion R a t e a t W e l l
Magmamax No. 1

4-76

Corrosion Rates Measured i n Fifteen-Day T e s t s


Using Wellhead F l u i d From Magmamax No. 1 i n
t h e S a l t o n Sea KGRA

4-78

Corrosion Rates Measured i n Fifteen-Day Tests


Using F i r s t Flash F l u i d From W e l l Magmamax No.
1 i n t h e Salton Sea KGRA

4-79

..................
......

. . . . . . . . . . . . . . . .

4-44

..............

4-45

...........

4-46

Corrosion Rates Measured i n Fifteen-Day T e s t s


Using F i r s t Flash Steam From Well Magmamax No.
1 i n the Salton Sea KGRA

. . . . . . . . . . . 4-80

ix

LIST OF TABLES (CONT'D)


Page
4-47

Corrosion Rates Measured in Fifteen-Day Tests


Using Scrubbed First Flash Steam From Well
Magmamax No. 1 in the Salton Sea KGRA . . . .

4-81

4-48

Corrosion Rates Measured in Fifteen-Day Tests


Using Second Flash Fluid From Well Magmamax No.
1 in the Salton Sea KGRA . . . . . . . . . . . . 4-82

4-49

Corrosion Rates Measured in Fifteen-Day Tests


Using Second Flash Steam From Well Magmamax No.
1 in the Salton Sea KGRA . . . . . . . . . . . . 4-83

4- 50

Corrosion Rates Measured in Fifteen-Day Tests


Using Scrubbed Second Flash Steam From Well
Magmamax No. 1 in the Salton Sea KGRA. . . . .

4-84

Results of Erosion-Corrosion T e s t s of Possible


Turbine Component Alloys in Acidified Salton
Sea Geothermal Fluid . . . . . . . . . . . . .

4-87

4-51

4-52

Electrochemical Corrosion Rates Measured in


Acidified Flashed Fluid From Well Magmamax No. 1
at the Salton Sea KGRA . . . . . . . . . . . . . 4-89

5 -1

Forms and Causes of Corrosion for Metals in


Liquid Geothermal Streams (Summary of Information
Presented in Sections 5 . 1 through 5 . 6 ) and Ways
to Prevent Attack . . . . . . . . . . . . . . . 5 - 3

5-2

Corrosion of Plain and Low Alloy Steels in


Natural Geothermal Liquids . . . . . . . .

5-3

. . .

5-12

. . . .

5-25

. . . . . .

5-31

Comparison of SCC and SSC in Geothermal


Environments . . . . . . . . . . . . . .

5-4

Sulfide Stress Cracking of Some High


Strength Alloys . . . . . . . . . .

5-5

Sensitivity of Titanium Alloys to Crack


Progagation . . . . . . . . . . . . . .

5-6

Corrosion of Plain and Low Alloy Steels in


Stream From Liquid-Dominated Sources . . .

5-7

Reduction in Fatigue Endurance Limit at


Cerro Prieto after 1 5 0 Days Exposure . .

6-1

High Temperature Strengths of PolymerImpregnated Mortar . . . . . . . . . .


X

. . . .

. . .

5-58
5-67

. . . . 5-70

. . . . .

6-3

LIST OF TABLES (CONT'D)

6-2

Polymer Concrete Testing in Geothermal Fluids.

6-3

Performance of Corrosion Resistant Cements in


250F Seawater (12-Month Exposure) . . . . .

6-4

FRP Laminates in Flowing Seawater at 250"F,

30 PSIG After 15 Months of Exposure.

xi

Page
6-5

. . 6-6

......

6-9

1
I

bi

LIST OF FIGURES

Page

2-1

Direct Cycle (Rankine) f o r Steam-Dominated


Geothermal Resource

2-2

Single Flash Steam Cycle f o r Natural Pressure,


Liquid-Dominated Geothermal Resource . . . .

2- 3
2-4
2-5

. . . . . . . . . . . . . . 2-5

Dual Flash Steam Cycle f o r Natural Pressure,


Liquid-Dominated Geothermal Resource . . .
Direct Binary Cycle f o r Natural Pressure ,
Liquid-Dominated Geothermal Resource . .

. 2-7

. .

. . .

Flashed Steam Binary Cycle f o r Natural P r e s s u r e , Liquid-Dominated Geothermal Resource

. .

2-9

2-7

Direct Binary Cycle f o r Pumped, Liquid-Domin a t e d Geothermal Resource . . . . . . . . .

2-8

Flashed Steam Binary Cycle f o r Pumped, LiquidDominated Geothermal Resource . . . . . . . .

4- 1

5-1
5-2

2-19

. .

2 -21

Corrosion Rate of 1010 Mild S t e e l i n 250F


Seawater Versus Dissolved Oxygen

. . . . . . .

Weight-Loss Corrosion Rates of Mild Steel i n


High Velocity, High Temperature Seawater . .

4-18

5-6
t

5-7

5-3

Galvanic Series of Selected Alloys i n Hot Acid


Treated/Deaerated S e a w a t e r (GE-117) . . . . . . 5-10

5-4

Effect of Seawater pH on t h e Corrosion Rate of


1010 Mild Steel a t a Typical Deaerator Tempera5-14
ture . . . . . . . . . . . . . . . . . . . . .

5-5

Average Corrosion R a t e of Carbon Steels vs


Salinity . . . . . . . . . . . . . . . . .

xii

. . 2-17

Ratios of FEL A f t e r Exposure-to-FEL Before


Exposure as a Function of Corrosion P i t Depth
(TO-089) . . . . . . . . . . . . . . . . . .

_.

2-13

Two-Phase Expander Cycle f o r Natural Pressure ,


Liquid-Dominated Geothermal Resource . . . . . 2-15

Two-Phase Expander Cycle f o r Pumped, LiquidDominated Geothermal Resource . . . . . . .

I
i

2-11

2-6

2-9

1
1

. .

5-15

LIST OF FIGURES (CONT'D)

Page
5-6

P i t t i n g and Corrosion P o t e n t i a l s of S t e e l
i n Oxygen-Free Chloride Solutions 25C . .

. .

5-17

5-7

Corrosion R a t e of A212B Carbon Steel i n


Deaerated 4 M
- N a C l as a Function of pH and
Temperature . . . . . . . . . . . . . . .

. .

5-19

P i t t i n g and Corrosion P o t e n t i a l s of S t e e l
as a Function of Temperature i n Heber Geotherm a l Fluid . . . . . . . . . . . . . . . . . .

5-21

Approximate Correlation o f Hardness, Time t o


F a i l u r e and Applied S t r e s s f o r Carbon Steels
(3000 ppm H 2 S i n 5% NaC1)

5-27

5-8

5-9

......

5-10

5-11
5-12

Approximate Correlation of F a i l u r e Time f o r


Carbon Steels i n 5% N a C l Containing Various
Concentrations of H2S . . . . . . . . . . .

5-27

Yield Strength-Threshold Stress Relationship


f o r Low Alloy S t e e l s

.............

5-28

Effect of Chloride Ion A c t i v i t y on SteadyState C r i t i c a l P o t e n t i a l f o r P i t t i n g ,


25C..

5-36

...................

5-13

5-14

P i t t i n g P o t e n t i a l s and Corrosion P o t e n t i a l s
o f Types 304 and 316 S t a i n l e s s Steel i n 4 M,
N a C l as a Function of Temperature . . . . .

.............

Relationship Between t h e C r i t i c a l P i t t i n g
P o t e n t i a l s (EcSCr Measured i n Deaerated Synt h e t i c Seawater a t 9O"C, pH = 7.2k0.2) o f
Fe-Cr-Mo Based Alloys and Their Resistance t o
Crevice Attack A f t e r a 14-Day Exposure t o
S y n t h e t i c Seawater a t 1 2 1 C and ~ 6 ppm
0
Oxygen

5 -42

E f f e c t of Chloride and Oxygen on Time t o


Cracking Type 204 S t a i n l e s s Steel Wire Held a t
Constant Load i n Single Phase Aqueous Environment..

5-44

....................

5-16

5-38

Comparison o f t h e C r i t i c a l P i t t i n g P o t e n t i a l s
of Fe-Cr-Mo Alloys with Several Commercial
Alloys i n Deaerated Synthetic Seawater a t 9O"C,
pH = 7.2k0.2
5-41

...

5-15

. . . . . . . . . . . . . . . . . . .
xiii

LIST OF FIGURES (CONT'D)

Page
5-17

5-18

5-19

5-20

Effect of pH, Chloride Content, and Temperat u r e on t h e Stress Corrosion Cracking of


Type 304 S t a i n l e s s Steel Under Residual Weld
Stresses . . . . . . . . . . . . . . . . . .

5-45

Anticipated Corrosion Performance of


Unalloyed Titanium (ASTM Grade 2) i n Chloride
Brines and Under N a C l Solid S a l t
Deposits . . . . . . . . . . . . . . . . . . .

5-52

Effect of Temperature and pH on Crevice


Corrosion of Unalloyed Titanium (GR.2) i n
Saturated N a C l Brine . . . . . . . . . . .

5-53

. .

E f f e c t of Temperature and pH on Crevice


Corrosion of Ticode-12 (Gr. 12) i n Saturated
N a C l Brine . . . . . . . . . . . . . . . . .

xiv

5-54

'bi
1.0

INTRODUCTION

This manual was prepared for the Department of Energy,.


Division of Geothermal Energy, by Radian Corporation under
Contract No. EG-77-C-04-3904. It presents guidelines for selecting construction materials for power production from liquiddominated United States geothermal resources.

i
I
~

I
1
1

ii

1.1

Background and Purpose

The goal of the Federal Geothermal Program is to stimulate development of geothermal energy as an economic, reliable,
operationally safe, and environmentally acceptable energy source.
One aspect of geothermal development that merits attention is
that of materials reliability. The objectives of the materials
work in the Divison of Geothermal Energy are to identify reliable
materials for geothermal applications and to help reduce materials
costs where they have a significant effect on the cost of utilization of geothermal energy.

1
i

i
i

I
i

i
I

The effectiveness of the development of geothermal


energy will be determined by the amount of geothermal power that
is made available, and this amount will be influenced by the
effect that materials problems have on efficiency and downtime.
Since every technological effort is limited to some extent by
the performance of materials, it is prudent to consider corrosion and materials problems which may limit the development of
geothermal energy. The av ilability of durable and cost-effective
construction materials for processing geothermal fluids has a
definite impact on the development of geothermal energy.

This manual serves two purposes. First, it is a collection and interpretive summary of existing data on materials performance in geothermal fluids. This data summary will reduce the
need for lengthy testing of a large number of materials at each

1-1

new geothermal site. It provides a way to help screen potential


construction materials through past experience.
The second purpose of the manual is to provide some
guidelines for selecting materials for geothermal power plants.
The manual establishes a framework of background information that
defines an approach to materials selection. It identifies the
processes (power cycles) and equipment used to produce electricity,
discusses the importance of fluid chemistry, and defines the forms
and mechanisms of corrosive attack that can occur in geothermal
process streams.
A l l of this information must be considered in selecting reliable construction materials. Once a geothermal resource

is selected for utilization, the power cycle used to produce


electricity can be specified. Selection of the power cycle is
based on the physical and chemical characteristics of the resource. The steps in the power cycle and the fluid composition
can be used to define specific process stream characteristics
(e.g., chemical composition, temperature, and fluid velocity).
This knowledge of process stream characteristics is essential
because it defines the corrosiveness of the various environments
to which construction materials will be subjected.
The next step is to consider the results of previous
materials performance tests and the operating experience in existing facilities. This information helps predict which materials
will be resistant to attack at the specific conditions in each
process stream. It is important to consider whether the test
conditions or operating conditions are the same as those in the
process stream of interest. And it is also useful to consider
the various possible modes of failure for materials in geothermal
fluids. The effects of fabrication practices, equipment configuration, and stresses during operation must also be taken into account. In light of all of these sources of information, materials
can be selected or the need for further testing can be defined.
1-2

Most corrosion failures are due to well known phenomena.


Minimizing these failures often depends upon knowing the environment to which the materials are exposed and being aware of past
materials experience. Close cooperation is required between corrosion and design engineers. Attention must be given to the
characteristics of the geothermal resource, the power cycle to
be applied, the durability of potential materials under these conditions, and the economics of these materials. Materials considerations and concern begin during the design phase but should
continue through plant construction, start-up, and operation.
1.2

Scope

Geothermal resources include steam-dominated sources,


liquid dominated sources, geopressurized sources, and dry (hot
rock) sources. There are numerous geothermal resource areas in
the United States. Some have been designated as known geothermal
resource areas (KGRA's) with potential for the extraction of
thermal or electrical energy. This manual considers materials
performance in liquid-dominated U . S . resources with sufficient
temperatures to be useful for electric power generation. There
are seven such liquid-dominated KGRA's for which fluid chemistry
is adequately deined. Predictions about the corrosiveness of
fluids from these resources can be made based on the fluid
characteristics. Corrosion rates have been measured and materials
performance tests have been ne using fluids from five of the
seven KGRA's: Baca, New Mexico; East Mesa, California; Heber,
California; Raft River, Idaho; and Salton Sea, California. Test
data available for Heber and Baca are rather limited, but Raft
River, Salton Sea, and East Mesa have been studied in more detail.

L 4

Other useful data on materials performance have been


accumulated in saline fluids and operating geothermal power plants.
Materials performance data are available for seawater distillation

1-3

plants, foreign operating power plants (Cerro Prieto, Mexico and


Wairakei, New Zealand) and The Geysers, a power plant utilizing
a steam-dominated resource. The information is useful in selecting construction materials for liquid-dominated resources and is
included in the Appendix.
The manual summarizes currently available information
in a format which allows new information to be added as it becomes available. The manual can be updated in the future by
incorporating the results of further testing or data for other
KGRA' s .
1.3

Summarv and Overview

The information in this manual is presented in six


sections and six appendices. Section 2 defines and diagrams
nine potential power cycles for the generation of electricity
from geothermal fluids. One power cycle is applicable to steamdominated resources, five are for liquid-dominated sources recovered by natural pressure, and three are for liquid-dominated
sources recovered by pumping. General fluid properties that
influence the applicability of power cycles to a particular geothermal resource are discussed. The corrosivity of individual
process streams in power cycles is described based on variations
in chemical composition and temperature.
Results of materials performance tests are analyzed
based on the chemical composition of the corrosive medium and
physical factors such as temperature, duration of exposure, and
fluid velocity. These variables must be well defined in order
to use test results to predict materials performance in other
systems. Geothermal fluids are complex, variable mixtures whose
characterization is difficult but essential. Section 3 identifies the key chemical components in geothermal fluids that are

1-4

significant in determining corrosivity. The key chemical components in seven United States liquid-dominated KGEU's are
defined.
Section 4 gives both summarized and detailed results
of materials performance tests in U.S. liquid-dominated resources.
The seven KGRA's treated in Section 3 are classified according to
relative corrosiveness. Detailed results of corrosion rate measurements are given for Baca, East Mesa, Heber, Raft River, and
Salton Sea KGRA's in two formats. The first format is a "screening"
table which serves as a guide to the test results. Corrosion
results in the screening tables are classified according to detection and severity of attack. The second format includes detailed
summaries and discussions of the corrosion rate measurements.
The results in Section 4 summarize available test results, but
they should be used cautiously. Test conditions, test duration,
and completeness of the tests should be considered in applying
the results.
Currently available test data are mostly the result
of uniform and localized corrosion rate measurements. But there
are other kinds of corrosive attack for metals in geothermal
fluids. Section 5 describes the various forms and mechanisms of
corrosive attack that can occur in geothermal process streams.
These generalizations are especially useful when materials must
be specified for conditions at which tests have not been done.
If the corrosion rate of a material has been tested at the stream
conditions of interest, the information in this section is still
useful. It explains how fabrication practices, equipment configuration, and operating stresses influence materials performance. And it can be used to predict whether other forms of
attack that have not been studied in tests will be important.
~

1-5

Section 6 discusses the application of nonmetallic


materials in geothermal environments. Information on the behavior of nonmetallics in these systems is limited.
The appendices contain information on (1) operating
experience at geothermal power plants, (2) corrosion in desalination facilities, (3) reliability of geothermal plants, ( 4 ) elastomeric materials, ( 5 ) comparative alloy costs, and (6) geothermal equipment manufacturers. The corrosion experience from operating geothermal power plants is particularly important to designers of future facilities. Operating experience points out
failures and problem areas that may not be encountered in shortterm corrosion tests.

1-6

GEOTHERMAL POWER CYCLES

2.0

A thermodynamic power cycle is the process employed

to extract and utilize geothermal energy to produce electricity.


The methods used in the power cycle to produce steam or other
vapor to drive a turbine depend on the characteristics of the
geothermal fluid. The four general types of geothermal resources found in the United States are steam-dominated, liquiddominated, hot dry rocks, and geopressured resources. National interest in electrical generation is focused on the first
two types of resources, and it is these resources for which typical power cycles are described.
This section of the manual defines nine potential
power cycles: one for steam-dominated sources, five for liquiddominated sources recovered by natural pressure, and three for
liquid-dominated sources recovered by pumping. The three pumped
source power cycles are the same as those for sources recovered
~y natural pressure except for the pumping equipment. Process
Elow diagrams, heat balances, and process stream conditions are
presented as well as a list of major equipment items for each
power cycle. General fluid properties that influence the applicability of power cycles to a ,particulargeothermal resource
are discussed. Finally, three power cycles are considered in
detail. The corrosivity of individual process streams is described based on variations in chemical composition and temperature.
,

2.1

Description of Nine Power Cycles

Nine generalized power cycles are potentially applicable to steam- and liquid-dominated geothermal resources. They

2-1

TABLE 2 - 1
POTENTIAL GEOTHERMAL POWER CYCLES
Steam-Dominated Sources
0

Rankine Cycle

Liquid-Dominated, Natural Pressure Sources


0
0

e
0
0

Single Flash Steam Cycle


Dual Flash Steam Cycle
Direct Binary Cycle
Flashed Steam Binary Cycle
Two-Phase Expander Cycle

Liquid-Dominated, Pumped Sources


0
0
0

Direct Binary Cycle


Flashed Steam Binary Cycle
Two-Phase Expander Cycle

are listed and classified in Table 2-1 according to whether the


source is steam- or liquid-dominated and whether it is recovered
by natural pressure or pumping.
The power cycles include three major process steps:
recovering the geothermal fluid from the well, producing steam
or other vapor to drive a turbine, and recovering condensate

2-2

and noncondensable gases. Power cycles differ mainly in the


methods used to generate steam or other vapor to drive the turbine. The Rankine Cycle uses steam directly from steam-dominated sources. Single and dual flash cycles employ a change
in pressure to separate steam from a liquid-dominated source.
Binary cycles use a second liquid as an intermediate heat transfer medium. In direct binary cycles, vapor to drive the turbine
is produced from the second liquid by heat exchange with the
geothermal fluid. In flashed steam binary cycles steam is separated from the geothermal fluid and used to vaporize the second liquid. Two-phase expander cycles use a mixture of both vapor and liquid from the geothermal fluid to drive the turbine.
Power cycles are also classified based on the method
of recovering the geothermal fluid from the well. Liquid-dominated resources can be recovered either by natural pressure or
by a downhole pump. Recovery by natural pressure has the advantage that little hardware is required down the borehole, reducing the cost and complexity of equipment installation and
maintenance. Downhole pumping can be used to increase well production, keep noncondensable gases dissolved, and prevent uncontrolled chemical changes in the well head fluid caused by flashing during the recovery process. The economic advantage of
higher well flow rates from pumping may offset the cost of installation and maintenance of downhole pumps.
Figures 2-1 through 2 - 9 are process flow sheets for
the nine power cycles listed in Table 2-1. These diagrams show
the primary flow paths, major equipment items, geothermal fluid
mass per unit of fluid introduced into the cycle, bulk fluid
temperature and pressure, and the anticipated bulk velocity of
the fluid in each stream.

2-3

Heat balances were calculated using steam table Values and ideal cycles. Heat balances and geothermal fluid concentrations for a specific plant design may therefore differ
from the range of values given in the flow sheets. The differences arise because of the deviation of geothermal fluid thermodynamic data from the pure water thermodynamic data of the steam
tables and the irreversibilities associated with each piece of
equipment. Other assumptions used in calculating the heat balances are noted on each flow sheet.

An equipment list (Tables 2-2 through 2-10) has been


formulated for each of the nine potential power cycles. The
equipment item number corresponds to the circled number on the
flow sheet for the respective power cycle. The major components within each equipment item have been listed with the associated bulk temperature and geothermal fluid phase in contact
with the equipment. Local geothermal fluid velocities within a
piece of equipment may differ significantly from the bulk geothermal fluid velocity indicated on the flow sheets. The local
velocity must be used for material selection purposes and for
design of materials compatibility experiments. Because components of a major piece of equipment will probably be of dissimilar materials, they are listed separately under each equipmen t item.
The equipment lists are not intended to be all encompassing and do not include every equipment item which may be
used. However, equipment types and operating conditions can be
selected from the lists which closely correspond to equipment
for material selection or material compatability test programs.
For instance, lube oil and hydrogen coolers are similar in service to the conditions found in condensers.

2-4

2 -5

TABLE 2-2
EQUIPMENT L I S T FOR DIRECT CYCLE USING STEAM DOMINATED
GEOTHERMAL RESOURCE
Equip Description
Well

Component

NO.

Wellhead

stmfwtr Sep.

Turbine

a
b
c
a
b
c
d
a
b
c
d
e
f
a
b

c
d
e

f
g
h
Main Condenser a
b
c
d
e
f
g
h

Casing
Production Pipe
Compactor
Valves (gate/globe/needle)
Gauges (press/temp)
Tees C Crosses
Blow-out Preventer
Press. Vessel
Internal Baffles C Mist Elim.
Valves (gate/globe/needle)
Level Control
Relief Valve C Silencer
Gauges (pressltemp)
Casing C Fixed Blades
Rotor, Blades 6 Shrouds
Seals
Nozzle Block
Valves (gate/globe/needle)
Relief Valve
Gauges (press/temp)
Strainers
Shell
Tubes
Ferrules C Packing
'
Gaskets
Baffles
Valves (gatefglobefneedle)
Gauges (press/temp)
Ejector

2-6

Stm/

2 Temp
OF
327-373

- & Phase

J
J
J
J
J

J
J
J
J
J
f
J
J
J
J
J
J
J
J
J
J
J

240-368

340-368

115-368

J
J

J
J
J
J
J
J

f
Nan-condensing Gas Piping
J
Condensing Spray Jets
J
1 Internal Piping
J
Inter Condenser same as 5
J
After Condenser same as 5
J
Condensate
a Casing
J
Pumps
b Shaft
J
c Imueller
J
d Pakking
e Glands. Lantern Rings, Bushings;
J
f Sealing Rings
g Gauges (pressftemp)
J
Cooling Tower
a Cold Water Basin
J
b Frame Work
J
c Splash Bars
J
d Splash Plates
J
e Downspouts
J
f Sprayers
J
g Drift Eliminators
h Fanstack
i Fanguard (if ID)
j Valves (gate/globe/needle)
4
k Screens
J
1 Fan (if ID)
m Fan Drive Motor (if ID)
n Fan Gear Set (if ID)
o Gauges (pressltemp)
J
Circ Water Pump same as 8
J

10

Liq

J
J
f
J
J
J
J
J
f
J
J
J
J
J
f
J

J
J
J
J
J
J
J
J
J
J
J
J
J
J
J

80-125

80-125
80-125
95-120

80-125

80-125

c
VENT NON
CONENSABLE
G A B

;i
2.

fCCWOMlC OP7fMuU R A S H POlNT OCCURS A T


Ko(ML F M ~ A T U Z EOfFFEW?XG.
L WELL UEAO # F L A W TAN<.
6. F L A y l TANK # CCWDENSR RF M - 4 q
Pb 4-4

A N , I??.

Figure 2-2.

w-ffo7-s

Single Flash Steam Cycle for Natural Pressure, Liquid-Dominated Geothermal


Re source

TABLE 2 - 3
EQUIPMENT L I S T FOR SINGLE FLASHED STEAM CYCLE USING
TURAL PRESSURE, LIQUID D O M I ~ DE
CG
-

Equip

Description

Component

No.

1
I

Well

a
b
c
d
a
b
c
d
a
b

Casing
Production Pipe
Compactor
f
Pump
Wellhead
Valves (gatefglobefneedle)
Gauges (pressltemp)
Tees & Crosses
Blow-out Preventer
Flash Tank
Press. Vessel
Internal Baffles & Mist Elim.
C Valves (gatelglobelneedle)
d Level Con rol
e Relief Vaive 6 Silencer
f Gauges (pressltemp)
Steam Scrubber a Press. Vessel
b Scrubber Elements
C Valves (gate/globe/needle)
d Relief Valve & Silencer
e Gauges (pressltemp)
Turbine
a Casing & Fixed Blades
b Rotor. Blades, & Shrouds
C Seals
d Nozzle Block .
e Valves (gatelglobelneedle)
f Gauges (pressltemp)
Relief Valve & Silencer
Strainers
f
Condenser
a Shell
f
b Tubes
(Main)
f
C Ferrules & Packing
f
d Gaskets
J
e Baffles
f
f Valves (gate1 lobelneedle)
f
Gauges (press$temp)
Ejector
f
i Seals
j Non-condensable
J
k Condensing Spray Jets
f
1 Internal Piping
f
Condenser (Inter) same as 6
J
Condenser (After) same as 6
f
same
as
12
Condensate Pump
f
Cold
t?ater
Basin
Cooling Tower
a
f
b Splashbars 6 Splashplates
J
C Downspouts
f
d Sprayers
e Drift Eliminators
f Fanstock 6 Fan uard (if ID)
f
g Valves (gatelgfobelneedle)
h Screens
i Fan (if ID)
j Fandrive Motor h Gear Set
(if ID)
f
k Gauges (pressltemp)
J
same
as
12
Circ Water Prrmp
f
Casing
Reinjection
a
f
b Shaft
f
C Impeller
/
d1 Packine
e Glands: Lantern Rings. Bushings?
J
f Sealing Rings
f
g Gauges (pressftemp)

7
8
9
10

11
12

Liq Stml
2 Temp
Phase OF
f
335-500

2-8

f
f
f
f
J
f
f
f
f
f

f
f

f
f
f
f
f

335-500

335-500

f
f

f
335-500
f

4
109-500

f
f
f
J
f
f
80-135

J
f
f
f
f
f
f
f
f
f

80-135
80-135
80-135
80-135

f
J
J
f
f
f
f
f
80-135
180-320

TABLE 2-4
EQUIPMENT FOR DUAL FLASHED STEAM CYCLE U S I N G NATURAL

1
Equip

Component

Description

Well

Liq

Stm/

-vap
a Casing

b Production Pipe
Compactor
J
d Pump
We 1lhead
a Valves (gate/globe/needle)
b Gauges (press/temp)
C Tees & Crosses
d Blow-out preventer
.
Flash Tank
a Press. Vessel
(1st)
b Internal Baffles & Mist Elim.
C Valves (gate/globe/needle)
d Level Control
Relief Valve & Silencer
Gauges (press/temp)
Steam Scrubber a Press. Vessel
b Scrubber Elements
C Valves (gate/globe/needle)
d Relief Valve & Silencer
e Gauges (press/temp)
Flash Tank (2nd) same as 3
same as 4
Steam Scrubber
Turbine
a Casing & Fixed
b Rotor, Blades, & Shrouds
C Seals
d Nozzle Block
e Valves (gate/globe/needle)
f Relief Valve & Silencer
Gauges (pressltemp)
Strainers
J
a Casing
Reinjection
J
b Shaft
pump
J
C Inmeller
J
d Pa'cking
e Glands, Lantern Rings, Bushings/
f Sealing Rings
J
g Gauges (press/temv)
J
a Shell
J
Condenser
b Tubes
J
(bin)
c Ferrules & Packing
J
d Gaskets
J
e Baffles
J
f Valves (gate/ lobeheedle)
g Gauges (pressftemp)
h Ejector
i Seals
J
j Non-condensable Gas Piping
k Condensing Spray Jets
J
1 Internal Piping
J
J
Condenser (Inter) same as 9
J
Condenser (After) same as 9
J
Circ Water Pump
same as 8
Condensate Pump
same as 8
J
J
Cooling Tower
a Cold Water Basin
J
b Splashbars & Splashplates
J
c Downspouts
J
d Sprayers
e Drift Eliminators
f Fanstzck & Fanguard (if ID)
J
g Valves (gate/globe/needle)
h Screens
i Fan (if ID)
j Fan Drive Motor 6 Gears Set
(if ID)
J
k Gauges (oress/temp)
C

10
11
12
13
14

2-10

2 Temp
Phase OF
J
320-400
J
J
/
J
J

320-400

J
J
J
J

265-365

J
J

J
J

1'

265-365

r'

210-310
210-310
105-365

214-265

80-135

J
J
J

J
J

80-135
80-135

80-135
80-135

95

J
J
J
J

2-11

TABLE 2-5
EQUIPMENT L I S T FOR DIRECT BINARY CYCLE USING
NATURAL PRESSURE, LIQUID-DOMINATED GEOTHERMAL RESOURCE

Equip

Description

Component
a Casing

2 Temp
Phase O F
J
400-230

b Production Pipe
c Compactor

Liq

Well

Stm/
Vap

No.

J
d m P
Wellhead
a Valves(gate/globe/need
b Gauges (press/temp)
c Tees & Crosses
d Blow-out Preventer
BrinelBinary
a Press. Vessel
Heat Exchanger b Tubes or Coils
c Valves (gate/globe/needle)
d Relief Valve
e Silencer
f Gauges (press/temp)
g Internal Baffles & Clips
J
Reinjection
a Casing
f
b Shaft
J
pump
c Impeller
J
d Packing
J
e Glands, Lantern Rings, Bushings/
f Sealing Rings
J
g Gauges (pressltemp)
J
Vent Condenser a Press. Vessel
b Tubes or Coils
c Valves (gate/globe/needle)
d Gauges (press/temp)

2-12

J
J
J
J

400-200

370-190

J
J

J
J

J
J

90-180

J
J
J
J

90-160

U
2-13

tid*

I)

0 0

TABLE 2-6
EQUIPMENT LIST FOR FLASHED STEAM BINARY CYCLE U S I N G
NATURAL PRESSURE, LIQUID-DOMINATED GEOTHERMAL RESOURCE

Equip Description
No.
1

Well

Wellhead

Flash Tank
(1st)

Component

6
7

10

Stml
2 Temp
-&
Phase

OF

a
b
c
d
a
b

c
d
a
b
c
d
e

f
4

Liq

Steam Scrubber a
b
c
d
e
Flash Tank (2nd)
Steam Scrubber
SteamIBinary
a
Superheater
b
c
d
e
Steam/Binary
a
Evaporator
b
c
d
e
Vent Condenser a
b
c
d
Reinjection
a
b
c
d
e
f
g

Casing
Production Pipe
Compactor
Pump
f
Valves (gate1 lobetneedle)
Gauges (press$temp)
Tees & Crosses
Blow-out Preventer
Press. Vessel
Internal Baffle & Mist. Elim.
Valves (gate/globe/needle)
Level Control
Relief Valve & Silencer
Gauges (pressltemp)
Press. Vessel
Scrubber Elements
Valves (gatelglobelneedle)
Relief Valve & Silencer
Gauges (pressltemp)
same as 3
same as 4
Press. Vessel
Tubes or Coils
.
Valves (gate/globe/qeedle)
Relief Valve & Silencer
Gauges (pressltemp)
Press. Vessel
/
Tubes or Coils
J
Valves (gate/globe/needle)
J
Relief Valve & Silencer
Gauges (pressltemp)
J
Press. Vessel
J
Tubes or Coils
J
Valves (gate/globe/needle)
J
Gauges (press/temp)
J
Casing
Shaft
Impeller
Packing
J
Glands, Lantern Rings, Bushings/
Sealing Rings
J
Gauges (pressltemp)
J

2-14

J
J
J
J
J
J
J
J
J
J
J
J
J
f
J
J
f
J
/
J
J
J
J
J
J
J

J
J
J

230-500

J
J
J
J
J

230-500

230-500

J
J

J
225-380
J

J
f
J

f
/
J
J
J
J
J
J
J

225-380
160-225
225-380

160-225

160-225

130-250

Figure 2-6.

Two-Phase Expander Cycle for Natural Pressure, Liquid-Dominated


Geothermal Resource

TABLE' 2'-7
EQUIPMENT LIST FOR TWO PHASE EXPANDER CYCLE USING
NATURAL PRESSURE, LIQUID-DOMINATED GEOTHERMAL RESOURCE

Equip
No.

5
6

8
9
10

11

Description

Well

Component

a
b
c
d
a
b
c

Casing
Production Pipe
Compactor
-P
Wellhead
Valves (gatelglobelneedle)
Gauges (pressltemp)
Tees & Crosses
d Blow-out Preventer
Steam Separator a Press. Vessel
b Internal Baffles & Mist Elim.
c Valves (gatelnlobelneedle)
d Level Control
e Relief Valve & Silencer
f Gauges (pressltemp)
Wing Chamber a Press. Vessel
b Mixing Elements
c Internal Baffles
d Valves (gate/ lobelneedle)
e Gauges (pressftemp)
f Metering Device
2 Phase Exp
a Venturi
Nozzle
b Valves
c Gauges (pressltemp)
Impulse Turbine a Casing & Fixed Blades
b Rotor, Blades & Shrouds
c Seals
d Nozzle Block
e Valves (gatelglobelneedle)
f Relief Valve
g Gauges (pressltemp)
h Strainer
Barometric
a Gaskets
Condenser
b Baffles
c Valves (gate1 lobelneedle)
d Gauges (press$temp)
e Ejector
f Seals
g Non-condensable Gas Piping
h Spray Jets & Piping
Inter Condenser
same as 7
After Condenser
same as 7

Liq
2 TT~
Vap Phase
Stml

J
J
J
J
J

2-16

292-465

292-465

J
J
f
J
/

f
J
J

292-465

4
/

J
J
J
J

J
J
J
J
J
J
J

292-465
Indeterdnate

J
d
f
/
J
J
J
J

Casing
J
Shaft
J
Impeller
J
Packing
J
e Glands. Lantern Rings, Bushings/
f Sealing Rings
J
g Gauges (pressltemp)
J
Condensate Pump
same as 10
J
Condensate Pump a
b
c
d

/
J
J
J
J

J
J

J
J

302-467

J
J

/
J

J
J
f

/
J
J

J
J
J
J
J

120

J
/

J
J

J
J

J
J

120
120
95-120

95-120

. ,

Figure 2-7.

..

. , . ..

.,

, . -.

~-

Direct Binary Cycle f o r Pumped, Liquid-Dominated Geothermal Resource

..

i
i
i

TABLE 2-8
EQUIPMENT LIST FOR DIRECT BINARY CYCLE USING
PUMPED, LIQUID-DOMINATED GEOTHERMAL RESOURCE

Equip

No.
1

Description

Component

Well

a
b
c
d
Wellhead
a
b
c
d
Brine/Binary
a
Heat Exchanger b
c
d
e
Reinjection
a
P-P
b
c

d
e
f
g

Liq

Casing
Production Pipe
Compactor
J
pump
Valves (gate/globe/needle)
J
Gauges (press/temp)
J
Tees & Crosses
J
Blow-out Preventer
J
Press. Vessel
J
Tubes or Coils
Valves (gate/globe/needle)
J
Relief Valve & Silencer
J
Gauges (press/temp)
J
Casing
J
Shaft
J
Impeller
J
Packing
J
Glands, Lantern Rings, Bushings/
Sealing Rings
J
Gauges (press/temp)
J

2-18

Stm/ 2 Temp
Vap Phase O F
JJ
212-662

J
J
J
J

J
-J
J
J
J
J
J

212-662

i
t

t
t

i
i

i
&

212-662

80-180

VENT
NW CaWENSddlE

GASES

ASSL4WPTloNS

JAN., I 9 7 8

.-

Figure 2-8. Flashed Steam Binary Cycle for Pumped, Liquid-Dominated Geothermal
Resource

TABLE 2-9.
EQUIPMENT LIST FOR FLASHED STEAM BINARY CYCLE USING
PUMPED, LIQUID-DOMINATED GEOTHERMAL RESOURCE

Equip

No.

Description

Well

Wellhead

5
6

10

Liq

Stml

Vap

Component
(L

casing

6 Production Pipe
c Compactor

f
f
f
f

d Pump
a Valves (gatel lobelneedle)
b Gauges (press$temp)
c Tees h Crosses
d Blow-out Preventer
Flash Tank
a Press. Vessel
b Internal Baffles h Mist E l b .
(1st)
c Valves (gate/globe/needle)
d Level Control
e Relief Valve h Silencer
f Gauges (pressltemp)
Steam Scrubber a Press. Vessel
b Scrubber Elements
c Valves (gatelglobelneedle)
d Relief Valves h Silencer
e Gauges (pressltemp)
Flash Tank (2nd) same as 3
Steam Scrubber
same as 4
SteamIBinary
a Press. Vessel
Superheater
b Tubes or Coils
c Valves (gatelglobelneedle)
d Relief Valve h Silencer
e Gauges (pressltemp)
SteamIBinary
a Press. Vessel
f
Evaporator
b Tubes or Coils
f
c Valves (gatelglobelneedle)
f
d Relief Valve h Silencer
e Gauges (pressltemp)
J
Vent Condenser a Press. Vessel
J
b Tubes or Coils
/
c Valves (gatelglobelneedle)
4
d Gauges (pressltemp)
f
Reinjection
a Casing
f
b Shaft
f
pump
c Xmpeller
f
J
d Packing
e Glands, Lantern Rings, Bushings4
f
f Sealing Rings
g Gauges (pressltemp)
J

2-20

f
f
J
f
J
f
f
f
f

2 Temp
Phase OF
f
230-662
f
f
f
f
d
f
f

230-662

230-662

f
f
f
185-401
f

J
f
J
J
J
J
J
f

f
f
J

J
f
f
f
f
J
J

f
J
/
J
f

185-401
160-300
185-401

f
140-250

f
J
130-250

130-250

Figure 2-9.

Two-Phase Expander Cycle f o r Pumped, Liquid-Dominated Geothermal Resource

TABLE 2-10
EQUIPMENT L I S T FOR TWO PHASE EXPANDER CYCLE U S I N G
PUMPED, LIQUID- DOMINATED GEOTHERMAL RESOURCE

Equip
No.
1

4
5

7
8
9

Description

Component

Liq

J
Casing
Production Pipe
J
Compactor
J
Pump
J
Valves (gate/globe/needle)
J
Gauges (pressltemp)
J
J
Tees 6 Crosses
Blow-out Preventer
J
Press.Vesse1
J
J
Mixing Elements
J
Internal Baffles
Valves (gates/globe/needle)
f
Gauges (pressltemp)
J
f
f Metering Device
2Ph Exp Nozzle a Venturi
J
J
b Valves (gate/globe/needle)
/
c Gauges (pressltemp)
Impulse Turbine a Casing IS Fixed Blades
b Rotor, Blades. 6 Shrouds
c Seals
d Nozzle Block
e Valves (gatelglobelneedle)
f Relief Valve
g Gauges (pressltemp)
h Strainer
f
Barometric Cond..a Gaskets
J
b Baffles
c Valves (gatelglobeheedle)
J
d Gauges (press1temp)
J
e Ejector
f Seals
J
g Non-condensable Gas Piping
h Spray Jets 6 Piping
J
J
Xnter Condenser same as 6
J
After Condenser same as 6
Condensate
a Casing
J
b Shaft
J
PmP
c Impeller
J
d Packing
J
e Glands, Lantern Rings, Bushings/
f Sealing Rings
J
g Gauges (pressltemp)
J

Stm/
2 Temp
Vap Phase OF

Well

a
b
c
d
Wellhead
a
b
c
d
Mixing Chamber a
b
c
d
e

2-22

J
J
J

302-662

/
/
J
J
J

302-662

J
f
f

280-662

/
J

280-662

J
J
J
f

Indeterminate

J
J

>120

J
J

J
f
J
J
J
J

>120

J
J

J
J
f
J
J

J
J
J
J
J

>120
95-.120

2.2

Effect of Geothermal Fluid Properties on the Applicability of Power Cycles

The applicability of a power cycle to a specific geothermal resource depends on characteristics of the fluid. Properties that influence the applicability of a power cycle include (1) total dissolved solids and scaling potential, (2) pressure and temperature, (3) the liquid to vapor ratio, ( 4 ) chemical comppsition of the fluid, and (5) concentration of noncondensable gases. The influence of these properties is discussed in
a general way in this section. The following Section 2 . 3 describes some potential materials performance problems associated
with fluid characteristics for specific process streams in three
power cycles.
Scaling in geothermal systems is a complex phenomenon
which is outside the scope of this discussion except as it affects corrosion and cycle selection. Scaling tendencies of a
given resource depend on its temperature and the concentration
of relatively minor concentration species: silica, calcium,
carbonate, sulfate and heavy metal ions. The tendency for silica
scaling increases with decreasing temperature, but pH effects
are also important and these depend on both temperature and processing conditions. The pH of most fluids increases on flashing. The scaling problem depends heavily on the chemical composition of the individual KGRA fluid. Scaling affects cycle
but requires a numbe of tradeoffs and cannot be generalized.
The Rankine Cycle is applicable to steam-dominated
sources. Eight cycles are presented for liquid-dominated
sources, five for sources recovered by natural pressure and
three for sources that require pumping to increase well flow

rate or to keep noncondensable gases dissolved. As discussed


above, liquid-dominated sources can be treated in flashed steam,
binary, or two-phase cycles.
Flashed steam cycles are useful for liquid-dominated
resources with fluid temperatures above 180C, but they are extremely sensitive to noncondensable gases. The energy obtained
from noncondensable gases in a turbine is small compared to the
energy available from steam. So a turbine which handles steam
and noncondensable gases must be larger (and more expensive)
than one with an equivalent rating which handles steam alone.
Noncondensable gases must be continuously removed from condensers
and heat exchangers. Flashed steam cycles are applicable for
resources with noncondensable gas concentrations less than three
weight percent ( 3 wt. %). Intermediate binary cycles are a useful alternative to use of gas ejectors and compressors for resources with higher noncondensable gas concentrations.
2.3

Effect of Fluid Properties on Materials Performance


In Specific Process Streams

The corrosive nature of geothermal fluids depends


mainly on the chemical composition, temperature, and local fluid
velocity. Section 3 describes the key chemical species that
determine the corrosiveness of geothermal fluids. This section
describes how the temperature, local velocity, and chemical composition of the wellhead fluid are altered during the energy
extraction process. Defining variations in the corrosive nature
of the geothermal fluid in the specific process streams provides
a useful framework for selecting construction materials and preventing materials problems.
The following sections identify potential materials
problems in specific process streams in three power cycles for
2-24

natural pressure, liquid-dominated resources. Dual flashed


steam, direct binary, and flashed steam binary cycles are considered. These cycles were selected because they are representative of those for other cycles. The discussions refer to stream
numbers on the flow diagrams in Section 2.2. The absence of
oxygen in the process streams is assumed unless otherwise stated.
As discussed further in Section 5, prevention of oxygen inleakage
is a major design goal for any geothermal process.
2.3.1

Dual Flashed Steam Cycle

Figure 2-3 shows the process streams in a typical dual


flash steam cycle.

Stream 1. Wellhead Fluid This is the highest temperature saline stream in the process. The aqueous pH is relatively low due to dissolved CO2 and H2S. Corrosivity is determined primarily by the combined effects of temperature, pH, and
chloride concentration. Materials problems may be increased by
localized flashing leading to high local fluid velocities. This
can cause erosion/corrosion by entrained solids or impingement.
Several observed failures of pipe ells may have been caused by
such attacks.

Scale deposition from solution may increase loca-

lized corrosion problems.


Steps must be taken to prevent severe corrosion due
to oxygen inleakage during a plant outage. The sinking of
fluid level in a well-duringprolonged shutdown can cause air
inleakage and considerable damage to well piping.
Stream 2. Fluid from Pretreatment to First Stage
Separator - The change in corrosiveness of this stream depends
on the pretreatment method. Acidification to reduce scaling
can fncrease the corrosion rate of carbon steel by a factor of
2-25

three or four per unit decrease in pH. Removal of H P S would


generally reduce corrosion of downstream components.
Streams 3 and 10. First Stage Steam to Turbine and
Air Ejectors - The high temperature steam will normally contain
significant quantities of C O P , some HZS, and lesser amounts of
Efficient steam separation and scrubbing to remove as much
"3.
entrained liquid as possible are desirable. This stream should
be kept as dry and oxygen-free as possible.
Stream 4 . First Stage Flashed Liquid to Second Stage
Flash Tank - The liquid stream loses a large fraction of its
dissolved C O P and H 2 S on flashing, and the temperature decreases. Loss of dissolved C O P and H 2 S increases the pH. These
effects should offset the increase in chloride concentration due
to steam l o s s , and Stream 4 should be less aggressive than
Stream 2.
Stream 5 . Second Flash Steam - This steam should contain significantly less C O P than the high temperature steam.
may be present due to the higher pH of the
Relatively more "3
flashed liquid. The risk of localized condensation is greater
for this stream. Entrained liquid removal, dryness, and nonaeration are still important.
Stream 6. Second Stage Flashed Liquid to Disposal This stream has undergone changes similar to those described
under Stream 4 . The absolute changes in C O P , HzS, and pH may
be less than for the first flash liquid. The temperature drop
is significant, however, and this stream should be less aggressive even though chloride concentration is higher. Oxygen inleakage is an increasing problem since pressure is approaching
atmospheric. At this point, the fluid is still hot enough to

2-26

cause stress corrosion cracking of susceptible materials in the


presence of small amounts of oxygen.
The post-treatment process (most likely for prevention
of injection well plugging) is poorly defined at present. If
significant cooling occurs in this process, sulfide stress
cracking or hydrogen blistering of downstream components (such
as the reinjection well piping) could occur. This form of attack fs more prevalent at lower temperatures in aqueous solution
and does not necessarily require high concentrations of sulfide.

Stream 7 . Turbine Exhaust to Condensers This stream


will contain little chloride but significant quantities of CO2,
from absorption of part of these
H2S, and in some cases "3
gases by steam condensate. The aggressiveness of this stream
depends on the concentrations of these gases (and their related
species) in the liquid and especially on the pH resulting from
mixing the "acidic" CO2 and H2S species with "alkaline" "3.
The main corrosion problem at Cerro Prieto was in the cooling
water system, where condensate was employed in the cooling towers
(Appendix A).
Emission of H2S from condensate in cooling towers may
be a problem. Addition of ferric salts was used as an emission
control method at the Geysers. Although mDderately effective
as an H2S control method, the addition of ferric salts signifid sludge disposal problems.
cantly increa

Streams 8 , 11, 12. Condensate and Cooling Water As


cooling water streams can prenoted above , the condensate
sent signif
t problems.
ling tower aeration can make
these problems more acute both by introducing oxygen and by
causing the oxidation of sulfide to sulfate which will make the

L)
2-27

Ld
stream more acidic. Possible solutions include:

1) increase of-the pH of the circulating stream,


2 ) addition of corrosion inhibitors, and
3 ) use of nonmetallic materials or corrosion resistant alloys.
The use of resistant materials for critical areas (e.g., hydrogen and oil coolers, instrumentation) is advisable.
2.3.2

Direct Binary Cycle

Process streams for this cycle are shown in Figure 2 - 4 .


The comments for Streams 1 and 2 prior to the heat exchanger are
the same as for the dual flash cycle.
Stream 3 in this cycle is saline fluid from the binary
heat exchanger. Chemical changes occurring in the saline/binary
heat exchanger are more difficult to predict than in the flashed
steam case. Since less flashing occurs, the concentrations of
C O P and H2S will not be decreased as much, and the pH increase
due to CO2 and H2S release will be less than in the flashed steam
case. Temperature effects on aqueous equilibria and gas solubility
will be more important and may tend to make the cooler fluid more
acidic.
The precautions given for the cooled, flashed fluid
stream generally apply to Stream 3 of the direct binary cycle.
The binary cycle Stream 3 may have relatively lower pH and higher dissolved H2S and CO, concentrations. Combined with lower
temperature, these factors could make it more aggressive with
regard to sulfide stress cracking or hydrogen blistering. Nonmetallic materials may be useful for some applications in this
environment.
2-28

L E J

'L/
Conventional materials will most likely be used for
the binary fluid equipment. The thin-walled parts of the heat
exchanger must be resistant to pitting and crevice corrosion to
prevent leakage of hot saline fluid to the binary loop. Resistance of the material to solutions used for scale removal must
also be considered.

At some sites it may be necessary to use part of


Stream 3 for cooling water. Usefulness will depend on control
of the scaling tendencies of the fluid after concentration and
possibly on cooling tower H2S emissions. Although probably
lower in H2S and'C02 than the flashed steam condensate, this
stream is more saline. Cooling tower aeration will make it
more aggressive due to the added dissolved oxygen and the lower
pH from sulfide oxidation. Control methods given for condensate Steams 8, 11, 12 in the dual flashed steam cycle are recommended.
2.3.3

Flashed Steam Binary Cycle

The effects of processing on the geothermal fluid are


the same as for the dual flashed steam cycle.
,

The main distinction from a corrosion standpoint is


that steam is used in the binary heat exchangers instead of
saline liquid.

The use of steam circumvents scaling problems but


does not prevent corrosion problems. Steam containing H,S and
C02 has been found to be innocuous at Wairakei and Cerro Prieto
when "dry," but high corrosion rates for several materials have
been found at Salton Sea. Steam condensate can be a corrosive
liquid depending on the concentrations of dissolved H2S, CO2,

2-29

and NH3 and t h e r e s u l t t n g pH. E f f i c i e n t steam s e p a r a t i o n and


scrubbing are important t o minimize c h l o r i d e carry-over from t h e
liquid.
The discussion of f l a s h e d geothermal l i q u i d f o r cooling w a t e r i n Section 2 . 3 . 1 a l s o a p p l i e s t o f l a s h e d steam binary
cycles.

2-30

3.0

CHEMICAL COMPOSITION OF GEOTHERMAL FLUIDS


FROM A CORROSION STANDPOINT

Results of materials performance t e s t s are analyzed


based on t h e chemical composition of t h e c o r r o s i v e medium and
physical f a c t o r s such as temperature, duration of exposure, and
f l u i d v e l o c i t y . These v a r i a b l e s must be w e l l defined i n order
t o use t e s t r e s u l t s t o p r e d i c t materials performance i n o t h e r
systems. Geothermal f l u i d s are complex, v a r i a b l e mixtures whose
c h a r a c t e r i z a t i o n i s d i f f i c u l t b u t e s s e n t i a l . This s e c t i o n ident i f i e s chemical components i n geothermal f l u i d s t h a t a r e s i g n i f i c a n t i n determining c o r r o s i v i t y . The u t i l i t y of e x i s t i n g chemi c a l composition d a t a f o r p r e d i c t i n g f l u i d c o r r o s i v i t y i s cons i d e r e d . A summary of chemical composition of f l u i d s from seven
U . S . geothermal resources i s presented.

3.1

Key Corrosive Chemical Species

Geothermal f l u i d s contain s i x key chemical s p e c i e s t h a t


produce a s i g n i f i c a n t c o r r o s i v e e f f e c t on m e t a l l i c c o n s t r u c t i o n
materials. These key species w e r e i d e n t i f i e d from an a n a l y s i s
of corrosion l i t e r a t u r e and an examination of t h e d a t a on chemi c a l composition o f f l u i d s from liquid-dominated geothermal resources. They are t h e most common and aggressive c o r r o s i v e s p e c i e s
and t h e r e f o r e t h e ones t h a t should be analyzed i n a l l geothermal
environments.
Geothermal f l u i d s are complex chemical s o l u t i o n s cont a i n i n g many d i f f e r e n t species. The s i x most s i g n i f i c a n t species
and t h e i r important gas and l i q u i d phase chemical forms are l i s t e d
below:

Hydrogen ion

3-1

Chloride ion
Hydrogen s u l f i d e
Carbon dioxide, Carbonate and Bicarbonate i o n

S u l f a t e ion
The i d e n t i f i c a t i o n o f t h e s e s p e c i e s as t h e most s i g n i f i c a n t i s complicated by t h e following f a c t o r s :
Materials respond t o a given chemical s p e c i e s i n
d i f f e r e n t ways and degrees.
The importance of a given species o f t e n depends
on i t s concentration relative t o o t h e r s p e c i e s .

The i n t e r a c t i o n of two o r more chemical s p e c i e s


may give r e s u l t s d i f f e r e n t from those obtained
with t h e individual species.
The temperature dependence of corrosion by
a given s p e c i e s i s o f t e n undefined.
The importance of a given species depends on
t h e form of a t t a c k (uniform, l o c a l i z e d , cracking).
Other chemical s p e c i e s t h a t are less common o r aggressive can
a l s o produce c o r r o s i v e e f f e c t s i n some geothermal f l u i d s . Examp l e s are f l u o r i d e ion, heavy metals, and boron. Oxygen, while
n o t normally a component of high-temperature geothermal f l u i d s ,
g r e a t l y i n c r e a s e s t h e i r corrosive effects.
The a c c i d e n t a l

3-2

i n t r o d u c t i o n of oxygen t o a geothermal process stream has produced very s e r i o u s corrosion problems i n e x i s t i n g geothermal
e l e c t r i c power p l a n t s .
Scaling o r s o l i d s deposition i s another aspect o f geothermal f l u i d chemistry t h a t influences materials performance.
P r e c i p i t a t i o n of l i q u i d phase species i n s o l u t i o n o r on equipment s u r f a c e s can influence corrosion rates and cause e r o s i o n .
The composition of t h e scale-forming s o l i d s and t h e r a t e of prec i p i t a t i o n depend on f l u i d composition and s p e c i f i c process
stream c o n d i t i o n s , so scale-forming s p e c i e s are n o t included i n
t h e l i s t o f key species.
Some g e n e r a l i z a t i o n s about t h e corrosive effects of
t h e key s p e c i e s , oxygen, and t r a n s i t i o n metal ions on construct i o n materials are given i n t h e following paragraphs. This subj e c t i s t r e a t e d i n more depth i n Section 5 . 0 , which provides det a i l s about t h e forms of a t t a c k f o r s p e c i f i c metals and a l l o y s .
Hydrogen ion (pH) - The general c o r r o s i o n r a t e o f carbon
steels i n c r e a s e s r a p i d l y with decreasing pH, e s p e c i a l l y below pH
7. P a s s i v i t y o f many a l l o y s i s pH dependent. Breakdown of pass i v i t y a t l o c a l areas can l e a d t o s e r i o u s forms of a t t a c k , e . g . ,
p i t t i n g , crevice c o r r o s i o n , and stress corrosion cracking.

Chloride causes l o c a l breakdown of p a s s i v e


Chloride
f i l m s which p r o t e c t many metals from uniform a t t a c k . Local penet r a t i o n of t h i s f i l m can cause p i t t i n g , crevice c o r r o s i o n , o r
stress corrosion cracking. Uniform corrosion rates can a l s o
i n c r e a s e with i n c r e a s i n g c h l o r i d e c o n c e n t r a t i o n , b u t t h i s a c t i o n
is g e n e r a l l y less s e r i o u s than l o c a l forms o f a t t a c k .
Hydrogen S u l f i d e - Probably t h e most severe e f f e c t o f
H2S i s i t s a t t a c k on c e r t a i n copper and n i c k e l a l l o y s . These
metals have performed w e l l i n seawater b u t are p r a c t i c a l l y

3-3

unuseable i n geothermal f l u i d s containing H 2 S . The e f f e c t of H 2 S


on iron-based materials i s less p r e d i c t a b l e . Accelerated a t t a c k
occurs i n some cases and i n h i b i t i o n i n o t h e r s . High-strength
s t e e l s are o f t e n s u b j e c t t o s u l f i d e stress cracking. H 2 S may
a l s o cause hydrogen b l i s t e r i n g of s t e e l s . Oxidation of H2S i n
a e r a t e d geothermal process streams i n c r e a s e s t h e a c i d i t y of t h e
stream.
Carbon Dioxide - I n t h e a c i d i c r e g i o n , C02 can a c c e l e r a t e t h e uniform corrosion o f carbon s t e e l s . The pH of geothermal f l u i d s and process streams i s l a r g e l y c o n t r o l l e d by C O 2 .
Carbonates and bicarbonates can d i s p l a y mild i n h i b i t i v e e f f e c t s .
Ammonia
of copper a l l o y s .
o f mild s t e e l s .

Ammonia can cause s t r e s s corrosion cracking


It may a l s o a c c e l e r a t e t h e uniform corrosion

S u l f a t e - S u l f a t e plays a minor r o l e i n most geothermal


f l u i d s . I n some low c h l o r i d e streams, s u l f a t e w i l l be t h e main
aggressive anion. Even i n t h i s c a s e , i t r a r e l y causes t h e s a m e
severe l o c a l i z e d a t t a c k a s c h l o r i d e .
Oxygen - The a d d i t i o n of s m a l l q u a n t i t i e s of oxygen t o
a high-temperature geothermal system can g r e a t l y . i n c r e a s e t h e
chance of severe l o c a l i z e d corrosion of normally r e s i s t a n t metals.
The corrosion of carbon s t e e l s i s s e n s i t i v e t o t r a c e amounts of
oxygen.
T r a n s i t i o n Metal Ions - "Heavy" o r t r a n s i t i o n m e t a l
ions might a l s o be included as key s p e c i e s . Their a c t i o n a t low
concentrations on most construction materials i s i l l - d e f i n e d .
However, t h e poor performance of aluminum a l l o y s i n geothermal
f l u i d s may be due i n p a r t t o low l e v e l s of copper o r mercury i n
t h e s e f l u i d s . Salton Sea geothermal f l u i d s contain many t r a n s i t i o n

3- 4

metal ions a t greater than "trace" concentrations. Some oxidized


forms of t r a n s i t i o n metal ions (Fe+3, CU'~, e t c . ) are corrosive,
but t h e s e ions are present i n t h e lowest oxidation s t a t e (most
reduced form) i n geothermal f l u i d s . Oxygen can convert Fe+2
t o Fe+3 which i s another reason t o exclude oxygen from geothermal
streams.

3.2

Key Corrosive Chemical Species i n Selected KGRA's

The concentrations of key species i n geothermal f l u i d s


must be defined i n order t o u s e t h e r e s u l t s of materials p e r f o r mance t e s t s . I f corrosion t e s t conditions a r e a c c u r a t e l y and
completely d e f i n e d , then t h e r e s u l t s can be used t o p r e d i c t mat e r i a l s performance i n o t h e r systems. So i t i s u s e f u l t o cons i d e r t h e a p p l i c a b i l i t y of e x i s t i n g composition d a t a . Analyses
of s p r i n g s o r o t h e r r e l a t e d s u r f a c e sources are of no use f o r
p r e d i c t i n g corrosion i n geothermal power c y c l e s . Although a
l a r g e number of geothermal w e l l analyses have been completed
re of l i m i t e d u t i l i t y f o r p r e d i c t (LA-312), much of t h e s e d a t
i n g materials performance. The u t i l i t y of t h e d a t a may be l i m i t e d
f o r t h e following reasons :
One o r more of t h key species were not analyzed
(H2S and N H 3 are t h e most common omissions).

Other important
c t o r s such as temperature,
w e l l flow r a t e , o r flow Cime were n o t s p e c i fied.
The accuracy
the analytical r e s u l t s was not
i n d i c a t e d . Error l i m i t s were n o t s p e c i f i e d ,
and t h e method of sample a c q u i s i t i o n and analy-

ses were not described. Obtaining a represent a t i v e sample o f downhole f l u i d p r e s e n t s a number


of experimental d i f f i c u l t i e s (NE-302).
3-5

Chemical analyses w e r e done on f l a s h e d f l u i d , and


the conditions under which f l a s h i n g occurred w e r e
e i t h e r uncontrolled o r unspecified.
Flashing causes changes i n t h e pH and t h e concentrations
of H Z S , C 0 2 and NH3 i n t h e f l u i d . I f t h e s e components are measured i n t h e f l a s h e d f l u i d , t h e r e s u l t s are n o t r e p r e s e n t a t i v e
of concentrations i n t h e unflashed f l u i d . The usefulness of
flashed f l u i d d a t a i s l i m i t e d i f they cannot b e used t o c a l c u l a t e
concentrations i n t h e unflashed streams. The f l a s h i n g conditions
must be s p e c i f i e d and t h e f l a s h e d steam must be analyzed f o r H 2 S ,
CO2 and " 3 .
Such d a t a are scarce and hard t o o b t a i n because of
d i f f i c u l t i e s i n t h e sampling procedures.
A p a r t i a l l i s t of information r e q u i r e d w i t h any reported
a n a l y s i s i s given below.

w e l l shut-in periods,
r e c e n t r e s e r v o i r engineering,
t o t a l s t a b i l i z a t i o n time,
f l u i d flow r a t e from w e l l ,
i d e n t i f i c a t i o n of two-phase flow, and
s p e c i f i c sampling procedures and conditions
T y p i c a l concentrations of key c o r r o s i v e chemical s p e c i e s
i n f l u i d s from seven "known geothermal resource areas" (KGRA's)
are shown i n Tables 3-1 and 3-2. These d a t a are t h e r e s u l t of
a review and a n a l y s i s of a l l a v a i l a b l e chemical composition d a t a
f o r U.S. and f o r e i g n geothermal resources. The review showed
t h a t d a t a c h a r a c t e r i z i n g key species a r e a v a i l a b l e f o r seven
U.S. KGRA's and two f o r e i g n resources (Cerro P r i e t o , Mexico and
Wairakei, New Zealand, see Appendix A ) . KGRA's f o r which reasonably complete c h a r a c t e r i z a t i o n s o f key s p e c i e s are a v a i l a b l e
include Salton Sea, East Mesa, Heber, Mono-Long Valley, Baca
(Valles Caldera), Beowawe, and 'Raft River.

3-6

TYPICAL CONCENTRATIONS OF KEY CORROSIVE CHEMICAL S P E C I E S I N F L U I D FROM SEVEN KGRA'S

TABLE 3-1.

T'aprrBhlIe

KGU

saltno sea.

met

c..

m, c..

*C
and location

Properties of the Geothe-1


Resource
Wncrntration of Key Species i n the ? h i d (ppd
pa
ClTotal UJ,
Total RtS
Total l l s r

60;

Fluid
Description

10-30

300

20

unfluhed
well-head fluid

800

41

20

unf lashed
well-head fluid

9.000

180

%2

13

152

unflaahed
well-head fluid

6.5

227

180

14

0.1

96

unf lashed
well-head fluid

171
(well-head
a t 110 pBig)

6.8

3.770

128

59

fluhed fluid

132
(mll-bud)

9.3

50

209

89

flashed fluid

Ub

7.2

780

60

0.1

61

d l a s h e d fluid

250
(bore-hole)

5.2

115.000

1MI-200

5.7

11.wo

1-200
(bore-hole)

7.1

175
(bore-hole)

L.000

(bora-hole)

Caent.
Them data are the reaulta
Of eXtmBiVB aM1YB.s Of
several wells. BO they are
repreaentati*. of the resource. Variation. occur;
UJr concentratiom u high
u 10.000 p p haw been
measured.
Thm data are for v e l l 6-1.
which he. rsceived the m0.t
study. It M y M t be tlpie e l of the field. UQher
pH (6.5) and lover C 1 and
COX h e w been meuured at
other wells. TIIB fluid
also contains .bout 9 ppm
?e.

h f t River. Id.

bore-hole)

These data are from two


separate analpea of fluid
from the well m l i n 1.
The fluid elao c a n t a h
about 4 ppm Fe.
Theae data are for w e l l
Endogenous 4. It is the
only well for which ltsS
eoncentratloas were measured. &8UlCB Of -8lyBeS
Of other BpeCieB i n flUfdB
m in the
from other d
area agree with the ruults
for this W l l .
These data represent the
re8ultr of three .hilar
analyses of f l u h e d fluid
from w e l l B ~ C B11. They
are not repressntativa of
values in t h e unflmhed
fluid.
These data are repreaentr
ti- Of wells V d U D 2. 3.
and 4 . Dats for BrS. Wz.
W, and pB are not representative of the unfluhad
fluid.
These data are for vell
#XtX 1 which is W11 eb.r
ecteriaed. W e l l RRCE 2 bu
e s w l a r colpoaition.
Ikll #XtX 3 h u a .hilaremposition except for C l
Vhieh b .bout 3 t b C B
higher.

TABLE 3-2.

TYPICAL COMPOSITION OF NONCONDENSABLE GASES IN SEVEN KGRA'S

Concentration of
Noncondenaable Gases

KGRA
Salton Sea, Ca.
East Mesa, Ca.

co 2

vol X of steam

80.-90.

0.3

70-92

1.0

1.7

90.16

1.89

a 4

no data available

Heber, Ca.

0.2 wt X of total flow

Mono-Long Valley, Ca.

0.87 wt X of eteam

98.2

Baca (Valles Caldera),


N. M.

1.72 vol X of steam


4.10 wt X of steam

(47,390)a

Beowawe, Nev.

0.19 wt X of steam

97.6

Raft River, Id.

1.6 vol X of total flow

co

0.2-0.3

Composition of Noncondensable Gases


(volume X of gas)
H2S
"3
NB
At
HB
He

1.4-9.5

7.2

(567)
0.93

0.022

(109)

1.8-3.8

(4)

0.148

e0.01

2.9-15

0.39

0.049

0.369

(6)

u n i t s are ppm in steam

bMeasured oxygen concentration was 0.459 vol X of gas.


Cbalmce is

Sample was probably contaminated with air.

+ Ar

C'

Table 3-1 g i v e s t y p i c a l concentrations of key s p e c i e s


i n unflashed f l u i d from a l l b u t two of t h e KGRA's. Data f o r Baca
and Beowawe are from analyses of f l a s h e d f l u i d , s o t h e values f o r
H 2 S , C O 2 , N H 3 , and pH are n o t r e p r e s e n t a t i v e of those i n t h e unf l a s h e d f l u i d . Flashed steam w a s analyzed as shown i n Table 3-2.
The comments i n Table 3-1 i n d i c a t e t h e degree t o which
t h e s e d a t a can be considered t y p i c a l of t h e e n t i r e f i e l d . Some
KGRA's have been c h a r a c t e r i z e d i n more d e t a i l than o t h e r s . V a r i a t i o n s i n t h e r e s u l t s of analyses of f l u i d s from d i f f e r e n t w e l l s
i n a f i e l d are q u i t e common. These v a r i a t i o n s make i t d i f f i c u l t
t o define t y p i c a l o r r e p r e s e n t a t i v e concentrations of key s p e c i e s ,
e s p e c i a l l y i f only one w e l l has been s t u d i e d . The d a t a f o r S a l ton Sea, Raft River, and Mono-Long Valley a r e based on m u l t i p l e
analyses of s e v e r a l w e l l s , s o t h e r e i s a good b a s i s f o r assuming
t h e y are t y p i c a l of t h e f i e l d . On t h e o t h e r hand, d a t a f o r E a s t
Mesa and Heber are from t h e a n a l y s i s of a s i n g l e w e l l , s o t h e r e
i s some p o s s i b i l i t y t h a t t h e d a t a are not t y p i c a l of t h e e n t i r e
f i e l d . Other w e l l s a t East Mesa have lower c h l o r i d e and C02
concentrations and s l i g h t l y higher pH values than those given
h e r e , b u t corrosion t e s t i n g has been done i n t h e f l u i d shown.
Table 3-2 shows t y p i c a l concentrations of noncondensab l e gases i n f l a s h e d steam o r t o t a l f l u i d from s i x of t h e seven
KGRA's. Concentrations o f n i n e components are given. These
d a t a are p a r t i c u l a r l y s i g n i f i c a n t f o r Beowawe and Baca KGRA's
because t h e key species concentrations i n Table 3-1 are f o r
flashed f h i d .

3-9

4.0

RESULTS OF CORROSION TESTS IN GEOTHERMAL FLUIDS

This s e c t i o n of t h e manual gives both summarized and


d e t a i l e d r e s u l t s of m a t e r i a l s performance t e s t s i n U.S. l i q u i d dominated resources. F i r s t an overview i s presented which
d e f i n e s f o u r sources o f information about corrosion tests on
m e t a l l i c c o n s t r u c t i o n m a t e r i a l s i n s a l i n e f l u i d s . The r e l a t i v e
usefulness of t h e t e s t r e s u l t s f o r m a t e r i a l s s e l e c t i o n purposes i s discussed. Then t h e form i n which t e s t s r e s u l t s are
presented i s explained t o show where t o f i n d t h e r e s u l t s and
how t o i n t e r p r e t them. Sections 4 . 1 through 4.5 contain t h e
a c t u a l t e s t r e s u l t s f o r U. S. liquid-dominated KGRA's. Results
of tests and o p e r a t i n g experience f o r o t h e r f l u i d s are included
i n t h e appendices.
There are f o u r sources of information about a c t u a l
m a t e r i a l s performance i n s a l i n e f l u i d s :
Results of corrQsion tests a t f i v e U.S. l i q u i d dominated KGRA's (presented i n t h i s s e c t i o n )
P r a c t i c a l o p e r a t i n g experience from two f o r e i g n
power p l a n t s using liquid-dominated geothermal
resources (presented i n Appendix A)
Results of corrosion t e s t s a t The Geysers, a U.S.
steam- dominated geothermal resource (presented
i n Appendix A)
Results of corrosion t e s t s i n seawater desalinat i o n p l a n t s (presented i n Appendix 3 ) .

4-1

Previous experience i s of t h e utmost importance i n


corrosion engineering. Development of U. S. liquid-dominated
geothermal resources i s i n t h e e a r l y s t a g e s , but power p l a n t s
using t h i s t y p e of resource are already o p e r a t i o n a l a t Wairakei,
New Zealand and Cerro P r i e t o , Mexico. Appendix A contains a
summary of corrosion d a t a from t h e s e two s i t e s . The d a t a from
Cerro P r i e t o are p a r t i c u l a r l y important because t h e p l a n t i s
l o c a t e d on t h e California-Mexico border. The geothermal f l u i d
p r o p e r t i e s a t Cerro P r i e t o are s i m i l a r t o those i n some C a l i f o r n i a
resource areas.
The United States has an operating power p l a n t a t t h e
Geysers, a steam-dominated resource. Operating experience from
t h e Geysers p l a n t i s of i n t e r e s t because i t provides d a t a on
corrosion i n steam and condensate. But t h e s e streams have lower
c h l o r i d e concentrations than equivalent streams from l i q u i d dominated resources.
Many materials have been t e s t e d i n seawater d e s a l i n a t i o n p l a n t s a t temperatures up t o 120C. T e s t r e s u l t s may i n d i c a t e some m a t e r i a l s s u i t a b l e f o r lower temperature process
streams i n geothermal power cycles. General f i n d i n g s and comments on a p p l i c a b i l i t y t o geothermal systems are given i n
Appendix B.

4.1

Corrosion Tests a t U. S. Liquid-Dominated KGRA' s

Emphasis i n t h i s s e c t i o n i s placed on recent corrosion


t e s t s a t U . S . liquid-dQminated K G R A ' s .
Some g e n e r a l i z a t i o n s are
made about m a t e r i a l s performance i n f l u i d s from seven KGRA's.
T e s t r e s u l t s f o r f i v e of t h e KGRA's a r e presented i n s e p a r a t e
sections.

4-2

Wellhead f l u i d s from seven liquid-dominated KGRA's


have been c l a s s i f i e d i n t h r e e broad c a t e g o r i e s : most c o r r o s i v e ,
moderately c o r r o s i v e , and l e a s t corrosive. The information
a v a i l a b l e about corrosion i n t h e s e f l u i d s i s s t i l l too l i m i t e d
t o allow accurate p r e d i c t i o
about t h e performance of s p e c i f i c
materials. The broad c a t e g o r i e s are u s e f u l because they provide a framework f o r comparing r e s u l t s f o r d i f f e r e n t resources.

4.1.1

Most Corrosive:

Salton Sea

High uniform corrosion r a t e s and l o c a l i z e


p l a i n carbon s t e e l s by Salton Sea f l u i d s have been observed.
Many commonly used a l l o y s are s u b j e c t t o l o c a l i z e d a t t a c k i n
t h e s e f l u i d s . Resistant materials are a v a i l a b l e , but t h e appare n t marginal usefulness of carbon s t e e l i s of concern.
The chloride concentration of most Salton Sea f l u i d s
i s about t e n t i m e s higher than t h a t of t h e next highest KGRA.
COP and HzS concentrations re f a i r l y high but not exceptional
compared t o Cerro P r i e t o and Wairakei f l u i d s . The ammonia conc e n t r a t i o n does appear t o be high compared t o t h e s e sources
and o t h e r KGRA's. The pH (5.2) o f thds resource is relatively
low, but ac'idification t o pH
. 5 may be needed t o c o n t r o l s c a l ing. The s u l f a t e concentration i s n e g l i g i b l e compared t o o t h e r
c o r r o s i v e components i n t h i s f l u i d .

4.1.
Long Valley, Raft River
The compositions and l i m i t e d corrosion r e s u l t s f o r
esources i n d i c a t e t h a t
behavior should be s i m i l a r .
ompositions are b
those a t Wairakei and Cerro
P r i e t o f o r which long-te
e r a t i n g experience i s a v a i l a b l e .
However, s i m p l e power cycles a r e used a t these p l a n t s and mater i a l s s e l e c t i o n may be c r i t i c a l f o r more complex cycles.

4-3

Lid
The most extensive data are available for Raft River.
Limited data are available for East Mesa (well 6-1), Baca, and
Heber. Corrosion data are not available for Mono-Long Valley.
A brief overview of results and reasons for the moderately
corrosive classification is given below.
Available results indicate that the uniform corrosion
rate of plain carbon steels should be about 2-10 mpy in'these
fluids. Pitting and crevice corrosion were observed at Q f t
River and crevice corrosion at East Mesa. These forms of corrosion will probably limit the use of carbon steels to relatively
thick-walled equipment.
Material selection for thin-walled and critical components will be more difficult. Test results at Raft River are
instructive since extensive localized corrosion of many "resistant" alloys was observed even in this relatively low chloride
(~780ppm) and near neutral (pH 7.2) fluid. Shorter duration
tests at East Mesa and Heber show similar results. Preliminary
indications are that attack is no worse at these sites than at
Raft River. Alloys such as Type 316 and 26Cr-1Mo are subject
to localized attack. More detailed information in presented in
Section 4 . 5 .
The low H2S content of Raft River fluids is probably
unusual, and the copper-based alloys found to be acceptable may
be subject to H2S attack in most other fluids. Performance of
copper-nickel alloys was poor even in Raft River fluid.
As noted in Section 3 , Table 3-1, most new wells at
East Mesa have significantly lower chloride concentrations and
somewhat higher pH values than well 6-1 where most corrosion
testing has been done.

4-4

Corrosion d a t a i n Baca wellhead f l u i d are l i m i t e d .


Corrosion i n t h e f l a s h e d steam from t h i s source has received
more a t t e n t i o n . The r e l a t i v e l y low pH of t h e f l a s h e d f l u i d a t
Baca i n d i c a t e s p o t e n t i a l corrosion problems. If t h e pH o f
unflashed f l u i d i s much lower, w e l l piping could be s u b j e c t t o
s e r i o u s a t t a c k . The H2S content of unflashed f l u i d i s of s i m i l a r concern.
Mono-Long Valley i s t e n t a t i v e l y included i n t h i s c l a s s
even though i t has a low c h l o r i d e concentration. The pH o f t h i s
f l u i d i s lower, and wellhead temperature i s higher than R a f t
River. Combined with r e l a t i v e l y high H 2 S levels, t h e s e f a c t o r s
make it p o t e n t i a l l y as corrosive as o t h e r members o f t h i s class.
4,l. 3

Least Corrosive :

Beowawe

The c h l o r i d e concentration of Beowawe f l u i d s i s low


and pH of t h e f l a s h e d f l u i d i s high (pH $9.3).
These f a c t o r s
should make t h i s f l u i d less corrosive t o iron-based a l l o y s than
those i n t h e moderately corrosive category. However, t h e H2S
content o f t h i s f l u i d w i l l make it aggressive toward c e r t a i n
copper-based and nickel-copper a l l o y s . S u l f i d e stress cracking
and hydrogen b l i s t e r i n g of c e r t a i n steels are a l s o p o s s i b l e . The
c h l o r i d e content i a hxgh enough t o cause stress corrosion
cracking and l o c a l i z e d a t t a c k of s u s c e p t i b l e a l l o y s , e s p e c i a l l y
i n t h e presence of oxygen.
Tables 4-1 and 4-2 show t h e f e r r o u s and nonferrous
materials t h a t have been t e s t e d a t e i g h t geothermal resources
including Cerro P r i e t o , Wairakei, t h e Geysers, and f i v e l i q u i d dominated U.S. KGRA's. Table 4-3 describes t h e nominal composit i o n s of brand name a l l o y s t h a t have been t e s t e d .

4-5

TABLE 4-1
FERROUS MATERIALS TESTED AT GEOTHERMAL SITES

Ember.

6dtm Ilu.

Nair.L.i,
U.Z.

mifomia

California

htd

Tested
h.td

ui-rniat

Ct.

h
.

Type 2 -I(i-*..i.t*
22Ni-ductile cast iron

h'td
TUtd
h.td

Tutd
h.td

TUtd

TUtd

htd

TUtd

zutd

htd

Iutd

htd

htd
TWtd
?e. td

htd
h.td

htd
Testd
TUtd
I..td

Tuud

h'td
Turd
h.td
h.td

h.td

htd
h.td
1"td

?...tad
Iutd

hud

TUtd
T..td
TUtd

htd
Iutd

T"td

h.td
h.td

TWtd
htd

T..td

1"td

h.td
TUtd
h.td
Turd

1e.t.d
1ee.t.d
h.td

htd
htd

M
u
d
htd
T**td
I..td
h.td

*.td
h.te.3

?uta

TUtd

h.td

h.td

h.td

mtd
Tutd
T..td
TUtd
TUtd

Tutd
h'td
h.td

htd
htd
h.td

hud
Twtd

Tutd
htd
nntd

1e.t.d
h.td

htd
htd
h O t d

im-3m
lscr-1.7m
17Cr
17h-211i
10Cr-3SNi
18R-8Ui
10Cr-8Ai-m
18RdNl-3m
18Cr-12Ni-lllb

18m-lzwi-zm
.
.. .
. ..

h'td
I*.td

Tutd
T.St.6

mmtd
h.td
Testd
T...td
1e.t.d

Tested
Tested

Upe. N l o y 20 Mod

4=6

TABLE 4-2

NONFERROUS MATERIALS TESTED AT GEOTHERMAL SITES

1nt.d

1nt.d

I...t.d

T..tSd

d
.
tT

1nt.d

1"t.d

1"td

1"t.d

1nt.d
1nt.d
1nt.d

1nt.d
1"t.d

h.td
Tntd
1nt.d

T..t.d

1eet.d

Tntd

4- 7

TABLE 4-3
COMPOSITIONS OF BRAND NAME ALLOYS
Standards

~.siwsti~t~

Iron Bsma
-Ni-resist

c a s t iron
Type 2 Ni-resist c a s t iron
COB-Tw B steel
Mariner S t e e l
ASTM A690
Nlegheny-Ludlm 216
Nlegheny-ludlru 6X
Nleshay-Ludlm 29-4
Nleghmy-Ludlm 29-4-2
Carpenter 20
A I S 1 Type 329
Carpnter 7 0
S.ndvik 3BE-60
ASTM A669
E-Brit.
26-1
U 152
A 286
Rex 326
Haynss 20 Hod

15Ni. 1.2h. 1.8%. 6.1CU. 2.9C


18-22111. 2.2-3.oh.
1-1.5M1~ 2.2-3C
1.2M 0.52Cr. O.O2Ni, 0.010, 0.31Cu. 0.050. 0.06N. 0.07C. OJ)lP, 0.03s
0 . 5 0 ~(.in),~
0.08-O.15P. 0.0% (mu) , 0.1OSi (mx) , 0.22 (mu)
0.4&.75Ni,
0.60-0.90%.
2 0 h . 6Ni. 2.50. 8.25M. 0.08C (UX)
20Cr, 24Ni. 6.00. 8.25%. 0.08C (mu)
29Cr. bn0, O.15NI ( M X ) . 0.01c (nU)
29Cr. 4%. 2Ni. 0.01C (ux)
29Cr. 20N1, 2.250, 3.250~. 0.07C ( M X )
27Cr 4.15111, 2.25n0. 3.4Cu. 0.82Cb + Ta, 0.2M. 0.03C
18Cr: 4.7111, 2.7wO. 1.5M. 1.7St.. 0.03P (mx). 0.03s ( u x ) . 0.03C (maX)
2 6 h . Wo. O J N I . 0.0015C
12Cr. 2.75111, 1.750. 0.851h. 0.3V. 0.14C. 0.03N
15Cr. 25.511, 1.251b. 1.5%. 0.1V. 0.3N. 2.1Ti. 0.06C
17Cr. 17.5111, 3.Wo. 3%. 7.1c4. 2.4Nb. 0.3C
22Cr. 26Ni. 4n0. 0.84%. 0.36T1, 0.013P. 0.01OS. 0.03C. 0.5851

IC-0nal
Inconel X-750
Inconel 600
Inconel 625
Incoloy 825
Ni-0-ne1
nastelloy F
8.stalloy c
Hastellop S
Hostelloy C-276

31131. 1.35Fe
JOCu, lFe, 2.75Al. 0.5Ti. 0.51h
15.5Cr. 7.0Fe. 0.7Al. 2.5Ti. 0.95Nb + Ta. 0.50 %, 0.04C
16Cr. 8Fe. 0.2CU. 0.08C
21.5Cr. 2.5Fe. 9Uo, 3.65Nb + To, 0.2A1. O.2Ti
21.5Cr. 30Fe. 3Ih. 2.25Cu. 0.7h. 0.03Cu
(replaced by Incoloy-825)
22Cr. 17Fe. 7%. 3Co. l W , O.lCU, 0.05C
22.5Cr. 19.5Fe. 6.50. 2.5120. 2Nb Ta, 2Cu. 1 W
153%. 14.50. l.OFe, 0.50M. 0.2W1, 0.02L.a. 0,0091). 0.40Si. 0.02C t u x )
14.5-16.5Cr. 15.0-17.00, 4.0-7.0Fe. 3.0-4.5U. 2.5Co (max). 1.0% (sax). 0.02C (mx)

Comer Esse
Ampco 8
h p c o 12
Ampco 483
85-5-5-5 bronze
Titanium Esse
-TiCoda-12
Oobalt Bas.
MP 3511
S t a l l i t a 16
Hamas 25
Habas 6B
Wlybdanim
TW

br..

CM 613
CDA 952
CDA 483

7 N . 2.5Fe bronze
9 N . 3Fe, bronze
9 N . 4.511, 4Pe bronze
85CU. 5Pb. 5Zn. 5Sn

WTH B 265 Cr. 12

0.811, 0 . 3 0
20Cr, 25N1, 9Fe. 7n0, 3Ti. 0.6Nb. 0.2N
6W ( u x ) . 3 . 5 h ( u x ) . 311 ( u x )
33Cr (ma.).
19-2lCr. 9-11Ni. 14-16W. 2Fe (ux),0.15C ( u x )
30Cr. 3 l i . 4 . N . 1.1%
0.5Ti.

0.08Zr. 0.015C

D e t a i l e d r e s u l t s of corrosion t e s t s are given f o r Baca,


East Mesa, Heber, Raft River and Salton Sea KGRA's i n t h e followi n g s e c t i o n s . The r e s u l t s a r e presented i n t w o forms. The
f i r s t i s a ( 1 screening'' t a b l e which serves as an index o r guide
to t h e t e s t r e s u l t s . The screening t a b l e s a r e based on t h e
numerical r e s u l t s of corrosion t e s t s . Both general corrosion
r a t e and l o c a l i z e d corrosion ( p i t t i n g , c r e v i c e c o r r o s i o n , and
s t r e s s corrosion cracking) a r e shown. Materials a r e c l a s s i f i e d
i n one of f o u r c a t e g o r i e s (A through D) based on measured
general corrosion r a t e s a s shown below:

Category

Measured Rate of
General Corrosion

B
C
D

1
10

rate
1 mpy
r a t e I 10 mpy
r a t e < 50 mpy
r a t e 2 50 mpy

Observations about l o c a l i z e d corrosion i n t h e screening t a b l e s


a r e l i m i t e d t o "detected" ( i n d i c a t e d by X) o r "not detected"
( i n d i c a t e d by N).
Results of l a b o r a t o r y t e s t s a r e given i n a d d i t i o n t o
f i e l d t e s t r e s u l t s . Laboratory r e s u l t s a r e given i n parentheses.
In a d d i t i o n t o t h e screening t a b l e s , d e t a i l e d summaries
of t h e corrosion t e s t r e s u l t s a r e provided. General and l o c a l i z e d corrosion r a t e s a r e presented i n t a b u l a r form. The p i t t i n g
and c r e v i c e corrosion r a t e s must be i n t e r p r e t e d j u d i c i o u s l y .
These r a t e s were c a l c u l a t e d assuming a l i n e a r i n c r e a s e i n p i t
o r c r e v i c e depth with time. This procedure allows comparison
of d a t a obtained over a wide range of exposure times. But l o c a l i z e d growth r a t e t s d i f f i c u l t t o predict, and t h e assumption

4-9

of a linear growth rate is not always accurate. In actuality,


a given pit may stop growing, grow at a slower rate for longer
times, or accelerate in growth. An induction time before pit
initiation is often observed which further complicates data interpretation.

4-10

4.2

Results of Corrosion Tests at Baca (Valles Caldera)


New Mexico KGRA

Corrosion data for Baca flashed fluids and steam are


summarized in Tables 4-4 and 4-5. The limited number of test
results was obtained in flashed wellhead fluid and steam; results
are unavailable for unflashed wellhead fluid. Localized corrosion rates are available only for flashed steam.
4.2.1

Test Conditions

Two series of corrosion tests were made at the Baca,


New Mexico geothermal site. The geothermal fluid underwent
flashing in the bore, and the composition of the two streams
used in the corrosion tests is given in Table 4-6.
In one test series, double-pipe heat exchanger materials were tested in (1) demisted steam, (2) steam with entrained fluid, and (3) flashed fluid. The steam and/or fluid
flow was on the shell side while cold, aerated water flowed
on the tube side. Uniform corrosion rates were measured (TO-089).
In another test series, candidate turbine materials
were exposed to demisted steam at 171C (340F) and 110 psig.
Coupons, U-bend specimens, and bent beam specimens were exposed to the steam for 150 days. The steam was then shut off
and the specimens were exposed to air-contaminated moisture
for 10 days. This represents worst case conditions (TO-089)
The testing of turbine materials also included corrosion fatigue tests. Specimens were exposed to demisted steam
and then subjected to cyclic stress, and the decrease in fatigue
endurance limit (defined in Section 5 ) was determined.

4-11

TABLE 4-4
CORROSION SCREENING RESULTS FOR BACA (VALLES CALDERA) FLASHED WELLHEAD FLUIDS
Nonaerated Fluid
Uniform
Corrosion

Iron Base
Carbon S t e e l
AIS1 Type 316
Carpenter 20Cb3
Carpenter 7Mo

C*
A
A
A

Nickel Base
P
I

Monel 400
Inconel 600
Incoloy 8 2 5

Pitting

SCC

Uniform
Corrosion

Pitting

Crevice
Corrosion

SCC

A
A

B
B

Crevice
Corrosion

Aerated Fluid

T i t a n i u m Base

Titanium
Copper Base
.\dmira.lty 3 r s s s
70-30 Cu?rx.l:Xel
10 Al brooza

*Other d a t a i z d i c a t e tSat a "B" r a t i n g i s more probable.


KEY TO T A B E

- g e n e r a l corrosion r a t e 51.0 mpy


((25 w / y r )
g e n e r a l corrosion r a t e >1.0 mpy b u t < 10 mpy (>25 pm/yr but <250 Um/yr)
c - g e n e r a l corrosion r a t e >lo mpy but <TO mpy (>250 pm/yr but'-<1270 pm/yr)
A

N
X

-- gfndfcated
e n e r a l c o r r o s i o n r a t e 250 mpy
form of corrosion not

(11270 wn/yr)

detected
i n d i c a t e d form of corrosion d e t e c t e d

Refer t o Tabla 1-7 f o r more complete d a t a .

c-

TABLE 4-5
CORROSION SCREENING RESULTS FOR BACA (VALLES CALDERA)
STEAM AFTER FLASHING

Uniform
Corrosion
Iron Base
22 Ni ductile cast iron
Carbon steel (AISI 1060)
1.5Cr (AISI E52100)
2.25Cr-lMo
lCr-l.25Mo-O.25V
1.5Cr-3.5Ni- 0.5Mo-0.1V
2.75Ni-O.SMo-O.lV
AISI Type 316
Carpenter 20Cb3
Carpenter 7Mo
AISI Type 403 (12Cr)
AISI Type 616
12Cr 4Ni
M152
A286

A
A

Nickel Base
Monel 400
Inconel 600
Inconel X -750
Incoloy 825

A
A
A

Titanium Base
Titanium
Ti-SA1-2.5Sn

A
A

Copper Base
Admiralfy Brass
22Ni-6Pb Brass
10 A1 bronze
70-30 Cupronickel
~

Demisted Steam
Crevice
Pitting Corrosion

SCC/
SSC

A
B

A
A
A
A
A
A
A

A
A

B
A

KEY TO T a L E
A
general corrosion rate il mpy
( ~ 2 5d y r )
B general corrosion rate > l m p y but 510 mpy (>25 um/yr but 2250 um/yr)
C general corrosion rate >10 mpy but c50 mpy (>250 pm/yr but
~ 1 2 7 0pm/yr)
eneral corrosion rate 250 mpy
(A270 d y r )
ndicated form of corrosion not detected
N
X
indicated form of corrosion detected
Refer t o Table 4-8 for more complete data.

---

D -- f

4-13

TABLE 4-6
COMPOSITION OF FLASHED STEAM AND FLUID FROM WELL NO, 11 USED
I N CORROSION TESTS AT BACA, NEW MEXICO KGRA

Characteristics of

Characteristics of
Fluid After Flashing
Wellhead Temperature ("C at 110 p s i $

171

Conductance (pmhos/cm)

10,630-11,230

S p e c i f i c Gravity

1.008

PH

6.6-7.1

c1'

(PFd

3,400-4,400

T o t a l COS (pprn)

57-128

T o t a l H2S (pprn)

1.5-6.

(PPd

50-70

Suspended S o l i d s (pprn)

520-690

Total

Not measured

"3

*Based on t o t a l production.
Reference : TO-089

6-

Flashed Steam
Noncondensable Gases
pH of Condensate

wt%
vol%

2.44-3 99
1.02-1.68*

4.3-4.9

CO2 (ppm by wt)

33,700-47,390

H2S (ppm by wt)

290-570

"3

(PPm by wt)

CH4 (ppm by wt)

C1'

(ppm by w t from
carryover, est.)

1.5-6.0
0.-6.
10

4.2.2

Results

Results of tests on heat exchanger materials are shown


in Table 4-7. Of the eleven metals tested, only carbon steel
showed significant uniform corrosion rates. Metallographic examination showed no evidence of intergranular corrosion. Localized corrosion data were not reported.
Results of tests on turbine materials exposed to
demisted steam are given in Table 4-8. Twenty alloys were tested,
and only carbon steel showed a general corrosion rate greater
than 1.0 mpy. Pitting was a major problem; only A286 showed no
pitting. The low hardness (Rc-23) Type 616 also had good pitting resistance (pit rate was 2 mpy), but the same alloy at
greater hardness (Rc-35) suffered an eight-fold increase in pitting
rate.
Because of test conditions, stress corrosion cracking
could not be distinguished from sulfide stress cracking. Most
of the alloys tested were Rc-22 or higher and failed the severe
U-bend stress corrosion test. These materials did better at
lower applied stress. These materials might a l s o give good service at higher applied stress if they were of lower strength/
hardness levels.
earance of the bent beam specimens
The macroscopic
brazed with a low heat source showed evidence of a black corrosion product on the 50Ag-20Cu-28Zn-2Nibraze alloy. None of
the specimens showed evidence of significant metal loss of the
braze alloy itself.

YP

dt

The results of corrosion-fatigue tests are expressed


as the ratio of fatigue endurance limit before exposure to FEL
after exposure. The decrease in fatigue endurance limit (FEL)
4-15

TABLE 4-7

RESULTS OF CORROSION TESTS OF HEAT EXCHANGER


MATERIALS AT

Material
Tested

ma, NEW

Corrosion Rate i n
Steam bPY)

MEXICO K G R A ~

Corrosion Rate i n
Steam w i t h Ent r a i n e d F l u i d (kpy)

Corrosion Rate
i n Flashed
Fluid (mpy)

I r o n Base
b
Carbon S t e e l
AIS1 Type 316
Carpenter 20Cb3
Carpenter 7Mo

31
0
0
0

18

2
0
0

2
0

0
0

3
5

2
5

0
0
0

32
0
0
0

Nickel Base
Monel 400
Inconel 600
Incoloy 825

Titanium Base
Titanium
Copper Base
Admiralty Brass
70-30 Cupronickel
10 Al Bronze

a
Tests were done a t 171OC f o r 69 days.

Samples were tubes i n a simulated h e a t


exchanger w i t h s h e l l s i d e exposed t o geothermal media and tube s i d e exposed
t o cold a e r a t e d water. Results are from r e f e r e n c e TO-089.
P i t t i n g , crevice
c o r r o s i o n and SCC d a t a were n o t reported. Meballographic examination showed
no i n d i c a t i o n of i n t e r g r a n u l a r corrosion.

bMost c o r r o s i o n w a s on t h e tube s i d e of t h e specimen (exposed t o cold a e r a t e d


water).
Reference:

TO-089

4-16

c
TABLE 4-8

CORROSION TEST RESULTS FOR TURBINE MATERIALS IN


FLASHED STEAM AT BACA (VALLES CALDERA)
Material R o p e r t i a s

Results of Corrosion Tests'


SCCISSC"

Standards
Dwignation

Alloy Tested
Carbon S t e e l

AIS1 1060
1.m
U S 1 E52100
2.2SCr-lllo S t e a l
ASTM-AS41 C16
lCr-1.2RIe.ZW
ASlU-A470 C 1 8
1.5h-3.5Ni-.5?le.lV
S t e e l ASlYkA470 C 1 6
2.75Ri-.5Mo-.lV
Steel
ASlM4470 C14
2mi Ikwtile cast Imn
I2Cr Steel.
403
12h Str\
Type 40)
12Cr S t m l
Type 403
ucr SteelC

me

1?Cr-llb-.zm

st

12Cr-1wO-lw-.2%
12Cr-4Ni S t e e l
11152 S t e e l
A286 S t e e l

n d

St

750
Ineonel X
2ZNi-6Pb-Brass
Ti-W-2.5Sn

Ihrdness
Rockwll-A'
69.0
70.0
57.3

60.2
60.2
59.5

61.1
73.0
--

-95

-so

115
110
105

90
95
85

--

105

43.1
69.3

80
190

140

67.5

- 120

---

0.1
0.2

0.1
.04

30

.04
.6'
.04

115

Bat-'
Bern

pit ti^' ll-bad'


LE!PYLA!L1.3
general
RD
Corrosion'

0.4
0.7
0.7
0.2

155

120
145
150
170

hiform

n .
t
-.
0.6

75
--

80
US
120
140
105

,1.25c).
Brazed a t high temperature ruing ...c braze md

TO-089

Yield
Strength
hi

61.9
68.1
67.7
70.0
67.2

:Cue h l f of specben f l r a c h a r d a e d t o RA 73.0


Brazed a t C)8EoC using 50Ag-200u-Z8En-2Ni b r a alloy
to a t t a c h Cobalt base erosion shield (65&3OCr4.5+

Reference:

Tuuila
Strength
hi

13.7
6.8
9.1
9.1

29.1
13.7
--

--

nF
MP
HF

ND
F

Wp(76)'
~ ( 7 2 ) ~
w(80)7

Fracture'
mde

T.1
T

2
16.0
13.7
16.0

nu

scale'
2

--

--

--

' S p c f i m s exposed t o separated d e d s t e d steam a t 171'C a d 110 psi8


f o r 150 days and t o air/moisture f o r f i n a l 10 days of 160 day period.
zCalcukted from W i g h t 1008 &ta.
'Calculated f m mlmm p i t depth.
'Stress c r a c k i q of U-bends and b e u t - l w u : key
ND no f i s s u r e s o r cracks detected
M microscopic fimsurea S I grain depth.
I
M C ~ O O C O P ~ C f i s s u r e s o r fracture.
T
'
transgranular mode
I
intergranular d e
\
When both d e s are listed. f i r s t entry i. dominant.
%A 61.5
22
' ~ e r c e u t of viem stream aoulied.
'Covered w i t i flaky nonadh&ent black scale.
'This is a minina corrosion rate. Coupon covered with very adherent
black s c a l e which could not be completely raoved.
" I n this test it in not possible t o distinguish betunm s t r e a s corrosion
cracking and .ulfi.de stress cracking.

--

--

would have been more severe if the cyclic stress had been applied
during exposure.
Fatigue fracture initiation generally occurred at corrosion pits. The FEL ratios are plotted as a function of corrosion
pit depth in Figure 4-1.

40

50

60
0

10
I

11
I

CORROSION PIT DEPTH, MILS


Figure 4-1. Ratios of FEL after exposure-to-FEL
before exposure as a function of
corrosion pit depth (TO-089).
All alloys exhibited significant reductions in the FEL
with the occurrence of pitting. FEL reductions of 16 to 28 percent were caused by pitting during the first 34 days exposure.
The most commonly used 12Cr (Type 403) bucket alloy exhibited
the smallest reduction. The 98-day exposure resulted in a relatively insignificant change in the FEL values. Compared to the
34-day exposure, a marked increase in pit depth occurred during
the 98 to 160 days exposure period.

4-18

A t t h e end of t h e f i n a l exposure, FEL values were reduced 36 t o 52 p e r c e n t . With p i t t i n g t o a depth of approximately


9 t o 10 mils, t h e FEL r a t i o s of Type 616 h e a t t r e a t e d t o "low"
and "high" hardness levels were lowered approximately 50 percent.
The two low t e n s i l e s t r e n g t h a l l o y s , Type 403 (RA 61) and Type
616 (RA 6 2 ) , d i d n o t e x h i b i t t h e same reductions i n FEL f o r comp a r a b l e corrosion p i t depths. This suggests t h a t a t comparable
hardness l e v e l s , t h e Type 403 i s less notch s e n s i t i v e i n f a t i g u e
than t h e Type 616.

4 - 19

L,
4.3

Results of Corrosion Tests at East Mesa, California KGRA

Summarized "screening" results of field corrosion tests


in East Mesa fluids are given in Tables 4-9 (wellhead fluid),
4-10 (first flash liquid), 4-11 (second flash liquid), 4-12
(first flash steam), and 4-13 (second flash steam). Field tests
were conducted after preliminary laboratory testing with wellhead
fluid. The field tests are short duration tests and should be
used cautiously, but they are useful as guidelines. Additional
field tests are underway at East Mesa.
4.3.1

Description of Test Streams

Corrosion tests were conducted in five different streams


from well Mesa 6-1. This well contains higher concentrations of
corrosive species than later wells drilled at East Mesa and represents worst case conditions for this KGRA. Table 4-14 gives detailed analyses of Mesa 6-1 and Cerro Prieto wellhead fluids.
Cerro Prieto data are included with the East Mesa because of the
proximity and similarity of the two sites. This similarity should
enable some corrosion data from Cerro Prieto to be extrapolated to
East Mesa. The lab 6-1 data are the compositions of solutions taken
at well Mesa 6-1 and used in laboratory corrosion studies.
The wellhead fluid in the -in situ tests was a two-phase
mixture because the geothermal fluid flashed in the bore of the
well. The fluid from the wellhead then passed through a separator and produced the first flash liquid and steam streams where
in situ testing was conducted. Additional -in situ corrosion test-ing was conducted in second flash streams after passing through
another separator. The compositions of the five -in situ test
streams are compared in Table 4-15 (NE-302).

4-20

- .._....

...

"

.__
. .

-.

..

..

..

.-... . ...

..

..

..

. . ....

"

- ..

-.

I
.

-.

...

"

C
TABLE 4-9
EAST MESA CORROSION SCREENING RESULTS FOR WELLHEAD FLUID
Aerated F l u i d

Nonaerated F l u i d
General
Corrosion

(A)

Pitting

Crevice
Corrosion

SCC

General
Corrosion

(N)

(N)

(B)

Pitting

Crevice
Corrosion

SCC

I r o n Base

N i c k e l Base
Hone1 400
I n c o n e l X-750
I n c o n e l 625
Hastelloy S
Hastelloy G
H a s t e l l o y C-276

Titanium Base
Titanium
Ti-1.7W
Ti-1.581

Ti-1OV
Aluminum Base
2024-T3
6061-T6
5005
Copper Base

er
cu-%e

Cop

90-10 Brass
70-30 B r a s s
90-10 C u p r o n i c k e l
70-30 C u p r o n i c k e l
Molybdenum

Baee

TZH

KEY TO TABLE
A
g e n e r a l c o r r o s i o n r a t e sl mpy
B
g e n e r a l c o r r o s i o n r a t e >1 mpy but

-d o mpy
g e n e r a l c o r r o s i o n r a t e > l o mpy but <50 mpy
D - g e n e r a l c o r r o s i o n rate G O mpy
N - i n d i c a t e d form of c o r r o s i o n n o t d e t e c t e d
X - i n d i c a t e d form of c o r r o s i o n d e t e c t e d
* - increased general corrosion
C

(125 um/pr)
( > 2 5 &yr
but d 5 0 m/yr)
( > 2 5 0 um/yr but (1270 pm/yr)
( > I 2 7 0 um/yr)

Data i n p a r e n t h e s e s a r e l a b o r a t o r y results.

See T a b l e s 4-16 and

4-17 for mare detailed information.

(N)

(N)

-....
~

TABLE 4-10
EAST MESA CORROSION SCREENING RESULTS FOR LIQUID STREAM AFTER FIRST FLASH

General
Corrosion
Iron Base
Carbon Steel (AISI 1020)
AISI 4130
A I S I Type 302
AISI Type 316L
A I S I Type 430
A C I Type CF-20
A C I T e CF-3M
Sandvz 3RE60
E-Brite 26-1
Carpenter 20

Nonaerated Fluid
Crevice
Pitting Corrosion
N
N

X
X
-

Nickel Base
Monel 400
Inconel X-750
Inconel 625
Hastelloy S
Hastelloy G
Hastelloy C-276
Titanium Base
Titanium
Ti-1.7W
T i - 1 .5Ni
Ti-1OV

Aluminum Base
2024-T3
6061-T6
5005
Copper Base
Copper
Cu- 2Fe
90-10 Brass
70-30 Brass
90-10 Cupronickel
70-30 Cupronickel
Molybdenum Base
TZM

KEY TO TABLE

-- general
corrosion rate 51.0 mpy
general corrosion rate >1.0 mpy but 110 mpy
- general corrosion r a t e >lo mpy but <50 mpy
- general corrosion r a t e 250 mpy
N - indicated form of corrosion not detected
X - indicated form of corrosion detected
A
B
C
D

R
general roughening of surface
See T a b l e 4-18 f o r more complete data.

4-22

SCC

TABLE 4-11
EAST MESA CORROSION SCREENING RESULTS FOR LIQUID

STREAM AFTER SECOND FLASH

General
Corrosion

Nonaerated Fluid
Crevice
Pitting Corrosion

Iron Base
Carbon Steel
AISI 4130
AISI Type 302
AISI Type 316L
AISI Type 430
ACI Type CF-20
ACI Type CF-3M
Sandvik 3RE60
E-Brite 26-1
Carpenter 20

SCC

X
X

Nickel Base
Monel 400
Inconel X-750
Inconel 625
Hastelloy S
Hastelloy G
m s t e l l o y C-276

Titanium Base
Titanium
Ti-1.7W
T i - 1.5Ni
Ti- 1OV

Aluminum Base
2024-T3
6061-T6
5005
Copper Base
I

Cu- Fe
90-10 Brass
70-30 Brass

90-10 Cupronickel
70-30 Cupronickel
1
I

Molybdenum Base

---

TZPl

Specimens covered with adherent scale.


a C o r D rating.

BLd

-----

---

--

--

Other experience j u s t i f i e s

KEY TO TABLE
A general corrosion rate (1.0 mpy
B
general corrosion rate >1.0 mpy but 510 mpy ,(>25 pm1y-r but 2250 p m / y r )
C
general corrosion rate >10 mpy but <50 mpy
(>250 pm/yr
D
general corrosion r a t e 250 mpy
(21270
p m / y r )but <1
N indicated form of corrosion not detected
X - indicated form of corrosion detected
See Table 4-18 for more complete data.

---

4-23

TABLE 4-12
EAST MESA CORROSION SCREENING RESULTS FOR STEAM FROM FIRST FLASH
General
Corrosion

Lcno Alloy Steels


Low Carbon
Carbon
AISI 4130
1Cr-1.3%- 0.25V
1.5Cr-lA1-0.25Mo
3.5Ni-1.8Cr-0.4Mo- 0.1V
ASTH A285
Stainless Steels
AISI Type 304
AISI Type 316L
. AISI Type 430
ACI Type CF-8
ACI Type CF-3M
E-Brita 26-1
12cr
12cr-1PIo-lW
12cr-0.2A1
15cr-1.m

Nonaerated Steam
Crevice
Pitting Corrosion

SCC

Erosion

General
Corrosion

--

*B

--B
-

B
B

C
B

--

X
X

---X
X
X

----

--

N
N
N
N
N
N
N

--

Aluminum Based Alloys


1100
5005

Nickel Based Alloys


Inconel 625
Raatelloy S
Rastelloy C-276

A
A
A

---

N
N
N

--

Titaniwn Based Allox


Ti- 1.511

Cobalt Based Allor


Stellitc #6

Comer Based Alloy


Cbpper

B
B
B

A
B

A
A
A
A
A
A
A
A

KEY TO T A B U
A general corrosion rate 3 mpy
B general corrosion rate >l mpy but do mpy
C general corrosion rate >10 mpy but <50 mpy
D general corrosion rate G O mpy
N indicated form of corrosion not detected.
X
indicated form of corrosion detected.
npecimcn showed weight gain.
t i n t e r g m l a r carrosion.

---*-

N
N

---

N
N

A
A

-B

A
A

A
A

k.25 pmmlyrr)
(>25 pm/yr but ~ 2 5 0pmlyr)
(>250 p m / p but ~ 1 2 7 0p m / p )
(L1270 r u n l ~ )

See Table 4-39 fer mere complete data.

-----

B
B

Aerated Steam
Crevice
Pitting Corrosion

--X
X
-

--

------

---

SCC

-X
I

---

Erosion

---

---

-----

d
X

N
N

TABLE 4-13
EAST MESA CORROSION SCREENING RESULTS FOR
STEAM FROM SECOND FLASH

General
Corrosion

Nonaerated Steam
Crevice
Pittinp; Corrosion

SCC

Erosion

Low Alloy Steels


Low Carbon

Carbon
AISI 4130
lCr-1.3Mo-0.25V
1.5Cr-lAl-O.25Mo
3.5Ni-l.8Cr-0.4Mo-O.lV
ASTM Has

Stainless Steels
AISI Type 304
AISI Type 316L
AIS1 Type 430
A C I Type CF-8
A C I Type CF-3M
E-Brite 26-1
12Cr
12Cr- lMo- 1W
12Cr-0.2A1
15Cr-1.7Mo
Copper Based Alloy
Copper
Aluminum Based Alloys
1100
5005
Nickel Based Alloys
Inconel 625
Hastelloy S
Hastelloy C-276
Titanium Based Alloy
T i - 1 5Ni
Cobalt Based Alloy
S t e l l i t e 46
~~

KEY TO TABLE
A
general corrosion rate 11 mpy
B
general corrosion r a t e >1 mpy but 110 mpy
C
general corrosion r a t e >lo mpy but <50 mpy
D general corrosion r a t e 250 mpy
N
indicated form of corrosion not detected.
X
indicated form of corrosion detected.
See Table 4-19 for more complete data.

----

(125 W y r )
(>25 pm/yr but 2250 prn/yr)
(>250 pm/yr but ~ 1 2 7 0p m / y r )
(21270 d y r )

4-25

TABLE 4-14
COMPARISON OF MESA 6-1 AND CERRO P R I E T O

GEOTHERMAL FLUIDS
.b

Cerro

L w TDS
Plashed
Fluid

High TDS

Inflashed
Fluid

Flashed
Fluid

Unflashed
Fluid

7.70

Flashel
Fluid
1

NR

5.43

7.90

5.34

(ppm)

(PPI

(PPI

(PPd

(mg/l)

(mg/l)

17,068

NR

NR

32,250

18.847

27.123

k b 6-1

8.21

'

TDS

Well Mom 6-1

3 11)

B
)
Flashed
iflashed
Fluid
Fluid

PH

East &sa

Leto

7.60

(PPd

si02

974

590

1.345

300

101

Na

5,257

4,730

8,229

5,600

9.845

5.774

11$000

1,310

1,180

2,032

1,230

1,173

898

1,430

Ca

258

272

550

369

1,360

642

1,370

ng

0.04

0.2

0.34

0.8

20,80

13.80

21.8

10,128

9.040

16,129

11.400

19,400

10,942

18.000

10.0

9.p

12.0

27

<20.00

<10.00

16

32.49

38.0

59.11

27

45.70

223.0

NR

11.38

NR

ND

NR

ND

NR
NR
NR
NR

1.250

NR
NR

NR

310

ND
NR

a.0

NR

83.00

41.00

38.8

13

NR

NR

22.4

c1sop

HCO,

cor

610

341

NR

NR
NR
NR

25.80

15.52

12.0

Ba

5.72

NR
NR
NR

11.48

NR

42.00

18.00

36.5

NR

NR

NR

40.9

NR

12.40

26.00

4.0

30.00

37.00

55

6.00

7.20

56.00

58.00

COP

HIS
LWr

Br

12.5

'

25.5

CS

624
NR

Li

14.5

10.9

25.2

13.7

Rb

8.4

NR

12.3

Sr

7.3

NB

15

Al

0.03

0.03

AS

0.06

NR
NR

NR
NR
NR

NR

58
35

1.7
226
0.4

1.1

NR
NR

0.009

1,o

<0,004

0.007

NR

NR
NR

Be

e0.03

NR

<0.03

NR

co

(0.01

NR

so.01

NR

NR

NR

Cr

<0.05

NR

(0.05

0,03

<0,02

NR

NR

1.7

NR
NR

1.60

1.23

1.5

Fe

NR

NR

NR

NR

0,250

3.40

0.18

NR

NR

0.45

NR

0.7

NR

0.04

NR

NR

NR

Ni

(0.01

NR

(0.01

NR

Pb
Zn

NR

NR

NR

NR

NR

NR

NR

ND

--

Not Reported

0.95

0.9

NR

0.10

0.200

0.17

0.20

NR

4 0 , a05

a,io

0.02

References : Cerro

Prieto data

East Mesa d a t a

None Detected

Lab 6-1 d a t a

'pH a t 25'
'calculated

NR
1.260

value

4-26

- LA-312
- LA-312
- CA-430

TABLE 4-15
COMPOSITION OF TEST STREAMS FROM WELL MESA 6-1
AT EAST MESA SITE

c1-

PH

Na

si

Ca

m) ( P P ~ X
0 OOk

Ba
(PP~)

Wellhead F l u i d

5.6

11,800

6,153

613

129

771

16.8

Separator 1 F l u i d

6.8

12 062

5,867

645

125

795

15.9

Separator 2 F l u i d

8.1

1 2 735

6,667

645

135

850

18.8

Separator 1 Steam

5.2

2,803

323

44

300

16.3

Separator 2 Steam

5b7

10

82

<lo

<10

c.1

113,000-5,000
200-500

' D a t a d i s t o r t e d by c o n t r o l valve problems.

References:

(NE-302,

GE-119)

Test conditions and detailed results of the laboratory


and field corrosion tests are described in the following sections.
4.3.2

Laboratory Tests

Prior to field testing, preliminary laboratory tests


were conducted in East Mesa wellhead fluid. These tests were
screening tests to determine corrosion resistance of commercially
available metals and alloys in aerated and deaerated brines.
Twenty-five alloys were tested for uniform corrosion,
pitting, crevice corrosion, and stress corrosion cracking ( C A - 3 4 0 ,
HA-628). Carbon steel was used as,a control. General corrosion
and pitting samples were coupons. Crevice samples were made by
overlapping two strips of the alloy and fastening with Teflon
bands. Stress samples were bent around a pipe and retained under
stress with Teflon clips. .

4-27

The laboratory test solution was obtained from a sample of wellhead fluid from well Mesa 6-1, The composition of
this solution is given in Table 4-14.
The laboratory tests wete useful for establishing
guidelines and identifying potential problems, but they did not
directly simulate actual site conditions for the following reasons :

1. Laboratory test temperatures (105C) were


lower than wellhead temperatures (130C).
2.

Laboratory solutions did not contain noncondensable gases.

3. The pH of the laboratory solution was less


than that of the natural wellhead fluid.
Laboratory tests were run at 105C for 15 days in
aerated and deaerated media. Aeration was by constant air
bubbling, and deaeration was by continuous helium purge. The
etc.) were removed by
noncondensable gases (Con, HzS, " 3 ,
the flashing and the purging. The concentrations of sulfide
and carbonate species were also probably lower in the laboratory
fluid than in the actual wellhead fluid because gaseous H2S and
CO2 were lost in the flashing and purge gas. The solution pH
(6-7) was less acid than the actual wellhead brine which was
about 5 . 7 .
The results of the laboratory tests are presented in
Tabel 4-16. General field corrosion results are also listed to
compare with laboratory results of the same test duration, 15
days.

4-28

c
TABLE 4-16
RESULTS OF LABORATORY AND FIELD CORROSION TESTS I N EAST MESA WELLHEAD FLUID

Carbon St..l(AISI
4UO

AIS1
AIS1
AISI
AISI
ACI

Typa 302
Typa 316L
Type 430
CF-20

CF-311
Saadrit 3lWO

A C I Typm

&Brit.

261
carpcater 20

nic*.i

*
I

IQ

ha0

4m

nand

1roal x-750
fncoasl 625
R..talloy s
8.atUloy 0
8 . s t m l l o y 0-276
Titanium Ban
Timirn
Ti-1.m
Tid.mi
TI-1W

1020)

3.2
1.9

17.3
0.2
e0.05
<0.05

co.05
0.1

n
n
n
n

40.9
10.7
0.1
(0.05

0.4
<0.05
0.1

n
R
n

n
n
n

n
n
n

0.1
<0.8
0.2

--

0.2
(0.05

n
n

n
n

R
N
R

2.5
0.1
e0.05
0.1
0.1
0.1

N'
N

n
nN

go.

05

<0.05
eo. 05

e0.m
0.1
0.1

n
n
n
nn

<O. 05

0.1

--

n11
N

n
I

n
n

n
N

Q.05
eo. 05
go. 05
eo. 05

1.9
3.7

n
n
n

n
n
N
n

<0.05
g0.05
0.1
<0.05

n
n
n
N

--

--

N
I

63.1
11.6

Nn

3.6
4
.3
3.7
17.9

n
n

3.0

II

Xf

n
N
n

Alraina Barn

202CT3
6061-T6
5005

copper

cu-n.
9blO
70-30
90-10
70-30

kru.

Drama
cupronickel
cupronickel

Molybdenum

&M

TP(

----

1.2
2.2
0.9
5.7

0.2

n
nR
N

n
n

Nn
n

QI TO TABLE

R
X

--

not detected.

detect&.

Perfo-ec
of umt (MI)
alloy. baaed 011 wrought c o u n t e r

NOTE:
pert..

<O. 05

Cower Baa4

.d.Pfh*
I n c n u r d general corrorion in
fatreaaad arm of +bends,
e0.1 my.
G.1 epy but e l . 0 .py.
h>l.O q y but <5 mpy.

Reference for column 1 GE-119 and NE-302)


Reference f o r o t h e r data: CA-430)

in $ n:

A l l of the alloys had good uniform corrosion resistance


(less than 5 mpy) in the deaerated fluid except carbon steel and

70-30 cupronickel which corroded moderately. Carbon steel, AIS1


4130 steel, 2024-T3 aluminum, copper, Cu-2Fe, and 70-30 cupronickel
corroded severely when the fluid was aerated, Titanium and its
alloys, the Hastelloys, the Inconels, Sandvik 3RE60, Type 302
stainless steel, and Type 316L stainless steel had good resistance to general corrosion, and the corrosion rates were not
significantly affected by aeration (NE-302).
Pitting was detected only on aluminum alloy 2024-T3 in
the aerated solution; pits 60 mils deep were detected. Crevice
corrosion in deaerated fluid was detected only on Type 316L
stainless steel, but this corrosion was. detected on Type 302,
Type 316L, Sandvik 3RE60, Monel 400, titanium, 90-10 brass, and
70-30 brass in aerated fluid. The test conditions of pH, temperature, noncondensable gas concentrations, and test duration
are such that the laboratory pitting and crevice corrosion results may be misleading. Field tests indicate that metals may
be more susceptible to pitting and crevice corrosion in East Mesa
fluids than evidenced by the laboratory tests (NE-302).
None of the laboratory specimens showed any evidence
of stress corrosion cracking, but the alumiQum alloy 6061-T6
showed increased corrosion in the stressed area of the U-bends.
4.3.3

Field Tests

Ten alloys were tested in a dual flash simulation at


East Mesa. Coupons were exposed to wellhead fluid from Mesa
6-1, first and second flash liquid streams, and first and second
flash steams. The compositions of these streams are given in
Table 4-15. U-bend stress corrosion cracking specimens were
exposed to first flash steam.
4-30

All samples were visually inspected after removal from


the test environment, descaled, and examined for evidence of microscopic damage such as pitting, crevice corrosion, and SCC. The
corrosion rates were determined by weight-loss measurements of at
least four coupons (NE-302). These tests were to be included in
a 60-day, planned interval test, but well Mesa 6-1 failed on the
twenty-second day of testing. A massive carbonate scale plug
stopped flow from the well. Results were therefore available
only for the first fifteen-day interval.

In another series of tests at Mesa 6-1, the corrosion


rates of five alloys were determined as a function of temperature
and pH. Weight-loss measurements were made for coupons in wellhead fluid at (1) normal conditions, (2) lower temperature, and
(3) lower pH. Lower temperature fluids were obtained by passing
fluid through cooling coils, and acid injection was used to
lower pH.
The results of -in-situ corrosion tests in Mesa 6-1
wellhead fluid, flashed fluids, and flashed steams are given in
Tables 4-17, 4-18, and 4-19, respectively. All results are for
15 days exposure.
The corrosion rates did not appear to be affected by
the sample orientation (normal or tangential) in the flow of the
fluid or steam. Hastelloy C-276, Hastelloy S, Inconel 625,
Ti-2% Ni, and 316 L showed excellent resistance to general corrosion in all five environments with corrosion rates less than 0.1
mpy. Microscopic examination of these materials, however, showed
that only Hastelloy C-276 exhibited no visual evidence of corrosion. Type 316 L and Inconel 625 showed llocalized corrosion in
I

,
I
I

L,

4-31
I

TABLE 4-17
FIELD CORROSION

RESULTS IN EAST MESA WELLHEAD

FLUID^

Corrosion Results

Metal
Unif o m
c o r r o s i o n (mpy)

Crevice
Pitting

Corrosion

SCC

I r o n Base
Carbon S t e e l (AISI 1020)
AISI 4130
AISI Type 316 L
AISI Type 430
E - B r i t e 26-1
.+

3.2
1.9
<O .05
0.1
4.05

2x,
X

Nickel Base

c0.05
<O .05
c0.05

Inconel 625
Hastelloy S
Hastelloy C-276

'

N
N
N

NC

xC

Aluminum Base
5005

57.0

Titanium Base
c0.05

Ti-2Ni

%ellhead f l u i d w a s n o t a e r a t e d .
bMicroscopic p i t s were observed but were too small t o measure with an o p t i c a l microscope.
C
General microscopic roughening of t h e s u r f a c e .
dNo microscopically d e t e c t a b l e corrosion.

KEY TO TABLE

N
X

- not detected
- detected

References:

GE-119,

CA-430, NE-302

C
TABLE 4-18

CORROSION TEST RESULTS IN FIRST AND SECOND FLASHED FLUID AT EAST MESA

2.4

0.5

ACI Type CT-M


klhite 26-1

c0.05

3.3

1.6
(0.05

A I S 1 4UO
U S 1 Type 3161
M S I Type 430

--

C0.05

(0.05

--

21.4

(0.05

~ i c k e mar
l

P
I

w
w

I n c d 625
Butalloy s
b a t e l l o y 0.276

<0.05
(0.05

Titanitma mme
Ti-l.5Ni

'15 day f i e l d temt


'15 day f i e l d teat

Reference:

in f1r.t fhmh nesa

6-1 f h l d (pa

in recwd flash ? l e u 6-1 fluid (pa

GE-119

1.2

0.1
0.2
0.1

0.1

--

(0.0

<0.05
<0.05

ft
n

--

----

kicro.copic p i t . too .la11 to


measure d t h optical micrometer

b(NE-302).
S o u crevice corrodm (NE-302).
:Severe" pitting (NE-302).
V e r y .evere" crevice c o ~ ~ o . i o n
(NE-302).
'SpecLam
covered
h rnot
d .dherent Kale
vhichvith
could
be

r s o ~ r d(GE-US).

Note:

Puforunce of cast (MI)

alloy b a e d on wrought counter2.1.

eo.05

6.8. C
1
'
12,062 p p ) .
8.1, c1- 12,735 P a ) .
9

N
N

part.

TABLE 4-19

CORROSION TEST RESULTS IN FIRST AND SECOND FLASHED STEAM AT EAST MESA
l i r a t Stage Steam
Cerro Prieto Testa'
Noruerrted
General
Sorrosion
Alloy8 Teated

Erosion

A?B!L 0

Lar Alloy Steel.


Lw b r b o n S t e e l
Cnrbon S t e a l
4130
1Cr-1. 3U0-0.25V
1.5Cr-lAl-O.25Uo
3.5Ni-1.8Cr-0.4Uo-0.1V
Ml?I A285

1.4

--

3.3

Aerated
General
Corroaioa

8.3

1.6
2.7

13.4
2.6

-0.1
--

----

Stainlcaa Steel.

AIS1 Type 306


AIS1 Type 3161
AIS1 Type 430
MI FJPC CP-8
MI lyp. CP-34
& B r i t s 26-1
l2Cr
l2cr-lnO-lW
12cr-0. w

15cr-1.m

Copper Based Alloy


Deoxidized Copper
bhaipp. Baaed

Alloy.

ll00
5005
Nickel m.ad Alloy.
I n c o w l 625
Raatelloy S
Enrtelloy C-276
Titanium B u d A l l o r
Ti- 1.SRi
Cobalt Baaed Alloy
S t a l l l t e 16

'Omits
*Onlit.

1 5 dny t e a t a a t E. Meaa (GE-119 and NE-302).


150 day t e s t a a t C e r o P r i e t o ( ~ ~ - 1 1 and
9 TO-0~5).

KBT TO TABLE
11 no p o r a r t r a a a cotroeion c r a c w i l i l u r a e .
X
m o a e t r u a corroaim crackin&

--

0.1

1.1
0.4
0,7
0.5

----

Pitting

A!!n!L 0

---

33.5
21.6

----

second
Stage
Steam
E. Uesa
Teat'
General
Corrodon

3.1a
2.5'

--

0.5

47.3

0.1
0.ld
--

20.1

3.9
2.7

66.9
63.0

b.3

--

--

114.2

2.2

106.3

3.3

Caraantn

AeLL

0.1
<0.OSc

C0.05

C0.05
0.1
e0.05

(0.05

crevice corroaion.
%o atreaa corrosion cracking

detected.
'very mall shallow pita.
%o mlcroacopic evidence of
elocal corroaion.
Severe p i t t i n g and l o c a l
8Ucroscopic
fcorroo.ion. c r a c k obrerved.
Intergranular corroaion.

%allure due t o genernl


corroaion.
P i t t i n g r a t e is baaed on
rarfun p i t depth.
Note:

P e r f o m n e e of cant

(MI) a l l o y is baaed on t h e i r
Wrought counterparts.

4J
the form of very shallow pits, too small to be measur-d rith an
optical micrometer (less than 0.1 mil). A general surface roughening was noted on coupons of Ti-2Ni and Hastelloy s.
E-Brite 26-1 and Type 430 had excellent resistance to
corrosion in the two separated fluid and steam environments but
only fair resistance to corrosion ih the wellhead fluid. Microscopic examination of all Type 430 samples showed the sameshallow
pitting that was observed on Type 316 L samples. Only those
E-Brite 26-1 samples exposed to the wellhead fluid and to the
concentrated fluid from separator #l developed shallow pits.
There was no microscopic evidence of corrosion for E-Brite 26-1
samples either in the steam environments or in the concentrated
fluid from separator 12.
Both the 1020 carbon steel and 4130 steel had fair resistance to uniform corrosion in the five environments even though
the microscopic examination showed general corrosion attack (NE-302).
The corrosion resistance of aluminum 5005 in each of the
five environments was poor. I addition t o high general corrosion
rates, the aluminum samples were severely pitted and showed a high
susceptibility to crevice corrosion (NE-302).
None of the stress-corrosion U-bend samples exposed for
22 days in the steam from separator 81 showed evidence of stresscorrosion cracking.

In near-neutral pH, low-salinity geothermal fluids,


1020 carbon steel and 4130 steel appear to have value as materials
of construction. Their corrosion rates were not excessive and
they are low-cost materials.. Aluminum alloys cannot be utilized
in geothermal environments due to their low resistance to general,

4-35

pitting, and crevice corrosion in these chloride environments


(NE-302).
Table 4-20 presents the preliminary results of tests
to determine the effects of temperature and pH on the general
lcorrosion of East Mesa wellhead fluid. These results are for
Mesa 6-1 fluid at the following conditions:

1. 150C and pH 5.6-5.8 (normal conditions).


2. 50C and pH 5.6-5.8
3. 150C and pH 4.6-4.8.
i

The corrosion rates of AISI 1010, AISI 4130, and ASTM


A53B decreased with decreasing temperature while AISI 410 and
E-Brite 26-1 had low corrosion rates at both temperatures.
The acid injection data confirmed the pH dependence of
carbon steel corrosion. Corrosion rates for AISI 1010, AISI 4130,
and ASTM A53B increased 3 to 4 times with an acidification of one
pH unit. The 410 chromium steel and E-Brite 26-1 showed no pH
dependence over the range tested (SH-381).

4-36

TABLE 4-20
EFFECT OF TEMPERATURE AND ACIDIFICATION ON
GENERAL CORROSION AT EAST MESA
Mesa 6 - 1
fluid*
150C
pH 5 . 6
5.8
(mPY1

Mesa 6-1
fluid*
50C
pH 5 . 6
5.8
(mpY1

Mesa 6 - 1
fluid*
150C
pH 4 . 6
4.8
(mPY1

AISI 1010

6.0

1.7

25

AISI 4130

6.8

3.5

22

ASTM A53B

5.4

1.8

15

AISI 410

1.3

1.3

1.8

E-Brite 2 6 - 1

0.1

0.3

0.1

*Si02 = 300 mg/R, C 1 - =


Reference: SH-S-379

13,300 ppm, H2S = 1 . 3 mg/R, O 2 <10ppb

4-37

4.4

Results of Corrosion Tests at Heber, California KGRA

Limited corrosion testing has been done at the Heber


KGRA. The results are summarized in Table 4-21. Their utility
is somewhat limited by the fact that scale and corrosion products were not removed before weight losses were determined.
As a result, corrosion rate calculations based on weight loss
are suspect.
4.G.1

Test Conditions

Heat exchanger and in-situ coupon testing were conducted at the Heber, California geothermal site (SY-028).
Coupons of potential construction materials were exposed to flowing fluid from well Nowlin No. 1 for 42 days.
Fluid composition is given in the second column of Table 4-22.
After exposure, the coupons were examined and the weight change
was determined. However, the coupons were not cleaned or descaled which makes accurate general corrosion rates difficult
to obtain. No significant weight loss was found except for
carbon steel. The observed weight changes and observations
about localized corrosion are given in Table 4-23.
4.4.2

Results

The data in Table 4-23 indicate a uniform corrosion


rate of about 2.5 mpy for carbon steel. This value compares
reasonably well with the uniform corrosion rate of carbon steel
at East Mesa of 3.2 mpy. Compositions of these two fluids are
similar. Only Type 316L and $-Brite 26-1 showed signs of local
corrosion (small pits). This pitting behavior is similar to
results obtained at East Mesa (NE-302).

4-38

c
TABLE 4-21
HEBER CORROSION SCREENING RESULTS FOR WELLHEAD F W I D
Nonaerated F l u i d
Uniform
Crevice
Corrosion P i t t i n g Corrosion
I r o n Base
Carbon Steel

AlSl Type 316L

Haynrs Alloy 20 Mod

Carpenter Alloy 20 Cb-3

E - B r i t e 26-1

Inconel 625

Hastelloy G

276

Titanium ( T i 50A)

T i Code 1 2

SCC/

SSc

Nickel Base

Hastelloy C

Titanium Base

Note:

Specimens were not descaled b e f o r e weight-loss determination.

Key t o Table
A

B
C
D
N
X

- g e n e r a l corrosion rate slmpy


- g e n e r a l corrosion rate .lmpy b u t SlOmpy
- g e n e r a l corrosion rate >lOmpy but t5Ompy
- g e n e r a l corrosion rate 250mpy
- i n d i c a t e d form of corrosion d e t e c t e d

- i n d i c a t e d form of

corrosion not d e t e c t e d

Refer t o Table 4-22 f o r more d e t a i l e d information.

(< 2 5 w / y r )
( > 2 5 w / y r b u t S250w/yr)
(>250w/yr b u t <1270pm/yr)
(21270pm/yr)

TABLE '4-22

COMPOSITION OF GEOTHERMAL FLUID FROM TWO WELLS


AT HEBER, CALIFORNIA K G R A ~
Concentration i n
W e l l Nowlin No. 1
(PPd

Fluid
Component
Key Species:

c1-

9000

8242

SG;

100

148

H2S
HCOj

pb

Not r e p o r t e d

20

Not r e p o r t e d

Not r e p o r t e d

100-180b
b
5-13

Not r e p o r t e d

PH
SiO,

7.1

7.4

120

187

Na

3600

4720

360

231

Li

6.6

4.1

Ca

880

1062

Ba

Not r e p o r t e d

3.

Mg
F

2.4

23

1.6

1.5

Al

0.04

12

4.8

8.

cu

0.2

0.4

Fe

0.9

5.

Mn

Not reported

0.9

Pb

0.1

0.6

Sr

nr

42

Zn

0.7

0.1

14100

16330

co;
co2
"3

Other Species:

Concentration i n
Well Hotz No. 2
(PPd

T o t a l Dissolved S o l i d s

Not r e p o r t e d

a
There are only traces of C02, H2S, and o t h e r noncondensable gases i n Heber
f l u i d s (LA-312).
bRef erence : SY-028
4-40
Other d a t a from LA-312

" ^

"

"

. .

..

~-

. . .....

~.

TABLE 4-23

CORROSION TEST RESULTS FOR WELLHEAD FLUID AT HEBER, CALIFORNIA

Weighta
Change

Crevice
Pitting

Corrosion

vg/cm2 day

-145

AlSl Type 316L

+O. 24

Haynes Alloy 20 Mod

+1.4

Carpenter Alloy 20 Cb-3

+O. 48

E - B r i t e 26-1

+0.48

Nickel Base

Inconel 625

+1.4

Hastelloy G

+O .24

0.00

Titanium ( T i 50A)

+O. 7 1

T i Code 12

+2.9

Hastelloy C-276
Titanium Base

Coupons exposed t o flowing Nowlin 111 wellhead f l u i d for 42 days.


Reference:

SY-028

Comments

I r o n Base
Carbon S t e e l

SCCI

ssc

%eight l o s s determined
without d e s c a l i n g of
specimens
bFew small p i t s

"..

. ....

Short-term tests of a tube-in-shell heat exchanger


were performed at the Heber site by the San Diego Gas and Electric Company. No quantitative corrosion data were available,
but the following comment was made.
"A small-scale, tube-in-shell heat exchanger with

four sections in series was tested with geothermal


brine from the Nowlin No. 1 well at Heber, California, in the Imperial Valley in late 1974. The
brine inlet temperature was approximately 355F
and contained 14,500 ppm dissolved solids.
Three tube materials commonly used in heat exchangers were tested. These materials were titanium, carbon steel, and 90% copper-10% nickel. No
corrosion was observed on the titanium tubes after
560 hours of testing. The carbon steel tubes sustained slight pitting and decarburization during
560 hours exposure to the geothermal brine. Some
corrosion of the copper-nickel tubes was evident
after exposure for 200 hours. The copper-nickel
tubes corroded at a much more rapid rate than the
carbon steel.'* (LO-208)

4-42

4.5

Results of Corrosion Tests at Raft River, Idaho KGRA

The summarized "screening" results of corrosion tests


at Raft River are shown in Table 4-24. The rates of uniform,
pitting and crevice corrosion have been studied in coupon exposure tests using wellhead fluid. Another series of tests investigated galvanic and crevice corrosion in potential heat exchanger materials (MI-305). The results of both test programs
are described in the following sections.
4.5.1

Results of Coupon Tests

Field tests at Raft River evalua-ed materials for


binary cycle heat exchanger, valves, pumps, and other equipment
items. Coupons mounted on a test rack with TFE Teflon insulators and washers were exposed to wellhead fluid from well RRGE 1
at 133C. Fluid composition is described in Table 4 - 2 5 .
A "planned interval" test procedure was employed in

which the duration of coupon exposure was varied up to a maximum


of 109 days. The results of planned interval tests indicate
whether corrosion rates increase or decrease with time and whether the corrosivity of the fluid changes during the test period.
After exposure the coupons were visually inspected,
cleaned, and weighed. The measured weight losses measured after 109 days of exposure were used to calculate uniform corrosion rates. Coupons were examined with a monocular metallurgical microscope in order to measure depth of pits and crevices.
Pit and crevice depths were measured to the nearest +lpm. Maximum pit or crevice depths w
rates.

4-43

TABLE 4-24

RAFT RIVER CORROSION SCREENING RESULTS FOR WELLHEAD FLUID


I

Metal Tested
Iron Base
Gray Cast Iron (ASTM A48)
AISI 1018
Low Carbon Steel Plate
(ASTM A515)
AISI 4140
COR-TEN (ASTM A242)
9Cr Steel (ASTM A182 Gr.F9)
AISI Type 304
AISI Type 316
AISI Type 410
AISI Type 440A
ACI Type CF-8
ACI Type CF-8M
ACI Type CF-12M
ACI Type CA-15
Allegheny-Ludlum 216
Allegheny-Ludlum 6X
Allegheny-Ludlum 29-4
Allegheny-Ludlum 24-4-2

Nickel Base
Monel 400
Inconel 625
Hastelloy G

Uniform
Corrosion

Non.aerated Fluid
Crevice
Pitting Corrosion

B
B

X
X

B
A
B
A
A
A
A
A
A
A
A
A
A
A
A
A

X
X
X
X
X
X
X
X
X
X
X
X
X
N
N
N

SCC

X
X

D
AA

Titanium Base
Titanium (ASTM B265 Gr2)
Aluminum Base
1100
5052
6061

D
D
D

X
X
X

X
X
N

--

Copper Base
Ampco 8 (7A1 bronze)
Ampco 12 (9A1 bronze)
h p c o 483 (9A1 4.5Ni bronze)
Muntz Metal (61Cu 39zn)
90-10 Cupronickel
70-30 Cupronickel

B
B
B
C
D
D

N
X
X
X
N
N

X
X
X
X
X
X

----

Cobalt Base
Haynes 6B

- -

KEY TO TABLE

A
B
C
I)

N
X

general corrosion rate 11.0 mpy


--- general
general corrosion rate >1.0 mpy but 110 mpy
corrosion rate >10 mpy but <50 mpy

corrosion rate 250 mpy


--- general
indicated form of corrosion not detected
indicated form of corrosion detected

See Table 4-25 for moEe complete data.

4-44

(125 um/yr)
(>25 pm/yr but 5250 um/yr)
(>250 pm/yr but 4 2 7 0 um/yr)
(21270 um/Yr)

TABLE 4-25
COMPOSITION OF WELLHEAD FLUID FROM THREE WELLS
IN THE RAFT RIVER, IDAHO KGRA

Fluid Component
Key Species:
PH
c1-

Other Components:

Concentration (ppm)
Well
Well
Well
RRGE 3
RRGE 2
RRGE 1
6.70
7.46
7.23
2170
708
776
44.4
41.3
63.9
53.3
54.1
60.2
NR
0.256
0.1
NR
NR
NR

Si02
Na
K
Li

91
445
31.3
1.5

Mi3

2.4

Ca
Sr
F
Br
I

53.5
1.6
6.3
1.5
0.04

Total Dissolved Solids

1215

NR
not reported
Reference: MI-305

4-45

'

170
416
33.4
1.2
0.6
35.3
1.0
8.3
1.5
0.03

114
1185
97.2
3.1
0.6
193
6.7
4.6
1.5
NR

2000

NR

The planned interval test procedure showed that corrosion rates decreased with time. The maximum calculated rates
are given in Table 4-26. Based on the results in Table 4-26, materials were classified in five categories, based on uniform and
local corrosion resistance. Resistance to stress corrosion cracking and sulfide stress cracking was not considered. The results
are shown in Table 4-27. Class 1 materials have the highest resistance to corrosion in Raft River fluid. Materials in Class 2
showed acceptable corrosion resistance. Class 3 materials had
moderate corrosion rates, but are still useful as construction
materials. Materials in Class 4 had high corrosion rates, and
their usefulness is limited to special applications. Class 5
materials showed very little resistance to corrosion and are not
useful, especially where crevices occur. Some generalizations
about the performance of various steels and alloys in Raft River
fluids are given in the following paragraphs (MI-305).
4.5.1.1

Cast Iron, Carbon Steels and Low Alloy Steels

The low alloy steels suffered general corrosion as


well as pitting and crevice attack. Plain carbon steels and
gray cast iron were pitted worse than the low alloy steels.
4.5.1.2

Stainless Steels

AIS1 Type 410 and 440 steels showed the most catastrophic attack. The weight loss of these alloys was primarily due
to severe pitting in the area of the beveled edge of the TFE
washer, as well as the nonoccluded areas. These results lead
to the conclusion that these, and similar, alloys should not be
used in the hot geothermal fluid under conditions where crevices
can be generated. Such applicationp include pump shafts where
seals and bearings could provide the mechanical condition necessary for promotion of crevice corrosion. These alloys are
4-46
!

c
TABLE 4-26
RATES OF UNIFORM, PITTING, AND CREVICE CORROSION FOR METALS

EXPOSED TO RAFT RIVER WELLHEAD J?LUID

Material Tested
Iron Base
Gray Cast Iron (ASTM A48)
AISI 1018
Low Carbon Steel Plate
,
(ASTM A515)
AIS1 4140
COR-TEN (ASTM A242)
9 Cr Steel (ASTM A182 Gr.F9)
AISI Type 304
AISI Type 316
AISI Type 410
AISI Type 440A
.ACI Type CF-8
ACI Type CF-8M
ACI Type CM-12M
ACI Type CA-15
Allegheny-Ludlum 216
Allegheny-Ludlum 6X
Allegheny-Ludlum 29-4
Allegheny-Ludlum 29-4-2
Nickel Base
Monel 400
Inconel 625
Hastelloy G
Titanium Base
Titanium (ASTM 8265 Gr.2)

Corrosion Rate in Nenaerated Fluida


Uniform
Crevice
SCC/
Corrosion' pitting' Corrosion'
ssc
(mpy)
(mpy)
(mpy)
1.6
1.8

7.9
43.Sb

13.2
33.6

1.9
0.83
1.1
0.39
0.02
0.11
0.22
0.28
0.02
0.11
0.11
0.22
0.038
0.0035
0.0037
0.0035

33.1
32.9'
7. Sd
17.4
.
30. 3s
8.7'
39.5k
76.Sm
30.3
8.7
8.7
39.5
47.9
N
N
N

36.9
14.7
13.2
Xf
Xh

Cobalt Base
Haynes 68

X
41.0
X"
N
X0

X'

N
N

0.0063

s
S

79.P
NP
0.0035

Aluminum Base
1100
5052
6061
Copper Base
Ampco 8 (7Al bronze)
Ampco 12 (9A1 bronze)
Ampco 483 (9A1-4.5Ni bronze)
Muntz Metal (61 Cu 39 Zn)
90-10 Cupronickel
70-30 Cupronickel

xj

41. O1
100
X

X
X

3.9
7.5
9.8
20y
275p
164p
0.017

KEY TO TABLE

N
X

--

indicated form of corrosion not detected.


tndicated form of corrosion observed but not quantified.

----

Comments

'Based on weighL loss data after 109 day exposure unless


otherwise indicated in comment column.
*Penetration rate calculated from maximum pit depth
(measured to fl um).
'Penetration rate calculated from maximum crevice depth
(measured to 21 urn).
"Fluid from RRGEl at 133'C(272'F)
:General broad shallow pitting under scale.
,,Numerous pits of varying depth and breadth.
.Numerous small pits.
fDeep pits.
"I)eep"crevice corrosion- no numerical data given.
:Numerous pits.
iCrevice corrosion observed but not quantified.
j$ignificantly less pitting than AISI Type 304.
Some" crevice corrosion not quantified.
:Numerous narrow deep pits.
,Severe crevice corrosion.
Scattered deep pits extending in direction of
"machining marks.
Pit under edge of washer could be crevice
corrosion.
'Minor evidence of crevice corrosion at 109 days.
'Exposure was for 2 weeks (preliminary test).
:No evidence of corrosion was found.
Few small scattered pits no depth given.
SExposure for 11 weeks all alloys were severely
corroded. Some coupons showed 25% weight loss.
,Severe erosion.
Dealloying under washer.
:Small pits with dealloying into pits.
"Grooving" around washer.

....

---

..-

.-.

-I

.. .

.. . .

~~

-. . .

- --

- - ..

. .

.~~
..~

..

TABLE 4-27
CLASSIFICATION OF METALLIC CONSTRUCTION MATERIALS BY CORROSION
RESISTANCE USING RESULTS OF COUPON TESTS AT RAFT RIVER, IDAHO K G R A ~

Class 1
Most .Resist,ant

Class 3
Moderate Resistance

Class 5
No,Resistance

Allegheny-Ludlum 29-4
Allegheny-Ludlum 29d4-2
Inconel 625
Haynes Alloy 6B
Titanium (ASTM B 265 Gr

AISI Type 316


Ampco 12 (9A1 bronze)

AISI
AISI
1100
5052
6061

P
03

Class 2
Acceptable Resistance
Allegheny-Ludlum 216
Allegheny-Ludlum 6X
Hastelloy G
Ampco 8 (7A1 bronze)
Muntz Metal*

Class 4
Marginal Resistance

Type 410
Type 440
Aluminumb
Aluminumb
Aluminumb

Gray cast iron


AISI 1018
Low carbon steel plate
AISI 4130
COR-TEN
9Cr- s tee1
AISI Type 304
Ampco 483 (9A1-4.5Ni-bronze)
90-10 cupronickel*
70-30 cupronickel*
Monel 400*

aCoupons were tested in fluid from Well RRGE 1 for varying periods up to 109 days.
Classifications are based on calculated rates of uniform pitting and crevice corrosion
(See Table 4-25).
bAluminurn coupons were exposed for 11 weeks, after which all showed severe corrosion
and erosion.

....

martensitic and other high chromium martensitic stainless steels


have shown great susceptibility to sulfide stress cracking.
,

The
pitting and crevice corrosion of AISI Type 304 were similar to
the attack on AISI Types 410 and 440, though the pits were not
as numerous or deep. Though localized attack was severe, this
material may be usable in some applications. AISI Type 316 was
also pitted, but to a much lesser extent than Type 304. On the
basis of these data, Type 316 would be acceptable in many applications. Both of these alloys are susceptible to stress corrosion cracking in dilute chloride solutions.
Two austenitic stainless steels were tested.

Precipitation-hardening stainless steels such as 17-4PH


are modifications of the austenitic stainless steels. In these
alloys the nickel content is lower and elements such as aluminum,
copper, molybdenum and niobium are added to generate the second
phase that results in hardening. These materials are similar to
AISI 304 stainless steel in regard to corrosion resistance in
most environments. Because the 17-4PH material is used in valve
stern applications, its use in the Raft River geothermal fluid
should be preceded by careful testing and evaluation.

The super stainless steels, Allegheny-Ludluzn Alloys


216 (20Cr-24Ni-2.5Mo), 6X (20Cr-24Ni-6Mo), 29-4 (29Cr-4Mo), -and
29-4-2 (29Cr-4Mo-2Ni) were resistant to general and local corrosion. The alloy 216 did show some pitting near the TFE washer.

The stress corrosion cracking resistance of these


alloys is high. Nickel-free 29-4 is 'more resistant, though all
will resist cracking in boiling 20% NaCl (GE-119).

u
4-49

4.5.1.3

Nickel-Based Alloys

Inconel 625 was very resistant. No general or local


corrosion was detected after 109 days exposure. Hastelloy G
was also resistant to general corrosion, but a few small pits
were observed. Monel 400 is a nickel-copper alloy, and like all
the nickel-bearing copper alloys in this study, it was severely
attacked .
4.5.1.4

Copper-Based Alloys

The nickel-free copper alloys, Ampco 8 (7Al-bronze),


Ampco 12 (9Al-bronze) and Muntz Metal, were all fairly resistant. Ampco 8 performed best. The nickel bearing alloys,
Ampco 483 (9Al-4.5Ni-bronze), 90-10 cupronickel and 70-30
cupronickel, all suffered severe general or local attack. Dealloying occurred in some of these materials.
4.5.1.5

Titanium-Based Alloys

The titanium alloy (ASTM B 265 Gr2) was resistant to


general corrosion. No local attack was observed.
4.5.1.6

Cobalt-Based Alloys

The Haynes 6B alloy was resistant to general corrosion.


No local attack was observed.
4.5.1.7

Aluminum-Based Alloys

Three aluminum alloys, 1100, 5052, and 6061, were


exposed in eleven-week trials. General and local corrosion
were severe. Weight losses of more than 25 percent were observed after eleven weeks exposure.
4-50

4.5.2

Results of Tests of Potential Heat Exchanger Materials

Simulated tube and shell heat exchangers were exposed


to RRGE 1 wellhead fluid for 34 days to investigate galvanic and
crevice corrosion. Table 4-28 shows the tube and tube sheet combinations tested.
TABLE 4-28
TUBE TO TUBESHEET COMBINATIONS TESTED AT RAFT RIVER

Tube Material

Tubesheet Material
Low-Carbon Steel
Naval Brass

Low-Carbon Steel
304 SS
316 SS
Allegheny-Ludlum 6X
Admiralty Brass (As)
7OCu/3ONi
Hastelloy G

Yes
Yes
Yes
Yes
No
Yes
Yes

No
No
No
No
Yes
Yes
No

Generally, no severe degradation due to galvanic and/


or crevice corrosion was noted in the materials likely to be selected for use in Raft River heat exchangers. Some pitting was
identified in the 70Cu/30Ni tubing but this material is no
longer considered a viable candidate for the boiler/preheater
system due to excessive corrosion induced by hydrogen sulfide in
the geothermal fluid (MI-305).

4-51

4.6

Results of Corrosion Tests in Salton Sea, California,

The geothermal resource at Salton Sea, California has


been the subject of extensive laboratory and field testing. The
results are summarized in "screening" format in Tables 4-29
through 4-36. Laboratory results are given in parentheses.
The following sections provide details about the test
conditions and give numerical values for corrosion rates. Generalizations about performance and applicability of various
steels and alloys are presented. Laboratory results are presented in Section 4i5.1. Results of field tests follow in Section 4 . 5 . 2 .

4.6.1

Results of Laboratory Tests Using Synthetic Fluids

Two types of laboratory tests using synthetic fluids


have been conducted (NE-302). One series of tests was done in
a high pressure autoclave at 232C. The second series was done
at atmospheric pressure at 105C. Both series of tests used a
solution made in the laboratory by dissolving metal chlorides,
silicates, and metaborates in water and adjusting the pH with
sodium hydroxide. The composition is defined in Table 4-37.
The composition of the test solution is based on that of flashed
fluid frdm well IID 2.

4.6.1.1

Results of Autoclave Tests at 232C

Twenty-three commercially available alloys were


in the autoclave tests. Coupons, U-bend stress corrosion
ments, butt-welded samples, and specimens with fabricated
ices were exposed to 1300 ml of unstirred synthetic fluid
tained in a two-liter, high pressure glasslined stainless

4-52

tested
specicrevconsteel

Lid

Table 4-29
SALTON SEA CORROSION SCREENING RESULTS FOR

WELLHEAD FLUID

General
Corroeion
Iron Base
Carbon Steel (AIS1 1020)
AIS1 4130
COR-TEN B
Uariner
AISI Type 3161.
AISI Type 430
ACI
e Q-3M
S a n d 2 3M60
c a r p m t a 20
Allegheny-Ludltlm 6 X
All. heny-Ludlm 29-4
I-llrfte 26-1
Nickel Base
llonel 400
Inconel X-750
Inconel 625
bitalloy S
Haatellog C
IIaatalloy 0 2 7 6
Copper Base

70-30 Cupronickel
T i t a n i m Base
Titaniuu
Ti-1.7U
Ti-1.5Ni
Ti-1OV
Ti-0.2Pd
Ticode-12
Molybdenum Base

Tm

AISI 4130

--

'Stick
Shielded metal-arc welding.
'Tig
I n e r t gas rungaten-arc welding.
for more detailed data.
See Tabla

TO TABLE
&enera1 CorroSion r a t e s1.0 mpy
general corroaion r a t e >1.0 mpy but d 0 mpp
0
.C
general corroaion r a t e >10 mpy but ~ 5 mpy
eneral corroaion r a t e 250 mpy
ndicated form of corroaion not detected
X
indicated form of corroaion detected
ntergranular corroaion
CC detected
Data i n parmtheae. are from laboratory itudiea.

KEY

-Kf
A

f:9

4-53

Aarated Fluid
crevice
Corroiion

Pittinn

SCC

..............

..................

- - ..................................

...........

.......

. . . . .-

TABLE 4-30

SALTON SEA CORROSION SCREENING RESULTS FOR FLUID (LIQUID STREAM)

AFTER F I R S T FLASH
General
Corromion

Nonaerated Fluid
Crevice
Pitting
Corrosion

Iron Base
Carbon S t e e l (AISI 1020)
AISI 4130
COR-TEN B

Mariner
AISI Type 316L
AIS1 Tvue 430
ACI
- k CF-3W
Sand%
3RE60
Carpenter 20
Allegheny-Ludlum 6X
Allegheny-Mlum 29-4
E-Brite 26-1
Nickel Base
M e 1 400
Inconel X-750
Inconel 625
Hastelloy S
hstelloy C
-Aantelloy C-276
Comer Bane
70-30 Cupronickel
Titanium Bane
Titanium
Ti-1.7W
Ti- 1.511
Ti-1OV
Ti-0.2Pd
TiCode-12

Holybdenum Base

TM
KEY TO TABLE
A

corrosion r a t e (1.0 mpy


-- general
general corrosion rate >1.0 mpy but 110 mpy

corroaion rate >10


but
-- general
general corrosion r a t e
-- indicated
form of corroTion not detected
Indicated form of corronion detected
I - intergranular corrorirm

B
C
D
N
X

mpy
>50 mpy

<50 mpy

(a270 Wyr)

Refer t o Table 4-45 for more detailed data.

SCC

General
Corrorion

Aerated Fluid
Crevice
P i t t i n g Corrosion

SCC

..

..-

- _

~.

-.

__

..I .._...I._ ".I._

.... ..

.. .. ~ . .

"

TABLE 4-31
SALMN SEA CORROSION SCREENING RESULTS FOR STEAM FROM FIRST FLASH

General
Corrosion
Iron Base
Carbon Steel (AIS1 1020)
AISI 4130
COR-TEN B
Mariner
AISI Type 316L
AISI Type 430
ACI T
CF-3M
SmdvE 3RE60
Carpenter 20
.
Allegheny-Ludlum 6X
Alleghen Ludlm 29-4
E-Brim

*
I

. c n
cn

SCC

---

--

X
X

N
X

-X
X

1&1

Nomerated Steam
Crevice
P i t t i n g Corrosion

N i c k e l Base
Hone1 400
Inconel X-750
Inconel 625
Bastelloy S
Hastelloy G
Hastelloy C-276

Copper Base
70-30 Cupronickel
Titanium Base
Titantus
Ti-1.m
Ti- 1.5191
Ti-1W
Ti-O.2Pd
TiCode- 12
Molybdenum Base
Tal
KEY TO TABU
A
general corrosion r a t e 51.0 m p y

--- general
corrosion r a t e >1.0 mpy but 3 0 m p y
general corrosion r a t e >10 apy but
mpy
D - general corrosion r a t e
mpy
N - indicated form of corrosion not detected
- indicated form of corrosion detected
I - intergranular corrosion
B

250

4 0

(125 U d F )

~ 1250 d p r )
0 2 5 m / but
>250 u d y r but 4 2 7 0 um/pr)
L 2 7 0 um/yr)

Refer t o Table 4-46 f o r more exact data.

General
Corrosion

Aerated Steam
Crevice
PittinR
Corrosion

SCC

~.

,,

,. . .

.. ..

...~

""... . -.-.

..

...

...

"...

.___.
~

..

. . ..

._~.

._.

. .

. . ,.

~.

TABLE 4-32
SALTON, SEA CORROSION SCREENING RESULTS FOR SCRUBBED STEAM FROM FIRST FLASH

General
Corrosion
Iron B M ~
Carbon Steel (AISI 1020)
AISI 4130
COR-TEN B
Mariner
AISI Type 316L
AISI Type 430
e CF-3U
3RE60
Carpenter 20
Allegheny-Ludlum 6X
Alleghm -Ludlum 216
E-Brite $6-1
Nickel Bare
Moonel 400
Inconel X-750
Inconel 625
Hartellay S
Hastelloy G
Hastellay C-276

Nonaerated S t e m
Crevice
Pitting Corrosion

SCC

C
C

X
X

X
X

-X

N
X

N
N

--

-N-

-N

-N-

A
A
A

N
N
N

N
N
N

N
N
N

--

A
A
A

--

General
Corrosion

Aerated Stem
Crevice
PittinR Corrorion

SCC

--

N
X

-N

Copper Base
70-30 Cupronickel
Ntanita Emre
Titanium
Ti-1.m
Ti-1 .5N1
Ti-1W
Ti-0.2Pd
TiCoda-12
Molybdenum Base
TZM
I[gP TO TABLE

corrosion rate S1.0 mpy


--- general
general cortosion rate >1.0 mpy but 510 mpy
general corrosion rate >10 mpy but e50 mpy
D - general cortosion rate 250 mpy

B
C

-- indicated
indicated form of corrosion not detected
form of corroaion detected
I - intergranular corrosion

(125 W / P )
>25 u m / p but 1250 um/Yr)
[>250 d p t but 4 2 7 0 u m / v )
(11270 u d p )

Refer to T a b l e 4-47 for more data.

C'

..

.. ..

c
TABLE 4-33
SALTON SEA CORROSION SCREENING RESULTS FOR FLUID (LIQUID STREAM)
AFTER SECOND FLASH
General
Corrosion
I r o n Bane
Carbon S t e e l
AIS1 4130
COR-TEN B
Mariner
AISI Type 316L
AISI Type 430
e CP-3U
3RE60
carpenter 20
Alleghmy-Ludlm 6X
.Alleghmy-Ludlm 29-4
E - B r i t s 26-1

Nonaerated Fluid
Crwice
Pittint? Corrosion

N
N

C
B-C

--

X
X
X

-N

A
A

--

Hans1 Baee
Hone1 400
Inconel X-790
Inconel 625
Aastellap S
Hastellby G
Rastellap C-276

X
X

A
A
A

--

gtk%

A
A
A
A

11
N

m e r Bast
70-30 Cupronickel
T i t a n i t n Base

TI-iov

Ti-0.2Pd

TiCode-12

wy To TABLE

indicated fonn of c o r r o h n bbt detected


X - Indicated form of corrosion detected
I - intergranular corrosion
R e f e r t o T a b l e 4-48 f o r more detailed data.
-

_______.
~

SCC

N.1
N
N.1

General
Corrosion

Aerated Fluid
Crevice
Pitting
Corrosion

SCC

SALTON SEA CORROSION SCREENING RESULTS FOR STEM FROM SECOND FLASH

General
Corrosion
Iron Base
Carbon Steel (AIS1 1020)
AISI 4130
COR-TEN B
Mariner
AISI Type 316L
AISI Type 430
e CF-3M
3RE60
Camenter 20
Alligheny-Ludlum 6X
Alleghen Ludlum 29-4
E-Brite {'a-1
Nickel Bare
Mona1 400
Inconel X-750
Inconel 625
Hartelloy S
Bastelloy G
Hastelloy C-276

Nonaerated Steam
Crevice
Pitting Corrorion
X

SCC

General
Corrosion

--

C
B

N
N

N
N

A
A
A

X
N

X
N
X

N
N
N

-A
A
A
A

Aerated Steam
Crevice
PittlnK Corrosion

--

--

SCC

---

N
N
N
N

N
N
N

Copper B u e
70-30 Cupronickel
Titanirrm Base
Titanlm
Ti-1.7W
Ti-1.581
Pi-1ov
Ti-0.2Pd
TiCodc-12
Molybdenum Base
T1W
KEY TO T A B U

-- general
corrorion rate 4.0 mpp
general corrosion rate 71.0 mpy but e10 mpy
-- general
general corrosion rate >10 mpy but G O mpy
corrosion rate 250 mpy
-- indicated
form of corrosion not detected
indicated form of corrosion detected
I - intergranular corrosion

C
D
N
X

(25 d y r )
(>25 umlyr but 4250 vmlyr)
(>250 vmlyr but-cl270 umlyr)
(21270 umlyr)

Refer t o Table 4-49 for more d e t a i l e d data.

TABLE 4-35
SALTON SEA CORROSION SCREENING RESULTS FOR SCRUBBED STEAM FROM SECOND FLASH

General
Corrosion
I r o n Base
Carbon S t e e l ( U S 1 1020)
AISI 4130
COR-TEN B
Mariner
A I S I Type 316L
AISI Type 430
e CF-3M
$ E d % 3Re60
Cazpenter 20
Allegheny-Ludlm bx
Allegheny-Ludlm 29-4
E - B r l t e 26-1

CI
I

cn
\o

Nickel Base
Monel 400
Inconel X-750
Inconel 625
Hastelloy s
Hastelloy G
Has t e l l o y C- 27 6

Honaerated Fluid
Crevice
Pitting
Corrosion

SCC

C
C

--

A
B

-A-

N
N
N

--

N
N
N

A
A
A

Copper Base
70-30 Cupronickel
Titad-

Base

Titanium
TI-1.m
Ti- 1.5Ni
Ti-1OV
Ti- 0.2Pd
TiCode-12
Molybdenum Base

TZM
KEY TO TABLE

-- general
corrosion r a t e s l . 0 mpy
general corrosion r a t e >1.0 mpy but 110 mpy
C - general corrosion r a t e >10 mpy but (50 mpy
D - general corrosion r a t e 250 mpy
N - i n d i c a t e d form of corrosion not detected

X
I

--

Indicated form of corrosion detected


i n t e r g r a n u l a r corrosion

(125 I r m / p )
(>25 v m / p but 5250 IJm/p)
( ~ 2 5 0W / p but 4 2 7 0 v m / p )
W 2 7 0 Irmm/pZ)

Refer t o Table 4-50 for more, detailed data.

General
Corrosion

Aerated Fluid
Crevice
Pitting
Corrosion

SCC

TABLE 4-36
SALTON SEA CORROSION SCREENING RESULTS' FOR CONCENTRATED GAS-FREE FLUID AT 105OC
General
Corroeion

Nomerated FlU l d
Crevice
Plttim
Corrorion

Aerated Fluid

SCC

General
Corrosion

Pitting

Crwice
Corrosion

SCC

N
N
N

X
X

N
N

N
N
N

N
d

X
N

N
N

Iron Bare
Carbon S t e e l (AIS1 1020)
AISI 4130
COR-TEN B
Mariner
AISI Type 316L
AISI Type 430
e CF-3H
3RE60
Carpenter 20
Allegheny-Mlum 6X
Alleghen -Ludlum 29-4
E - B r i t e %6-1

P
I
Q\

Nickel Bare
Wonel 400
Inconel X-750
Inconel 625
Hartelloy S
Hartelloy G
Hartelloy C-276

N
N
N
N
N

A
A
A
A

N
N
N
N

A
A
A
A

C
C

ti

N
N
N
N

N
N

A
A

N
N

N
N
N

N
N

X
N

*
*

N
N

Comer Bare

2%:
70-30 Cupronickel

B
B

A
A
A
A

A l d u m Bare
2024-T3
6061-T6

B
C

X
X

Molybdenum Bare
T1M

T l t w l m Base
Titanium
Ti-1.7W
Ti- 1.5NI
Ti-1OV
Ti-0.2Pd
TlCodc 12

N
N
N

N
N
N

KEY TO TABLE
A
B
C

-- general
currorion r a t e
general corrosion r a t e >1.0 mpy but s10 mpy t% $$sb
)ut
s.250
- general c o r r o r i a r a t e > I O but <50
(>250 pm/yr but e1270 pmfyr)
r 1 . 0 mpy

pm/v)

apy
general corrosion rate 250 mpy

mpy

-- indicated form of corrosion not detected. (A270 umlyr)


indicated form of corrosion detected.
I - intergranular corrosion.
* - much increaeed general corrosion i n rtressed area.
D

N
X

b f e r to, Table 4-41 for maze detailed data.

TABLE 4-37.

Constituent
Na
Ca
K
Fe
Mn
Zn
Sr

si0 2

B
Ba
Li
Pb
Rb

cs

Mg
Ge
As
A1

c1

Sulfide

COMPOSITION OF SYNTHETIC SALTON SEA


F L U I D USED I N LABORATORY TESTS (NE-302)

Nominal b
53,000
28,000
16 ,500
2 ,000
1,370
500
440
400
390
250
2 10
80
70
20
10

Concentration (ppm) a
A f t e r 15 days
A s Prepared'
a t 232C
68,250
59,250
19,350
22 ,400
13,150
16,700
3.6
3.9
1,650
1,710
542
345
313
706
47
21
-1
200
344
294
178
182
69
14
89
74

-27
-

155,000
30

140,200
34

148,200
<. 1

adash means n o t measured


bbased on t h e composition of unflashed f l u i d from w e l l 1 1 D
No. 2 , pH = 6.4
'Prepared by d i s s o l v i n g reagent grade c h l o r i d e s , s u l f i d e s ,
s i l i c a t e s and metaborates i n water and a d j u s t i n g t h e pH t o
Some c o n s t i t u e n t s f a i l e d t o d i s s o l v e o r p r e c i p i t a t e d
6.1.
from s o l u t i o n a t room temperature.
d A f t e r prolonged h e a t i n g , pH = 5.0.
Reference:

NE-302

4-61

c
autoclave. The coupons and crevice specimens were suspended in
the solution with glass supports while the U-bend specimens rested
on the bottom of the autoclave. Alloys were tested in separate
exposures for periods of 15 to 30 days.
Tests specimens were immersed in the test solution, the
solution was vacuum degassed, and the autoclave was sealed and
heated to 232+2"C. The vapor pressure over the solution at these
conditions was about 360 psig. In some tests another gas was
injected into the autoclave from a cylinder. Either oxygen, C 0 2
or methane was added until the pressure in the autoclave reached
a specified value. The pressures of added gases were calculated
based on Henry's Law Constants so that a specific concentration of
the gas would be dissolved in the solution at the test conditions.
Tests were done with no added gases, with 100 ppm O 2 in the liquid, 250 ppm C O P , and 100 ppm CH4.
After exposure the specimens were cleaned and examined
microscopically. Uniform corrosion rates were determined by
weight loss for both coupons and U-bend specimens. Pitting and
crevice corrosion rates were calculated based on optical measurements of pit or crevice depth.
Weld-related corrosion failures were studied in deaerated and oxygenated fluid at 232C. Weight-loss samples were
butt-welded together following practices recommended by the American Society for Metals. These samples were not heat treated to
relieve stresses prior to corrosion testing.
Thenumerical corrosion rates measured in autoclave
tests are summarized in Tables 4-38, 4-39, and 4-40. Table 4-38
shows results of tests of coupons, crevice specimens, and U-bend
specimens in deaerated fluid and tests in which oxygen was added

LiJ
4-62

TABLE 4-38
CORROSION RATES MEASURED IN FIFTEEN-DAY AUTOCLAVE TESTS USING DEAERATED AND
OXYGENATED SYNTHETIC SALTON SEA FLUID

Dcacrated Solution

General
Corroaioa'
(WY)
I r o a Base
Carbon S t e e l (AIS1 1020)
AISI 4130
COR-m B

50

<O. 05
<O. 05
2.0

N
N
N
N
N

0.1
0.3

nick1 b e
m a e l 400
IaC0nclX-750
IUCOM~
625
Rastelloy S
Raatslloy C
Hnstelloy 0 2 7 6

1.7
0.3
(0.05
<O. 05
0.1

Solution Coat.iniag 100 ppm


General
corrosion'

SCC'

(mm)

(rpY)

4.8
3.8
1.3
1.6

Huiaer
AISI Type 3161
A I S I Type 430
Sadvik 3lU60
E-Brite 26-1
Carpenter 20

pitting'

Crevice
Corrosion'

1060

i
n

(0.05
1.0
0.1
0.3

1180
1310
245
345

12.0
0.4

N
N

CO.05

-19.2

530

N
N
N

6.0

125

225

2.2

iN
N
XC

N
Xc

i
N

N
II

3
X

Xc

x
N
X

0.05

'0.05
0.4
0.1

3.2

7.8

0.3

100

fl

N
N

2
N
N
-

0.5
<0.05
0.2
<0.05
<0.05

N
N
N
N
N

-20.7
288

02

Crwico
~ i t t i a g ' ~ o r r o s i o a ~ SCC'
(
m
!
?

3
36.5

81
345

39.3
-

--

11.3
22.4

x
x
x

Titad-

TI-1.m

<O. 05
0.1
c0.05
0.05

~i-i.5~1
Ti-109
Ti-O.2Pd
TiCodcl2

n
n

0.6

T
_ _M

* - stea t a b l e value.
Reference: NE-302
232OC (450F) pres

422.6 psi.* C1-

- 1%m

PP..

0.8

<0.05

C0.05

Ilolybdwcom Base

I)ub

T i U d U

N
N

0.1
-

'Baaed oa w i g h t loss.
'Based on UU~JMIE p i t depth.
'Spechean with fabricated crevices.
%-bend mpcetclls ( m n e r i c a l data
are g m e r a l corrosion r a t e s of
U-bead specimens.
:Light
pitting" (NE-302).
c<l
d>l
mpy but e 5 q y .
=PY.
.5 -9.

Copper B n e

70-30 Cupronickel

Cormenta

0.1

C0.05

TABLE 4-39
CORROSION RATES MEASURED IN FIFTEEN-DAY AUTOCLAVE TESTS USING SYNTHETIC
SALTON SEA FLUID WITH ADDITION OF cor, AND CHI,

Iron B e n
Carban S t n l (AIS1 1020)

2.4

A M Y 4130

3.3

COR-TUN 1

0.4

1.5
(0.05
<0.05

Herim
AISI Type 31&
AISI Type 430
S.ndrik 3RJI66

2.1

55

30

(0.05 1

?Ionel 400
hc-1
X-750
I n c d 625
betalloy s
8astalloy 0
betalloy 5276
Comer Bema

tltmica Beme
Tit&Ti-1.7W

' m e d 011 weight lo.


' h e d on rarCmr p i t depth.
' ~ p m c i m ewith
~
fabricated crevice..
'U-bead apecimeaa ( n m r i u l data are
.general com8ion rate. of U-bend
U-bend . p @ e i w ~ .
3 i g h t pitting" (m-302).
c<l
(1 mpy
.PI.but >5 mpy.

% .PI.

M i C k d b.M

70-30 copronickel

<0.05 x
(0.05 X

II

.<0.05:

B-Britm 26-1
Carpentar 20

--

A
Xa
A

1.0

II

3.0

<O .05

Ti-1. W i

--

Ti-105'
Ti-0. ZPd
TiCode-12

0.05
0.05

-II
n

TABLE 4-40
RESULTS OF LABORATORY TESTS OF THE EFFECT OF WELDING

ON UNIFORM CORROSION RATE IN SYNTHETIC SALTON SEA

FLUID^

to the autoclave. Table 4-39 shows results obtained when COn and
CHI,were added. Results of tests of welded and non-welded specimens are given in Table 4-40. Results are shown for both deaerated
fluid and oxygen addition. The following paragraphs summarize the
findings for carbon steels, stainless steels, and nickel, titanium,
copper, and molybdenum alloys.

In deaerated fluid, the uniform corrosion rates of carbon and low alloy steels were less than 5 mpy. Carbon steel (AISI
1020) developed deep pits while the other alloys were resistant or
suffered only slight attack. The crevice corrosion rates were
severe. Only AISI 1020 and 4130 were tested for stress corrosion
cracking. Both were resistant, but the weight loss of the AISI
4130 U-bend specimen was three times the weight loss of the AISI
4130 coupon. In the case of 1020 carbon steel and 4130 steel,
welding increased the uniform corrosion rate tenfold in the deaerated fluid.
The addition of oxygen increased general corrosion of
low alloy steels Q1000-fold. There were no differences in weight
loss for the welded and non-welded samples of 1020 and 4130 steel
in tests when oxygen was added.
Stainless Steels

In non-aerated fluid stainless steels had general corrosion rates of less than 2 mpy. Some were subject to slight or
moderate crevice corrosion though no pitting was observed. Only
E-Brite 26-1 was resistant to stress corrosion cracking. Welding
caused a slight increase in weight loss, and stress corrosion
cracking was noted in welded specimens of the 316 L.
Addition of oxygen caused severe increases in general
corrosion, pitting and crevice attack. Intergranular corrosion

4-66

lj
of Type 316 L was observed. Oxygen increased severity of stress
corrosion cracking in all alloys except E-Brite 26-1. Welding
of E-Brite 26-1 caused a seven-fold increase in weight loss.
Addition of CO, caused slight increases in severity of
general corrosion and pitting but did not effect the rate of
local corrosion.
Addition of CHt, caused a severe increase in pitting and
slight reductions in general corrosion.

Nickel Based Alloys

In non-aerated fluid, the general corrosion rates of


the nickel alloys were less than 2 mpy. Pitting was light or did
not occur. Inconel 625, Hastelloy S and Hastelloy G had significant crevice corrosion. None of the alloys displayed stress
corrosion cracking, but the weight loss of Monel-400 U-bend specimens was seven times that of Monel coupons.
Aeration caused a very severe increase in uniform corrosion rate of Monel 400. The uniform corrosion rates of the other
alloys also increased. Pitting and crevice corrosion of Inconel
625 and Hastelloy C-276 were severe and both alloys failed due to
stress corrosion cracking. Welding caused a slight increase in
weight loss of Inconel 625, the only nickel alloy tested in nonaerated fluid.
Addition of oxygen appreciably increased the general
corrosion of nickel alloys and caused severe pitting and crevice
corrosion of Inconel 625 and Hastelloy C-276. Stress corrosion
cracking was observed in U-bend specimens of Xastelloy C-276
and Inconel 625. The weight loss of welded specimens of Inconel
625 was four times that of unwelded specimens in tests done with
oxygen.
4-67

The addition of C02 had little effect while CH4 caused


increased crevice corrosion of Inconel 625 and Hastelloy C-276.
Titanium Based Alloys
In nonaerated fluid, all the titanium alloys had general corrosion rates of less than 0.5 mpy. Severe pitting and
crevice corrosion of (commercially pure) titanium occurred. The
rate of crevice corrosion for Ti-1.5Ni was between 1 and 5 mpy.
None of the other titanium alloys were susceptible to pitting or
crevice corrosion. No stress corrosion cracking was observed and
welding of Ti-0.2Pd had little effect on weight loss.
The performance of titanium a l l o y s improved in tests
when oxygen was added. All uniform corrosion rates were less
than 0.05 mpy and no local corrosion or stress cracking was observed. Welding had little effect on weight loss of Ti-0.2Pd.
Additions of CO2 and CHI,produced results similar to the addition of oxygen.
Copper Based Alloy
This alloy (70-30 cupronickel) was fairly resistant to
all modes of corrosion in non-aerated fluid and fluids containing
CH4 and C02. Addition of O2 caused a severe increase in the rate
of uniform corrosion as well as pitting and crevice corrosion.
Addition of H2S to any of these environments would probably cause
severe corrosion.
Molvbdenum Allov
TZM was tested only in nonaerated fluid.
resistant to all modes of corrosion.

4-68

It was very

4.6.1.2

Laboratory Tests at 105C

Another series of tests using the synthetic Salton Sea


fluid described in Table 4-37 was done at atmospheric pressure
at the boiling point of the fluid (105C). Tests were done in a
1-liter erlenmeyer flash fitted with a sparger (bubbler) and a
water cooled condenser. Coupons and specimens with fabricated
crevices were suspended in the boiling test solution. U-bend
specimens lay on the bottom of the flask. In some tests the solution was deaerated with a constant helium purge; in the other
series the fluid was aerated by continuous air purge. Tests were
conducted for 15-day periods. Duplicate samples of each material
were tested, and each test was done in a separate flask.
The coupons and U-bend specimens were cleaned after
exposure and the uniform corrosion rate was determined by weight
loss. Specimens were examined microscopically for pits, cracks
and crevice corrosion. Corrosion rates calculated from 15-day
weight loss and maximum pit or crevice depth are given in Table
4-41. The following observations about the performance of ferrous,
nickel, copper, titanium, aluminum and molybdenum alloys are
based on the corrosion rates summarized in Table 4-41.
I

Iron Based Alloys


All ferrous alloys
cept AIS1 1020 carbon steel had
uniform corrosion rates of less than 0.05 mpy in nonaerated fluid.
Uniform corrosion rates for these alloys increased in aerated
fluid, though all were less than 5 mpy.
Pitting was not observed in either aerated or nonaerated
fluid. Type 316 L, Sandvik 3 RE60, and Carpenter 20 showed slight
(cO.1 mpy) crevice attack in nonaerated fluid. Crevice corrosion

4-69

TABLE 4-41
CORROSION RATES MEASURED I N FIFTEEN-DAY LABORATORY TESTS AT 1 0 5 O C USING DEAERATED
AND AERATED SYNTHETIC SALTON SEA FLUIDS
TABLE 5-33

SITE:

salton

FWIR0N"T:

sei. California .
Cas-Ree Wellhead Fluid

Deaernted Fluid
General

Corrosion' pitting'
(mm)
(mw)

Crevice
Corrosion

Aerated Fluid
General
SCC'

Corrosion'

Pitting'

(1DJ)

(mw)

5.8
4.0
4.0
0.9
2.2
3.6

N
N
N
N

Iron Base
Carbon S t e l (AISI 1020)
AISI Type 316L
MI Type CF-m
&odvik 3m60
Carpenter 20
E-Brite 26-1

4.2
eo. 05
<o. 05
eo.05
(0.05
<O. 05

N
N
N
N
N
N

;
.
X'
N

N
N
N
N
N

2.8

N
N
N
N
N
N

N
N

X'

X8

I
11

Crevice
Corrosion

SCC'

Colments

Xe
X=

N
N
N
N

'Boned on weight loan after 15 daw.


'Bnasd on maximum p i t depth.
'U-bmd npecfrcll..
30.1 spy

$
i

N
N

.>0.1 mpy but <1mpy


d" wy but <5 q y
spy but
rPY
f>mmIm
Ten-fold incruse in general corrosion. concentrated In bend aren.

Nickel Base

f
U

Hone1400
Incoml x-750
Inconel 625
Eastalloy S
Eaatelloy G
Hawelloy C-276

(0.05
<O. 05
<o. 05
CO. 05
CO.05

N
N
N

3.7
3.4
<O. 05

N
N

a
.
0
5

N
N

0.1
<0.05

N
N
N
N
N

12.5
13.3
5.8

N
N
N

Performance of cast (MI) alloy based


on wrought equivalent.
Composition of the f l u i d is given
in Tnble 4-

XC

Copper Bane
Copper
Cu-Za
7&30 Cupronickel

3.1
2.7
0.6

Titanium Bone
Titaniu
Ti-1.7W
Ti-1.5Nl
Ti-1OV

eo. 05
<0.05
<o. 05
<o. 05

N
N

Aluminum Bane
2024-T3
6061-T6

1.3

30.4

XC

N
N

N
N
N

<0.05
<o. 05
(0.05
<0.05

N
N
N
N

xa

N
N
N

71400
,1400

X'
N

N
N

34.9
56.6

N
N

Xe
N

1.4

(0.05

References:

NE-302, CA-430

N
N

b,

r a t e s i n a e r a t e d f l u i d were g r e a t e r than 50 mpy. S t r e s s corrosion


cracking w a s not observed i n t e s t s with e i t h e r a e r a t e d o r nonaerated
fluids

Nickel Based A l l o y s
Inconel
and Inconel X-750
deaerated f l u i d .
g r e a t l y increased

625, Hastelloy S , Hastelloy G and Hastelloy C-276,


had uniform corrosion r a t e s l e s s than 0.05 mpy i n
Monel 400 d i d l e s s w e l l (2.8 mpy). Aeration
t h e corrosion of Inconel X-750. The uniform

corrosion rates of t h e o t h e r nickel-.based a l l o y s were n o t a f f e c t e d


much by a e r a t i o n .

No p i t t i n g o r stress corrosion cracking w a s observed i n


e i t h e r environment. Both'Monel 400 and Inconel X-750 experienced
some c r e v i c e corrosion i n nonaerated media. Only Inconel 625 and
Hastelloy C-276 d i d not s u f f e r c r e v i c e a t t a c k i n a e r a t e d f l u i d .
Copper Based Alloys
Copper and Cu-2Fe a l l o y were f a i r l y r e s i s t a n t t o general
corrosion i n nonaerated media.
s i o n r a t e s by a f a c t o r of f o u r . No p i t t i n g o r c r e v i c e corrosion
was observed i n e i t h e r f l u i d .
70-30 cupronickel w a s more r e s i s t a n t t o uniform corros i o n (0.6 mpy) i n nonaerated f l u i d , b u t a e r a t i o n caused a t e n f o l d i n c r e a s e i n t h e uniform corrosion rate. It w a s s u b j e c t to
c r e v i c e corrosion i n both f l u i d s .
/

These t e s t s were i n HZS-free f l u i d . Experience has


shown t h a t copper-based a l l o y s , e s p e c i a l l y cupronickels, a r e s e v e r e l y a t t a c k e d i n f l u i d s c o n t a b i n g H2S (MI-305).

42.71

Titanium Based Alloys


All four titanium alloys were resistant to uniform corrosion, pitting and stress corrosion cracking in both aerated and
deaerated fluid. Commercially pure titanium showed ~ 0 . 1mpy crevice corrosion in aerated fluid. No other crevice corrosion was
observed.
Aluminum Based Allovs
These alloys are not suitable for exposure to Salton
Sea geothermal fluids. Both 2024 and 6061 alloys pitted.badly
in nonaerated fluid. The pitting rate, calculated from pit depth
after fifteen days, was >1400 mpy. Crevice corrosion of 2024-T3
was severe (>50 mpy). A ten-fold increase in uniform corrosion
rate in the stressed area of the U-bend specimens was noted in
tests with aerated fluid, though no cracks were observed.
Molybdenum Based Alloy
TZM was the only dolybdenum based alloy tested, Uniform
corrosion was very slight (c0.05 mpy) in deaerated fluid; no local corrosion or stress corrosion cracking was detected. Aeration increased general corrosion to 1.4 mpy and significant crevice corrosion (>5 mpy but <50 mpy) occurred. No stress corrosion cracking was observed.
4.6.2

Results of Field Tests at Well Magmamax No. 1

Three test programs have been conducted at Well Magmamax


No. 1 in the Salton Sea KGRA. One test series resulted in qualitative observations of corrosion after 30-day exposures of coupons in wellhead fluid. In the second program specimens were

tested in two 15-day test periods at the Bureau of Mines Geothermal Loop Experimental Facility. These tests were done in
seven process streams typical of a dual flash binary power cycle.
Uniform corrosion and pitting rates were measured, and crevice
corrosion and stress corrosion cracking observations were made.
The third test program was conducted at Lawrence Livermore Laboratory's (LLL) field test station. The tests employed an acidified mixture of steam and brine from Magmamax No. 1. Two kinds
of tests were done with the acidified fluid. One series examined
stress corrosion cracking and erosion-corrosion of specimens exposed to two-phase expander nozzle discharge. In the second
series, uniform corrosion rates were measured electrochemically
in 16-20-hour tests using exhaust fluid from the expander nozzles.
I

Table 4-42 shows the physical characteristics and chemical composition of fluids from three wells in the Salton Sea KGRA.
The table indicates the range of temperature, pH, and chemical
composition for wells in the resource area. The data for well
Magmamax No. l.(middle column) are for flashed fluid. Limited *
data are available describing the characteristics of fluids used
in the three field test programs. The composition and temperature
of fluids used in the field tests are somewhat different from
those given in Table 4-42. The test conditions and results are
described in the following sections.
4.6.2.1

Qualitative Corrosion Tests in Wellhead Fluid

Coupons of ten alloys (carbon steel, Type 316 L, E-Brite


26-1, Haynes Alloy 20 Mod, Carpenter 20Cb3, Inconel Alloy 625,
Hastelloy G, Hastelloy C-276, cammercially pure titanium, TiCode
12) were exposed to wellhead fluid from Magmamax fl for 30 days
(SY-029). Published information about the test procedures did
not include data on fluid composition.
I

w.
4-73

TABLE 4-42
CHARACTERISTICS OF GEOTHERMAL FLUIDS FROM THREE

WELLS IN THE SALTON SEA KGRA


Uxture of
Steam Conden-

Fluid
Characteristic#
Temperature
Depth o? Well
Bnthdphy (Btu/lb)

PE
conductance

(@CS/CIU)

Flashed Fluid
Irom Well
lfa(lclmmau Ho. 1
28OOC
21om

Flashed Fluid
Prom Well
&mnaIMx

NO.

265'C

316'~

875m

159h

450 Btu/lb
6.10

432 Btu/lb
5.30
257360.00

sate and Flashed


Fluld From Well
IID No. 1

5.20

226297.00

--

203,106
425.6

257,800
400.0

46,282

50,400

chemical Camposition ( P P I :

TDS (Residue)
T r s sum)
si02
Ea.

183,700
1539300

350.0
36,340

p.

7,820

1,789

17,500

ca

14,550
780.0

23,090
io?. 6

28,000

c1Em;
a;

93,650
60.00

120.314

155,000

59.69

UR

UR

48

NR

Ba

UR
340.0
210.0
540.0

150.00
IIR
16.0
409.0

Br

UR

cs

WR

L1

lag

mb+
B

Rb

Sr

557.7
UR
54.11
ER
244.6

390.0
235.0
120.0
14.0

49.00

74.00

215.0

ER

48.92

135.0
400.0
4.200

100.10

360
UR
10.00

Al
As
Be
co

UR

UR

Cr

0.1830

ER

0.078

BR

HR

UR

0.290

IOR

11.74

2.400

166.0

168.3

ER

NR

bkl
Ei

410.0
ER

UR

Fe

51.00

pb

80.00

zn

nR

1.030
35.42
276.9

IPB not reported


Reference : LA-312

4-74

ER
UR

15.00
2.290
nR
1,400
NR

102.0
540.0

ki

The carbon steel coupon exhibited the highest corrosion


rate. It was visibly sxdaller at the end of the test and disintegrated when handled. The coupons were not descaled, so weight
loss data could not be used to calculate uniform corrosion rates.
None of the stainless steel, nickel based, or titanium alloys
appeared to have suffered significant corrosion. Type 316 L,
Haynes Alloy 20 Mod, Carpenter 20Cb3, and E-Brite 26-1 were pitted.
No pitting was observed on the otherspecimens.
4.6.2.2

Corrosion Rates Measured in Seven Process Streams at


the Geothermal Loop Experimental Facility

Corrosion rates were measured in two 15-day tests conducted at the Bureau of Mines' Geothermal Loop Experimental Facility (GLEF). The test facility employs fluid from well Magmamax No. 1 in seven process streams typical of those in a dual
flash steam binary power cycle (wellhead, first and second flash
steam, scrubbed first and second flash steam, and first and
second flash fluids). Fluid characteristics for the seven process streams are summarized in Table 4-43.
Coupons of thirteen commercially available alloys were
tested for weight loss and evidence of pitting and crevice corrosion. The coupons were fastened to rods using washers designed
to minimize the extent of crevice areas. Stress corrosion cracking was studied by microscopic examination of a punch area. All
samples were examined optically for evidence of local corrosion
or cracking. Weight loss was measured after descaling, and pit
depths were measured with an optical micrometer.
Rates of uniform corrosion and pitting calculated from
maximum weight loss and pit depth are given separately for

4-75

TABLE 4-43
FLUID CHARACTERTSTICS OF SEVEN GLEF PROCESS STREAMS I N TESTS
OF CORROSION RATE AT WELL MA(72UMAX NO. 1

Fluid C h a r a c t e r i s t i c s
Chloride
Bicarbonat e
Pressure,
Concentration, Concentration,
pH
ppm
ppm
psi?

Process Stream

Temperature,
'C('F)

Wellhead f l u i d

234 (450)

280

5.07

112,100

5,300

First flash
fluid

207 (405)

200

5.11

127,700

5,580

NR

200

6.15

120

8,760

NR

200

NR

178(352)

120

178(352)

NR

First flash

steam
Scrubbed first
f l a s h steam
Second f l a s h
fluid

NR

NR

5.5

127,600

5,510

120

6.1

50

2,800

120

NR

Second f l a s h

steam
Scrubbed second
f l a s h steam

Reference:

CA-S-563

4-76

NR

NR

materials in each process stream in Tables 4-44 through 4-50.


Crevice corrosion detected -in areas where coupons were secured is
indicated by X (detected) or N (not detected). Stress corrosion
cracking is shown in the same way. In several process streams,
significantly different uniform corrosion rates were measured
in separate fifteen-day tests. In such cases, both rates are included in the table of results.
The results in Tables 4-44 through 4-50 indicate that
pitting did not occur in tests of nickel and titanium alloys.
While the tests were not designed to measure stress corrosion
cracking, intergranular corrosion was observed for AIS1 Type
316 L.
Although precautions were taken to minimize crevice
areas at coupon fastenings, crevice corrosion occurred on the
iron-based alloys in all seven streams and on Hastelloy S in
scrubbed second flash steam. Both pitting and uniform corrosion
were observed between ceramic insulators and metal coupons. When
pitting corrosion occurred in thepe areas, the pits were deeper
than the pits in noncrevice areas. Crevice corrosion occurred
least frequently in materials exposed to wellhead fluid and most
frequently in materials exposed to scrubbed second flash steam.
For both 15-day test series, the nickel alloys, the
titanium alloys, and alloy 29-4 and alloy 6X stainless steels
had the greatest resistance to uniform corrosion in all streams.
Measured rates were less than 0.1 mpy. E-Brite 26-1 and Type
316 L stainless steels had excellent resistance to general corrosion (less than 1 mpy) in all streams. Type 430 stainless steef
had excellent corrosion resistance in all environments except the
wellhead fluid and the scrubbed steam environments, where the
corrosion rate was 1 to 5 mpy. The 1020 carbon and 4130 alloy

lj
4-77

TABLE 4-44
CORROSION RATES MEASURED I N FIFTEEN-DAY TESTS USING WELLHEAD FLUID FROM
MAGMAMAX NO. 1 I N THE SALTON SEA KGRA

Gcneral
Corroriyn
<my)

Iron Bare
Carbon Steel (AISI 1020)
AISI 4130
e 316L
%e 430
ACI m e CF-3H
E - b i t e 26-1
Allegheny-Ludlum 6X
Allegheny-Ludlum 29-4

%f

Nickel Bare
Inconel 625
Rartelloy S
Hartalloy G
Harteeloy C-276

X 1

<o. 1
<o. 1
1

n
n
n
n

n
n
n
n

n
n
n
n

(0.1
eo.1

n
n

n
n

n
n

180b
i50bpd
6Eb
100;

3
n

<o. 1
<o. 1

CA-S-563

5,
5n

15 day e o m r e t o Magmamax $1 wellhead f l u i d .


234 c ( 4 8 0 0 ~ ) . 280 prig, pn
5.07, a- 112.000 ppm.
not detected.
detected.

Reference:

-8lktE

n
n
n
X
n
n

67

13-33.
0.7
0.6-2.2.
0.7
0.2

eo.

KEY TO TABLE

Sa'

mDY)

eo. 1

Titanium Base
Ti-1. 5 N i
Ticode- 12

*-

Wellhead Pluld*
Crevice'
Pitting
Cortorion

nco;

5.300 ppa

'Bared on weight loor.


'Bared on maxiarus p i t depth.
'Effort made t o minimize crevice area.
'Bared on aicrorcopic examination of punch area.
aRerultr of 2 t r i a l . reported re a r a t e l
bwidth of p i t r ir 4 t o 5 timer
daptg:
'Severe intergranular corrorion obrerved.
*Edge p i t t i n g .

tL

(Performance of c a r t (ACI alloy bared on


equivalent 'wrought alloy.

..

-. .

.~

- -

..

... ... .-

- ..

. .-

..

..

. .

TABLE 4-45
CORROSION RATES MEASURED I N FIFTEEN-DAY TESTS USING F I R S T FLASH FLUID
FROM WELL MAGMAMAX NO. 1 I N THE SALTON SEA KGRA

F i r s t Flash Fluid (Nonaerated)*


General
Crevice
see'
COtrOrf~d pitting' Corrosion'
(mpY1
(mpr1
Iron Base
Carbon Steel (AISI 1020)
AISI 4130
AISI Type 316L

AISI

me 430

ACI Tme CP-3M


E - B r i t e 46-1
Allegheny-Ludlum 6X
Allegheny-Ludlm 29-4

Nickel Bare
Inconel 625
Hastallby S
Hastelloy G
Rastelloy C-276
Titanium Base
Ti-l.5Ni
TiCode- 12

*-

27-62'
3.8-6.8'
0.1
0.2
0.1
0.2
<0.1
(0.1

2aob

<o. 1

N
N
N

loob

27b

%Ob

27b

(0.1
<o. 1
(0. 1

n
N
N

N
N
N
N

<o. 1

N
N

N
B

(0.1

Fifgeen d8g exposurea ta f l u i d from f i r s t flasher.


5.11, C1'
127.700 p p , Urn;
207 c (405 P). 200 p r i g , pH

KEYTOTABLE

- not detected.
x - detected.

N
N

(Performance of c a s t (ACI) alloy based on


equivalent wrought alloy.)

5580 ppm.
c
.

Reference:

:Based on weight loss.


Based on maximum p i t depth.
'Effort made t o minimize crevice area.
*Based on microscopic examination of punch area.
:Results of 2 t r i a l s reported separately.
,Width of p i t s is 4-5 times the depth.
Severe intergranular corrosion observed.

llOb

Cments

CA-S-563

TABLE 4-46
CORROSION RATES MEASURED I N FIFTEEN-DAY TESTS USXNG FIRST FLASH
STEAM FROM WELL MAGMAMAX NO. 1 I N THE SALTON SEA KGRA
F i r r t Flarh Steam CNonaerated)x
General
Crevice
SCC'
Corrosion' Pitting; Corrorion'
Iron Bare
. Carbon Steel (AISI 1020)
AISI 4130
AISI Type 316L
AISI Twe 430
E-Brikb 26-1
Alleghetay-Ludl& 6X
Allegheny-Ludlum 29-4

P
I

03
0

mPY1

mPY)

26
7.7

0.4

150'
70'
32:

0.0

00

0.4
0.2
<o. 1
eo. 1

N
N

3
N.

'Bared on weight l o r r .
'Bared on maximum p i t depth.
'Effort made t o minimize crevice area.
'Bared on microrcopic examination of punch area.

N
N

N
N
N

:Width of p i t s i s 4-5 timer the depth.


Severe intergranular corrorion.
'Edge pitting.

N
N
N
N

N
N
N
N

N
N

32.
90'
39'

<o. 1

N
N
N
N

T i t a n i m Bare
Ti-1.5191
TiCode-12

<o. 1

*-

1
1

co.1

CO.

Steam from f i r s t flarher (unrcrubbed).


200 prig. C1'
120 ppm, HCOj
0,760 ppm.
KEY TO TABLE
N
not detected.
X
detected.

--

Reference:

CA-S-563

'

Nickel Bare
Inconel 625
Hartellop S
Hartelloy G
Hartelloy C-276

CO.
CO.

ComPcntr

XD

(Performance of c a r t (ACI) alloy bared on


equivalent wrought alloy.)

..

....

..

"..

~ _ . _ ~
~

~,

..-...

. .

.... .

..,

..

- ..

...

...

TABLE 4-47
CORROSION RATES MEASURED I N FIFTEEN-DAY TESTS USING SCRUBBED FIRST FLASH
STEAM FROM WELL MAGMAMAX NO. 1 I N THE SALTON SEA KGRA
Scrubbed F i r r t Flarh Steam*
(Nonaeratad)
General
Crevice
Corrorion' Pitting' Corrorion'
arpY)

Iron Base
Carbon Steel (AIS1 1020)
AISI 4130
AISI Type 316L
A I S-I T w e 430
..__
ACI e*
cp-3~
E - B r i t s 26-1
Allegheny-fudlum 6X
Allegheny-fudlura 29-4

Hickel ,Bare
Incanel 625
Hartalloy S
Hastelloy G
Haatelloy C-276

03

Titmitm Bare

I-'

Ti-1.51%

TiCode-12

0.2

TO

'X

Reference: CA-S-563

n
n
Nc

'Bared on weight loor.


'Bared on maximum p i t depth.
'Effort made t o avoid c r w i c e area.
'Bared on nicrorcopic examination of punch area.

t R e m l t r of tua t r i a l 8 reported reparately.


,Width of p i t a i r 4-5 times the depth.
Swerc intergranular corroafon.

5n

0.4
0.2
0.2
c0.1

<O.i

19

*o. 1
*o.1
<O.l
eo. 1

n
n
n
n

n
N
n
n

n
n
n
n

eo.1

n
n

eo.

day

Conunentr

21-40.
18

19

- Fifteen
exporurcr t o acrubbed f i r r t flaah rteam.
200 psig.
REY
TABLE
I - not detected.
- detected.
*

Scc'

UW)

(Performance of c a r t (ACI) alloy bared on


equivalent wrought alloy.)

..

~~~~

. ..... ~.

-. ..___ ,

..

. .

TABLE 4-48
CORROSION RATES MEASURED I N FIFTEEN-DAY TESTS USING SECONb FLASH FLUID
FROM WELL MAGMAMAX NO. 1 I N THE SALTON SEA KGRA
Second Flash Fluid (Nonaerated)*
General
Crevice
Corrorion Pitting* Corrorion
SCC
QUY)

Iron Bare
Carbon S t e e l (AISI 1020)
AISI 4130
AISI Type 316L
AISI Type 430
A C I Type CF-3M
E - B r i t e 26-1
A l l e g h m y - L u d l ~6~X~
Allegheny-Ludlrmr 29-4

48
2.2-10.3.
0.3
0.6
0.3
eo.1
eo.1
eo.1

240b
8ab

Nickel Bare
Inconel 625
Hamtelloy S
Hartalloy G
Hartalloy C-276

eo.1
(0.1
eo.1
eo.1

Titanium Bare
Ti-1.5Ni
TiCode-12

eo.1
eo.1

*
m

44=

#
#N

X
X

41b
44b
39b
2gb

X
X
N

N
N
N

--

Reference:

CA-S-563

N
N

N
N

il

- Fifgeen
dag exparurea t o f l u i d f r c a recond flasher.
127,600 ppp. HCO;
5510 p p .
178 C (352 F), 120 prig, C1-

To TABU
N not detected.
X
detected.

WYl

Coenuent8
Bared on wi h t lorn.
Bared on -m
! um
p i t depth.
Effort made t o avoid crevice area.
Bared on microrcopic examination of punch area.
:Rerult. of fwa trial8 reported reparately.
,Width of p i t s i r 4-5 timer the depth.
Severe intergranular corrorion.
(Performance of cart (ACI
equivalent wrought alloy.

alloy bared on

TABLE 4-49
CORROSION RATES MEASURED IN FIFTEEN-DAY TESTS USING SECOND FLASH
ST&
FROM WELL MAGMAMAX NO. 1 IN THE SALTON SEA KGRA
Second Flash Steam*
Crevice
corrosion P i t t i n g Corrorion'
General

(my)

Iron
Base
_
_~
Carbon Steel (AISI 1020)
AISI 4130
AISI Tme 316L
Ais1 *e 430
ACI Type CF-3M
E-Brltite 26-1

l i c k e l Base
Inconel 625
Hasteltoy S
Bastellay 0
Bastalloy C-276

25
8.2
0.3

0. s

0.3
0.3
0.1
0.1

0.1
0.1
0.1
0.1

Titanium Baee
T i - 1 .%?I
Ticode-12

0.1
0.1

200.

110.
83'
100.
83.
100.
37.

KEY

m TABLE

- not detected.
X - detected.
n

Reference:

'

CA-S-563

n
n
X

X
X

:Width of p i t s is 4 t o 3 times the depth.


Severe intergranular corrosion.

n
n
n
n

n
n
n
n

n
n
n
n

n
n

(Performance of c a s t (ACI) alloy based on


equivalent wrought alloy.)

from second flasher.


2800 ppa.

50 ppm, HCO;

Ccmwnts
:Based on weight loss.
Based on maximum p i t depth.
'Effort made t o avoid crevice area.
'Bared on microscopic examination of punch area.

X
A

* - Fiftgen day exposurer


t o steam (unscrubbed)
6.10, C1'
120 psig, pH
'178 C (352'F).

SCC'

(mpt)

TABLE 4-50
CORROSION RATES MEASURED IN FIFTEEN-DAY TESTS USING SCRUBBED SECOND FLASH
STEAM FROM WELL MAGMAMAX NO. 1 IN THE SALTON SEA KGRA
Scrubbed Second Flanh Steam*
(Nonaerated)
General
havice
Corrorion' Pitting' Corrorion* see'
QPY)

Iron Base
Carbon Steel (AISI 1020)
AISI
.
.__
- 4130
.- - .
AISI Tme 316L

Allegheny-Ludlum 6X
Allegheny-Ludlum 29-4

N i c k e l Bane
Inconel 625
Hantelloy S
tiantelloy G
liartelloy C-276

18-27.
25
0.2
1.4
0.2
0.1

mPY)

'Baned on weight lose.


'Bared on maxlmm p i t depth.
'Effort made t o avoid c r w i c e area.
'Bared on microrcopic ex.nination of
punch area.
29"
N

X
N

eo.1
(0. 1
eo.1

N
N
N
N

N
N
N

eo. 1

N
N

(0.

(0.1

(0. 1

19
N

Titanium Bare
Ti-1.5Ni
TiCode-12

*X

Fifteen day exposurer t o scrubbed rteam from necond flaaher.


120 pnig.

KEY M TABLE
N

(0.1

-- ndetected.
o t detected.

Reference : CA-S-563

Conmentr

b R e n u l t n of 2 trial. re orted re a r a t e l
:Width of p i t # ir 4 t o
times t t e deptg:
Severe intergranular corrorion.

(Performance of c a r t (ACI) alloy bared on


equivalent wrought alloy.)

L d
steels had the poorest corrosion resistance in all streams and
were more severely corroded in the fluids than in the steams.
!

In several of the streams, the average corrosion rates


of 1020 carbon steel, 4130 alloy steel, and 430 stainless steel
were significantly different for each of the two 15-day series of
corrosion tests. However, the corrosion rates for each set of
metal samples in any one stream for a single 15-day test series
were in good agreement. Where the average corrosion rates of
each 15-day test series were significantly different, both rates
are reported.

I
!

I
I

!
I

!
t

/
With the exception of Allegheny-Ludlum 29-4, all of the
iron-based alloys were pitted in one or more streams. The 1020
carbon steel pitted most severely in liquid streams while the
alloy steels pitted worse in steam. Pitting was more severe in
"clean" steam than in "dirty" steam. The widths of the pits were
four to five times greater than their depths. This is a mild form
of attack and indicates that corrosion over the surface of the
metal is proceeding faster than penetration into the body of the
metal.

:
1

!
1i

4.6.2.3

Tests in Acidified Salton Sea Geothermal Fluid

Lawrence Livermore Laboratory (LLL) has shown that


acidification of Magmamax No. 1 fluid to a pH t4.5 will prevent
scale formation for "a substantial period of time." The concentration of HC1 in the acidified fluid is about 200 ppm. LLL
has done some materials testing in acidified geothermal fluid
from well Magmamax No. 1 and preliminary results have been reported (AU-064, TA-136).

i
#I

ii
I

The field tests were conducted using a mobile test bed


which includes a flash steam separator and.has the capability

4-85

for producing both pure brine or steam and two-phase mixtures.


Test fluids are discharged through two-phase expander nozzles.
There are provisions for modifying the test fluids by adding
chemicals. The test equipment includes simulated turbine cases,
atmospheric pressure chambers containing static wearblades.
The results of two series of tests are reported here.
In one series, corrosion specimens were mounted on the base of
the fixed wearblades to test potential turbine materials for resistance to erosion, pitting and crevice corrosion, and stress
corrosion cracking. Specimens of the alloys to be tested were
prepared by bending two strips of each alloy around a mandrel
and retaining the sandwich under tension with a clamp. The
specimens were mounted so that the broad face of the specimen was
perpendicular to the expander nozzle discharge. The assemblies
were exposed to acidified brine/steam mixtures at 100C for
periods varying from 7 . 5 to 110 hours. The nozzle discharge
rate was 240 mps (787 fps). Fluid pH varied from 2 . 5 to 4 . 5 .
The alloys tested and the test conditions are summarized in
Table 4-51. Qualitative observations about the condition of
the tensile face of the specimens exposed to spray impact are
also given in the table. Pitting, cracking and erosion were observed. Examination of the tensile face not exposed to spray impact showed that much of the pitting was a result of erosioncorrosion. There was no detectable erosion of the edge of the
Ti-6A1-4V wearblades.
In the second series of tests, sixteen ferrous and nonferrous alloys were exposed to acidified nozzle exhaust effluent.
Steam had been removed from wellhead fluid in the flash steam
separator before discharge through the expander nozzles.

4-86

--

... .

...

..

.-~--

.. .

.. -..

.......

~~

. ~-

._I

. ..

... ...

. . __ ....~._
. .
..

.- . _ .

~- _ .
~ .
,.

TABLE 4-51
RESULTS OF EROSION-CORROSION TESTS OF POSSIBLE TURBINE COMPONENT
ALLOYS IN ACIDIFIED SALTON SEA GEOTHERMAL FLUID

EQterlal
4130 S t e e l

Quenched sad teap.red

7.5

2.7

bbny p i t s up t o

3 mila deep, several

4130 Ma m d i f i e d s t e e l

Quenched and tempered

7.5

2.7

Smy p i t s up t o

3 mils deep

Quenched .md t e q e r e d

37

2.6

305

M i l l .anemled

37

2.9

6-

Type 316

Mill wealed

37

3.1

m y p i t s 0.6

severe p i t t i a s corrosion/emsion

Type

pits d . 2

Type 410

Quenched and tempered

37

2.6

18 cr

Mll weal&

59.5

1.5

Some p i t a 0.1

29 cr

-I

up t o 9 m i l s deep

severe p i t t i n u corroaion/erosion

2.25 Cr-1 Ho steel

f00

Expressed S u p l e '
Condit ion

b e pII

Condition

2 nD rteel

-4

Mo steel

W35N (cobalt b u e d

&or)

- 0.4 d l r d-p

M i l l annealed

59.5

5.5

scme cracks 0.4

40 percent cold rolled and w e d


at 538OC f o r 4 hours

37

3.1

bbny

p i t s 0.6

2.0 mils t e p

0.2 mils deep

- 0.6 mila deep

- 2.0 mils deep

Ti-kAl-3Ho-lV

M i l l umealed

22.5

3.7

T i - 8 N - l L - l V

Duplex milled utb annealed

25

2-5

&my cracks 1.0

T i - 6 N - k Q

Mill annealed

25

2.5

Crack I, 0.6 m i l s deep at base of


pre-stress notch

ll0

2.9

Several cracks in notch %%.l


mil
d n p . One crack 0.8 mil deep.

110

2.9

Several cracks in notch I, 0.1111


deep. h e Cmck 0.8 mil deep

3.7

No cmcka found

+B umealed. mter quench&


r t r e r s reliewed
annealed, sir cooleb
relieved

~ - 6 f l - h V

Ti-6Al-SQ

wealed,

BtresS

sir cooled stress

22.5

relieved
'&bend strear corrosion cmcking apecimms with t p i t s u r h c e exposed t o tve-pbue nossla d i r c h u m .
No. 1brine a t I, 100 C and 240 4 8 .
n u i d yu 6cidified

Reference:

AU-064

2.0 mila' deep

Corrosion rates were measured in an electrochemical


cell in 16 to 20-hour tests using a Petrolite Instruments Co. corrosion rate meter. The meter employs a probe assembly with interchangeable electrodes fabricated from the test materials. The
pH of the test fluid was in the range of 2.0 to 4 . 5 , and the temperature was 86 to 98OC. Table 4-52 shows the measured uniform
corrosion rates. The test method does not indicate susceptibility
to pitting or other forms of local corrosion. The measured uniform corrosion rates indicate that some low alloy steels may be
suitable for use in low-temperature streams while stainless steels
and'nonferrous alloys might be applicable at higher temperatures.

4-88

TABLE 4-52
ELECTROCHEMICAL CORROSION RATES MEASURED IN ACIDIFIED FLASHED
FLUID FROM WELL MAGMAMAX NO. 1 AT THE SALTON SEA KGRA

Material

Ferrous Alloys
Carbon steel ( A I S 1 1018)
1 Cr
0.2 Ma (Soo-90)
0 Cr
0.5 Mo (A-204 Grade B)
0.9 Cr
0.5 Mo (A-387 Grade 12)
2.2 Cr
1 Mo (A-387 Grade 64)
8 Mo (4-43)
3.7 Cr
0.5 Mo
5.6 Cr
9 Cr
1 Mo

100
76
12
14
29
15
8-23
20
0.3
0.5
1.0
1.5
0.1

Type 317 LM
Carpenter 20 Cb-3
E-Brite 26-1
29 Cr
4 Mo
29 Cr
4 Mo 2 Ni

General
Corrosion'
(mPY1

Non-Ferrous Alloys
Ti-6Al-4V
Hastelloy C-276
Inconel 625

0.1
0.06
0.3

'Rates determined by electrochemical method during final two hours of 16-20


hour tests.
TEST CONDITIONS:
Acidified Magmamax No. 1 fluid with pH = 2.0-4.5.

REFERENCES :

TA-136, AU-064

4-89

Temperature 86-98OC.

5.0

CORROSION MODES FOR METALS IN GEOTHERMAL SYSTEMS

Section 4 presented available data from tests of materials performance in geothermal fluids. Most of these tests
measured the rates of uniform corrosion and localized (pitting
and crevice) corrosion of coupon specimens, though some tests
of stress corrosion cracking of U-bend specimens have been done.
The results of these tests are helpful in selecting materials,
because they can be used to predict how fast a metal deteriorates
uniformly or from pitting at a specific fluid composition, temperature, and flow rate. But the uniform and localized corrosion rates described in Section 4 do not supply all of the information needed to specify construction materials for piping,
vessels, or process equipment.
There are three reasons they do not tell the whole
story. First, the corrosion rates are dependent on fluid composition and process stream characteristics. Therefore , the test
results do not describe materials performance in streams with
different .compositionsa temperatures , pressures or flow rates.
Second, metallic construction materials are subject to
other forms of attack besides uniform, pitting and crevice corrosion.
Catastrophic component failures can occur suddenly
with little evidence of metal loss due to sulfide stress cracking (SSC). SSC occurs in hard, high strength alloys exposed
under stress to aqueous environments containing even small
amounts of H,S. Hydrogen blistering, another form of attack,
causes rupture of metallic materials when hydrogen trapped in
voids accumulates at a sufficient pressure. Improper heat
treatment or welding can result in intergranular corrosion near

5-1

grain boundaries (weld decay) which causes alloys to disintegrate


or lose strength. Dealloying, dissolution of one component of an
alloy, is another form of corrosion. Failures also occur due to
corrosion fatigue when cyclic stresses occur in a corrosive environment.
Finally, the rate at which metals deteriorate depends
on some factors that are not taken into account in tests using
coupons. In practice it is not a metal coupon that fails due
to metal deterioration but a pipe, vessel, pump, or other equipment item fabricated from metal. The rate of metal deterioration or the mode of,corrosive attack also depend on fabrication
practices, equipment configuration and geometry, and stresses
that occur during operation.
This section describes the forms and mechanisms of
corrosive attack that can occur in geothermal process streams.
These generalizations are especially useful when materials must
be specified for conditions at which tests have not been done.
If the corrosion rate of a material has4been tested at the
stream conditions of interest, this information is still useful.
It explains the effects of fabrication practices, equipment configuration, and operating stresses. And it identifies some
additional ways materials can deteriorate.
The information is presented in three parts. Modes of
corrosive attack in wellhead and flashed liquid streams are described first. The forms of failure that can occur in liquids
are described for mile and low alloy steels (Section 5.1), stainless steels (Section 5.2), titanium alloys (Section 5.3), nickel
alloys (Section 5.4), copper alloys (Section 5.5) and cobalt,
Table 5-1 is a guide to
zirconium and aliminum (Section 5.6).
the information about the performance of specific metals in
liquid streams given in Sections 5.1 through 5.6. It summarizes
5-2

kl

TABLE 5-1

FORMS AND CAUSES OF CORROSION FOR METALS I N LIQUID GEOTHERMAL

STREAMS (SUMMARY OF INFORMATION PRESENTED I N SECTIONS


5.1 THROUGH 5 . 6 ) AND WAYS TO PREVENT ATTACK

chloride

--

nlfide

m w

Qsla interactLoru; m u
5.1.4.

Id

llui.u t..puecure for ruletmce W a d e

pa. w. 5.3.2.

on chloride and

Senre1 allhave mch better


remistme than pure T1.
hecracked Ti u y underce
*true mrrosion crecklng.
(5.3.4)

electrical contact
u i t b mre r t i w metal

coupling to large UUIof mre


utln Mu1 u). cmue hydrosen mhrittlment of Tl; ees
5.3.3.

Iulstence depede m alloy


amposition; e n 5.4.1.
M y be
mucepclble to hydrqen ab r l t t l . r o t uheo coupled t o
ec-1.

ahlorid.. r r p n t u n

u La u 0.1 PpI M
I attack.
b.5 tor pB ani alloy
denC..

&sIVuliC

eoupliatg to

1 or other actin wtel.

Lnrrl alloye h v e p o d sulfide


e t n u cracking nsistmce et
W h etremgth; also H e 5.1.4.
le*lecaut to l o w pa. bot chloride
w l uCion..
M y be useful u a t e r i o r aiding
.Id coostruction uteriel.

the information presented f o r each metal, defining t h e kinds of


corrosive a t t a c k t h a t can occur f o r a p a r t i c u l a r metal and t h e
f l u i d o r process stream c h a r a c t e r i s t i c s t h a t determine corrosiveness. The conditions under which a t t a c k i s minimized a r e defined
and precautions f o r design , f a b r i c a t i o n and operation a r e given,
Materials performance i n condensate (Section 5 . 7 ) and
steam (Section 5.8) i s t r e a t e d i n t h e l a s t two s e c t i o n s . While
much of the information given f o r l i q u i d streams i n Sections 5 . 1
through 5.6 i s also a p p l i c a b l e t o condensate and steam environments, t h e r e a r e some a d d i t i o n a l considerations f o r t h e s e streams.
Corrosion f a t i g u e and erosion caused by e x f o l i a t i o n o r d r o p l e t
impingement a r e most l i k e l y t o occur i n these environments.

5-4

5.1

Mild and Low Alloy S t e e l s

The low c o s t , a v a i l a b i l i t y , and ease of f a b r i c a t i o n of


low carbon steels (mild s t e e l s ) make them a t t r a c t i v e construction
materials f o r geothermal power p l a n t s . However, t h e r e l i a b i l i t y
of t h e s e s t e e l s depends upon t h e i r a p p l i c a t i o n s i n t h e power
plants.

5.1.1

General Guidelines f o r Using Mild Steels

By t a k i n g appropriate precautions, mild s t e e l s can be


used f o r thick-walled a p p l i c a t i o n s i n contact with most geothermal f l u i d s . Thin-walled a p p l i c a t i o n s w i l l be l i m i t e d by
t h e s u s c e p t i b i l i t y of t h e s e m a t e r i a l s t o l o c a l i z e d a t t a c k such
as p i t t i n g and crevice corrosion. Hfgh-salinity geothermal
f l u i d s w i l l cause high uniform corrosion as w e l l as l o c a l i z e d
corrosion and w i l l severely l i m i t t h e use of low carbon s t e e l s .
The a p p l i c a t i o n of mild s t e e l s t o .geothermal environments req u i r e s t h a t precautions be taken f o r a e r a t i o n , flow r a t e , s c a l i n g ,
galvanic coupling, e x t e r i o r s u r f a c e s , and s t e e l s p e c i f i c a t i o n s .

Aeration
Acceptable uniform corrosion rates of carbon s t e e l s i n moderate s a l i n i t y geothermal f l u i d s are due mainly
t o t h e reducing: oxygen-free n a t u r e o f t h e f l u i d s . The i n t r o duction of small q u a n t i t i e s o f oxygen can g r e a t l y i n c r e a s e uniform corrosion and i n i t i a t e p i t t i n g and crevice corrosion.

The effect o f oxygen on t h e corrosion o f a mild s t e e l


i s shown i n Figure 5-1 f o r an otherwise n e a r l y gas-free seawater
stream. The same effect occurs i n geothermal systems. The solub i l i t y o f oxygen i n s a l i n e f l u i d s decreases with i n c r e a s i n g temperature up t o 100C a t which p o i n t i t i n c r e a s e s again (CR-162).
The electrochemical r e a c t i o n rate i n c r e a s e s with temperature.

W
5-5

Figure 5-1.

E f f e c t of Oxygen on Uniform Corrosion Rate


of 1010 Mild Steel i n 250F Seawater (Based
on d a t a presented i n GE-117)

Aeration damage during p l a n t operation should be minimized by guarding a g a i n s t leaks i n the lower temperature vacuum
s e c t i o n s o f t h e p l a n t . The h i g h e s t p o t e n t i a l f o r s e r i o u s damage
from a e r a t i o n occurs due t o inleakage during p l a n t outages o r
layups. Stagnant conditions are conducive t o crevice and p i t t i n g
corrosion promoted by oxygen. Oxidation of ferrous i o n s and H2S
i n t h e geothermal f l u i d can produce f e r r i c ions and l o c a l acidi t y which a c c e l e r a t e a t t a c k . Procedures f o r avoiding damage
during shutdowns include draining and r i n s i n g equipment and
purging with an i n e r t gas. Oxygen scavengers might be a p p l i c a b l e ,
b u t p o s s i b l e s i d e r e a c t i o n s with species i n t h e s p e c i f i c f l u i d
should be evaluated.

Flow Rate
The b e s t performance of carbon steels occurs
when l i q u i d flow rates are l i m i t e d t o 5-7 f t / s e c . Localized, unc o n t r o l l e d f l a s h i n g i n geothermal streams can cause high flow

Lid
5-6

rates in the system. This action can produce bubbles of noncondensable gas which can cause impingement attack. Entrained solids
in the stream can cause erosion-assisted corrosion. The relative
hardness of particle and metal has little effect on this type of
corrosion.
Failure of components such as pipe ells has occurred in
fluids as diverse as those at Salton Sea and Raft River. These
failures are probably caused by the flow conditions noted above.
Designs to avoid direct impingement on carbon steels and localized
flashing should alleviate these types of failures. Providing liquid buffer zones may help. Pump impellers, especially for downhole applications, may be subject to severe cavitation damage.
The Con content of many geothermal fluids can cause an apparent
vapor pressure that exceeds steam table values by tens to hundreds
of psi. Caution in design and material selection is required.
Effects of high velocities are illustrated in Figure
5-2 for seawater at 250'F.

Figure 5-2.

Weight-Loss Corrosion Rates of Mild Steel in High


Velocity, High Temperature Oxygen-Free Seawater.
(Based on data presented in GE-117)
5-7

S c a l i n g - Some nrechanical p r o t e c t i o n a g a i n s t uniform


corrosion may r e s u l t from s c a l e s formed on s t e e l by p r e c i p i t a t i o n
from geothermal f l u i d s , but l o c a l i z e d corrosian can a l s o occur
under t h e s c a l e s . Scales i n geothermal systems a r e porous and
prone t o cracking by d i f f e r e n t i a l thermal expansion. The expos u r e of the base metal t o a geothermal f l u i d can l e a d t o l o c a l
a c i d i t y and high chloride concentration s i m i l a r t o conditions
during c r e v i c e corrosion. Accelerated a t t a c k by H2S i s i n creased i n a c i d i c environments such as t h i s .
Attack a t small exposed areas can become more s e r i o u s
i f the s t e e l i s g a l v a n i c a l l y coupled t o a more noble metal. In
extreme c a s e s , t h i s concentration of t h e s t e e l d i s s o l u t i o n curr e n t can cause p e r f o r a t i o n of thick-walled steel components.
Chemical cleaning s o l u t i o n s used t o remove s c a l e should
be evaluated c a r e f u l l y s i n c e some types (such as i n h i b i t e d HC1)
a c c e l e r a t e corrosion of mild steel. Severe a t t a c k can occur if
aggressive cleaning s o l u t i o n i s trapped i n o r under incompletely
removed s c a l e .
Galvanic Coupling - Carbon steels w i l l be anodic t o
high a l l o y s t e e l s , o r n i c k e l , copper o r t i t a n i u m a l l o y s t h a t may
be used f o r instrumentation, cladding, h e a t exchanger tubing, and
valve and pump t r i m . Galvanic corrosion of t h e carbon s t e e l can
occur when i t i s e l e c t r i c a l l y connected t o t h e more noble metal
( e i t h e r d i r e c t l y o r through grounding) and when both materials are
i n contact with t h e l i q u i d stream. Corrosion w i l l be severe when
t h e d i s s i m i l a r metals a r e c l o s e t o g e t h e r and t h e area of steel
exposed t o t h e l i q u i d i s small compared t o t h a t of the more noble
metal. Some noble metals may be s u b j e c t t o embrittlement when
g a l v a n i c a l l y coupled t o s t e e l .

5-8

I
,

A galvanic series c h a r t obtained f o r metals i n degassed

seawater a t 225F i s shown i n Figure 5-3. The corrosion rate of


a given m e t a l w i l l be a c c e l e r a t e d when i t i s g a l v a n i c a l l y coupled
t o a m e t a l w i t h a more p o s i t i v e open c i r c u i t p o t e n t i a l . A s i m i l a r o r d e r w a s observed i n Heber geothermal f l u i d s during s h o r t term measurements (SY-028). The order of metals i n t h e series
may change w i t h v a r i a t i o n s i n cheinistry and temperature. If t h e r e
is doubt, t h e series should be determined experimentally under
f i e l d conditions.

The e x t e r i o r of mild s t e e l p i p e s ,
E x t e r i o r Surfaces
vessels and s t r u c t u r a l components r e q u i r e s p r o t e c t i o n . Leaks
and sprays of s a l i n e f l u i d combined with a i r and occasional H2S
emissions can produce r a p i d a t t a c k . P r o t e c t i v e coatings should
be used t o minimize uniform and l o c a l i z e d a t t a c k of e x t e r i o r
s u r f a c e s . High q u a l i t y coatings should be s p e c i f i e d t o avoid
l o c a l i z e d a t t a c k a t pores o r exposed areas.

,Steel S p e c i f i c
on
S u l f i d e s t r e s s cracking and hydrogen b l i s t e r i n g can be c o n t r o l l e d t o a l a r g e e x t e n t by 'use o f
low s t r e n g t h , m e t a l l u r g i c a l l y clean and void-free s t e e l (see
Mill s
e l e f t on s t e e l can a c c e l Sections 5.1.4 and 5.1.5).
erate p i t t i n g o r c r e v i c e corrosion
s p e c i a l l y i n t h e presence
of s u l f i d e s . Effects o f low a l l o y a d d i t i o n s t o s t e e l a r e d i s cussed i n Section 5.1.2.

5.1.2

Uniform and Localized Corrosion of Mild S t e e l s

Uniform and l o c a l i z e d corrosion a r e the t w o main modes


o f corrosion of low s t r e n g t h mild s t e e l s i n geothermal systems.
Localized corrosion i n t h i s discussion r e f e r s t o p i t t i n g and
crevice corrosion.
r'
#

5-9

216
316
304

430

NOBLE
Titanium
Carpenter 20
Hastelloy C
Stainless Steel
Stainless Steel
26-1
Stainless Steel
18-18-2
Stainless Steel
CA 122
CA 687
CA 715
CA 706
Hastelloy B
Cor-Ten
AIS1 1010
3003 Aluminum
5052 A1 umi num
ACTIVE

-100

-200 -300

-400 -500 -600 -700

-800 -900 -1000 -1100 -1, 3

CORROSION POTENTIAL(millivolts)
Vf.

Figure 5-3.

S.C.E.

Galvanic Series o f Selected Alloys i n Hot


Acid Treated/Deaerated Seawater (GE-117)

5-10

Corrosion r e s u l t s f o r mild and low a l l o y s t e e l s i n


geothermal f i e l d t e s t s are shown i n Table 5 - 2 . Although obtained
i n a wide range o f environments, uniform corrosion rates are
about 1 t o 10 mpy when t h e pH i s g r e a t e r than 6 and t h e c h l o r i d e
concentration i s less than 2%. Localized corrosion occurs t o
some e x t e n t i n most f l u i d s and becomes predominant i n f l u i d s
where uniform corrosion i s less severe.

The relative importance of uniform and l o c a l i z e d corros i o n depends mainly on pH and chloride concentration. Above a
c r i t i c a l pH, uniform corrosion rates a r e r e l a t i v e l y low, and t h e
major problem f o r mild steels i s l o c a l i z e d corrosion. Since
p i t t i n g and crevice corrosion are more severe forms of a t t a c k
than uniform corrosion, p l a i n s t e e l s should n o t be considered
immune t o a t t a c k a t high pH values. Chloride ion i s t h e main
i n i t i a t o r of l o c a l i z e d a t t a c k . Hydrogen s u l f i d e can i n c r e a s e
t h e s e v e r i t y of l o c a l i z e d corrosion.
P i t t i n g and crevice corrosion are similar with regard
t o environmental e f f e c t s and material s u s c e p t i b i l i t y . Both
forms of corrosion are most o f t e n a s s o c i a t e d w i t h t h e l o c a l i z e d
breakdown o f a p r o t e c t i v e f i l m on t h e = t a l s u r f a c e . A moment a r y breakdown o f t h i s f i l m can r e s u l t i n r a p i d anodic m e t a l
d i s s o l u t i o n a t t h e exposed area driven by cathodic r e a c t i o n s on
t h e rest o f t h e s u r f a c e . Cathodic reduction of oxygen can supply
a high electrochemical driving force. Water o r hydrogen ions
may a l s o serve as t h e o x i d i z i n g agent, b u t the d r i v i n g force i s
lower and t h e exposed area has a b e t t e r chance t o repassivate
b e f o r e growth starts. Once growth s t a r t s , t h e p i t o r crevice
area becomes acidic and chloride ions are t r a n s p o r t e d i n t o the
area. Both of these effects discourage repair of t h e p r o t e c t i v e
f i l m and growth can become s e l f - s u s t a i n i n g .

5-11

TABLE 5-2
CORROSION OF PLAIN AND LOW ALLOY STEELS IN NATURAL GEOTHERMAL LIQUIDS

Site/liquid Source

P"

Temp
('C)

Uniform

Chloride
cancentration

cattoeion

local
~orrosion'

Steel m e

V)

East Hesa
--

Wellhead

First Flash
Second Flash

150
150
150

5.6-5.8

8.1
8.1

1.1

9,000

2.2*

AIS1 1010

780
780
700
780

1.8
1.9
0.8
1.1

AISI 1018
ASlX AS15 (1- carbon)
AISI 4l30
Asm A242 ( a R - T x )

5.6-5.8

130
l30

5.6
5.6

50
50

5.6-5.8

50

5.6-5.8

AIS1 1010
A
S
m U3S
AISI 4130
AIS1 1020
AISI 4130
AIS1 1010

l3.350
l3 ,350
13,350
11,800
11,800
13.350
13.350
13.350
12,060
12.060
12.740
12,740

5.6-5.8

5.6-5.8

6.8
6.8

6.0

5.5
6.8

3.2
1.9
1.1

A
S
m AS3n

1.8
3.5
2.4
1.6
3.1
1.2

AISI
AIS1
AISI
AISI
AISI

4l30
1020
4130
1020
4130

Heber
Uellhead

-200

Raft River
-Wellhead

130
l30
130
130

7.05-7.40
1.05-7.40
7.05-7.40
7.05-7.40

234
234
207
207
178
178

5.07
5.07

Salton Sea
-Wellhead
First Flash
Secmd Flash

Wairekei, N. 2.
Wellhead

Separeted Water

240

240
121
50-100
50-100
125
125

5.ll
5.11
5.50
5.50

112.000
112.000
127.000
127.000
127,600
127.600

67
13-33
27-62
3.8-6.8
48
2.2-10.3

1,500

-4.0
a.0

1.500
1.500

2
1.0-10
1.0-10
c1.0
a.0

*lbt deacaled.

'Measured near ambient tmpereture


pitting
crevice
N not detected

P'
C

Pitting and crevice corrosion rates given in Section 4.

5-12

AIS1 1020
AISI 4130
AIS1 1020
AISI 4130
AIS1 1020
AISI 4130

Carbon steel.
Carbon Xn ate8la
Carbon ateel.
Carbon steel.
Carbon Xn steel.
Carbon stsela
Carbon Xn .teela

The growth r a t e of p i t s i s d i f f i c u l t t o p r e d i c t . I f
i n i t i a l t e s t i n g i n a geothermal f l u i d i n d i c a t e s p i t i n i t i a t i o n ,
p i t growth rates should be measured p e r i o d i c a l l y during extended
testing.

5.1.2.1

E f f e c t of p H on Uniform Corrosion

Low pH a f f e c t s t h e uniform corrosion r a t e of low carbon


and low a l l o y s t e e l s . This e f f e c t i s i l l u s t r a t e d i n Figure 5-4
f o r r e l a t i v e l y low temperature degassed seawater. A c i d i f i c a t i o n
of E a s t Mesa F l u i d a t 150C from pH 5.7 t o pH 4.7 increased corrosion rates by a f a c t o r of 3 t o 4 (SH-381). The c r i t i c a l pH
below which r a p i d corrosion can occur i s i n t h e range of pH 5 t o
7. More accurate general d e f i n i t i o n of a c r i t i c a l pH i s hampered by t h e following.
Most pH measurements are made n e a r ambient
temperature. The actual pH a t high temperat u r e s may be h i g h e r o r lower depending on
t h e composition of the f l u i d and on f l u i d
processing (Section 5.2).
The c o r r o s i v i t y of dissolved C02 and HZS i s
pH dependent and can change d r a s t i c a l l y i n
t h e range of pH 5 t o 7 . The e q u i l i b r i a are
a l s o temperature dependent.
0

The pH o f t h e l i q u i d i n contact with t h e


metal i s o f primary importance. This pH can
b e q u i t e d i f f e r e n t from bulk l i q u i d pH i n
c r e v i c e s , under s c a l e , and n e a r trapped gas.

5-13

Figure 5-4.

5.1.2.2

Effect o f Seawater pH on the Corrosion Rate of


1010 Mild S t e e l a t a Typical Deaerator Temperature
(GE- 117)

E f f e c t of Chloride on Uniform and Localized Corrosion

The e f f e c t of c h l o r i d e concentration on uniform corros i o n of mild s t e e l s can be discussed i n terms of two main conc e n t r a t i o n regions.
High corrosion r a t e s of mild steels begin t o
occur a t high c h l o r i d e concentrations (about
10 t o 15% as NaC1).
,

Changes i n c h l o r i d e concentration below about


3% (as N a C 1 ) have r e l a t i v e l y l i t t l e e f f e c t on
uniform corrosion r a t e .
The t r a n s i t i o n p o i n t between t h e s e two regions i s unc e r t a i n , but t h e c h l o r i d e concentrations i n a l l present KGRA
f l u i d s f a l l i n t o one of the above two regions.

5-14

The abrupt increase in corrosion rate with chloride concentration is illustrated by the laboratory results in Figure
5-5 (SH-381). Later results indicate that even higher corrosion
rates may occur above the breakpoint at 10% NaCl shown in the
figure. Field corrosion tests in high salinity Salton Sea fluid
show mild steel corrosion rates of 40 to 100 mpy. These fluids
have a natural pH of about 5.2, but other laboratory tests in
high salinity fluids show little change in corrosion rate from
pH 5 to 7 (PO-230). Allowances can be made for uniform corrosion of thick-walled components in high chloride solutions; but
localized corrosion is also more likely and establishing allowgmces for this corrosion is difficult.

(,J

Figure 5 - 5 .

Average Corrosion Rate of Carbon Steels vs


Salinity 25OOC pH 4.5-4.8
Pressure 6 8 . 9 Bars (1000 psig)
4.01 ppm
Oxygen
(Based on data in SH-381)

bi

The low sensitivity of uniform corrosion rates in low


chloride solutions relative to a high chloride solution is qualitatively shown by results obtained in geothermal fluids with
5-15

L
d i f f e r e n t c h l o r i d e concentrations (Table 5-2). This t r e n d i s supported by l a b o r a t o r y s t u d i e s a t lower temperatures w i t h o t h e r
v a r i a b l e s h e l d constant (CH-A-453).
A t high pH, c h l o r i d e concentration i s more c r i t i c a l
t o p i t t i n g and crevice corrosion than t o uniform corrosion. Chlori d e effects on p i t i n i t i a t i o n can be described by an experimentally
measured p i t t i n g p o t e n t i a l . P i t t i n g i s p o s s i b l e i f t h e e l e c t r o d e
p o t e n t i a l of a metal exceeds t h e p i t t i n g p o t e n t i a l . Therefore,
both t h e corrosion p o t e n t i a l and t h e p i t t i n g p o t e n t i a l of a m e t a l
must be known t o make p r e d i c t i o n s . No standard method has been
e s t a b l i s h e d f o r measuring p i t t i n g p o t e n t i a l s , and r e p o r t e d values
vary with experimental techniques. The most active value r e p r e s e n t s a conservative estimate and should be used a t t h i s t i m e .
This value i s o f t e n t h e "protection p o t e n t i a l . " An equivalent
value found by a metal s c r a t c h technique can a l s o be used.

Although t h e s e techniques have promise f o r f a c i l i t a t i n g f u t u r e t e s t i n g , present r e s u l t s are t o o scarce t o do more


than i l l u s t r a t e t r e n d s . While general t r e n d s a r e probably a p p l i c a b l e , crevice corrosion may be i n i t i a t e d more r e a d i l y than
p i t t i n g . Most present techniques are less a p p l i c a b l e t o crevice
corrosion. Localized corrosion e i t h e r under scale o r a t breaks
i n scale cannot be p r e d i c t e d from t h e s e measurements. P i t
growth rate may be proportional t o t h e amount by which t h e
corrosion p o t e n t i a l exceeds t h e p i t t i n g p o t e n t i a l , but t h i s has
received l i t t l e study.
Variation of corrosion and p i t t i n g p o t e n t i a l s with
chloride concentration a t 25C i s i l l u s t r a t e d i n Figure 5-6.
According t o t h i s , steels should be r e l a t i v e l y immune t o p i t t i n g
i n oxygen-free c h l o r i d e s o l u t i o n s a t 25C s i n c e t h e corrosion
p o t e n t i a l i s more active (negative) than t h e p i t t i n g p o t e n t i a l .
The d i f f e r e n c e i s small a t h i g h e r c h l o r i d e concentrations and
5-16

0.0

-0.2

-0.3

-0.4

-0.5

PITTING POTENTIAL

SEA WATER

HEBER

SY NTHETlC

CORROSION POTENTlAL

-0.6

0.01

0.02

0.04

0.07

0.1

0.2

0.4

0.7

1.0

CHLORIDE CONCENTRATION tg MOLE/LITER)

Figure 5 - 6 ,

Pitting and orrosion Potentials of Steel in


Oxygen-Free Chloride Solutions 25OC. Pitting
Potential Curve is from Equation by K. J. Vetter
.in ST-566, p. 240. Corrosion Potentials are
Represerrkative Values. The Slope of the Corrosion Potential Line is Based on Laboratory
Measurements (CH-A-453)

5-17

trace amounts of oxygen could raise t h e oorrosion p o t e n t i a l


above t h e p i t t i n g p o t e n t i a l .
5.1.2.3

Effect of Temperature on Uniform and Localized Corrosion

S p e c i f i c e f f e c t s of temperature on uniform corrosion of


mild s t e e l s are d i f f i c u l t t o define due t o t h e s c a r c i t y of experimental d a t a i n t h e 100" t o 250C region and t o simultaneous
changes i n t h e equilibrium d i s t r i b u t i o n of chemical species with
temperature.
A t e n t a t i v e f i n d i n g based on geothermal r e s u l t s (Table
5-2) i s t h a t uniform corrosion rates do n o t i n c r e a s e as r a p i d l y
with i n c r e a s i n g temperature (in t h e 100C t o 250C range) as
e a r l y experimental s t u d i e s a t temperatures less than 100C would
i n d i c a t e ; t h e l a t t e r g e n e r a l l y y i e l d a c t i v a t i o n energies of 10
t o 1 2 kcal/gmole f o r i r o n and mild s t e e l s . A decrease i n corros i o n r a t e of low carbon steels w i t h i n c r e a s i n g temperature i n
simulated geothermal f l u i d s has been reported a t a constant COP
p a r t i a l p r e s s u r e (SH-381). This phenomenon might be explained
i n terms of formation of more p r o t e c t i v e magnetite f i l m s a t high
temperature. A t constant CO2 p a r t i a l p r e s s u r e , a c t u a l s o l u t i o n
pH may i n c r e a s e with i n c r e a s i n g temperature, providing an addit i o n a l reason f o r t h e observation. These r e s u l t s may simulate a
binary c y c l e w i t h very l i m i t e d f l a s h i n g .

Laboratory measurements o f the corrosion rate of A212B


s t e e l as a function of temperature are shown i n Figure 5-7. A l though of i n t e r e s t , t h e s e masurements may n o t be t y p i c a l of
most geothermal sources due t o t h e high c h l o r i d e concentration
and t h e absence of COP which a f f e c t s t h e temperature dependence
of pH.

5-18

('a

io00

T
100

250225200175 150 125


I

75

50

25

2000

'a\*

AIooo

\*

0 .t

1.8

2.0

"
1
.

2.2

2.4

2.6

2.8

3.0

3.2

3.4

io3/1

Ffguxe 5-7,

3.6

(~9

Corrosion Rate of A212B Carbon Steel in


Deaerated 4 M NaCl as a Function of pH
and Temperatcre (PO-230)

5-19

Although l i t t l e data are a v a i l a b l e , v a r i a t i o n s i n tempe r a t u r e may have as g r e a t an i n f l u e n c e on p i t t i n g as changes i n


c h l o r i d e concentration. Figure 5-8 shows t h e e f f e c t of temperat u r e on t h e p i t t i n g and corrosion p o t e n t i a l s i n a geothermal
f l u i d . Increasing the temperature d r a s t i c a l l y a f f e c t s t h e p i t t i n g p o t e n t i a l but t h e corrosion p o t e n t i a l remains r e l a t i v e l y
constant. P i t t i n g i n c r e a s e s as t h e temperature i n c r e a s e s . The
end p o i n t s i n Figure 5-8 a t 25C and 200C a r e average values
measured i n Heber f l u i d (SY-028). The l i n e a r r e l a t i o n s h i p s
and ranges shown a r e assumptions. In deaerated seawater t h e
In
corrosion p o t e n t i a l i n c r e a s e s above about 120C (SM-A-191).
r e l a t i v e l y a l k a l i n e low-chloride s o l u t i o n s t h e p i t t i n g p o t e n t i a l
may go through a minimum and then i n c r e a s e (become more p o s i t i v e ) a t high temperature (ST-566, p. 415).
I n s p i t e of t h e v a r i a b i l i t y noted, t h e r e s u l t s show
t h a t temperature can have a s u b s t a n t i a l e f f e c t on s u s c e p t i b i l i t y
t o l o c a l i z e d corrosion.
5.1.2.4

E f f e c t of Other Key Species on Uniform, P i t t i n g , and


Crevice Corrosion of Low Alloy Steels

The key species considered are H z S , H 2 C 0 3 , NHb , and


The f i r s t t h r e e s p e c i e s are of r e l a t i v e l y g r e a t e r i m SO4
portance i n condensate streams than i n high-temperature s a l i n e
f l u i d s because t h e i r e f f e c t s a r e n o t masked by c h l o r i d e and because they c o n t r o l pH. S u l f a t e becomes important only i n those
geothermal f l u i d s which have low c h l o r i d e concentrations. Small
amounts of oxygen leaked i n t o a geothermal system produce more
l o c a l i z e d corrosion than t h e normal environmental f a c t o r s d i s cussed. This i s p r i m a r i l y a design and operation problem i n lowp r e s s u r e equipment and during shutdown.

5-20

TEMPERATURE ("C)

F i w r e 5-8,

Pitting and Corrosion Potentials of Steel as


a Function of Temperature in Heber Geothermal
Fluid. Data at 25" and 200C are from SY-028.
This graph is for illustration of trends only;
linear forms are assumed for lack of other data.
See Table 4-22 for f l u i d chemistry.

U
5-21
i

H,S

Hydrogen s u l f i d e i n a c i d i c media can g r e a t l y


An i r o n s u l f i d e
a c c e l e r a t e s t e e l corrosion (MA-A-770, IO-A-21).
l a y e r can form on s t e e l s i n t h e presence o f H 2 S , but it o f f e r s
no r e a l p r o t e c t i o n a g a i n s t uniform corrosion. I f p a r t of t h e
l a y e r f l a k e s o f f , t h e exposed s t e e l i s s u b j e c t t o l o c a l i z e d corrosion a c c e l e r a t e d by galvanic coupling t o t h e cathodic i r o n
s u l f i d e l a y e r . The exposed area may also become l o c a l l y a c i d i c
allowing increased H 2 S a t t a c k . Crevice o r p i t t i n g corrosion
i n i t i a t e d by o t h e r means may be a c c e l e r a t e d by H 2 S which stimul a t e s t h e anodic d i s s o l u t i o n r e a c t i o n .
Cop - Dissolved COP i n d i r e c t l y a f f e c t s corrosion by
t h e b u f f e r i n g a c t i o n of the aqueous s p e c i e s H2CO3, HC03 , and
COB . Release of COP during f l a s h i n g i n c r e a s e s t h e pH of t h e
f l a s h e d f l u i d . Maintaining CO2 pressure while cooling geothermal f l u i d s may decrease pH due t o t h e temperature dependence of
t h e equilibrium c o n s t a n t s . I n mildly a c i d i c s o l u t i o n s (pH about
3 t o 5 ) , H2CO3 a c c e l e r a t e s t h e uniform corrosion of mild s t e e l s .
Results obtained i n 1%N a C 1 , 0.05 t o 1 . 0 a t m C 0 2 up t o 80C i n d i c a t e t h a t t h i s e f f e c t i s due t o a c c e l e r a t i o n of t h e cathodic
(hydrogen evolution) r e a c t i o n (DE-A-315).
Therefore, H2CO3
should n o t have as adverse an e f f e c t on l o c a l i z e d corrosion rates
as H 2 S , which s t i m u l a t e s t h e anodic (metal d i s s o l u t i o n ) r e a c t i o n .

&

Flashed ammonia absorbed i n condensate tends t o


n e u t r a l i z e t h e a c i d i t y produced by C02 and H2S, but t h e a c i d i c
s p e c i e s are p r e s e n t i n much l a r g e r amounts than N H 3 i n most geothermal sources. Limited seawater d e s a l i n a t i o n tests showed t h a t
t h e uniform corrosion r a t e of mild s t e e l s increased approximately
65% when 15 ppm N H 3 ( i n s o l u t i o n ) w a s added as ammonia gas (GE-117).

5-22

SOb -

When t h e c h l o r i d e i o n concentration i s low, s u l f a t e becomes t h e main aggressive i o n a f f e c t i n g uniform corrosion


of mild steels. S u l f a t e i s much l e s s aggressive than c h l o r i d e i n
promoting p i t t i n g o r c r e v i c e corrosion.
E f f e c t of Low Alloy Additions on General Corrosion

5.1.2.5

In moderate c h l o r i d e and pH systems, t h e uniform corros i o n r a t e s of low a l l o y s t e e l s a r e somewhat lower than low carbon steels, b u t t h e absolute d i f f e r e n c e i s u s u a l l y small. P i t t i n g and crevice corrosion a t t a c k i s s i m i l a r t o mild s t e e l s and
sometimes more severe f o r low a l l o y s . High-strength low a l l o y
steels may be more s u s c e p t i b l e t o s u l f i d e s t r e s s cracking o r
stress corrosion cracking.
I d e n t i f i c a t i o n of r e s i s t a n t low a l l o y s t e e l s may be
necessary f o r u t i l i z a t i o n of high c h l o r i d e , low pH geothermal
f l u i d s due t o t h e high corrosion r a t e s of p l a i n s t e e l s ; P i t t i n g
and c r e v i c e corrosion of low a l l o y s t e e l s i n t h e s e environments
are major concerns. Further t e s t i n g i s being conducted by
Lawrence Livermore Laboratory.
The l i m i t e d success i n moderate s a l i n i t y - p H f l u i d s
should n o t preclude f u r t h e r t e s t i n g of low a l l o y steels. Long

term tests i n a seawater b o i l e r at about 200C showed t h a t s t e e l s


containing 0.2% t o 0.3% copper hadt lower p i t t i n g rates than p l a i n
Since l i t t l e i p known about long term p i t t i n g
s t e e l s (BU-A-307).
rates i n geothermal f l u i d s , comparative t e s t i n g of p l a i n carbon
and copper o r o t h e r low a l l o y s t e e l f o r extended periods i s of
interest

Extensive seawater d e s a l i n a t i o n t e s t i n g of low a l l o y


steels showed t h a t they were seldom worth t h e a d d i t i o n a l c o s t

5-23

(GE-117). A p o s s i b l e exception w a s Cor-Ten steel a t high f l u i d


v e l o c i t i e s . This a l l o y w a s t e s t e d a t Raft River w i t h l i m i t e d
success, b u t more extensive t e s t i n g i s d e s i r a b l e .
5.1.3

Stress Corrosion Cracking of Low Alloy S t e e l s

S t r e s s corrosion cracking of l o w a l l o y steels i n


H2S-free chloride s o l u t i o n s has been observed. This corrosion
should n o t be a major problem i n the usual range of geothermal
environments, but i n - s i t u cracking tests should be conducted.
It could be a more severe problem i n a c i d i f i e d streams (BA-556,
HU-200). See Table 5-3 l e f t column f o r c h a r a c t e r i s t i c s o f SCC.
5.1.4

S u l f i d e Stress Cracking o f Low and Middle Alloy S t e e l s

S u l f i d e stress cracking i s t h e b r i t t l e f a i l u r e of h a r d ,
high s t r e n g t h a l l o y s when they are exposed under stress t o environments containing even small amounts of H2S i n an aqueous
phase. Often these envirmments are n o t p a r t i c u l a r l y severe from
a general o r l o c a l corrosion s t a n d p o i n t . The f a i l u r e i s sudden,
c a t a s t r o p h i c , and without warning. There i s l i t t l e o r no evidence o f metal l o s s . See Table 5-3 r i g h t column f o r c h a r a c t e r i s -

t i c s of SCC.
S u l f i d e stress cracking (SSC) has been a problem a t
Wairakei, N.Z. (FO-120, 34-160, MA-682, FO-119), and Cerro
P r i e t o , Mexico (GE-119).
It places d e f i n i t e r e s t r i c t i o n s on
materials and design f o r any geothermal resource containing HPS.
These l i m i t a t i o n s are t h e r e s u l t of a complex i n t e r a c t i o n of a
number of f a c t o r s involving both t h e environment and t h e mater i a l . Resistance t o SSC generally increases with i n c r e a s i n g
temperature, decreasing stress, decreasing y i e l d s t r e n g t h , decreasing H2S concentration, and i n c r e a s i n g pH. The e f f e c t s of

5-24

TABLE 5-3

COMPARISON OF SCC AND SSC IN GEOTHERMAL ENVIRONMENTS *

ssc

SCC

1. mechanism: active path dis- 1. mechanism: cathodic hydrosolution (rapid metal disgen embrittlement
solution at crack tip)
2.

promoting
species : usually
chloride ion

2.

promoting
species : H2S in
aqueous solution

3.

fcc steels most sensitive

3.

bcc steels most sensitive


fcc steels immune

4.

not notch sensitive

4.

notch sensitive

5.

severity increases with


increasing temperature
6. ppm 0 , causes drastic
increase in severity of
attack

severity decreases with


increasing temperature
6. ppm 10,has little if any
effect
attaek on severity of

7.

7.

5.

bulk pH has little effect

low pH greatly accelerates


failure
8. threshold of applied stress
below which failure does
not occur
9 . failure is sudden catastrophic fracture.

8. no threshold stress
,

9.

failure is sudden,
trophic fracture

*Some authors consider SSC to be a subset under SCC. In this


report, SCC and SSC are treated as separate processes, compared above.

5-25

H 2 S concentration, pH, stress, and y i e l d s t r e n g t h are interdependent and more s i g n i f i c a n t than o t h e r f a c t o r s such as microstructure
and a l l o y composition. A discussion of t h e s e f a c t o r s i s presented
f i r s t . Then discussion of t h e i n t e r a c t i o n of t h e s e f a c t o r s i s
given, followed by comments on o t h e r less s i g n i f i c a n t f a c t o r s .

5.1.4.1

E f f e c t of H2S Concentration

The f a i l u r e (cracking) of s t r e s s e d materials i n high


H2S environments (above 15-30 ppm) occurs i n days o r n o t a t a l l .
A t concentrations less than 3 ppm, considerably longer t i m e s t o
f a i l y r e are observed, and t h e incubation t i m e may approach t h e
s e r v i c e l i f e of t h e m e t a l (HU-199, HU-200). Concentrations of
H2S as low as 20 ppb accelerate hydrogen e n t r y i n t o s t e e l (HU-A-233).
Concentrations less than 0 . 1 ppm have caused f a i l u r e i n long-term
tests.

5.1.4.2

Effect of Stress and Yield Strength (Hardness)

S u l f i d e stress cracking i s stress dependent and t h e


t o t a l s t r e s s t o which t h e s t e e l i s s u b j e c t e d must be considered,
including applied t e n s i l e s t r e s s , r e s i d u a l t e n s i l e stresses res u l t i n g from phase transformation during o r a f t e r h e a t treatment,
thermal stress, and cold deformation during f a b r i c a t i o n and serv i c e (VO-067, NA-383, BA-550, HU-200). Even 1%cold work can
lower t h e t h r e s h o l d stress about 30% (BA-563). Cold worked
p a r t s should be heat t r e a t e d t o relieve r e s i d u a l stress. A
notch g r e a t l y reduces threshold stress. Threshold stress i s
t h e g r e a t e s t applied stress which does not cause SSC failures.
Notches g r e a t l y i n c r e a s e t h e effect of applied stress.

5-26

L/
Yield s t r e n g t h (YS)
important m a t e r i a l f a c t o r s i n
i s the standard c r i t e r i o n f o r
stress decreases as t h e YS of

and microstructure a r e t h e most


SSC. Yield s t r e n g t h o r hardness
SSC s u s c e p t i b i l i t y . The t h r e s h o l d
the s t e e l i n c r e a s e s .

Enteraction of H2S Concentration, S t r e s s , and Yield


Strength

5.1.4.3

The NACE starrdard f o r s o u r s e r v i c e i s 90-100 k s i


y i e l d s t r e n g t h , o r Rc 2 2 . This i s based on performance of
steels s t r e s s e d t o 100% YS i n NACE s o l u t i o n [5% NaC1, 0.5%
a c e t i c a c i d s a t u r a t e d with H 2 S ] (NA-423).
The a c t u a l l i m i t a t i o n s on usable hardness a r e a comp l e x i n t e r a c t i o n of y i e l d s t r e n g t h , a p p l i e d stress, temperat u r e and concentration of H2S: Figure 5-9 shows t h e e f f e c t
of l i m i t i n g a p p l i e d stress on usable hardness.
While a given s t e e l may be u t i l i z e d a t much g r e a t e r
y i e l d s t r e n g t h and hardness ( ~ 1 2 8k s i , Rc 30) i f s t r e s s e s a r e
l i m i t e d t o 60% of y i e l d , c a l c u l a t i o n shows t h a t t h e p o i n t of
maximum r e t u r n on usable s t r e n g t h has been passed (HU-200).
he i n c r e a s e i n usable hardness
with decre
5.1.4.4

E f f e c t of Microstructure and Composition

Strength and h
s s are inadequate f o r d e f i n i n g susc e p t i b i l i t y t o SSC (BO-256). Microstructure a f f e c t s t h e SSC
r e s i s t a n c e of s t e e l s with t h e same hardness, while composition

bd
5-27

40

Ill1

I I

I 111111

111111

..

35.
30

8
.
)

v)

25.
a

p:

9
20.

15.

- 60

10
TIME TO FAILURE, HOURS

Figure 5-9.

Approximate Correlation of Hardness, Time to


Failure and Applied Stress for Carbon Steels
(3000 ppm H2S in 5% NaC1) (Based on data presented in HU-199)

40

160

35

140

zs

30

120

v)

.
I

25

100

v)
v)

20
80

15
10

I1I

I 11111

.5

I I

I ""I

10

1 I I11111

I I

50 100

I Ill1

500 1000

1 ' 1 '

60

5000 10~OoO

TIME TO FAILURE, HOURS

Figure 5-10. Approximate Correlation of Failure Time for


Carbon Steels in 5% NaCl Containing Various
Concentrations of H2S (Based on data presented
in HU-199)

3-28

Ld
i s s i g n i f i c a n t only as i t a f f e c t s h a r d e n a b i l i t y and microstruct u r e (SN-060, SN-061, FR-233, HU-200). Quenched and tempered
steels are s u p e r i o r t o normalized and tempered steels of comp a r a b l e y i e l d s t r e n g t h s (SN-060). Normalized and tempered s t e e l s
are s u p e r i o r t o normalized steels (KA-280). Figure 5-11 i l l u s trates t h e s u p e r i o r i t y of quenched and tempered steel over normalized and tempered steels.

200

iao
160

.
-

140 *

120-

100

80

4
10

20

30

40

50

60

70

80

90

THRESHOLD STRESS, KS I
Figure 5-11. Yield Strength-Threshold Stress Relationship
f o r Low Alloy Steels (SN-060)
I n t h e r e g i o n below and l e f t of t h e shaded areas, no f a i l ures occurred. Above and r i g h t of t h e shaded a r e a s , a l l
specimens f a i l e d . I n t h e shaded area, some s t e e l s were
s u s c e p t i b l e , some were r e s i s t a n t .

5-29

Li
The most r e s i s t a n t m i c r o s t r u c t u r e s c o n s i s t of r e l a t i v e l y
f i n e spheroidized carbides uniformly dispersed i n f e r r i t e . This
i s t y p i c a l of m a r t e n s i t e tempered a t high temperature. S t e e l s
high i n chromium, s u l f u r , o r phosphorous are l e s s r e s i s t a n t
(SN-061).
,

The next most r e s i s t a n t microstructures contain coarse


. globular and/or laminar carbides (SN-061).
S u l f u r a l s o tends t o
form " s t r i n g e r s " of i n c l u s i o n s which favor cracking (OH-S-039).
Laboratory h e a t s of very low s u l f u r steels o r s t e e l s with t r a c e
lanthanide a d d i t i o n s , a r e very r e s i s t a n t t o SSC (OH-S-039 ,
SN-06 1, TR-090).
Microstructures containing untempered m a r t e n s i t e have
t h e worst r e s i s t a n c e of a l l . Even very small t r a c e s of untempered m a r t e n s i t e , e s p e c i a l l y as a network , d r a s t i c a l l y lower
t h e t h r e s h o l d s t r e s s . Such s t e e l s f a i l a t hardnesses far below
Rc 2 2 . These microstructures can occur i n e i t h e r Q and T , o r
N and T s t e e l s i f t h e tempering temperature exceeds t h e lower
c r i t i c a l temperature ( a u s t e n i z i n g temperature). Additions o f
n i c k e l and manganese reduce t h e lower c r i t i c a l temperature, i n c r e a s i n g t h e r i s k of forming untempered m a r t e n s i t e . This accounts f o r t h e poor performance of s t e e l s c o n t a i n i n g more than
one percent n i c k e l (NA-383). Low a l l o y s t e e l s containing more
than one percent n i c k e l should be t e s t e d c a r e f u l l y before use.
Additions of chromium and molybdenum worsen the s i t u a t i o n because
h i g h e r tempers a r e required t o g e t low enough y i e l d s t r e n g t h s .
5.1.4.5

E f f e c t of Temperature

The r e s i s t a n c e t o SSC of high s t r e n g t h , low a l l o y


s t e e l s i n c r e a s e s as temperature i n c r e a s e s (TR-090 , TR-S-119 ,

GR-233), but t h e r e i s no temperature above which immunity occurs


Table 5-4 shows the e f f e c t o f i n c r e a s i n g temperature on t h e
useable YS of a n d e r of a l l o y s .
5-30

TABLE 5-4

ai

SULFIDE STRESS CRACKING OF SOME HIGH STRENGTH ALLOYS

5-31

L,
5.1.4.6

Effect of pH

Sulfide stress cracking occurs in acidic solutions.


The severity of cracking in solutions below pH 4.5 is relatively
constant. Between pH 4.5 and 6, there is a moderate decrease in
severity. Resistance to SSC increases rapidly above pH 6, but
SSC has been observed at pH 12 (TR-S-119).
5.1.4.7

Effect of Chloride, Moisture, and Oxygen

Chloride ions are not required for SSC (BA-563, TR-S-119),


but they increase the severity of SSC in steels containing chromium. Little difference in SSC susceptibility was observed in
H2S-saturated chloride-free solutions, 30,000 ppm-chloride solutions, and 120,000 ppm-chloride solutions (TR-S-119). Whether
chloride affects SSC resistance at low H2S concentrations has
not been determined.
Laboratory tests (SM-A-184, FR-233) and Wairakei field
data (MA-682) confirmed that liquid water is required for SSC.
Dry steam containing H2S does not appear to be active, but SSC
may occur at any location where this steam condenses.
Oxygen has a negligible effect on SSC.
5.1.5

Hydrogen Blistering of Mild Steels

Hydrogen blistering occurs in low strength steels exposed to aqueous solutions containing H2S and has been a problem
at the Wairakei geothermal plant (MA-682).

In short-term laboratory tests, H2S partial pressures


of about 0.02 psia (~60ppm in solution) were required for hydrogen blistering of iron (GR-A-330). In long-term tests

5-32

(greater than 200 days) of cold rolled 1036 steel, 1.0 ppm HnS
in solution caused blistering while 0.1 ppm did not (HU-200).
Voids are required for blistering, and "killed" (voidfree) steels resist blistering. Though not necessarily subject
t o blistering, voids in welds may accumulate molecular hydrogen
and burst. Stress is not required for hydrogen blistering. The
equilibrium pressure of the Ho-H2trapped in a void is believed
to be on the order of l o 5 atmospheres, enough to rupture any
known engineering material (FO-118).
5.2

Stainless Steels

The uniform corrosion rate of most qtainless steels is


low in geothermal fluids, but many are subject to the more serious forms of corrosion: pitting, crevice corrosion, stress
corrosion cracking, sulfide stress cracking, intergranular
corrosion, and corrosion fatigue. Stainless steels have been
used in geothermal environments, but care must be taken in their
selection and application.
I

5.2.1

General Guidelines for Use of Stainless Steels

Aeration
Many stainless steels which could perform
well in oxygen-free geothermal environments can be subject to
severe pitting and crevice corrosion in the presence of small
quantities of oxygen. Stress corrosion cracking of commonly
used austenitic stainless steels in,high temperature chloride
solutions can occur minutes after introducing oxygen in ppm quantities or less. This failure is often catastrophic. Other alloys
are more resistant. Pits, crevice attack, or cracks initiated
during upset or plant outage conditions can continue to grow once
normal operation is resumed. Special care should be taken during
plant commissioning due to the likelihqod of unstable conditions.

5-33

Flow Rate - Stainless steels are more resistant to high


velocities than plain and low alloy steels. Continuous high velocity flow is more desirable than low flow rates or stagnant conditions. Under stagnant conditions, settling of entrained solids
or spot deposition of loose scale can lead to crevice corrosion.
Stagnant conditions should be avoided, and stainless components
should be drained and rinsed during plant shutdown. Resistance
to erosion-corrosion is more closely related to general corrosion
resistance than hardness of the metalScale - Local concentration cells can develop under
porous or cracked scale on stainless steel and lead to crevice
corrosion to which stainless steels are susceptible. After an
attack is initiated, local increases in acidity and chloride
concentration cause intense corrosion.
Welding - Good welding procedures are important to the
successful application of stainless steels. Sensitization to
intergranular corrosion by welding is discussed in Section 5.2.6.
Physically poor welds may have crevices that are susceptible to
crevice corrosion. Stress corrosion cracking may initiate at
pits close to poor welds.
Exterior Surfaces - Measures should be taken to protect
the exterior of stainless steel components that are exposed to
air. Leaks and splashes of hot chloride solutions combined with
the high oxygen content of air can subject these components to
stress corrosion cracking conditions. Flange leaks leading to
conditions in which geothermal fluid concentrates and dries
under insulation can be dangerous. Non-porous gaskets are required to guard against cracking at flanges.

5-34

3
L,
5.2.2

Corrosion Resistance of Major Classes of S t a i n l e s s


Steels

400 Series F e r r i t i c and M a r t e n s i t i c Steels

These mat e r i a l s have poor r e s i s t a n c e t o h o t geothermal l i q u i d s . The mart e n s i t i c steels A I S 1 410 and 440, o f t e n used as pump s h a f t s ,
s u f f e r e d deep p i t t i n g and severe crevice corrosion i n Raft River
tests (MI-305). Similar materials have been used w i t h more success i n geothermal steam. The 400 series f e r r i t i c s may be
a p p l i e d i n low c h l o r i d e systems, but t e s t i n g i s required.
Higher Alloy F e r r i t i c S t a i n l e s s Steels - The newer f e r r i t i c a l l o y s are much less s u s c e p t i b l e t o stress corrosion cracking
than t h e more common a u s t e n i t i c s . The 26Cr-1Mo a l l o y has shown
promise i n f i e l d tests a t East Mesa and i n deaerated flowing
seawater. The molybdenum content of t h i s a l l o y may n o t be high
enough t o withstand crevice corrosion i n s c a l i n g environments
o r i n a p p l i c a t i o n s where p e r i o d i c a e r a t i o n i s p o s s i b l e . The
h i g h e r a l l o y , high-purity f e r r i t i c s , 29Cr-4Mo and 29Cr-4Mo-2Ni,
generally have outstanding r e s i s t a n c e t o geothermal environments.
These materials can be considered f o r a l l a p p l i c a t i o n s where
t h e i r mechnical p r o p e r t i e s are acceptable. The n i c k e l containi n g a l l o y normally has s l i g h t l y b e t t e r r e s i s t a n c e t o general
corrosion, b u t i s more s u s c e p t i b l e t o stress corrosion cracking
than t h e n i c k e l - f r e e alloy..

A u s t e n i t i c S t a i n l e s s Steels
S u s c e p t i b i l i t y t o stress
corrosion cracking may l i m i t t h e use of a u s t e n i t i c s t a i n l e s s
steels i n geothermal l i q u i d s (see Section 5 . 2 . 4 ) .

Lower a l l o y a u s t e n i t i c a l l o y s are a l s o s u s c e p t i b l e t o
p i t t i n g and crevice corrosion. Type 304 g e n e r a l l y has t h e lowest
resistance; the a d d i t i o n of molybdenum significantly improved resistance. Type 316 w i t h 2% Mo has much b e t t e r r e s i s t a n c e t o p i t t i n g

5-35,

and crevice corrosion than Type 304, but i t i s s u s c e p t i b l e t o


corrosion i n geothermal f l u i d s , e s p e c i a l l y t o crevice corrosion.
1

Type 317 with 4% molybdenum has s i g n i f i c a n t l y b e t t e r


\
corrosion r e s i s t a n c e t o l o c a l i z e d corrosion)
and SCC than e i t h e r
304 o r 316. Further t e s t i n g of Type 317 i n geothermal f l u i d s
i s required.
The high a l l o y a u s t e n i t i c s are s i g n i f i c a n t l y more res i s t a n t t o l o c a l i z e d corrosion and somewhat more resistant to
SCC than the 300 s e r i e s , but they are n o t immune from a t t a c k .
Members of t h i s c l a s s include Alloy 20-Cb3 , Allegheny-Ludlum
6 X , and Haynes Alloy 20 mod. The e x t r a cost of t h e s e materials
should be weighed a g a i n s t t h a t of materials such as t h e 29Cr-4Mo
f e r r i t i c a l l o y s , titanium a l l o y s , Inconel 625 and Hastelloys,
which may give b e t t e r o v e r a l l corrosion performance i n many applications.

Cast S t a i n l e s s Steels - S u s c e p t i b i l i t y of t h e s e metals


t o corrosion i s determined primarily by t h e chemical composition
of t h e a l l o y . They a r e usually equivalent t o comparable wrought
a l l o y s . Cast a l l o y s a r e usually used f o r pumps and valves which
contain numerous l o c a t i o n s f o r crevice corrosion.

5.2.3

P i t t i n g and Crevice Corrosion of S t a i n l e s s Steels

P k t t i n g and crevice corrosion are t h e main problems f o r


s t a i n l e s s steels which a r e r e s i s t a n t t o SCC. Crevice corrosion
i s o f t e n t h e more s e r i o u s problem s i n c e s t a i n l e s s steels are frequently used i n complex equipment where crevice a t t a c k i s more
r e a d i l y i n i t i a t e d . While t h e d e t a i l e d mechanism of i n i t i a t i o n
may be d i f f e r e n t f o r p i t t i n g and crevice corrosion, environmental
e f f e c t s are similar i n geothermal systems.

5-36

The pitting potentials (see Section 5.1.2) of stainless steels are generally much more noble (positive) than plain
steels, and they should, therefore, be more resistant to localized
attack. However, the corrosion potentials of stainless steels
are also more noble, and it is the difference between the two
which is important (Section 5.1.2).
Corrosion potentials of
passive stainless steels can be made more noble by small quantities of oxidizing agents resulting in rapid localized attack.
5.2.3.1

Effect of Chloride

Stainless steels become more susceptible to localized


corrosion as the chloride concentration increases. This dependence is shown in Figure 5-12 for Type 304 stainless steel.

ACIVIN OF C1Figure 5-12. Effect of Chloride Ion Activity on Steady-State


Critical Potential f o r Pitting, 25C (LE-A-248)
5-37

The logarithmic dependence has been measured for other


stainless steels (LE-A-338, 50-262, SU-A-132). Chloride dependence data are not available at geothermal temperatures.
5.2.3.2

Effect of pH

According to low temperature work, pH has little influence on pitting potentials over the pH range of major interest
( 4 to 9) or geothermal systems. The pH effect on corrosion potential i also small in this region.

Laboratory tests with several stainless steels in Heber


geotherma fluid at 200C show a slight noble shift in pitting
potential as the pH (measured at room temperature) was increased
from 5.3 to 7 (SY-028). The corrosion potentials also shifted
in the noble direction by about the same amount so there is actually little change in pitting tendency.
5.2.3.3

Effect of Temperature

Temperature has a major effect on the localized corrosion of stainless steels. Most studies of the temperature dependence of pitting were at less than 100C. Pitting susceptibility
increases with increasing temperature as indicated by a shift in
pitting potential to more active values. An initial rapid decrease in pitting potential is often followed by a much slower
decrease or nearly constant value at higher temperatures. Studies
at 150" to 250C indicate that resistance to pitting may increase
with.increasing temperature in this range. Morphology~of pit
growth changes at elevated temperatures where the trend is to
the formation of a larger number of smaller pits.
Examples of pitting and corrosion potential behavior at
high temperatures in 4M NaCl are shown in Figure 5-13 (PO-230).
5 - 38

Ld

0
-0.4
A

-> -0.2

A\

v)

-0.3

v)

-Ia-

z
w -0.4

I-

O
Q

E -0.5

I-

5W -0.6
-0.7 -0.8

A304
PITTING
A 3,G } POTENTIALS

50

100

4 50

200

250

300

TEMPERATURE (0C)

Figure 5-13.

Pitting Potentials and Corrosion Potentials o f


Types 304 and 316 Stainless Steel i n 4 M
- NaCl
as a Function o
emperature (PO-230)

U
5-39

The region near 100C may a c t u a l l y be more dangerous than a t


higher temperatures. I n t h i s high c h l o r i d e f l u i d t h e d i f f e r e n c e
between p i t t i n g and c r e v i c e corrosion p o t e n t i a l s i s small f o r
Type 304 and Type 316, and p i t t i n g o r e s p e c i a l l y crevice corros i o n could occur i n t h e presence of s m a l l amounts of oxidizing
agents. S i m i l a r increases occur i n p i t t i n g p o t e n t i a l f o r metals
f o r 100" t o 225C i n pH 9 s o l u t i o n s with low chloride concentrat i o n s (SP-104, ST-566). The decrease i n p i t t i n g tendency a t high
temperatures shows t h a t materials should be t e s t e d n e a r t h e
temperature a t which they are t o be used even i f i t i s lower
than t h e wellhead temperature.
P i t t i n g k i n e t i c s have been s t u d i e d over a l i m i t e d t e m p e r a t u r e range (25"-50"C) f o r 18Cr-12Ni-2Mo-Ti i n 0.1N H 2 S 0 4 +
0.5M N a C l a t constant p o t e n t i a l s . The number of p i t s i n c r e a s e s
with i n c r e a s i n g temperature (SZ-A-022). Established p i t s grow
more slowly a t higher temperatures sYnce t h e current density
within each p i t i s r e l a t i v e l y low. S i m i l a r e f f e c t s w e r e noted
f o r p i t s growing i n f e r r i c chloride s o l u t i o n without an extern a l l y applied p o t e n t i a l . This i s s a i d t o be due t o d i s t r i b u t i o n
of t h e cathodic current over a l a r g e r number of p i t s .
5.2.3.4

E f f e c t s of Other Species

S t a i n l e s s steels are generally resistant t o corrosive


a t t a c k by contaminated seawater containing H 2 S and NH3 (GE-117).
Stagnant conditions should be avoided. H2S may cause p i t t i n g of
316 i n a c i d i c s o l u t i o n s by r e t a r d i n g t h e formation of passive
films and causing l o c a l i z e d a t t a c k i n regions o f low pH (IJ-A-003).

No direct evidence f o r the effect o f COP on t h e p i t t i n g


of s t a i n l e s s s t e e l s w a s found i n t h e l i t e r a t u r e . High concent r a t i o n s of H2CO3 i n f a i r l y a c i d i c s o l u t i o n s can c a t a l y z e t h e
hydrogen evolution reactior,.

P i t t i n g of a l l o y s with p i t t i n g
5-40

L;

p o t e n t i a l s more active than t h e hydrogen equilibrium p o t e n t i a l


could be a c c e l e r a t e d by C02 i n f a i r l y a c i d i c s o l u t i o n s . Bicarbonate may f u n c t i o n as a p i t t i n g i n h i b i t o r a t high concentration
i n alkaline solution.
S u l f a t e can i n h i b i t t h e p i t t i n g of s t a i n l e s s s t e e l s i n
c h l o r i d e s o l u t i o n . The minimum s u l f a t e a c t i v i t y needed t o i n h i b i t p i t t i n g of Type 304 a t 25OC depends on c h l o r i d e concen=
Equal
t r a t i o n . Approximately 0.08M SO4 i s needed f o r 0 . lM C1-.
=
molar concentrations of C1- and SOI, a r e r a r e l y found i n geothermal f l u i d s

5.2.3-5

E f f e c t of C r and Mo on P i t t i n g and Crevice Corrosion

The p i t t i n g and c r e v i c e corrosion r e s i s t a n c e of s t a i n less steels i s s t r o n g l y dependent on t h e i r C r and Mo contents.


These effects were explored i n a program t o develop f e r r i t i c
s t a i n l e s s s t e e l condenser tubes f o r use i n multi-stage f l a s h
evaporation d e s a l i n a t i o n p l a n t s (PE-268).
P i t t i n g potentials
by t h e s c r a t c h method were determined i n deaerated a r t i f i c i a l
sea water a t 90C and pH 7.2.
Results are shown i n Figure 5-14 f o r c r i t i c a l p i t t i n g
p o t e n t i a l as a function of (Cr + Mo) added (PE-268). The s t r o n g
i n f l u e n c e of Mo a d d i t i o n i s apparent. Results f o r commercial
a l l o y s containing n i c k e l show t h a t t h e i r r e s i s t a n c e i s due p r i marily t o t h e i r ( C r + Mo) content and n o t t o N i content. Some
b e n e f i c i a l e f f e c t s of ( S i
N i l a d d i t i o n were noted.
Crevice corrosion r e s u l t s i n a e r a t e d s y n t h e t i c s e a
water a t 1 2 1 C are given i n Figure 5-15. This i s a very severe
environment and t h e equal corrosion regions give a graphic repr e s e n t a t i o n of a l l o y behavoir. Severe c r e v i c e corrosion tests
a p p l i e d t o a number of a l l o y s show t h a t a t l e a s t 2-3% Mo i s needed

W
5 -41

Figure 5-14. Comparison of the Critical Pitting


Potentials of Fe-Cr-Mo Alloys with
Several Comercial Allovs in Deaerated Synthetic Seawaker at 90C,
pH = 7.2+0.2 (PE-268)

5-42

-malm

Figure 5-15.

arI

a
30
tCr +Mot in A Wt. Y

35

Relationship Bstween t h e C r i t i c a l P i t t i n g
P o t e n t i a l s (EcScr Measured i n Deaerated
Synthetic Seawater a t 90C., pH = 7 . 2 k 0 . 2 )
of Fe-Cr-Mo Based Alloys and Their Resistance t o Crevice Attack After a 14-Day
Exposure t o Synthetic Seawater a t 1 2 1 C
and ~ 6 ppm
0
Oxygen. The Numbers Associa t e d with Individual Points I n d i c a t e t h e
Weight Losses Expressed a s gms x 1OaAfter
t h e 1 2 1 C Exposure for Samples with I n i t i a l
Weights of ~1gm (PE-268)

5-43

for good crevice corrosion resistance regardless of alloy system


(SE-A-133).
5.2.4

Stress Corrosion Cracking of Stainless Steels

Stress corrosion cracking (SCC) promoted by chloride ion


is a severe threat in geothermal systems; austenitic steels are
the most vulnerable.
Austenitic stainless steels are susceptible to SCC in
hot chloride solutions. Since SCC is a catastrophic type of
failure, the use of austenitics in geothermal streams requires
careful evaluation. SCC depends on chloride, oxygen, pH, temperature, stress, and alloy composition. These factors are discussed below.
Ferritic stainless steels are generally much more resistant to SCC than are austenitic stainlesses. Some are susceptible to sulfide stress cracking or cathodic hydrogen embrittlement. However, the older alloys, (i.e., AIS1 Types 409, 430, 434,
and 4 4 0 ) , are much more susceptible to pitting and crevice corrosion. New alloys have been developed with much better resistance
to pitting and crevice corrosion, but these alloys are not always
immune to SCC (NE-207, GE-119, ST-A-570).
The resistance of precipitation hardened stainless
steels to SCC in boiling MgC12 varies. PH 13-8 Mo was resistant
for 15 days while 17-4 PH and 15-5 PH failed in less than one day.
5.2.4.1

Effect of Chloride, Oxygen, and pH

It is well established that the severity of SCC increases with increasing chloride concentration. The threshold
chloride concentration may be about 5 ppm (NE-207).

5-44

Only trace amounts of oxygen (less than 100 ppb) are


required for SCC of some austenitic steels (NE-207). In order for
the crack tip to propagate quickly enough to prevent repassivation, a rapid reduction reaction is required. Oxygen and oxidizing species such as Fe" satisfy this requirement. Figure
5-16 presents the effect of increasing chloride concentration at
two dissolved oxygen concentrations. In more concentrated chloride solutions (>lo00 ppm NaCl), changes in oxygen concentrations
have little effect on SCC resistance. In dilute chloride solutions (<lo0 ppm NaC1) , small changes in oxygen concentration have
a significant effect on susceptibility to SCC.

10,0oO

'

' "I

'

'

'

"I

'

17.

-f

0.38diameter wire at
W ' C ond 115 MPa
1,OOo~

loo

--

10.

l l l l

5-45

In the range normally found in geothermal environments,


bulk pH is not a major factor. Cracking is more rapid and numerous in the pH 1.2 to 2.5 range (EA-557).
5.2.4.2

Effect of Temperature

Severity of crackipg increases with increasing temperature (NE-207). For any given concentration of chloride, oxygen,
and pH, a "lower critical temperature" exists below which SCC does
not occur. This is illustrated for AIS1 Type 304 in Figure 5-17.

"9

No cmJting below each

M
40

respective line for pH shown.


I

102
._

lo3
Chloride content

Figure 5-17.

10'

12

ppn

Effect of pH, Chloride Content, and


Temperature on the Stress Corrosion
Cracking of Type 304 Stainless Steel
Under Residual Weld Stresses. Aswelded Tube Specimens; NaCl Dissolved
in H20 Under Air; Exposure Time up to
8000 Hours (GO-233).

Similar behavior has been observed for other austenitic


stainless steels (LA-A-338), but there are not enough data to construct figures similar to Figure 5-17. From a design standpoint,
the phenomenon of a lower critical temperature means that the
more resistant austenitic alloys (such as Type 317 with 4.2% Mo
or USS 18-18-2 with 2% Si) should be tested in low temperature
streams even if previous tests indicate they are not suitable
for exposure to wellhead fluids.

5-46

5.2.4.3

Effect of Stress

Stress is required for SCC, but there is no evident


lower critical stress. Time to fracture decreases sharply at
stress at or above the yield point (HI-191, H0-348). Total
stress is the critical factor. Applied stress actually presents
relatively little difficulty because it can be quantified and
allowed for. Residual stresses from cold work and welding are
unpredictable. Post-welding stress may be near the yield point.
Failures have occurred at zero applied stress (LA-A-338). Austenitic stainless steels should be fully annealed.
5.2.4.4

Effect of Alloy Composition

Nickel is the constituent having the major effect on


susceptibility to SCC in chloride solutions. Immunity from
chloride stress cracking is not normally obtained unless the
nickel content is less than 1% or greater than 45% (WA-347,
LA-A-338). All AIS1 austenitics are susceptible to SCC under
the severe te.st conditions of boiling MgC12, but increasing
nickel content above 10% gives some increase in resistance.

of molybdenum improve resistance to

SCC.

In boiling MgC12, austenitic 18Cr-8Ni-3Mo was more resistant


than molybdenum-free 18Cr-8Ni (HI-191). Special Type 317 steel
with 4.2% molybdenum is superior to Type 316 in resistance to
SCC and local corrosion in aerated and deaerated chloride solutions (3000 and 30,000 ppm C1-) over a wide range of pH (LI-A-230).
This same alloy was immune 0 SCC for 1464 hours (test duration)
in boiling, acidified 25% NaCl (pH 1.5), while Type 304 failed in
10 hours. The increased molybdenum content, and not the slightly
higher chromium and nickel content, was responsible for the superiority (LI-A-230, DU-153).

5-47

S i l i c o n addition a l s o improved r e s i s t a n c e t o SCC; USS


18Cr-18Ni-2Si i s 10 t o 100 times more r e s i s t a n t than Type 304
i n b o i l i n g MgC12 and has a good process i n d u s t r y record i n h o t
c h l o r i d e systems (LO-A-240). Type 310 containing 1.5% s i l i c o n
showed no SCC and no r e a c t i o n t o s u l f i d e s i n nonacid c h l o r i d e
s o l u t i o n s below 450OC.
t o machine.

Type 310 tends t o tear and i s d i f f i c u l t

Type 314 contains more chromium and n i c k e l than Type


317 and has 2-3% molybdenum and 1.5-3% s i l i c o n . This a l l o y
should be t e s t e d i n geothermal streams.
Additions o f small amounts of t i t a n i u m , niobium, tungs t e n , o r manganese may a l s o improve r e s i s t a n c e . Additions o f
c o n s t i t u e n t s which favor p r e c i p i t a t i o n o f carbides and n i t r i d e s

a t t h e g r a i n boundary decrease r e s i s t a n c e t o SCC.


F e r r i t i c s t a i n l e s s s t e e l s containing more than 1%n i c k e l
a r e s u s c e p t i b l e t o SCC i n MgC12 although some r e s i s t cracking i n
t h e wick test and i n b o i l i n g 20% N a C l (NE-207, ST-A-570, GE-119).
The a d d i t i o n of more than 0.5% copper i s detrimental t o f e r r i t i c
s t e e l s (GO-233). The 26Cr- lMo, 29Cr-4M0, and 29Cr-4Mo-2Ni a l l o y s
depend on l o w i n t e r s t i t i a l concentrations of carbon o r n i t r o g e n
t o r e s i s t SCC i n h e a t a f f e c t e d zones. 26-1 i s a l s o a v a i l a b l e i n
a t i t a n i u m o r niobium s t a b i l i z e d form. The 29Cr versions cannot
be s t a b i l i z e d i n t h i s way because t h e amounts of t i t a n i u m o r
niobium required adversely a f f e c t d u c t i l i t y and r e s i s t a n c e t o
SCC (ST-A-570).
5.2.4.5

Comment on Laboratory Test Methods

The o l d e s t t e s t f o r c h l o r i d e SCC i s t h e boiling MgClz


t e s t . This i s a severe environment, and i t i s o f t e n d i f f i c u l t
t o r e l a t e r e s u l t s from t h i s t e s t with r e s u l t s from less severe

5-48

L
i

it
i

L)
environments (NE-207). The b o i l i n g L i C l t e s t i s usable a t
higher p H ' s , does not form an insoluble hydroxide, has b e t t e r
chemical p u r i t y , and cracks Type 304 i n an i d e n t i c a l manner a t
similar t i m e s (WI-A-317).
The wick t e s t (DA-268) i s considered
by many t o be t h e most r e a l i s t i c t e s t f o r marine and d e s a l i n a t i o n
environments, A d i l u t e N a C l s o l u t i o n i s "wicked up" onto an
e l e c t r i c a l l y h e a t e d U-bend where evaporation concentrated t h e
NaC1.
This t e s t i s t h o u b t t o be e s p e c i a l l y good where chloride
s o l u t i o n s are flashed.
5.2.5

I n t e r g r a n u l a r Corrosion of S t a i n l e s s Steels

I n t e r g r a n u l a r corrosion i s severe l o c a l i z e d corrosion


a t o r adjacent t o g r a i n boundaries, with l i t t l e o r no a t t a c k on
t h e bodies o f t h e g r a i n s . The a l l o y d i s i n t e g r a t e s (grains f a l l
o u t ) and/or l o s e s i t s s t r e n g t h .
5.2.5.1

A u s t e n i t i c S t a i n l e s s Steels

I n t e r g r a n u l a r corrosion occurs i n a u s t e n i t i c s t a i n l e s s
steels when they are s e n s i t i z e d [ i . e . , heated i n t h e 510-790C
When
range] (FO-118). The range may extend t o 900C (CI-A-027).
s t a i n l e s s s t e e l s are welded, a zone c a l l e d t h e heat a f f e c t e d
zone o r HAZ along each s i d e of t h e weld i s heated i n t o t h e sens i t i z i n g range. HAZ i s
i t e of intergranular a t t a c k , often
c a l l e d weld decay.
t e r g r a n u l a r corrosion can be c o n t r o l l e d i n t h r e e
ways. F i r s t , t h e material can be quench-annealed o r s o l u t i o n
annealed (heated t o high temperature, t y p i c a l l y 1065 "C t o
1120 "C, and water quenched). The quenching i s important because
i f t h e a l l o y i s allowed t o cool slowly, t h e e n t i r e s t r u c t u r e
w i l l be s e n s i t i z e d . S t a i n l e s s goods are u s u a l l y s u p p l i e d i n
t h e quench-annealed form. I f they a r e welded during f a b r i c a t i o n ,
1

I
I

5-49

they must be re-treated (FO-118). HAZ intergranular corrosion


can be controlled by lowering the carbon content below 0.03%.
These alloys do not require quench-annealing after welding and
can be welded on-site. These alloys have a great propensity for
picking up carbon when welded. The surfaces around the weld
must be kept completely grease and oil free or sensitization will
occur. HAZ intergranular attack can also be prevented by the
addition of strong carbide formers or stabilizers, to combine
with the carbon. Niobium (or niobium plus tantalum) and titanium are used to stabilize stainless steels (FO-118).
5.2.5.2

Ferritic Stainless Steels

Ferritic stainless steels are alea subject to intergranular corrosion and weld decay. The same mechanism, chromium
depletion, is responsible.
The range of sensitizing temperatures is not established, but sensitization of nickel-free ferritic steels begins
at about 930C. Addition of 2% nickel raises the sensitization.
temperature to 1040C. Molybdenum has little effect.
Quenching prevents intergranular corrosion. Weld decay
of 1-2% nickel alloys can be prevented by one-hour treatment at
820C followed by water quenching. Lower nickel alloys require
four hours at 820C (BO-A-323).

Addition oE more than 0.47% titanium to 18Cr-2Mo alloys


completely prevents intergranular corrosion in the Strauss test
after all sensitizing treatments. Alloys containing more than
1.2% titanium are embrittled after annealing from 820C. This
embrittlement can be removed by water quenching from 1040C.
Additions of 0.'61% niobium prevent intergranular corrosion of
post-weld specimens in the Strauss test (BO-A-323).

5-50

LI

j
I

it
i

5.2.6

Sulfide Stress Cracking of Stainless Steels

Austenitic stainless steels are fcc and are generally


considered to be immune to SSC. AISI Types 301, 304, and 310,
at fully softened and partially work hardened conditions resisted
SSC at 162C (TR-090).
Martensitic stainless steels are very susceptible to
ssc at ambient temperatures (FR-233). AISI Type 410 and Carpenter
Custom 450 are susceptible at hardnesses we13 below Rc 22, A 13Cr
martensitic steel at the Wairakei geothermal plant resisted SCC
below Rc 10 (MA-672). A special 12Cr alloy has been described
that can be used in sulfide environments at Rc 27 or below
(NA-383).
AISI Types 405 and 430 ferritic stainless steels in
annealed condition with Rc <22 are suitable or H2S service at
ambient temperatures (NA-383).

AM-350, AM-355, aqd 18Nimaraging steels offer no improvement over low alloy steels with regard to SSC resistance,
(HU-200). 17-4 PH, 15-5 PH, and PH 13-8Mo are susceptible to
SSC at stresses between 30% and 50% of yield (RA-347). A-286
was not susceptible at 98% of yield strength at room temperature.
The resistance of A-286 decreases as temperature increases
(TR-090). Whether or not this effect is common to all precipitation hardening steels is not known.
5.3

Titanium and Titanium Alloys

Titanium and its alloys have given good results in all


but the most extreme environments when tested for geothermal
applications. Titanium was used successfully for hydrogen and
oil coolers exposed to aerated cooling water/condensate at the
5-51

Cerro Prieto geothermal facility (GE-119). Two other heat exchanger materials had failed in this environment.
5.3.1

Uniform Corrosion of Titanium

The uniform corrosion rate of titanium and titanium


alloys tested in geothermal fluids has been less than 0.3 mpy.
The corrosion rates of these materials when exposed to worst case
conditions of aerated geothermal fluids have been good with corrosion rates of less than 0.5 mpy.
Increasing temperature and chloride concentration do
not increase uniform corrosion of titanium alloys. Experience in
seawater desalination plants indicates that fluid velocities of
30 fps have no effect on uniform corrosion. Titanium is also
very resistant to impingement and cavitation damage (GE-117).
5.3.2

Pitting and Crevice Corrosion of Titanium

No significant local corros$on should occur in environments with less than 10% chloride. Desalination and chemical
process industry experience shows that crevice corrosion in tight
crevices may be a problem in high-temperature, high-chloride
solutions similar to Salton Sea fluid. Pitting may be an occasional problem.
The dominant factors controlling localized corrosion
of titanium and its alloys are chloride concentration, pH, and
temperature.
5.3.2.1

Effect of Chloride and Temperature

The interaction of chloride concentration and tempera&


ture is given in Figure 5-18.

5-52

u
METAL SURFACE TEMPERATURE

50

100

150

200

250

180
150

v)

120

P
W

90

l01

'i

60

IMMUNE
30

100

200

300

400

METAL SURFACE TEMPERATURE

Figure 5-18.

'F

Anticipated Corrosion Performance of


Unalloyed Titanium (ASTM Grade 2) in
Chloride Brines and Under NaCl Solid
Salt Deposits (Based on data in GE-117)

The critical temperature below which localized attack


does not initiate at any chloride concentration in neutral NaCl
rolutions is about 64OC. Below 10% chloride, resistance extends
above 250OC. Localized corrosion can still occur at sites of
local high temperature or local solution concentration (e.g.,
where flashing or evaporation occurs) even though the bulk solution will not cause attack.

5-53

2,

Oxygen is required for good local corrosion resistance


of titanium in hot, concentrated chloride solutions. Titanium
crevices exposed to deaerated Salton Sea fluid at 232C underwent
severe pitting and moderate crevice corrosion; samples in aerated
(100 ppm 0 2 ) fluid were resistant to local corrosion (NE-302).
5.3.2.2

Effect of pH

In the pH range normally found in geothermal fluids,


decreasing pH lowers the usable ceiling temperature. Figure
5-19 illustrates the effect of pH on crevice attack of pure
titanium. Much better results are obtainable with small alloy
additions.

12

10

Hydrogen Pickup and


I

No Hydrogen Pickup
or Corrosion

8-

Crevice Corrosion

Temperrtun 'F

Figure 5-19.

Effect o f Temperature and pH on


Crevice Corrision of Unalloyed
Titanium (GR.2) in Saturated N a C l
Brine (FR-S-267)

5-54

5.3.2.3

Effect of Alloying on Pitting and Crevice Corrosion


of Titanium
I

Some titanium alloys are much more resistant to local


corrosion than commercially pure titanium. Ti-0.2Pd is the most
resistant alloy (TA-134, SH-333) but may cost 70% more than
titanium. TiCode-12 has almost equal resistance (CO-598) and
may cost only about 20% more than titanium. Ti-1.5Ni, Ti-1.7W,
and Ti-1OV have given good results in Salton Sea tests. Ti-0.2Pd
and TiCode-12 have usable temperature ceilings above 260C in
the pH range anticipated in geothermal streams.
Figure 5-20 shows the effect of pH on crevice corrosion of TiCode-12. These results should be compared with those
for pure titanium in Figure 5-19.

No Hydrogen Pickup
or Corrosion

Figure 5-20. Effect of'Temperature and pH on Crevice


Corrosion of TiCode-12 (Gr.. 12) in Saturated
NaCl Brine (FR-S-267)

5-55

5.3.3

Galvanic Coupling and Other Precautions

Titanium is cathodic to most other metals in saline


environments. If the titanium area is large compared to the
other metal to which it is coupled, the second metal may corrode
severely.
Since titanium is the cathode in most galvanic couples,
hydrogen can be formed on titanium coupled to an active metal.
Titanium is capable of absorbing hydrogen and becoming embrittled
Some Ti-Ni alloys are susceptible to hydrogen em'(CO-598).
brittlement in desalination service (GE-117).
Titanium-tube-to-Monel-tubesheetcrevices strongly
resist crevice corrosion, but this couple has caused pitting of
titanium under salt scale at sites some distance from'the crevice. Titanium-to-Type 316 crevices are also resistant to
crevice attack. Tight titanium-to-Teflon crevices are much more
susceptible to attack than titanium-to-titanium crevices.

Iron particles left in scratches on titanium can initiate pits (CO-598). Care must be taken to avoid scratching the
tubes with ferrous alloy tools.
High-density, powder metallurgy titanium alloys are
generally comparable to wrought equivalents. They offer cost
advantages for complex shapes. MgCl inclusions in powder
metallurgy titanium serve as nucleation sites for pitting. A
low magnesium alloy will give better service than one containing
a few ppm MgC12 (BO-270).

5-56

5.3.4

Stress Corrosion Cracking of Titanium Based Alloys

Commercial titanium alloys are not considered to be


susceptible to cracking in 3% NaCl solutions at ambient temperatures. However, precracked specimens of many fail rapidly in 3%
NaCl solutions. This behavior indicates that the resistance of
some titanium alloys is dependent on the integrity of the protective oxide ilm and not on the intrinsic resistance of the
alloy lattice (BO-A-314). SCC should therefore not be a major
problem, provided that components are not pre-cracked during
fabrication and that the design does not allow excessive vibration of titanium parts.
The susceptibility of precracked titanium alloys to
SCC is adversely affected by aluminum, tin, manganese, cobalt,
and/or oxygen content. Some alloys containing more than 6 percent aluminum are especially susceptible. Additions of molybdenum,
niobium, or vanadium reduce or eliminate the.susceptibility to
chloride-enhanced propagation of cracks in precracked specimen
(BO-A-314).
Table 5-5 lists resistant alloys and alloys-which
are sensitive in the precracked condition.
Only chloride, bromide, or iodide ions are effective

as cracking agents. Fluoride, hydroxide, sulfide, sulfate, nitrite, nitrate, perchlorate, cyanide, and thiocyanate have no
effect. Different alkali or alkaline earth cations have little
effect on cracking (BE-A-501).
Both hydrogen embrittlement and active path dissolution
are involved in the mechanism of crack propagation (BO-A-314,
MA-705, CO-598).

5-57

TABLE 5-5
SENSITIVITY OF TITANIUM ALLOYS TO CRACK PROPAGATION
Titanium Alloys Which
Undergo Accelerated
Crack Propagation in
Ambient 3 wt. % NaCl

Titanium Alloys Which


Do Not Undergo Accelerated
Crack Propagation in
Ambient 3 wt. % NaCl

Unalloyed Ti (with high oxygen content, i.e., 0.317 percent)


Ti-8Mn
Ti-2.25Al-lMo-llSn-5Zr-O.2Si (IMI-679)
Ti-3Al-llCr-13V
Ti-4Al-4Mn
Ti-5Al-2.5Sn
Ti-6Al-2.5Sn

Ti-2A1-4Mo-4Zr
Ti-4Al-3Mo-lV
Ti-5Al-2Sn-2Mo-2V
Ti-6A1-2M0
Ti-6Al-2Sn-lMo-lV
Ti-6A1-2Sn-lMo-3V
Ti-6Al-2Cb-lTa-0.8Mo
Ti-6.5Al-5Zr-lV

Ti-6Al-4V
Ti-6Al-3Cb-2Sn
Ti-6A1-4V-lSn
Ti-dAl-4V-2Co
Ti-6Al-6V-2.5Sn
Ti-7A1-2Cb-1Ta
Ti-7Al-3Cb (as received and beta
annealed)
Ti-7Al-3Mo

Ti-7Al-2.5Mo (as received and


beta annealed + WQ + 1100 F,
aged for 2 hr)

Ti-7Al-3Cb-2Sn
Ti-8Al-lMo-lV
Ti-8Al-3Cb-2Sn

Reference:

BO-A-314

5-58

5.4

Nickel Based Alloys

High nickel alloys are frequently used to combat severe


corrosion problems. The Ni-Cr-Mo alloys appear to be the most
applicable to high temperature geothermal fluids. Similar alloys
containing iron in place of molybdenum face competition from the
most resistant stainless steels, but may find application where
their mechanical properties are desirable. Cupronickels will
have limited usefulness in geothermal streams containing even
trace quantities of H2S.
5.4.1

General Corrosion Resistance of Ni-Cr-Mo Alloys

The higher ranked members of this class of alloys such


as Inconel 625 and Hastelloy C-276 have given excellent
resistance to corrosion in geothermal systems. These two alloys
can normally tolerate very high flow rates and occasional aeration. Effects of alloy composition are complex, but high molybdenum content is important for best corrosion resistance. Some
pitting and crevice corrosion has been observed for Hastelloy G
in both Salton Sea and Raft River fluids. Inconel 600 contains
no molybdenum and was attacked at a rate of 10 mpy in 1% NaC1,
pH 5, 10 ppm H2S solution at 250C (SH-381). In the same tests
Hastelloy C-276 and Inconel 625 corroded at only 0.2 mpy.
t

5.4.2

Stress Corrosion Cracking of Nickel Based Alloys

Nickel-based alloys contain more than 45% nickel and


should therefore have good resistance to SCC.. If interstitial
carbon is not kept low (<0.004%), these molybdenum-bearing nickel
based alloys may be susceptible to SCC in heat affected zones from
welds (ST-A-563).

5-59

The following alloys were resistant in the unsensitized


state to boiling MgC12 for 15 days: Inconel 625, Inconel X-750,
Inconel 825, Monel K-500, Hastelloy C, Hastelloy C-276, and
Hastelloy C-4 (WA-347, ST-A-563). Other nickel-based alloys may
also be resistant to SCC,.
5.4.3

Sulfide Stress Cracking and Hydrogen Embrittlement

Monel (Rb 63) and K-Monel (Rc 37) were completely resistant to sulfide stress cracking during the standard NACE test
at ambient temperatures (HU-200, VO-067). Monel K-500 (Rc 36)
was resistant at 98% YS. Inconel 625 (Rc 20 and 39), Inconel
X-750 (Rc 37), and Inconel 718 (Rc 34) were resistant at 98% YS.
Hastelloy C-276 (Rc 41) and Hastelloy G (Rc 35) were also resistant (WA-347).
Hastelloys G and C-276, and Inconel 625 are susceptible
to hydrogen embrittlement when coupled to steel. In the presence
of dissolved oxygen, no H2S is required; but H2S reduced the
time-to-failure (KA-A-301). The effect of coupling to steel has
not been documented for other nickel-based alloys.
5.4.4

Intergranular Corrosion of Nickel Based Alloys

The mechanism of intergranular corrosion of Hastelloy


C, C-4, and C-276 is slightly different than that for austenitic
stainless steels. At carbon concentrations greater than 0.004%
a molybdenum-rich carbide (M6C) forms in the temperature range
649"C-l204"C,depleting molybdenum in the grain boundaries.
The molybdenum depleted zones are attacked by reducing acids
(ST-A-563) and 'could be affected by geothermal fluids.

5-60

5.5

Copper Based Alloys-

The use of copper alloys in geothermal fluids is


severely limited by the relatively high concentrations of sulfide found in most sources. The Raft River -KGRA, with a low
sulfide concentration of 0.1 ppm, appears to be an exceptional
case. Even in this fluid the performance of copper-nickel alloys
(Monel 4 0 0 , 70Cu/30Ni, and 9OCu/lONi) was very poor. Dealloying
of some copper alloys was observed. However, some nickel-free
brasses and bronzes gave acceptable performance (MI-305).
The cracking of some copper-based alloys, especially
a brasses, exposed to ammonia or ammonia derivatives is well
known under the name "season cracking" (FO-118). When cracking
is caused by ammonia species, cupric complexes {Cu(NH3)n+2 1 are
required at the metal surface in significant quantity. An
adsorbed layer of O2 or a thin oxide film also seems.necessary
(BO-A-313, PU-A-068). Unless: the NH3 or NHs+ level is high,
cracking by ammonia species in the liquid phase of geothermal
fluid should be limited to stagnant areas. Ammonia in the steam
phase could concentrate in moisture films, posing a considerable
hazard.
pH has a considerable effect on SCC of copper-based
alloys by ammonia species. Cracking does not appear to occur
at pH <3.9. Between 3.9 and 4.7 a red coating is formed and
cracking is transgranular. From pH 4.7 to 7.5 thin tarnish
films form, and the cracking is intergranular. At pH >7.5, no
film forms and cracking is again transgranular.

gsit

The susceptibility of copper-zinc brasses to cracking


by ammonia species increases with increasing zinc concentration.
In Cu-Ni brasses the susceptibility is maximum at about 10% Ni.
Resistance increases sharply above %30% Ni. The resistance of
5-61

i
i

Lid
Cu-A1 alloys is lowest between 1 and 2% A1 and increases sharply
above %5% A1 (PU-A-068).
SCC of admiralty brass under anodic polarization but
in the absence of ammonia has been observed (KA-A-302).
5.6

Applicability of Other Metallic Materials

A number of other metals and alloys may either have


important specialized but limited uses in geothermal applications or have not shown promise in geothermal tests. These
materials are discussed in this section.
5.6.1

Cobalt Alloys

Cobalt alloys may find application in services requiring high strength combined with resistance to sulfide stress
cracking and in services requiring wear resistance.
MP35N resists sulfide stress cracking at high yield
strengths and may be useful for well instrumentation cables,
pump springs, and other downhole tools. Haynes 2 5 was resistant
to very high velocity acidified Salton Sea fluid during a shortterm test (AU-064). No pitting or crevice corrosion of Haynes 6B, another wear-resistant alloy, was observed in Raft River
field tests.
Cobalt-base alloys generally have good resistance to
sulfide stress cracking. MP35N (Rc 51), MP159 (Rc 46); Haynes
Alloy 25 (Rc 47), were resistant at 89% YS (WA-347). Stellites
1 and 6 were also resistant (FR-233). However, MP35N may be
susceptible to sulfide stress cracking when coupled to a more
active metal such as iron (TR-090). The effect of galvanic

5-62

coupling on the SSC resistance of other cobalt alloys is not


known.
Alloys MP35N and MP159 are resistant to stress corrosion cracking in boiling MgC1, (WA-347). Data about other
cobalt alloys are lacking.
I

5.6.2

Zirconium and TantBlum

Zirconium and tantalum may be considered for severe,


hot acid chloride service such as injection nozzles for acidifying fluid with hydrochloric acid.
5.6.3

Aluminum Alloys

Aluminum alloys have not shown good resistance in


tests conducted in direct c.ontact with geothermal fluids. Low
levels of transition metal ions, especially copper and mercury,
greatly increase localized attack of aluminum alloys. These
ions are present in most liquid-dominated geothermal fluids.
Rapid pitting of a1
test coupons was observed in condensate and cooling water at
Cerro Prieto, Mexico (GE-11.9).
Aluminum alloys are subject to severe attack when galvanically coupled to almost any other metal likely to be used
in a geothermal plant.
Exterior siding and structural components of aluminum
are likely to give adequate service due to the good atmospheric
corrosion behavior of aluminum and resistance to occasional H2S
emissions. Fluoropolymer-coated aluniinum exterior sliding panels
are used in new housings at The Geysers power plant.

5-63

5.7

Condensate

The corrosivity of condensate streams depends to a


large extent on the following factors:
Efficiency of steam separation and thus
the chloride content of the condensate,
Quantity of the flashed noncondensable gases
C02, H2S, and NH3 which are absorbed by the
condensate,
pH of the condensate resulting from absorption of the above gases,
Aeration or mixing with aerated water.
These factors are interactive. Higher chloride concentrations
can be tolerated if the condensate is not aerated. The pH of
the condensate depends primarily on the amount of acidic C02
and H2S absorbed relative to basic NH3. The pH in turn determines the corrosivity of dissolved H2S and CO2 in contact with
mild steels. For most sources the NH3 is low compared to CO2
and H2S and the condensate pH will be fairly'low.
Previous sections can be consulted for discussion of
and oxygen. Corrosion problems
effects of pH, H2S, C02, " 3 ,
have occurred in the condensate systems of several operating
geothermal plants (see Appendix A). Although condensate streams
have relatively low chloride concentrations, their potential
corrosivity should not be underestimated.
Even with very efficient steam separation the chloride
content of the condensate can be high enough to cause problems.

5-64

For example, assuming 25% flashing of a wellhead liquid containing 1% chloride and 0.05% liquid carryover, the condensate
would contain about 20 ppm chloride. This is approximately
equal to the minimum chloride concentration needed to cause
pitting of plain steels at 25C (SZ-020).

If the condensate is aerated and temperature is greater


than 60" to 80"C, stress corrosion cracking of austenitic stainless steels could occur at this chloride concentration.
5.8

Steam from Liquid-Dominated Geothermal Sources

Steam from liquid-dominated geothermal fluids has


corrosion characteristics of its own, but general corrosivity
is dominated by two properties common to the saline fluid and
condensate streams.
Carryover of entr ined liquid provides the
chloride needed for localized attack. Highvelocity impingement of droplets is conducive
to localized attack. Efficient steam separation and steam scrubbing are important, but
may not preclude attack. For a given steam
separation and scrubbing e f f i c i e n c y , corrosivity may depend on the chloride content and
corrosivity of the liquid stream.
Areas where local condensation may occur are
subject to attack by low pH condensate containing H2S, C 0 2 and some chloride. Most
noteworthy of these locations are the low
pressure turbine section, liquid traps and
poorly insulated or stagnant parts of steam
transfer sections. The latter should be
eliminated by design.

5-65

5.8.1

General Corrosion in Geothermal Steam

Corrosion rates of low alloy steels in steam flow


from several geothermal sources are summarized in Table 5 - 6 .
Uniform corrosion rates in oxygen-free steam are generally low
except in separated Salton Sea steam. The reason for high cor-.
rosion rates in this steam is unclear. One possible explanation
'may be the entrained liquid. Each entrained liquid drop contains
essentially the same high chloride concentration as the wellhead
liquid. The metal surfaces in the steam flow are exposed to
these chloride concentrations in impinging droplets and not just
the diluted concentration of the condensate. The low chloride
contents quoted for the steam phase may therefore be misleading.
Steam scrubbing can reduce the number of drops but
not the chloride concentration of each drop; little reduction
in corrosion rate after steam scrubbing was found. It is also
noteworthy that the localized corrosion susceptibility of
resistant alloys is similar in Salton Sea wellhead liquid, separated steam, and scrubbed steam.
5.8.2

Corrosion Fatigue

Although corrosion fatigue occurs in both steam and


liquid media, this failure mode is discussed in this section
because turbines operating in geothermal steam are subject
to both environments. Turbines are the most important components in a geothermal plant that will be subject to corrosion
fatigue.
Metals under cyclic loading fail at stresses far
below those characterizing their normal mechanical properties.
When this phenomenon occurs in "inert" environments, (i.e. air),

5-66

TABLE 5-6
CORROSION OF PLAIN AND LOW ALLOY STEELS IN STEAM
FROM LIQUID-DOMINATED SOURCES
S i t e l s t e a m Source

Temp
('C)

PH'
(Condensate)

____

Chloride
(condensate)
(PPd

"2s

Ppm (-1

co2

East Mesa
~F i r s t Flash

Second Flash

5.2

3000-5000'

5.2

3000-50003

5.1

200-5002

5.7

200-5002

Uoisture

Uniform
Corrosion

ppm ( v t )

Local
Corrosion2

S t e e l Type

2.1

AISI 1020

1.3

AISI 4130

3.1

AISI 1020

2.5

AISI 4130

AISI 1020

S a_
l t o_
n -Sea
_
F i r s t Flash
Scrubbed F i r s t Flash

190*

6.15

120

10-20

3,900-6,600

-0.1%'

26

I90*

6.15

120

10-20

3,900-6,600

-0.1%'

7.7

AISI 4130

21-40

AISI 1020

-LYok

-LOO*

Second Flash
Scrubbed Second Flash

-173

6.10

50

-178

6.10

50

-178*

-L78*
Cerro P r i e t o .
--

18

AISI 4130

<0.1x5

25

A I S I 1020

<0.1z5

8.2
18-27

AISI 4130
AISI 1020

25

AISI 4130

M f

Single Flash

150

13

2,000

19,500

<1%

1.6

1 Cr-1.3 Mo-O.25V

15il

13

2.000

19,500

<1%

0.7

3.5 Ni-1.75 Cr0.4 Mo-O.1V

:so

13

2.000

19,500

<1%

1.6

<1%

<l.O

Carbon s t e e l s

<1%

c1.0

Carbon Mn s t e e l s

Wairakei, &N
S i n g l e Flash

190
190
140

nil

140

1,500

<1%

140

nil

140

1,500

<I%

140-160

115

:15

'Measured n e a r ambient temperature


2~

crevice corrosion

none d e t e c t e d

p i t t i n g corrosion

'Data d i s t o r t e d by c o n t r o l v a l v e problems
"Calculated
'Calculated from c h l o r i d e c o n c e n t r a t i o n i n condensate.
P i t t i n g and c r e v i c e c o r r o s i o r i r a t e s a r e given in S e c t i o n

143160

4.

ASTM A285

Carbon s t e e l s
Carbon Mn s t e e l s

10%

1.0-10

Carbon s t e e l s

10%

1.0-10

Carbon Mn s t e e l s

10%

Carbon s t e e l s

10%

Carbon Mn s t e e l s

it is called fatigue. When the applied stress range is plotted


against the logarithm of the number of cycles to failure (S/N
plot), the cycle-to-fail curve becomes asymptotic to a limiting
value of stress, and below this stress there will be no failure,
no matter how long the test. This is the "fatigue limit"
(GI-122, WE-317).
When the metal is exposed to a corrosive environment
while under cyclic stress, the S/N graph never becomes asymptotic
to the zero stress line. The corrosion fatigue 1imit.is the
greatest unit stress which may be applied under given conditions
of stress, rate of stress application, temperature, and corrosive environment without causing it to fail in a given number
of cycles of stress (WE-317). The values for "corrosion-fatigue
limits" are useless, except for comparison within one set of
tests, unless the number of cycles and cycle rate are given.
The combined effects of cyclic stress and corrosion
are often far more severe than the simple sum of their actions.
5.8.2.1

Low Alloy Steels

Based on tests of two alloys at Cerro Prieto, Mexico,


corrosion fatigue of low alloy steels is a significant factor
in material selection and design. After 150 days exposure to
nonaerated steam, the reduction in fatigue endurance limit (FEL)
of 1Cr-1.3Mo-0.25V [ Rb% 641 was 27.8% while 3.5Ni-1.75Cr-0.4Mo0.1V [Rb%68] showed a 38.6% reduction of FEL. These specimens
were not under cyclic stress during exposure. Cyclic loading
during exposure would have caused greater loss of endurance.
Some of the considerations for low alloy steels in
contact with corrosive liquids are discussed below in relation
to corrosion fatigue.

5-68

Tests on carbon s t e e l s and low and middle a l l o y s t e e l s


i n f r e s h , s a l t and s e a w a t e r show t h a t endurance l i m i t s i n a
m o d e r a t e l y c o r r o s i v e medium, ( i . e . s a l t w a t e r ) , a r e p r a c t i c a l l y

independent o f t h e chemical composition o f t h e s t e e l (ME-A-243).


A series of c o r r o s i o n f a t i g u e t e s t s w e r e done i n a

s o l u t i o n c o n t a i n i n g 34,400 ppm C 1 s o l u t i o n w i t h a d d i t i o n s of
A I S 1 1035 specimens were s t r e s s e d l o 7 c y c l e s a t
C 0 2 , H 2 S and 0 2 .
1 0 Hz (ME-A-243). C h l o r i d e had no s i g n i f i c a n t e f f e c t on t h e
f a t i g u e endurance of low a l l o y s t e e l s . I n a n e u t r a l , a i r - f r e e

(<0.1 ppm 0 2 ) s o l u t i o n , t h e f a t i g u e endurance l i m i t (compared


t o t h e f a t i g u e endurance l i m i t i n a i r ) i n c r e a s e d s l i g h t l y .
A d d i t i o n o f 3000 pprn H2S t o t h e c h l o r i d e s o l u t i o n
lowered t h e pH t o 4.5. The endurance l i m i t d e c r e a s e d 20%, and
c r a c k i n g and hydrogen b l i s t e r i n g o c c u r r e d . The e f f e c t of H 2 S
on h a r d e r m a t e r i a l s may be much more s e v e r e . These m a t e r i a l s
w i l l be cold-worked under c y c l i c s t r e s s and may become suscept i b l e t o s u l f i d e s t r e s s c r a c k i n g as w e l l a s c o r r o s i o n f a g i t u e .
A d d i t i o n of 700-800 ppm f r e e C 0 2 and 250-300 ppm H C 0 3
t o t h e c h l o r i d e s o l u t i o n reduced t h e pH t o 5 . 5 and reduced t h e
f a t i g u e endurance l i m i t 41%. Many c r a c k s w e r e o b s e r v e d . A l though C02 does n o t c a u s e s t r e s s c o r r o s i o n c r a c k i n g , i t a p p e a r s
t o be a n e f f e c t i v e c r a c k i n g a g e n t when combined w i t h c y c l i c
stress.

The combined e f f e c t o f C 0 2 and H 2 S i s worse t h a n t h e


sum o f t h e i r a c t i o n s . I n a c h l o r i d e s o l u t i o n c o n t a i n i n g 700-800
ppm f r e e C 0 2 and 60-70 ppm H2S, t h e f a t i g u e endurance l i m i t
d e c r e a s e d 62%. Both p i t t i n g and s u r f a c e c r a c k i n g w e r e o b s e r v e d .

5-69

The a d d i t i o n of l e s s t h a n 10 ppm O 2 d r a s t i c a l l y reduced


t h e f a t i g u e endurance l i m i t i n t h e c h l o r i d e s o l u t i o n (65% reduct i o n ) . A d d i t i o n of 3 ppm O 2 doubled t h e r e d u c t i o n i n endurance
l i m i t i n t h e c h l o r i d e / H , S s o l u t i o n , b u t caused l i t t l e i f any
i n c r e a s e i n damage i n t h e c h l o r i d e / C 0 2 s o l u t i o n .

5.8.2.2

S t a i n l e s s Steels

R e s u l t s from Cerro P r i e t o (Table 5 - 7 ) i n d i c a t e t h a t


i n c r e a s i n g chromium o r adding molybdenum a n d / o r t u n g s t e n r e d u c e s
t h e d e c r e a s e of f a t i g u e endurance l i m i t (FEL).
TABLE 5-7
REDUCTION I N FATIGUE ENDURANCE L I M I T AT
CERRO PRIETO AFTER 150 DAYS EXPOSURE

Alloy

Hardness
(approximate)

Reduction in
FEL %

18.5

12 Cr
12 Cr-1Mo-1W
12 Cr-0.2Al

15Cr-1.7Mo

%
%

74
49

41

14.6
18.8
11.7

%
I

- ..

Reference :

GE-119

Type 616, Type 4 0 3 , and M152 s t a i n l e s s s t e e l s were


t e s t e d a t Baca f o r 160 d a y s . Reductions i n FEL of 36 t o 52
p e r c e n t w e r e observed o v e r 1 6 0 d a y s . 1 2 C r m a r t e n s i t i c s t e e l was
more r e s i s t a n t t h a n t h e more a l l o y e d s t e e l s (TO-089).
I n n e i t h e r t h e t e s t s a t Cerro P r i e t o n o r Baca w e r e t h e
samples under c y c l i c s t r e s s d u r i n g exposure t o t h e geothermal
steam. C y c l i c l o a d i n g d u r i n g exposure would have caused more
severe damage.

5-70

The stainless steels are more resistant to corrosionfatigue than the low alloy and carbon steels. Chromium is the
most effective alloying element in the absence of H 2 S , while
nickel is more effective against H2S (WE-317). Best results are
obtained with a combination of chromium and nickel ( G I - 1 2 2 ) .
Molybdenum is also beneficial (WE-317).
5.8.3

Exfo1iation

Exfoliation of iron sulfide scales from steam lines is


another potential source of damage to turbines operating directly
on flashed steam. Iron sulfide coatings form on steel pipes
carrying steam containing H2S. There is a tendency for these
coatings to crack and flake off. If this occurs in lines upstream of the turbine, the scale particles can be carried to the
turbine causing erosion and possibly erosion-corrosion damage.

This problem has been encountered at the Cerro Prieto


geothermal plant. Measures taken to prevent turbine damage are
given in Appendix A . 2 . 4 . 2 .

A much slower exfoliation of magnetite scales has

caused serious damage to turbines in high temperature-high pressure fossil fuel plants. In most cases no damage was noted
until the plant was 10-15 years old. This experience accentuates
the need for close monitoring and frequent inspection of geothermal turbines.

6.0

NONMETALLIC MATERIALS

The search for construction materials in geothermal


environments has concentrated primarily on metallic materials,
but applications of nonmetallic materials are receiving increasing attention. Nonmetallic materials are required in some geothermal operations such as elastomers in drilling operations.
In other areas, they may be cost-effective replacements for metallic materials. Nonmetallic materials have some advantages.
They are generally resistant to corrosion at conditions that may
adversely affect metals and alloys, and their installation costs
may be lower than for metals. However, nonmetallic materials
are subject to degradation, and geothermal fluids severely test
their durability. Nonmetallics are not useful in heat transfer
equipment.

The performance of nonmetallic materials in geothermal


environments is in the early stages of investigation, and the
test results are somewhat limited. Some comparisons and trends
may be found by examining the results of nonmetallics in desalination fluids and from conventional drilling technologies.
Testing of nonmetallics as desalination materials has been conducted in flowing sea water u p to 250F (121OC).
Although these
temperatures are somewhat low f o r some geothermal applications,
the data are useful as general guidelines.
Nonmetallic materials that may find geothermal applications are:

1) concrete polymer composites,


2) cements,
3 ) elastomers,
4 ) fiber reinforced plastic laminates,

6-1

5)

thermoplastics,
6) fiber reinforced plastic and coated pipe, and
7) paints and coatings.

No systematic attempt has been made to identify processing steps


in a geothermal facility where nonmetallics may be used.

6.1

Concrete Polymer Composites

Brookhaven National Laboratory is conducting a program


to develop polymer concrete materials for geothermal app'lications. Polymer formulations and polymer concrete composites
which can be used as materials of construction for handling geothermal brines and steam at temperatures up to 260C (500'F) are
being investigated.
Formulations with the following constituents have produced monomer systems suitable for geothermal conditions.

1)

styrene - trimethylolpropane trimethacetylate


(TMFTMA)

2)

styrene - acrylonitrile -

3)

Derakane

TMPTMA

0-triallyl cyanurate

Acrylamide, methacrylamide, and crosslinking agents are being


added to styrene - acrylonitrile formulations to determine the
optimum compositions. The durability of polymer concrete is
dependent upon the aggregate composition. Above 218OC, only
polymer concrete materials containing mixtures of silica sand
and portland cement have been resistant to geothermal brine and
steam. The presence of portland cement in the aggregate greatly

6-2

enhances the durability. The evidence indicates that CaO reacts


chemically with the -CH2 groups in the monomers. Table 6-1
gives the compressive strength as a function of temperature for
a number of polymer concretes. The results in Table 6-1 are for
mortar containing fine aggregate consisting of 70 wt % silica
sand and 30 wt % Type 111 Portland cement. This composition is
representative of the material that will be used in thin-wall
pipe or as a lining material. Higher strengths result if larger
size aggregate is included.
TABLE 6-1
HIGH TEMPERATURE STRENGTHS OF POLYMER-IMPREGNATED MORTAR
Test Temperature
"C

21
66
150
175
204
238

13,889
14 154
12,154
13 619
9,475
11,207

Compressive Strength, psi


B
C
11 782
10,948
10,222
13 898
9,786
9 632

10,069
10 334
8,427
8,282
10,453
10,308

D
9 487
7,838
8,102
8,180
6 600
6,197

Monomer Formulations :
A. 55 wt % styrene - 36 wt % acrylonitrile - 9 wt % TMPTMA
B. 50 wt % styrene - 33 wt 7, acrylonitrile - 17 wt % TMPTMA
C. 60 wt % styrene - 40 wt % TMPTMA
D. 70 wt % Derakanea 470 - 30 wt X, triallyl cyanurate
Refermce: KU-161, KU-162
The structural durability of polymer concretes has been
tested both in the laboratory and field in simulated brine,
flowing brine, flashed brine, and steam at temperatures up to
26OoC. Laboratory data for exposure times greater than two
years are available, and field tests of over 18 months have been
conducted. Some of the field tests are still in progress. A

6-3

summary of t h e r e s u l t s of l a b o r a t o r y and f i e l d t e s t s i s g i v e n
i n Table 6-2.

6.2

Cements

Cements f i n d p o s s i b l e a p p l i c a t i o n s a s c o r r o s i o n r e s i s t a n t l i n i n g materials and i n w e l l c o n s t r u c t i o n .


Improved cementing m a t e r i a l s f o r t h e c o n s t r u c t i o n of
geothermal w e l l s are needed t o i n c r e a s e w e l l l i f e expectancy.
S p e c i f i c a t i o n s f o r w e l l cementing m a t e r i a l s a r e l i s t e d below:

1) Compressive s t r e n g t h , >lo00 p s i 2 4 hours


a f t e r placement.

2)

P e r m e a b i l i t y t o w a t e r , <0.1 m i l l i Darcy.

3)

Bond s t r e n g t h t o s t e e l c a s i n g ,

4)

S t a b i l i t y , no s i g n i f i c a n t r e d u c t i o n i n s t r e n g t h
o r increase i n permeability a f t e r prolonged

>lo

psi.

exposure a t 400C (%750"F) t o 2 5 % b r i n e s o l u t i o n s , f l a s h e d b r i n e , o r dry s t e a m .

5)

Placement a b i l i t y , c a p a b l e o f 3 t o 4 h r .
r e t a r d a t i o n a t e x p e c t e d placement t e m p e r a t u r e s .

6)

C o m p a t i b i l i t y of t h e cement w i t h d r i l l i n g mud.

7)

Non-corrosive t o s t e e l w e l l c a s i n g .

Polymer c o n c r e t e s and i n o r g a n i c cements such as C-S


cements and phosphate bonded g l a s s cements a r e b e i n g i n v e s t i g a t e d as p o t e n t i a l cementing materials.

6-4

TABLE 6-2
POLYMER CONCRETE TESTING IN GEOTHERMAL FLUIDS
Location

Conditions

Duration

Results

Laboratory

25% brine, 238C

325 days

Laboratory
Laboratory
Laboratory

25% brine, 177C


pH 1, HC1, 90C
pH 1, HC1, 200C

760 days
441 days
170 days

Geysers
Baca
Raft River
Raft River
Raft River
East Mesa
Niland

steam, 238C
flashed brine, 160'C
fluid, 135C
fluid, 150C
400 ppm brine, 204C
brine, 160C
brine, 220C

18 months
180 days
90 days
312 days
in progress
60 days
in progress

Reference : KU- 161, KU-162

Some slight corrosion at


corners; no previous
deterioration
No deterioration
No deterioration
No deterioration in silicaportland cement aggregates;
limestone aggregates cracked
after 25 days
No deterioration
No deterioration
No deterioration
No deterioration
No deterioration

Corrosion resistant cements may also find applications


as lining materials. Five corrosion resistant cements were
tested for twelve months at 25OoC, 30 psi in flowing seawater
during a study of desalination materials. The results of the
test are shown in Table 6-3. Only Prekrete G - 8 withstood the
exposure and did not degrade or break. Prekrete G-8 gave excellent service for six years in a desalination facility at Freeport, Texas.
TABLE 6-3
PERFORMANCE OF CORROSION RESISTANT CEMENTS
IN 250F S a m T E R (12-MONTH E X P O S U T

Name

Type

Appearance

Prekrete G-8

Alumina-Silicate

Excellent condition

SaureisenElectrical Refractory
Cement, No. 75

Calcium Aluminate

Good condition

Prekrete C-17

Calcium Oxide

Fair condition

Lumnite

Calcium Aluminate

Poor condition

SaureisenPourlay No. 54

Sodium Silicate

Complete failure

2eference GE-117

6.3

Elastomers

Elastomers have applications in geothermal drilling


technology. The Department of Energy is conducting research to
develop elastomers for geothermal use. Five research programs
are involved in various phases of the development and testing
of elastomers for use in geothermal wells. The goal is to seek
new materials and define tests methods for geothermal

6-6

applications. Of particular interest are packer seals and drill


bit cutter cone seals. The approaches range from basic research
to applied development and include synthesis of new polymers,
investigation of new but available (at high cost) elastomers,
modification of commonly known materials and development and
evaluation of test methods.
The goals of the five research programs are described
below.

1.) Test seals produced from new materials. A special device which simulates the environment of the cutter cone
has been developed.
Develop packer seals and a simulated test device
for down-hole condition duplication. The materials used for
packer seals are common hydrocarbon elastomers.
2.)

3 . ) Synthesize new quinoxaline and styrene type elastomers and investigate the modification of existing commercial
materials for packer seals. Tensile properties, thermal stability and stress relaxation tests are being conducted.

Synthesize new fluorinated elastomer systems and


look at carboranesiloxane (Ucarsil) systems. These materials
are being tested for thermal and hydrolytic stability, compression set, hardness and tensile properties.
4.)

Study the feasibility and value of coating O-ring


seals in an RF glow discharge apparatus.
5.)

The results of these ongoing studies are described in


Appendix D.

6-7

These programs have revealed that conditions are so


severe and different from those in other applications of elastomers that nearly all previous test data are of very little
value. Thermal stability is usually measured in an oxidative
atmosphere. The results of thermal stability tests give little
indication of polymer performance under typical geothermal
stresses such as reducing atmospheres and hydrolysis. Furthermore, some unpredicted reactions can take place at the extreme
pressures of the well. Elastomers for geothermal uses must be
investigated under appropriate test conditions.
6.4

Fiber Reinforced Laminates

Fiber reinforced plastic (FRP) laminates may be useful


because of their high corrosion resistance and reasonable cost.
FRP materials have not been adequately tested in geothermal
systems, but an indication of their potential can be obtained
from the results of testing in desalination environments (GE117). Table 6 - 9 summarizes the results of exposing FRP laminates to flowing seawater at 250'F
for 15 months. At high temperatures, only Bis-A epoxy systems and halogenated vinylester
Derkane @ systems gave acceptable results. Testing of FRP materials in geothermal environments is required.
6.5

FRP and Coated Pipe

Nonmetallic piping materials have been tested in desalination facilities (GE-117). Glass reinforced epoxy piping
systems were found to be acceptable for handling brines in the
210'F
to 250'F
range. Additional testing of nonmetallic pipes
should be conducted for geothermal applications.

6-8

TABLE 6 - 4

FRP LAMINATES I N FLOWING SEAWATER AT 2 5 0 " F , 30 PSIG


AFTER 1 5 MONTHS OF EXPOSURE

Resin Tested
Dow Epoxy-Novalac XD7380

m
I
a

F1exural
S t reng th

Percent Retention
Flexural
Tensile
Modulus
Strength

Appearance
Rating**

103

94

74

32.1

Shell Bis-Epoxy Epon@ 828

79

77

66

29.0

DOW Bis-A-EpOXy D. E. R. -331

55

88

46

28.3

Dow Hal. Vinylester Derakane@ 510

72

91

66

39.7

Dow Vinylester Derakane@ 470.45

47

99

43

26.9

Dow Vinylester Derakane@ 411.45

42

65

42

40.4

Quacorr Furane

39

46

35

40.0

Atlas Hal. Polyester Atlac@ 711.05

35

92

32

43.6

Reichold Bis-A-Epoxy Epotuf@ 37-130

43

71

29

69.3

Atlas Bis-A-Polyester Atlac@ 382.05

25

74

23

53.3

Atlas Bis-A-Polyester Atlac@ 4010-A

23

43

17

70.0

Hooker Ortho-Polyester Hetron@ 197

17

38

23

70.7

Freeman Ortho-Polyester Polylite@ 33.040

25

24

17

74.0

Reichold Ortho-Polyester Polylite@ 33-402

13

20

14

75.0

Freeman Iso-Polyester Stypol@ 40.2989

12

17

14

34.0

Freeman Iso-Polyester Stypol@ 40.2187

13

16

15

77.8

PPG Iso-Polyester Selectron@ 5899

74.0

PPG Iso-Polyester Selectron@ 5899

Freeman Ortho-Polyester Stypol@ 40.2187*

*Higher density air bubble inclusion.


0 = No change.
100 = Complete failure.
***Not tested due ta degradation of sample.
Reference : GE-117

***

***
***

79.8
77.4

6.6

Thermoplastics

Polysulfone has shown no sign of thermal distortion


or change in physical properties in seawater tests at 250'F.
The durability of thermoplastics in geothermal environments is
unproven.

6-10

7.0

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7-1

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7-2

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HI-191

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7-5

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Hoar, T . P , and J . G. Hines, "The S t r e s s - C o r r o s i o n


Cracking o f A u s t e n i t i c S t a i n l e s s S t e e l s , P a r t 1,
Mechanism of t h e P r o c e s s i n Hot Magnesium-Chloride
Solutions", J . Iron S t e e l I n s t . 1 8 2 ( 2 ) , 124-43

(1956).
HU-199

Hudgins, C h a r l e s M . , J r . , "Review o f S u l f i d e
Corrosion Problems i n t h e Petroleum I n d u s t r y " ,
Mater. P r o t . 8 ( 1 ) , 41-47

(1969).

Hu-200

Hudgins, C . M . , e t a l . , "Hydrogen S u l f i d e Cracking


o f Carbon and A l l o y S t e e l s " , Corrosion 22 ( 8 ) , 23851 (1966).

HU-A-2 3 3

Hudson, P. E . , e t a l , "Absorption o f Hydrogen by


C a t h o d i c a l l y P r o t e c t e d S t e e l " , Corrosion 2 4 ( 7 ) ,
189 (1968).

IO-A-21

I o f a , Z . A . , V. V. Batrakov and Cho-Ngok-Ba,


" I n f l u e n c e o f Anion Adsorption on t h e Action o f
I n h i b i t o r s on t h e Acid Corrosion o f I r o n and
C o b a l t " , E l e c t r o c h i m . Acta 9 , 1 6 4 5 - 5 3 ( 1 9 6 4 ) .

I J - A - 003

I j z e r m a n s , A . B. and Van Der K r o g t , " P i t t i n g


Corrosion of an A u s t e n i t i c C r - N i S t a i n l e s s S t e e l
i n H 2 S 0 4 c o n t a i n i n g HPS", Corros. S c i . 8 , '679-87

(1968)
50-262

Johnson, M. J . , " R e l a t i v e C r i t i c a l P o t e n t i a l s
f o r P i t t i n g Corrosion o f Some S t a i n l e s s , S t e e l s " ,
i n L o c a l i z e d Corrosion Cause o f Metal F a i l u r e ,
ASTM STP 5 1 6 , P h i l a d e l p h i a , ASTM, 1 9 7 2 , pp. 262-72.

7-6

L d
KA-280

Kane, Russell D. and J. Brison Greer, "Sulfide


Stress Cracking of High-Strength Steels in
Laboratory and Oilfield Environments", Paper No.
SPE 6144, NY, AIME, 1976.

KA-A-301

Kane, R. D., et al., "Factors Influencing the


Embrittlement of Cold Worked High Alloy Materials
in H2S Environments", Corrosion 33(9), 309 (1977).

KA-A-302

Kawashima, A., A. K. Agrawal, and R. W. Staehle,


"Stress Corrosion Cracking of Admiralty Brass
in Nonamxnoniacal Sulfate Solutions", J. Electrochem. SOC. 124(11), 1822 (1977).

KU-161

Kukacka, L. E., et al., Alternate Materials of


Construction for Goethermal Applications, Progress
Report No. 13 April June 1977, ERDA Contract No.
EY-76-C-02-0016,BNL 50699, Upton, NY, Brookhaven
National Laboratory, Dept. of Applied Science,
Process Technology Div., undated.

KU-162

LA-312

Kukacka, L. E., et al., Alternate Materials of


Construction for Geothermal Applications, Progress
Report No. 14 July - September 1977, ERDA Contract
No. EY-76-C-02-0016,BNL 50751, Upton, NY, Brookhaven National Laboratory, Dept. of Applied Science,
Process Technology Division, undated.
Lawrence Berkeley Laboratory, Geothermal Water
Data File, updated periodically, Berkeley, CA,
various dates.

w
1

7-7

LA-A-338

L a t a n i s i o n , R. M. and R. W. S t a e h l e , "Stress
Corrosion Cracking o f Iron-Nickel-Chromium Alloys",
i n Fundamental Aspects of Stress Corrosion Cracki n g , Ohio S t a t e U n i v e r s i t y , Sept. 1967, Conference
Proceedings, pp. 2 14f f .

LE-A-338

Leckie, H. P . , "A Contribution t o t h e A p p l i c a b i l i t y


of C r i t i c a l P i t t i n g P o t e n t i a l s " , J . Electrochem.
SOC. 117(3), 1152 (1970).

LI-A-230

L i z l o v s , E. A . , "Corrosion Resistance o f Types 316


and 317 S t a i n l e s s S t e e l s i n Simulated SO2 Scrubber
Environment", J . Electrochem. Soc. 124(12), 1887
(1977).

LO-208

Lombard, G. L . , Test and Evaluation of a Geothermal


Heat Exchanger, f i n a l r e p o r t , PB 247 218, EPRI 376,
RP 376, San Diego, CA, San Diego Gas & E l e c t r i c
Co., Sept. 1976.

LO-A- 240

Loginow, A.W., J . F. Bates, and W. L. Mat.hay,


"New Alloy Resists Chloride Stress Corrosion
Cracking," Mater. Perform. 1 1 ( 5 ) , 35 (1972).

MA-668

Marshall, T. and W. R. B r a i t h w a i t e , "Corrosion


Control i n Geothermal Systems," i n Geothermal
Energy, R e v i e w of Research and Development,
E a r t h Science Series No. 1 2 , P a r i s , UNESCO,
1973, pp. 151-60.

MA-672

Marshall, T. and A. J . H u g i l l , "Corrosion by


Low-pressure Geothermal Steam," Corrosion 1 3 ,
329t (1957).

7-8

MA-682

Marshall T. and A. Tombs, "Delayed Fracture


of Geothermal Bore Casing Steels," Aust. Corros.
Enp;. 13(9), 7 (1969).

MA-705

Mauney, D. A., E. A. Starke, Jr., and R. F.


Hochman, "Hydrogen Embrittlement and Stress
Corrosion Cracking in Ti-A1 Binary Alloys,"
Corrosion 29(6), 241 (1973).

MA-A-770

Makrides, A.C. and Norman Hackerman, "Effect


of Thiourea Compounds on Dissolution Rate of
Iron and Mild Steel," I&EC 47(9), 1773 (1955).

ME-A-243

Mehdizadeh, Parvis, R. L. McGlasson, and J. E.


Landers, "Corrosion Fatigue Performance of a
Carbon Steel in Brine Containing Air, H2S and
Con,' I Corrosion 22(12) , 325 (1966) .

ME-S-250

Mercado, Sergio, "Corrosion by Geothermal Fluids


in Cerro Prieto, B.C.N. Mexico," Paper No. 60,
Presented at the NACE National Conference, Corrosion/78, Houston, Texas, March 1978.

MI-305

Miller, R. L., Results of Short-term Corrosion


Evaluation sts at Raft River, TREE-1176, DOE
Contract EY-76-C-07-1570,EG&G Idaho, Inc.,
Oct. 1977.

NA-383

National Association of Corrosion Engineers,


Technical 'Practices Committee, Materials for
Valves for Resistance to Sulfide Stress Cracking in Production and Pipeline Service, Material Requirements, NACE Standard MR-01-75,
(Replaces NACE Publication 1F166), Houston,
Texas, March 1975.
7-9

NA-423

National Association of Corrosion Engineers,


Technical Practices Committee, Testing of
Metals for Resistance to Sulfide Stress Cracking at Ambient Temperature Test Method, NACE
Standard TM-01-77, Houston, Texas, July 1977.

NE-207

Neumann, P.D. and J.C. Griess, "Stress-Corrosion


Cracking of Type 347 Stainless Steel and Other
Alloys in High Temperature Water," Corrosion 19,
345t-53t (1964).

NE-302

Needham, P. B., Jr., et al., Materials for the


Construction of Geothermal Resource Recovery
Plants, draft report, College Park, MD, College
Park Metallurgy Research Centr., 1977.

OH-S- 039

Ohki, Teruhisa, et al., "Effect of Inclusions


on Sulfide Stress Cracking," Presented at the
Symposium on Line Pipe and Tubular Goods, Hollywood, FL, June 1977.

PE-268

Pessall, N. and J. I. Nurminen, "Development


of Ferritic Stainless Steels for Use in Desalination Plants, ' I Corrosion 30, 381 (1974).

PO-230

Posey, F. A., A. A. Palko, and A. L. Bacarella,


Corrosivity of Geothermal Brines Progress Report for Period Ending June 1977, DOE Contract
No. W-7405-eng-26, ORNL/TM-6159, Oak Ridge, TN,
Oak Ridge National Laboratory, Nov. 1977.

7-10

PU-A-068

Pugh, E. N., J. Y. Craig, and A. J. Sedriks,


"The Stress-Corrosion Cracking of Copper,
Silver, and Gold Alloys," in Fundamental Aspects
of Stress Corrosion Cracking, Ohio State University, Sept. 1967, Conference Proceedings, pp. 118ff.

SC-448

Scale Management in Geothermal Energy Development, San Diego, CA, Aug. 1976, Conference
Proceedings, ERDA Contract No. E(11-1)-2607,
Newton, MA, EIC Corp., 1976.

SH-333

Sheppard, R. S., et al., "Performance of


Titanium vs. Other Materials in Chemical
Plant Exposures , ' I Corrosion 18, 211t-18t (1962).

SH-S-379

Shannon, Donald W., "The Role of Chemical Components in Geothermal Brines on Corrosion", paper
no. 57, presented at the NACE National Conference,
Corrosion/78, Houston, TX, March 1978.

SH-381

Shannon, Donald W., Corrosion of Iron-Base Alloys


Versus Alternate Materials in Geothermal Brines,
interim report, ERDA Contract No. #Y-76-C-06-1830,
PLN-2456, Richland, WA, Battelle Pacific Northwest
Laboratories, Nov. 1977.

SM-160

Smith, John H., "Casing Failures in Geothermal


Bores at Wairakei," paper G/44, in United Nations
Conference on New Sources of Energy, Rome, August
1961, vol. 3, NY, United Nations, 1964, pp. 254
ff.

7-11

SM-A-184

Smialowski, Michael, Hydrogen in Steel, New York,


Pergamon, 1962.

SM-A-191

Smith, Carroll A., and Kenneth G. Compton,


"Potentials of Selected Metal Alloys in Seawater
at Elevated Temperatures," Corrosion 31(a), 320
(1975).

SN-060

Snape, E., "Roles of Composition and Microstructure in Sulfide Cracking of Steel," Corrosion 23,
154 (1967).

SN-061

Snape, E. "Roles of Composition and Microstructure in Sulfide Stress Cracking of Steel," Corrosion 24, 261 (1968).

SP-104

Spaepen, G. J. and M. J. Fevery-DeMeyer,


Electrochemical Corrosion Experiments at
Temperatures Above 100C," Corros. Sci. 7,
405-13 (1967).

ST-A-563

Streicher, Michael A . , "Effect of Composition and


Structure on Crevice, Intergranular, and Stress
Corrosion of Some Wrought Ni-Cr-Mo Alloys , I t
Corrosion 32, 79 (1976).

ST-566

Staehle, R. W., et al., ed., Localized Corrosion, Williamsburp;, VA, Dec. 1971, Conference
Proceedings, International Corrosion Conference
Series NACE-3, Houston, TX, NACE, 1974.

ST-A-570

Steigerwald, R. F., et al., "The New Fe-Cr-Mo


Ferritic Stainless Steels," Corrosion 3 3 ( 8 ) ,
279 (1977).

7-12

id

al

a
*VI

w
0

N
h

rl
v

d
a

l4

cv

al n

cn

0 k
GI 0

(d

al
N
*rl

u
a

-4 k

-u

cd

k
0

cd

c 5
3
.VI

c
m
0

cd

*rl 00

pc

cl

U
i
!lrl
3

m
I
3
a
a d

m
k
k

'td

*rl

24
5

ch u

al

Ei

*I4

al

al

0
u

m
0
k
k

*rl

a o

0 k
9 u
a w

.h
k
0
U

cd

n
d
v

sal

3 cdm

23

m
m

rl
I

cn

rl

m
0
k
k

co
I

cd

fk
al

a
k

c$

U pc

cd

s
8

v)

1
m

al

rl

F9

e
k

rl

0
4
m
0

k
k

U
L

rl

cd

n 0
d al

n
up1
a u
k 3
u

w *rl
u
co
N

0 H

0
rl

cn

a
al

s
m

or(

pc

al
a

n
b
QI

d
d
W

a
c
cd

0
ra

*rl

aJ

rl

al

m e
alo

d
I

*rl

0
al

w
w

i
3

!il

al

cd

-w

F9

c43
N

VI

0
N

cn

U
U
al

cd

cn

*d

m
I

TA-136

Tardiff, George E., "Using Salton Sea Geothermal


Brines for Electrical Power: A Review of Progress in Chemistry and Materials Technology-1976
Status," preprint, Presented at the 12th Intersociety Energy Conversion Engineering Conference,
Washington, DC, Aug. 28-Sept. 2, 1977.

TO-085

Tolivia, E., "Corrosion Measurements in a Geothermal Environment , I ' U.N Symp. on the Development and Utilization of Geothermal Resources, Pisa 1970, Vol. 2 (part 2), pp. 15961601.

TO-089

Toney, S. M. Cohen, and C. J. Cron, "Metallurgical Evaluation of Materials for Geothermal


Power Plant Applications ," Geotherm. Energy
Mag. 5(9), 9 (1977).

TR-054

Truesdell, Alfred H. and Wendy Singers, "The


Calculation of Aquifer Chemistry in Hot-Water
Geothermal Systems, USGS J. Research 2 (3),
271-78 (1974).

TR-090

Troiano, A . R. and R. F. Hehemann, Materials


Research and Evaluation for Geothermal Corrosion Environments, Progress Report for Period
December 15, 1975-December 15, 1976, ERDA
Contract No. EY-76-5-02-2602,Cleveland, OH,
Case Western Reserve University, Dec. 1976.

TR-S- 119

Troiano, A. R. and R. F. Hehemann, "Hydrogen


Sulfide Stress Corrosion Cracking in Materials
for Geothermal Power," Paper No. 59, Presented
at the NACE National Conference, Corrosion/78,
Houston, Texas, March 1978.

7-14

u
VO-067

Vollmer, L. W., "The Behavior of Steels in


Hydrogen Sulfide Environments , ' I Corrosioh 14,
324t-28t (1958).

WA-347

Watkins, M. and J. B. Green, "Corrosion Testing


of Highly Alloyed Materials for Deep, Sour Gas
Well Environments," J. Pet. Tech. 1976 (June),
698-704.

WE-317

Wescott, Blaine B., "Fatigue and Corrosion Fatigue


of Steels," Mech. Eng. 60, 813 (1938).

WI-A-317

Wilde, B. E., "The Role of Passivity in the


Mechanism of Stress-Corrosion Cracking and
Metal Dissolution of 18Cr-8Ni Stainless Steels
in Boiling Magnesium and Lithium Chlorides,"
J. Electrochem. SOC. 118(11), 1717 (1971).

7-15

APPENDIX A
CORROSION EXPERIENCE AT OPERATING UNITED STATES
AND FOREIGN GEOTHERMAL POWER PLANTS

A-1

CORROSION EXPERIENCE AT OPERATING UNITED STATES


AND FOREIGN GEOWERMAL POWER PLANTS

Previous experience i s o f t h e utmost importance i n c o r r o s i o n engineering. This s e c t i o n summarizes t h e c o r r o s i o n experi e n c e a t Wairakei, New Zealand, Cerro P r i e t o , Plexico, and The
Geysers i n C a l i f o r n i a . The f i r s t two geothermal power p l a n t s use
liquid-dominated resources while The Geysers i s steam-dominated.
Experience from a l l t h r e e f a c i l i t i e s provides v a l u a b l e informat i o n t h a t i d e n t i f i e s p o t e n t i a l problems and s o l u t i o n s . Data from
Cerro P r i e t o are p a r t i c u l a r l y valuable because i t i s l o c a t e d n e a r
several p o t e n t i a l s i t e s f o r geothermal development t h a t have s i m i l a r f l u i d chemistry.

A.l

CORROSION AT WAIRAKEI, NEW ZEALAND

The geothermal resource a t Wairakei has been e x t e n s i v e l y


developed and t h r e e major long-term c o r r o s i o n s t u d i e s have been
r e p o r t e d . This s e c t i o n b r i e f l y d e s c r i b e s t h e Wairakei geothermal
p r o j e c t and d i s c u s s e s t h e t h r e e tests and p l a n t experience.

A.l.l

Sys t e m Description

The Wairakei geothermal resource i s liquid-dominated


and i s u t i l i z e d by s i n g l e f l a s h recovery (bore f l a s h i n g ) . Steelcased bores 150m t o 1200m deep t a p geothermal f l u i d a t temperatures up t o 270C containing COP (90-8000 ppm), H2S (3-320 ppm),
N a C l and K C 1 (1000-2000 ppm Cl'), and S i 0 2 (150-500 ppm) as major
contaminants with many o t h e r c o n s t i t u e n t s as minor contaminants.
As t h e l i q u i d phase rises up t h e b o r e , t h e p r e s s u r e and temperat u r e decrease, and t h e l i q u i d f l a s h e s i n t o a two-phase f l u i d .
Steam and water are separated a t t h e wellhead, and t h e w a t e r cont a i n i n g n o n - v o l a t i l e contaminants and some non-condensable gases

A-2

i s run t o waste. Steam, c o n t a i n i n g most o f t h e non-condensables


and less than one p e r c e n t moisture ( d r o p l e t carry-over) a t 50-200
p s i g , passes through low p r e s s u r e t u r b i n e s . A f t e r t h e t u r b i n e s ,
r
t h e steam ( a t about 40C and 1 p s i a ) i s condensed by sprays of
0 2 - s a t u r a t e d c o l d w a t e r i n j e t condensers and removed v i a a barom e t r i c s e a l . Non-condensable gases a r e removed by vacuum pumps
(FO-120).
A.1.2

The Wairakei Geothermal F l u i d

L i t t l e d e t a i l e d d a t a are a v a i l a b l e on t h e composition of
t h e geothermal f l u i d a t Wairakei. A computer r e c o n s t r u c t i o n of
t h e composition of t h e f l u i d i n t h e geothermal s'trata around Bore
This i s n o t t h e composition a t t h e
No. 20 i s given i n Table A - 1 .
surface.
A.1.3

Corrosion Tests a t Wairakei

Two s t u d i e s o f comon engineering materials w e r e performed j o i n t l y by t h e New Zealand Ministry of Works and Department
o f S c i e n t i f i c and I n d u s t r i a l Research. The I n t e r n a t i o n a l Nickel
Company a l s o r a n a series of t e s t s . Tables A-2, A-3, and A-4 summarize t h e c o r r o s i o n t e s t r e s u l t s .
I n a l l t h r e e t e s t s , t h e g e n e r a l c o r r o s i o n r a t e w a s determined by t h e ASTM A 244 coupon method. I n t h e t e s t s r e p o r t e d
i n Table A-2, t h e stress c o r r o s i o n samples were c o n s t a n t d e f o r mation s t r i p specimens s t r e s s e d beyond t h e . y i e l d p o i n t . No p i t t i n g information w a s presented i n t h e source f o r Table A-2.
In
Table A-3 t h e stress c o r r o s i o n specimens were U-bend strips,
s t r e s s e d beyond t h e y i e l d p o i n t and r e t a i n e d under stress with
a b o l t . The specimens w e r e exposed t o geothermal media intended
t o span t h e range of c o n d i t i o n s found a t t h e Wairakei p r o j e c t .

A-3

TABLE A - l

AQUIFER F'LUID ADJACENT TO HOLE 20,

Temperature

Pressure
Enthalpy
PRZ
C02 partial pressure
HzS partial pressure
DisroLved
Constituents

---

--

1.5
38.3

Nr+

4.1

I(+

Rb+
Ca

0.025

0.014

ca+z

0.43

Y-+Z

0.0

F-

0.29
0.42
0.05
0,002

c1-

Br'
1-

sob-'

0.079
1.76
0.002
7.89

BYBOY

Blao,8zC3, + cot
aq
HCO I

0.35
0.00001

co1

HISf06

7.85
0.006

0.00001

HzSiO*-'

m*

0.002

0.011

"3aq
Hn S

0.25
0.022

%a*
we

BO.
HCL'
NaCl'
KCl.

0.050
0.0023
0.00006
1.27
0.097

KlgSOr '

casob'
=ob'

NaSO.
CaCOJ
Mgo"

Concentration
(by weight)
10
880
160
2.1
1.9

17
5.5

ppm
ppm
4 . 0 ppm
250
ppb
7 . 6 ppm
io8
ppm
120
ppb
489
ppm'
21
PPm
0 . 6 ppb
9 6 . 1 ppm
600
ppb
0.9 ppb
36
PPb
190
ppb
8 . 5 ppm
720
ppb
1.00 ppm
220
ppb
2 1 . 8 ppb
7 2 . 2 ppm
7 . 2 ppm

18

0.0002

20

0.0

'AS HzCOI.

TR-054

A-4

PPm
ppm
ppm
ppm
ppm
PPm

1520

0.0
0.025
0.015
0.15

'Saturated water enthalpy i s 4Sd. 28 Btullb.


'Neutral ptI at 246OC is 5 . 6 .

Reference :

1 1 . 4 6 psia

0.13 psfa

Concentration
( m l l k g HzO)

tL+

HbSiOb'

246'C
5 6 5 . 3 psia
4 5 5 . 0 4 Btullb
6.34

3 . 4 ppm
2 . 0 3 ppm

PPm
PPb

TABLE A-2a
MATERIALS T E S T S AT WAIRAKEI, NEW ZEALAND:

6aan.l Corrosion

&are Water Swarated Water


50-100.C
125'C. 80 psi;

B n Water

-2L0.C
--

1&

.rated S t e m
180 psi;

b3-60 l a ~ ~
1.0

1.0

10

- 10

- 10
- 10
1.0 - 10

'1.0

e1.0
Q.0

q1.0

>10

1.0

--

1.0

-2.0

c1.0

1.0

c1.0
a.0
c1.0
a.0

1.0

- 10

c1.0
c1.0
a.0

1.0

- 10

<l.O

P
I
Ln

q1.0
'

q.0

11.0

a.0

Q.0

a.0

'1.0
-1.0

c1.0
<l.O

-4.0
<l.O
a.0

13 Q-k
1: Cr
17cr-m
hutdtlt

-1.0
'1.0

ss

lorrcrrotr AllWS
Ti-

c1.0

c1.0

'1.0

Ti-Al-T
-

'1.0
'1.0

1 . 0 - 10
1 . 0 10
<l.O

1.0 10
a.0
1.0 10

1.0 10
a.0
1.0
10

1.0
1.0

- 10

e1.0

1.0

failed'
'lb srmciflution f r o LS. 970

mer-

- 10

'~roprtcums m : GO.LIJZ:
m 1.251: m 0.m
'hopriet.ry .toel: c 0.181:
m 0.71: ISD 0.661
n.sI: m 3.11
'xxperiwaul s t a l t c 0.1~1: Q
.Id *dattack

Reference:

FO-120

- 10

-- 10

GENERAL CORROSION

(-1

SI arsted Steam
Aerated S t e n
me-Aerated Condamace Ireshrster Qndensat
2-1&
40-8- ps1; 9&108*C. 0.3 psu
20-70% 0-180 p . i l
IUstnre :aerar.d)
Q k i s t u r r . 144 D.Ts
lbb b T S
60-122 h Y S
67 h i e

- 10
- 10
1.0 - 10
1.0 - 10
1 . 0 - 10
1.0 - 10
1.0

- 10
1.0 - 10
1.0 -. 10
1.0 - 10
1.0

1.0

(1.0

1.0

1.0

- 10

1.0

1.0
1.0

c1.0
c1.0
<l.O

1.0 10
1.0
10
a.0

e1.0

c1.0

1.0 - 10
1.0 1.0 - 10
1.0 10
c1.0
1.0 10
10

Q.0

a.0

'1.0

c1.0

f.114'

(1.0

>10

>10

>10

>lo
.lo

>10
>10
1.0 10

- 10

- 10
- 10

- 10

c1.0

1.0

1.0
1.0
1.0

- 10

- 10
- '10

>10
a.0

a.0

10

.10

,>lo
>10
>10
.10

a.o
a.0

a.0
c1.0

-..

.... .

.,

"

~~

..

..

"

. .

. .

TABLE Pa-2b
MATERIALS TESTS AT WAIRAKEI, NEW ZEALAND:

STRESS CORROSION CRACKING

bcbnll
Wdnas.

-_

?errow Allom

on,

ceet iron

La Allo? Steels
C30-31
B96-99
190-92
B68-72

Bore c u i n 6 e

C-St.l.

WO

c-m

8tul.

c-m

8td.

BSO
B95

MO
c21-22
u 5

M5
C37-39
C27-30
Cl8-19

c48

?
m

c53
C3bJ3
CZ8-30
c25-27
-7

ni-Steel
Bish Alloy Steel.
13 R

C30

C12-28

B60-90
C30

198
M5-94
c28-42
U93-C28
B70-B90
IC1131M
lull50
B30721W3
urmlB168-4lT
1SlOM
urml120JlT
Wl20-41T
B81400
ADlC-AB2C
BS4071.
181948
W1949
B378
Alwe 3003

C38

M7

B54
163
B93
159
M9
B50

- c - o.iam
- m-

'18 .pecification fm B.8. 970


'Prvpcietary areal:
' m p c i e u r y .t..il
'Experiuntel .teal:

e33
B93-98
a 5
B65-69
B68-77
E83

n55

- 0.122:

IIII

cr

1.22: No 0.402
0.721
0.662
1 2 . l : m 3.12

Reference: FO-120

QTlOTAMd

Kn Miem

0.282:

--

0 -lo ucroecopic cracUn6

or f r u t u r e i n

e group of e p e c i u l u

Mcroewpic creckin6 or fdlurs of one o r mre s p e c i n u t s in group teated


lo microewpic surface f i u u r u detected by n t a l l o g r e p h i c exnirurion
Microscopic surface fieeuree detected by u t a l l o g r e p h i c a n i n a t i o n
(rOn: lo chemical d y e e e of tha u t d e or of tb. test d i e ere eveilable)

I
(of)
(I)

....

.. .

~__

.- - .. . .~.
.

0
(1) 0
09
01
9
09

01
6

OL
09

t-

TABLE A-3b
CORROSION STUDY AT WAIRAKEI: STRESS CORROSION CRACKING
McXIIIc

1 of

s
m
1 P

he-xien
Dparatel
Steam
LO pal8
141.C

30-32
37
70
45
65

-30
40
43

30
40
41
4 0 4
41
40
4s

?
00

012
212

012

212

017
OIL
012
OIL
013
012
014
012
011
012
012

216

-31s
011

212
012
013
012
012
01 3
012

012
011
213
012
011

012
012

012
212

---

011

012
012

012
013

011
012

012
013

3s

so

--

--

-O I L
011

--

---

WI

012
012

2s
30

rill

212
212

26

Chrome ?lata (6 m i l )

014
012

--

012

30

Galvanired (1.5

011
012

011

40

h e e d Steel
Nickel P l e t e (10 m i l )

014
012

012
011
011
011
012

IS

A l w l n u ( A l e 0 0 35)

St.P

105.C
)=n.oVo

--

1C

Ti t a n i w

rS-30 PPI
0 ~ 6 0 0DDI

Aerated

--

---

rhrr Baael

ondenaote
1.C pW6

012

--

111
011

Referenee: MA-672

TABLE A-4
INTERNATIONAL NICKEL COMPANY CORROSION TESTS
AT WAIRAKEI, NEW ZEALAND

~~

Non-Aerated
Steer
General
Corrosion
( w )

(wv)
-

2.9
3.8

no p l t s

--

no p i t s

2.4
(0.1

no p i c e

--

--

nu p i t s

--

IK)

-----

no pit.

(0.1

no p i t s

2.8
5.2
0.1
(0.1
(0.1

no p i t s
no p i t s
no p l t s
no pit.
no p i t s

--

--

10Ni-SAL-bronze

--

pits

---

1.3

Growth of
Deepeat
Plt'
bpy)

General
Corrosion

no p i t a
nu p l t n

8.0
14.3
8.4
0.9

no p l t s

2.3
5.0
0.1

<O.l
co.1

--

no p i t s
no p l t s
no p i t s
no p i t s
no p i t s

Corrosion
( 3 Y1

--pit.

8.9
10.5
8.9
4.6

IIQ

no p i t a
4.6

C t a t t h of
Deepest
Pith

(w)

no pit.
29.7

no pit.

no pit.
no pit.

C0.l

--

no pit.

--

co.1
co.1

6.0

(0.1
0.2
0.1
0.3
co.1

no p i t s
29.8
23.8
20.5

CO.1

M pits

1.6

CO.1

(0.1

no p l t s
110 p i t s

co.1
c0.1

29.7
23.8
20.5
M pita
no pit.
no pit.

---

---

-----

10.8

4.0

1.7

0.5

-- .

-----

--

General

Growth of
Deepest
Pltl
(wy)

(UPY)

-no p i t s
no p i t a
-no p 1 t s
-no p i t s
------

--

<o. 1

capper b a s e

Growth of
kepest
Plt'

Turbine
Dimclmr8a

Aerated
Condensate

Nan-Aereted
Condensate

0.1

0.1

<O.l

--

---

----

29.8

29.8

(-) means no r e s u l t reported.

'Growth of deepest p i t based on depth o f nnxlmur p i t a f t e r 552 deye exposure.


'Sena i t I sed.
Dcncrlptlon o f Test h i v i r u n w n t s
Won-Aerated Steam:

F i e l d spool test holder I n geotltermal s t e a n l l n e . Temperature


1 percent nuncondensable Bases (IlaS. CO'. CII.).

Non-Arrnted Condensate:

-Aerated

--- - - - -

Temperature

116%. pH

5.25.

147*C-l53'C.

Cuntalna Cot. HIS and Nllr.

Cornlenscite: feml'ctrclttira
50%. pll
7.8, IICOS 662 ppu. Nlla
216 ppm. )(os
1 ppm,
C1
7 ppu. 1) 18 ppu, f r r u S
13 ~ ~ I I ITIIS..
119 p p ~ .
Ttrrblw Dlacltarwel Pield'upuul Imlder brtweeii t u r b i n e r ~ i db n r o m t r l c cudenmar. T e w r r o t u r e

Reference: BA-539

Steam eontaiaa

SO4

159 p p ,

52C.

A,1.3.1

General Corrosion
Because of chemical impurities in geothermal steam, particularly chlorides,
"2s and CO2, corrosion rates of common
engineering alloys are usually higher
than those encountered under similar
conditions of temperature and pressure
in clean boiler plant steam.
Corrosion of most common engineering
alloys in air-free geothermal media,
with the exception of some copper
alloys, is low enough to insure
adequate service life. Mild steel
is adequate for air-free service if a
moderate corrosion allowance is made.
Aeration of geothermal media drastically
increases (ten-fold or more) the corrosion of most engineering alloys with
the exceptions of austenitic stainless
steels (especially those containing
molybdenum), titanium, and chromium plated
steels. Galvanizing is unsuccessful in
aerated geothermal media.
Corrosion rates of most alloys in bore
water at 250C are 19w cornpared to those
in lower temperature media. Pitting is
characteristically absent in bore water
at 250C.

A-10

bd

A. 1.3.2

Erosion-Corrosion

Empirical tests at Wairakei indicated that the following steels have sufficient resistance to erosion-corrosion by
water droplets in steam (containing 9% moisture) at 900 fps (exhaust-end blading environment) to serve as turbine blading: 13
Cr, 18/8/1 Cr-Ni-Cb, 18/12/1 Cr-Ni-Cb, 18/8/3 Cr-Ni-Mo, "Rex 326,"
35/10 Ni-Cr. Erosion-corrosion resistance is directly related to
static corrosion resistance and not to hardness as is often assumed (MA-672).
A.1.3.3

Stress Corrosion Cracktng (SCC) of Austenitic


Stainless Steels

Tests indicate that even under conditions of high


stress, austenitic stainless steels are not susceptible to SCC
in oxygen-free media. In the presence of dissolved oxygen, the
lower temperature and chloride concentration limits appear to
be 50C and 5 ppm C1-. There appears to be no lower critical
stress limit for SCC.
A.1.3.4

Hydrogen Sulfide Effects

At Wairakei the following observations were made concerning sulfide stress cracking (SSC) :

Medium.and high strength steels are


susceptible to SSC in geothermal media
up to at least 190C.
Mild steels and low strength alloys
resist SSC even under severe constant
deformation tests. The highest safe

A-11

t e n s i l e s t r e n g t h appears t o be 88 k s i *
f o r carbon and low a l l o y steels and
110-120 k s i f o r high chromium a l l o y s .

L+

S u s c e p t i b i l i t y t o SSC i s o f t e n r e l a t e d t o
hardness r a t h e r than y i e l d s t r e n g t h (HU-200).
13 C r turbine blading was r e s i s t a n t a t a
hardness below B r i n e l l 180 (Rc-8) and
vulnerable above B r i n e l l 190 (Rc-11).
Delayed f r a c t u r e can occur i n s e v e r e l y
notched low s t r e n g t h a l l o y s exposed t o
c o l d H2S-bearing condensate a t s t r e n g t h s
below 88 k s i .
H2S-bearing dry steam i s innocuous.
SSC of h i g h l y s u s c e p t i b l e steels d i d n o t
occur i n bore water a t 240C b u t d i d occur
i n t h e same water a t 50C.

B l i s t e r i n g h a s been observed i n some


low s t r e n g t h a l l o y s .
Hydrogen i n f u s i o n rates decrease t o very
low values a f t e r two t o t h r e e weeks exposure
above lOO"C, probably because of c o r r o s i o n
films.
Permeation r a t e can be g r e a t l y reduced by
s u r f a c e c o a t i n g s such as Apexior No. 1
p a i n t o r by chemically formed Fe304 c o a t i n g s .
*ksi

thousand pounds p e r square i n c h .

Ld
A- 1 2

There i s an i n v e r s e r e l a t i o n s h i p between
i n f u s i o n r a t e and temperature i n bore
water due t o t h e formation of magnetite
a t higher temperatures. The magnetite on
t h e i r o n s u r f a c e appears t o impose a
b a r r i e r (equilibrium and/or k i n e t i c ) which
reduces t h e hydrogen concentration below
t h e corroding s u r f a c e (FO-123).
A.1.4

P l a n t Experience a t Wairakei

Overall p l a n t experience (MA-668), erosion and thermal


s t r e s s of production casings (SM-160), and w e l l casing problems
(FO-119) have been documented f o r t h e Wairakei power p l a n t .
A. 1 . 4 . 1

Bore Casings and Wellhead Equipment

Conventional low s t r e n g t h API grades 5-55 and H-40 production casings have been used. 5 - 5 5 has been adopted a s t h e
b e s t compromise between s t r e n g t h and s u s c e p t i b i l i t y t o s u l f i d e
s t r e s s cracking. I n t e r n a l corrosion h a s been minimal. Erosion
by e j e c t e d sand has been c o n t r o l l e d by s l o t t e d production
liners.
External corrosion of s u r f a c e casings has been severe
near t h e s u r f a c e where a e r a t e d ground water c o n t a c t s t h e c a s i n g s .
Multiple casing with c a r e f u l cementing of t h e a n n u l i has cont r o l l e d t h i s problem.

Thermal s t r e s s i s s e v e r e . It can exceed 60 k s i and may


cause mechanical f a i l u r e o f l o w s t r e n g t h casing a l l o y s . High
s t r e n g t h a l l o y s (N-80 and above) should be avoided because of
s u l f i d e s t r e s s cracking. The medium s t r e n g t h s u l f i d e r e s i s t a n t
'French s t e e l APS 10M4 has shown promise i n l a b o r a t o r y tests a t

i I)
A-13

Wairakei (MA-682). Thermal stress may be a l l e v i a t e d by careful


cementing t o avoid unsupported r e g i o n s . Careful cementing a l s o
prevents t h e formation of trapped w a t e r pockets which w i l l c o l l a p s e t h e c a s i n g once production i s begun. Keeping bores flowi n g after i n i t i a l "blow-in" w i l l reduce thermal stress and prev e n t t h e formation o f c o l d , nonaerated HzS-bearing condensate--the
main source o f s u l f i d e stress cracking.
Wellhead equipment o f low s t r e n g t h s t e e l s w i t h s t a i n less s t e e l valve t r i m h a s performed s a t i s f a c t o r i l y . External
protectj.on ( p a i n t o r cladding) a g a i n s t c o r r o s i o n by a i r b o r n e
c h l o r i d e sprays and steam i s r e q u i r e d . Transmission p i p e l i n e s
of carbon s t e e l are s a t i s f a c t o r y i f t h e media remains a i r free.
A i r inleakage must be avoided.

A.1.4.2

Turbines

The t u r b i n e s a t Wairakei are made of conventional t u r b i n e c o n s t r u c t i o n materials (cast s t e e l c a s i n g s , carbon s t e e l


r o t o r s , 13 C r s t e e l b l a d e s , shrouds, and l a c i n g s ) h e a t t r e a t e d
t o a low s t r e n g t h c o n d i t i o n . The shrouds and l a c i n g s are mechani c a l l y a t t a c h e d r a t h e r than brazed t o avoid l o c a l hardening o f
t h e 13 C r s t e e l . The rivets are annealed. Care i s used t o seal
t h e j o i n t s i n low p r e s s u r e casing as thoroughly as p o s s i b l e t o
avoid a i r i n g r e s s and a c c e l e r a t e d c o r r o s i o n by a e r a t e d media.
Blade v e l o c i t i e s are l i m i t e d t o 900 f p s and moisture t o 9 p e r c e n t t o avoid excessive blade c o r r o s i o n . These t u r b i n e s have
given good s e r v i c e .
A. 1.4.3

E l e c t r i c a l Equipment

Atmospheric H,S t a r n i s h e s copper and s i l v e r c o n t a c t s .


Erosion-corrosion o f copper c o n t a c t s exposed t o H2S i s r a p i d .
A t Wairakei, s i l v e r c o n t a c t s are replaced i n c r i t i c a l equipment

A-14:

L4
t

1
i

w i t h platinum c o n t a c t s . This problem h a s been s t u d i e d e x t e n s i v e l y


a t The Geysers i n C a l i f o r n i a . Their r e s u l t s are given i n S e c t i o n
A.3.4.

1
I

I
!

i
I

i
I

A.2

CORROSION AT THE CERRO PRTETO GEOTHERMAL POWER PLANT

The Cerro P r i e t o geothermal power p l a n t has operated


s i n c e 1973. I n s p i t e o f some s e r i o u s material problems, t h e p l a n t
has operated continuously except f o r scheduled downtimes. The
Cerro P r i e t o p r o j e c t provides o p e r a t i n g experience and c o r r o s i o n
t e s t d a t a from a s i n g l e - f l a s h , liquid-dominated system. The simil a r i t y between Cerro P r i e t o geothermal'media (Table A-5) and t h e
f l u i d s of East Mesa, H o l t v i l l e , and Heber, C a l i f o r n i a i n d i c a t e s
t h a t c o r r o s i o n phenomena may be similar a t a l l s i t e s , and Cerro
P r i e t o experience w i l l a i d i n t h e design of f u t u r e power p l a n t s .
A.2.1

Syst e m Description

The Cerro P r i e t o geothermal resource i s liquid-dominated.


Surface m a n i f e s t a t i o n s cover an area of about 30 square k i l o m e t e r s .
The u t i l i z a t i o n mode i s s i n g l e - f l a s h ( b o r e - f l a s h i n g ) . A s of 1976,
53 deep w e l l s had been d r i l l e d i n t h i s area w i t h depths o f 70Om
t o 200Om. F l o w i s o b t a i n e d through p r e s l o t t e d or gun p e r f o r a t e d
casings a f t e r cementing t h e production c a s i n g , except t h e bottom
150m t o 30Om, where h o t s t r a t a a r e l o c a t e d . High enthalpy water
a t 275-320C flows through t h e p e r f o r a t e d c a s i n g and i s conducted
t o t h e s u r f a c e through t h e 7 5/8" production c a s i n g (SC-448). As
t h e w a t e r ascends through t h e production c a s i n g , t h e h y d r o s t a t i c
p r e s s u r e drops and t h e water p a r t i a l l y f l a s h e s t o steam. The
flow through t h e w e l l t r e e i s a two-phase f l u i d c o n t a i n i n g from
20 t o 40 weight p e r c e n t steam. The f l u i d i s passed through a
Webre type c e n t r i f u g a l s e p a r a t o r a t t h e wellhead (SC-448) and
through a secondary s e p a r a t o r a t t h e power p l a n t (GE-119). The
s e p a r a t e d water i s s e n t t o an evaporating pond (SC-448).

A-15

TABLE A-5

COMPAFUSON OF FLUIDS FROM PRODUCTION


WELLS AT CERRO P R I E T O
M u m
(UCU

Uter-ILUh
npidl

(ppn)

8.35'
22.28
633
6.913
1JbO
b63
0.16
l3.205
18
5T.82

--

6.32

18
7.14

i
I
1

550
0.35

16e l 2 9
K
59.11

U.b8

36.4

34.9

L0.9
25.2

0.03

0.89
< 0.03
co.01

c0.5

0.26

0.54
0.15
(0.01

0.02

0.01

,
I

II
1
I

I
Source:

1,315
6,229
2.032

13
18.b
9.1
15.3

7.90'

n .K3

&3K

A- 16

l2.3
15
0.03

1.1
< 0.03
co.01
c 0.5

--

0.7

co.01

20 t o 80 tons/ho lr of s t
t 100 p s i g are obtained
from each w e l l . A s o f 1976, 13 w e l l s provide steam t o maintain
two u n i t s o f 3 7 . 5 MW each, a t f u l l load, a t a steam r a t e of 9.4
kg/&lh (SC-448).
A.2.2

Cerro P r i e t o Geothermal Fluid

Based on i s o t o p i c a n a l y s e s , t h e Cerro P r i e t o geothermal


f l u i d i s meteoric and i s derived mainly from t h e Colorado River
(SC-448). The production s t r a t a i s sandstone w i t h a lava overlay.
The geothermal f l u i d i s s a t u r a t e d w i t h s i l i c a (from q u a r t z ) a t
t h e temperatures and p r e s s u r e p r e s e n t i n t h e production s t r a t a
(SC-448). Analyses of geothermal f l u i d from t h r e e production
w e l l s are given i n Table A-5. The t h r e e analyses (from 115 presented i n LA-312) show t h e range of b r i n e compositions a t Cerro
Prieto.

A.2.3

Corrosion Tests a t Cerro P r i e t o

From 1969 t o 1970 a c o r r o s i o n test program w a s performed


j o i n t l y by t h e Comision Federal de E l e c t r i c i d a d of Mexico and
Tokyo Shibaura Company (Toshiba) of Japan. The purpose w a s t o
confirm t h e c o r r o s i o n r e s i s t a n c e o f previously s e l e c t e d materials
t o be used f o r c o n s t r u c t i o n of t h e power p l a n t which w a s ordered
i n 1968.
Coupons were used i n t h e g e n e r a l corrosion t e s t . The
stress c o r r o s i o n specimens were U-bend s t r i p s s t r e s s e d beyond the
y i e l d p o i n t and r e t a i n e d under stress by a b o l t . The e r o s i o n c o r r o s i o n specimens were c y l i n d e r s 6 c m long and 1 e m i n diamter
(GE-119). The r e s u l t s of t h e tests and d e t a i l s of t e s t condit i o n s a r e p r e s e n t e d i n Table A-6. Compositions and uses of materi a l s t e s t e d are i n Table A-7. No d i s t i n c t i o n w a s made between
stress c o r r o s i o n cracking and s u l f i d e stress cracking.

A-17

I
I

TABLE A-6a
CORROSION STUDY AT CERRO P R I E T O

Sten

I'

TABLE A-6b
CORROSION STUDY AT CERRO PRIETO:

hp.d to k r a t d

Lfon Capwun

Sten

- -

13.S

s3.9

S1.3

28.4

*
I

EFFECT ON MECHANICAL PROPERTIES

-- --

41.0
bS.2

39.3
31.7

39.9
54.)
24.3
1.1

43.1

- -

50.7

-- - -

2b.l

31.0
17.1
1b.S

47.3
bS.3
39.0

3e.1
11.3
24.0
10.8

30.8

lij
19.9

If

11.1

11.4

21.3
2b.S
13.9
14.s

- I-

15.4

n.r
10.)

I15.2

n.r

-. .

....

...

._

.,

..I.

__

... ..

., . .-..I.__.I"

__ ._".
. ...-

... , . .. ,.

. ...

. -. .

..

TABLE A-7
CHEMICAL COMPOSITION AND USE OF MATERIALS TESTED AT THE
CERRO P R I E M GEOTHERMAL POWER PLANT

AI

0 . m

l-cr-0-0.25 v
1 . 5 Cr-1 1s-0.25 WI

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A. 2.3.1

Corrosion Results i n Steam


Low Alloy Steels
The c o r r o s i o n r a t e of carbon s t e e l (ASTM
A285) i n nonaerated steam w a s s a t i s f a c t o r y
(1.6 mpy) f o r t u r b i n e c a s i n g and p i p i n g .
Aeration of t h e steam almost doubled t h e
corrosion rate.
The c o r r o s i o n r a t e of 1 Cr-Mo-0.5 V s t e e l
w a s s i m i l a r t o t h e corrosion of carbon s t e e l
i n nonaerated steam. Microscopic cracks
were observed i n the stress corrosion specimen. Aeration increased general c o r r o s i o n
rates by a f a c t o r of f i v e . One of two stress
c o r r o s i o n specimens f a i l e d .

I n nonaerated steam t h e g e n e r a l c o r r o s i o n
r a t e of 3.5 Ni-Cr-Mo-V a l l o y w a s less than
1 Cr-Mo-0.5 V a l l o y . It w a s n o t stress
c o r r o s i o n tested i n nonaerated steam. The
endurance l i m i t decrease w a s 39 p e r c e n t .
Aeration increased general c o r r o s i o n 20
t i m e s . S t r e s s c o r r o s i o n specimens showed
intergranular attack.
I n a e r a t e d steam 1 . 5 Cr-1A1-0.25 Mo a l l o y
( n i t r i d e d s t e e l ) showed a p a r t i a l s p a l l i n g
b u t had good general c o r r o s i o n r e s i s t a n c e .

IV

A-21

I n nonaerated steam aluminum w a s n o t corroded.


Aeration of steam l e d t o p i t t i n g i n excess of
100 mpy.
S t a i n l e s s Steels
I n nonaerated steam, 1 2 C r a l l o y (used f o r
t u r b i n e buckets) had a v e r y low (<0.5 mpy)
g e n e r a l c o r r o s i o n r a t e . There w a s s l i g h t
p i t t i n g . It w a s n o t s u s c e p t i b l e t o s t r e s s
c o r r o s i o n cracking. Resistance t o e r o s i o n corrosion was a c c e p t a b l e . There w a s no change
i n t e n s i l e s t r e n g t h , only a s l i g h t decrease
i n y i e l d s t r e n g t h , and a decrease i n endurance
l i m i t (15 t o 1 9 p e r c e n t ) . Aeration increased
general corrosion t e n t i m e s and p i t t i n g 70
t i m e s . Microscopic cracks were observed on
t h e stress c o r r o s i o n specimen.
I n nonaerated steam 1 2 Cr-Mo-W s t e e l w a s comp a r a b l e t o 1 2 C r i n terms of general c o r r o s i o n ,
p i t t i n g , and stress corrosion cracking. Erosionc o r r o s i o n r e s i s t a n c e w a s b e t t e r than 1 2 C r
s t e e l . Changes i n mechanical p r o p e r t i e s w e r e
similar t o 1 2 C r s t e e l . Aeration caused a
ten-fold increase i n general corrosion, a
seventy-fold i n c r e a s e i n p i t t i n g , and i n t e r g r a n u l a r c o r r o s i o n of t h e stress c o r r o s i o n specimen.
I n nonaerated steam, 1 2 Cr-0.2 A 1 a l l o y (used
f o r nozzle p a r t i t i o n s ) had a low g e n e r a l c o r r o s i o n r a t e . No p i t t i n g w a s r e p o r t e d . The
a l l o y w a s r e s i s t a n t t o stress c o r r o s i o n and
erosion-corrosion r e s i s t a n c e w a s s i m i l a r t o

A-22

1 2 C r s t e e l . Aeration increased general c o r r o s i o n t o a lesser degree than f o r 1 2 CR-Mo-W


s t e e l , and no p i t t i n g w a s r e p o r t e d . 15 Cr-1.7
Mo s t e e l w a s n o t s u s c e p t i b l e t o stress c o r r o s i o n
i n a e r a t e d steam. Erosion-corrosion r e s i s t a n c e
w a s q u i t e good. Changes i n t e n s i l e and y i e l d
s t r e n g t h w e r e n o t as severe as f o r 1 2 Cr-Mo-W.
A.2.3.2

Corrosion R e s u l t s i n Condensate*
The c o r r o s i o n r a t e i n high v e l o c i t y (1.5 f p s )
condensate w a s excessive f o r materials commonly
used i n h e a t exchangers (deoxidized copper,
n a v a l b r a s s , and carbon s t e e l ) .
The p i t t i n g r a t e of aluminum w a s g r e a t e r than
100 mpy.

AISI Type 410 s t e e l p i t s a t a r a t e o f more than


30 mpy. General c o r r o s i o n w a s t e n t i m e s t h a t
of AISI Type 304.
A I S I type 304 steel showed t h e b e s t c o r r o s i o n
r e s i s t a n c e (of t h e s t a i n l e s s steels t e s t e d )
i n condensate. Uniform c o r r o s i o n w a s very
low. P i t t i n g and stress c o r r o s i o n w e r e n o t
detected.

P l a n t experience i n d i c a t e d t h a t AISI Type


304 h e a t exchanger tubing would n o t s e r v e i n
a e r a t e d condensate. Titanium tubes have
given good service.
*It w a s n o t . c l e a r whether o r n o t t h e condensate used i n t h e tests
w a s a e r a t e d and t h e H2S c o n c e n t r a t i o n w a s n o t given. The pH
w a s about 7.

A-23

.
A.2.4

Epoxy coatings cured a t high temperature


showed no d e t e r i o r a t i o n i n low v e l o c i t y
condensate a f t e r 150 days of exposure.

ODeratine ExDerience a t Cerro P r i e t o

The s u c c e s s f u l o p e r a t i o n of t h e Cerro P r i e t o geothezm a l power p l a n t has provided valuable materials experience t h a t


may b e used i n t h e design o f U.S. p l a n t s . The s i m i l a r i t y of
geothermal f l u i d s i n southern C a l i f o r n i a makes t h e Cerro P r i e t o
data particularly useful.
Carbon and low a l l o y s t e e l s have served s a t i s f a c t o r i l y
i n nonaerated l i q u i d o r steam. When oxygen w a s introduced t o
t h e geothermal media, carbon s t e e l w a s s e v e r e l y corroded. S t a i n less s t e e l s , t i t a n i u m , o r nonmetallic materials are r e q u i r e d i n
a e r a t e d steams.

Materials experience i n t h e v a r i o u s p a r t s o f t h e power


p l a n t i s discussed below.
A. 2.4.1

Bore Casines and Surface EauiDment

Several problems and two blowouts have occurred due


t o t h e r u p t u r e o r c o l l a p s e of bore casings a t Cerro P r i e t o . It
i s n o t known when and t o what e x t e n t s t r e s s c o r r o s i o n , s u l f i d e
stress cracking, galvanic c o r r o s i o n , j o i n t o r c a s i n g e r o s i o n o r
excess stress have been involved because t h e broken casings
could n o t be recovered (GE-119).
A f t e r geothermal w e l l s have been completed, they remain
o u t o f production u n t i l t h e i r temperature, which decreased during
d r i l l i n g , .rises again and f a c i l i t a t e s t h e i r a c t i v a t i o n . During
t h i s t i m e , i n t e r n a l pipe w a l l s o f some o f t h e w e l l s have been

A-24

a t t a c k e d by e l e v a t e d c o n c e n t r a t i o n s o f H 2 S . Reservoir ga es si :h
as C O n and H2S flow i n t o a w e l l o u t of production and cause t h e
w a t e r level t o o s c i l l a t e s i g n i f i c a n t l y . H 2 S becomes concentrated
i n t h e c o l d e s t area n e a r t h e s u r f a c e and a t t a c k s t h e p i p e . The
e x t e n t o f damage h a s n o t been measured, b u t when a w e l l i s activ a t e d , t h e i n i t i a l discharge of w a t e r has a h i g h e r i r o n s u l f i d e
c o n t e n t (ME-S-250).
S u l f i d e stress cracking i s a l s o a hazard
under these c o n d i t i o n s . To minimize t h e s e problems, w e l l s are
a c t i v a t e d as soon as p o s s i b l e a f t e r completion.
S u l f i d e stress cracking appears t o have occurred once
under c o n d i t i o n s s i m i l a r t o those described above. Well M-5,
cased w i t h A P I grade H-40 s t e e l , f a i l e d when c o l d water w a s i n j e c t e d during repair o p e r a t i o n s (GE-119). This behavior c o r r e sponds t o t h a t a t Wairakei where c a s i n g steels H40 and K55 have
f a i l e d r a p i d l y i n c o l d H2S-bearing condensate (FO-120, MA-682,
SM-160, FO-119).
Leaks o f hydrothermal f l u i d s between w e l l c a s i n g s o r
between c a s i n g s and t h e w a l l s of t h e h o l e l e a d t o degradation o f
t h e cement and t o expansion and c o n t r a c t i o n of t h e w e l l c a s i n g .
Small f r a c t u r e s allow t h e passage o f geothermal f l u i d s from t h e
production s t r a t a a t the bottom of t h e w e l l up t o t h e s u r f a c e .
The r e s u l t i s bubbling and escape of gases and steam promoting
c o r r o s i o n on t h e o u t s i d e o f t h e w e l l c a s i n g . This i s prevented
through i n t e n s i v e maintenance w i t h temperature r e s i s t a n t p a i n t s
o r by adding h i g h temperature l u b r i c a n t s (ME-S-250).
Galvanic coupling of production p i p e w i t h packing
f l a n g e s has promoted c r e v i c e c o r r o s i o n of t h e casing a t t h e w e l l head. T h i s h a s been c o r r e c t e d by preventing metal-to-metal cont a c t of t h e p i p e s a t t h e s u r f a c e and by e l i m i n a t i n g t h e packing
f l a n g e s . The space is f i l l e d w i t h cement o r high temperature
l u b r i c a t i n g g r e a s e s (ME-S-250, GE-119).

A-25

P i t t i n g and g e n e r a l c o r r o s i o n of t h e i n t e r i o r s of mild
steel s u r f a c e p i p e s c a r r y i n g nonaerated geothermal media have
been " i n s i g n i f i c a n t . " Erosion-corrosion has been f r e q u e n t l y observed a t s u r f a c e i n s t a l l a t i o n s where t h e r e i s a sand-water-steam
flow a t high v e l o c i t y (GE-119).
Purge l e a k s and atmospheric discharges o c c a s i o n a l l y
form s a l t d e p o s i t s on valves, Christmas trees, and p i p e s . The
s u r f a c e c o r r o s i o n t h a t r e s u l t s i s c o n t r o l l e d by c o n s t a n t s c r a p i n g
and a p p l i c a t i o n o f p r o t e c t i v e p a i n t s .
The Cerro P r i e t o discharge w a s i n i t i a l l y passed through
s t e e l vertical s i l e n c e r s . The combination of geothermal media
and atmospheric \oxygen caused severe c o r r o s i o n of t h e s t e e l . This
problem w a s eliminated by c o n s t r u c t i n g s p e c i a l s i l e n c e r s w i t h
concrete bases and towers o f wood o r f i b e r g l a s s (ME-S-250).
There have been few c o r r o s i o n problems i n t h e conduct i o n l i n e s f o r t h e s e p a r a t e d h o t water (16O-18O0C) which t r a n s p o r t t h e b r i n e from t h e s e p a r a t o r s t o t h e evaporating pond. However, t h e r e has been a case i n which severe s c a l i n g w a s accompanied
by c o r r o s i o n . I n t e r r u p t i o n s i n t h e flow exposed t h e i n t e r n a l w a l l s
o f t h e pipe t o combined a t t a c k by s a l t s and atmospheric oxygen.
I f t h e l i n e s are k e p t h o t , t h e r e i s almost no i n t e r n a l c o r r o s i o n .
Lines are n o t p r e s e n t l y i n s u l a t e d , and some e x t e r n a l a t t a c k by
t h e s a l t spray and oxygen r e s u l t s (ME-S-250).
A.2.4.2

Steam Conduction System

Carbon-steel steam conduction l i n e s normally s u f f e r a


s l i g h t i n t e r n a l a t t a c k and become coated w i t h an i r o n s u l f i d e
f i l m . The f i l m i s u s u a l l y n o t a problem, b u t o c c a s i o n a l l y t h e
f i l m dislodges and blocks steam t r a p s o r e n t e r s t h e t u r b i n e .
Steam traps r e q u i r e i n t e n s i v e maintenance t o prevent and clear

A-26

w
,
,

blockage by i r o n s u l f i d e f l a k e s . The problem has been somewhat


remedied by s u b s t i t u t i n g continuous condensate purges f o r most
o f t h e steam t r a p s (ME-S-250).
A.2.4.3

Turbines

During t h e f i r s t two years of o p e r a t i o n , t h e t u r b i n e s


w e r e i n s p e c t e d twice. There w a s no observed corrosion o r cracking of t h e t u r b i n e buckets ( 1 2 C r r s t e e l ) . A t t h e s i x t h s t a g e
o f b l a d e s , t h e S t e l l i t e No. 6 f a c i n g s were i n "very good condit i o n , " w i t h only s l i g h t e r o s i o n of t h e s i l v e r used t o s o l d e r t h e
f a c i n g s t o t h e 1 2 C r s t e e l b l a d e s (GE-119). The major pzoblem
w a s t h e s c a l i n g of s i l i c a i n t h e f i r s t s t a g e nozzles and buckets
(GE-119, SC-448). This problem w a s due t o t h e poor s e p a r a t i o n
o f water and steam i n the wellhead and secondary s e p a r a t o r s ,
allowing carryover of d r o p l e t s s u p e r s a t u r a t e d w i t h s i l i c a ( S i 0 2 )
and calcium carbonate (SC-448).
. A f t e r two y e a r s o f o p e r a t i o n , improved steam s e p a r a t o r s
were i n s t a l l e d t o give 99.99% q u a l i t y steam, The s e r v i c e c y c l e
has been extended t o 18 months, and a two-year c y c l e i s p o s s i b l e
(ME-S-250).
I

The r o t o r and 1 2 C r t u r b i n e buckets have shown only


s l i g h t a t t a c k a f t e r f o u r y e a r s of o p e r a t i o n . Their h i g h e s t a t t r i t i o n rate i s due t o e r o s i o n from: ( a ) water d r o p l e t s , (b) c a r r y over o f i r o n s u l f i d e p a r t i c l e s i n t h e steam, o r ( c ) sand b l a s t i n g
c a r r i e d o u t during preventive maintenance t o e l i m i n a t e t h e s c a l e
which i s r e g u l a r l y deposited during o p e r a t i o n . Corrosion i s
s l i g h t l y more accentuated i n seals where steam i s mixed w i t h geothermal gases and atmospheric oxygen (ME-S-250).

IW
~

A-27.

A. .4.4

Cooling Water System

The major c o r r o s i o n problems a t Cerro P r i e t o have been


i n t h e cooling w a t e r system. The cooling w a t e r i s a e r a t e d steam
condensate c o n t a i n i n g H2S, C 0 2 , N H 3 , c h l o r i d e s , o t h e r i m p u r i t i e s ,
and s u l f ide-oxidizing b a c t e r i a .
Extensive c o r r o s i o n occurred o r i g i n a l l y on t h e water
s i d e o f t h e aluminum tubes i n t h e h e a t exchangers of t h e o i l
cooling system. A l a r g e percentage w a s p e r f o r a t e d i n 15 days
of o p e r a t i o n , and a l l showed s i g n s of p i t t i n g . The tubes w e r e
r e p l a c e d by Type 304 t u b e s , and some of t h e s e w e r e a l s o p e r f o r a t e d a f t e r several months. The problem i s now c o n t r o l l e d by
d r a i n i n g and drying t h e tubes when t h e equipment is o u t of opera t i o n . Bacterial growth, which promotes t h e p i t t i n g , i s accele r a t e d when t h e w a t e r i s n o t flowing. Titanium tubing i s planned
f o r use i n t h e n e x t u n i t (ME-S-250).
O r i g i n a l l y t h e tubes i n t h e h e a t exchanger of t h e hydrogen cooling system o f t h e g e n e r a t o r w e r e aluminum. These tubes
w e r e s e v e r e l y p i t t e d , b u t w e r e n o t p e r f o r a t e d because t h e w a l l s
were t h i c k e r . They w e r e replaced w i t h t i t a n i u m t u b e s , and t h e r e
has been no d e t e c t a b l e c o r r o s i o n i n f o u r y e a r s (ME-S-250).
The barometric condenser i s t h e d i r e c t c o n t a c t type
where cooled condensate containing oxygen i s sprayed i n t o
t h e steam. The condenser i s carbon s t e e l covered w i t h an epoxycoating on t h e upper p a r t and c l a d w i t h Type 304 on t h e bottom.
Water removes t h e p r o t e c t i v e c o a t i n g i n some areas, and a t t a c k on
t h e carbon s t e e l w a l l s occurs. There h a s been no c o r r o s i o n
through t h e s t a i n l e s s s t e e l l a y e r . Condensers f o r f u t u r e u n i t s
w i l l be c l a d with Type 316. The gas e j e c t o r c o n t a i n s some carbon s t e e l tubes which corrode due t o t h e steam, g a s e s , and oxygen. The chimneys used f o r high a l t i t u d e gas discharge are

A-28

f i b e r g l a s s and have performed very w e l l (ME-S-250). The barometr .c


l e g s of t h e secondary condenser were o r i g i n a l l y carbon s t e e l . They
s u f f e r e d severe c o r r o s i v e a t t a c k and were destroyed i n &o y e a r s .
The problem w a s solved when they w e r e r e p l a c e d w i t h f i b e r g l a s tubing. F i b e r g l a s s o r Type 316 i s planned f o r u s e i n f u t u r e u n i t s

(ME-S-250).
The carbon s t e e l valves which handle t h e c o o l i n g w a t e r
have s u f f e r e d severe a t t a c k . They are now p r o t e c t e d with a l a y e r
of Type 316 and an epoxy coating.
Closed c o n c r e t e channels are used f o r conducting cooling
water between t h e condenser and cooling tower. These channels
were o r i g i n a l l y p r o t e c t e d w i t h a c o a l t a r epoxy. A f t e r two y e a r s
o f o p e r a t i o n , loosening of t h e epoxy c o a t i n g and a t t a c k of t h e
concrete i n t h e upper p a r t of t h e channel w e r e n o t e d . The a t t a c k
had become so e x t e n s i v e a f t e r f o u r y e a r s t h a t t h e cement w a s
degraded, and sand and g r a v e l were dislodged. R e p a i r s w e r e made,
and t h e c o n c r e t e w a s p r o t e c t e d by PVC covers.
The combination of H 2 S , steam, and anaerobic b a c t e r i a
caused degradation i n t h e concrete channel c e i l i n g s i n a zone w i t h
almost no a i r . Concrete below t h e w a t e r l i n e w a s n o t a t t a c k e d
because t h e w a t e r i s t r e a t e d w i t h b i o c i d e s t o c o n t r o l b a c t e r i a .
Some of t h e b a c t e r i a found i n t h e system o x i d i z e H2S t o H 2 S 0 4 ,
r e s u l t i n g i n low
v a l u e s t h a t l e a d t o degradation. Future i n s t a l l a t i o n s a t Cerro P r i e t o w i l l prevent degradation o f t h e concrete on channel c e i l i n g s by flooding o r i n s t a l l i n g PVC p l a t e
coverings.
During f o u r years o f o p e r a t i o n , wood i n t h e c o o l i n g
tower has degraded s l i g h t l y i n t h e upper p a r t of t h e s p r a y zone
and i n t h e r e g i o n of t h e water l e v e l . Parts of t h e transmission
supports and v e n t i l a t i o n motors are carbon s t e e l p r o t e c t e d w i t h

A-29

c o a l tar epoxy. S l i g h t c o r r o s i o n has r e s u l t e d where t h e p a i n t


has worn o f f . Most o f t h e screws and metal f i t t i n g s are Type
304 and have shown s l i g h t p i t t i n g . During p r e v e n t i v e maintenance
shutdowns, t h e wood i s t r e a t e d with b a c t e r i c i d e s and a l g i c i d e s
i n t h e a t t a c k e d areas. The carbon s t e e l p a r t s are cleaned and
coated w i t h epoxy p a i n t (ME-S-250).

A.2.4.5

E l e c t r i c a l System

The e l e c t r i c a l system i s g e n e r a l l y p r o t e c t e d by u s i n g
"clean" rooms w i t h f i l t e r e d a i r conditioning systems. Copper
w i r e p l a t e d w i t h t i n o r cadmium h a s p r e s e n t e d no problems. Some
o f t h e s i l v e r and copper p a r t s have been a t t a c k e d by H 2 S , r e q u i r i n g maintenance. E x t e r i o r high v o l t a g e c o n t a c t s i n t h e s u b s t a t i o n
are copper t h a t w a s covered w i t h gold b e f o r e being r e p l a c e d i n
o p e r a t i o n . These c o n t a c t s are a l s o a t t a c k e d by H2S b u t have
given no problems (ME-S-250).

A.3

CORROSION AT THE GEYSERS

The steam-dominated geothermal r e s o u r c e a t The Geysers,


C a l i f o r n i a , i s t h e only developed geothermal r e s o u r c e i n t h e
United States. R e l a t i v e l y long-term c o r r o s i o n experience w i t h
geothermal steam and condensate from t h i s p l a n t has been accumul a t e d , b u t c a u t i o n should be used i n applying c o r r o s i o n experience
from The Geysers t o liquid-dominated r e s o u r c e power p l a n t s . The
steam a t The Geysers i s n o t s a l i n e , and t h e condensate c o n t a i n s
only t r a c e c h l o r i d e . Table A-8 g i v e s t h e nominal composition of
steam a t The Geysers (TO-089).

A-30

TABLE A-8

NOMINAL COMPOSITION OF GEOTHERMAL STEAM


AT THE GEYSERS (TO-089)

Component

p p m (by weight)

co2

3260

H2S

222

"3

194

56
-

H2
I

7.7

pH (condensate)

A. 3 . 1

- 8.1

T e s t Methods and Conditions

I n o r d e r t o evaluate t h e e f f e c t of H2S abatement w i t h


F e 2 ( S 0 4 ) 3 , long-term c o r r o s i o n t e s t s of a number o f a l l o y s w e r e
begun i n 1972. Sets of 2-1/4 i n c h diameter coupons o f nons t r e s s e d m e t a l w e r e mounted one-fourth inch a p a r t on an i n s u l a t e d
c e n t e r p i n . Sets were placed n e a r t h e top of t h e barometric
condensers o f units 1 and 2 , where they w e r e exposed t o a washm i s t o f a e r a t e d cooling water/condensate mixture. Other sets
were placed i n t h e hot w e l l s of u n i t s 1 and 2 , where they w e r e
covered w i t h a e r a t e d condensate. The t e s t media of both u n i t s
I and 2 w e r e similar in the amount of HzS, C O 2 , N H 3 , and trace
C1- p r e s e n t , The media i n u n i t 2 a l s o contained approximately
30 ppm i r o n as Fez(S01,)~ f o r t h e abatement o f H 2 S emission.
General c o r r o s i o n was measured by weight l o s s . The growth rate
of t h e deepest p i t w a s c a l c u l a t e d from t h e measured depth o f t h e
deepest p i t a t t h e end o f t h e test period; t h e c r e v i c e growth
r a t e w a s c a l c u l a t e d i n t h e same way. The crevice w a s formed
between t h e coupon and t h e i n s u l a t i n g s p a c e r (GE-119). The res u l t s o f t h e s e tests are p r e s e n t e d i n Table A-9. Tests w i t h t h e
a d d i t i o n o f Fe+3 are n o t t y p i c a l of f l u i d s i n power p-lants u n l e s s
t h e media are oxidized f l u i d s o r u n l e s s F e t 3 i s added f o r H2S
abatement.

A-31

TABLE A-9
CORROSION STUDY IN CONDENSATE HOT WELL AT THE GEYSERS, CA

P l t tIns

Plttlai

( f ~ r a t r hof
deepest p i t
in mpy)

(8ratth of
deepeat p l t
i n WYI

-uta

w Alloy Iror Base

Hild S t e a l (1010)
Cruy lrm
32 W l Gray Iron
Ductlle Iron
Type 2 N1-res4ut
Cor-Tan

--

>14.3

CM.nta

8.0
8.4

>78

--

Matrix deatroyed (sraphltlzed)

14.3
0.9

>73

Hat r i x dent royed (8raphitlz.d)


.ow u r a p h l t i r a t l o n
broad dspreaalona

--

> 7.6

16.8

rrlnleas Steeln
Type 304
Type 304 ( u m s l t l z e d )
Type 316
Type 316 (aensitlzed)
Type 409
Type 410
TYP. 430
Carpenter 2Wb3

1
w

1 7 - 4 ~ ~

ru

0.7
0.9

--

--

< 0.1

'

perforat ionr
perforationsa
parforationa'

0.2
0.1

0.3
0.1

--

Base

lurlnua Base

perforated'
per forateti'

--

--

--

--

0. I

----

Alcoa 1100
Alcoa 2024
Alcoa 3003
Alcoa 6061

3.4
3.5
0.1

---

< 0.1

Admiralty Braas
90-10 CuNI
10 Al-5 pl Bronze

extanalw pitting

< 0.1
< 0.1

< 0.1

< 0.1

CF 8 (cast)
CP 8M (cant)
*Der

< 0.1

0.8

0.6
0.8

0.1

0.9

2.1

0.4

broad
broad
broad
broad

pit
pit
pit
plt

attack
attack
attack
attack

Lckel Baa*
)tonel 400

--

'Expnrura
590 day.
5815 daya
'Exposure
'Obaervcd a t end of test
Teat conditionur
Syacimena l a r a e d i n hot v e l 1
f l u i d . No quontltatlva data
on the h i d urd avalleble but
i t i u aerated and contalna
0 1 H,. S, NHa and posaibly
traces of C1'.

Reference:

CE-119

Teat condltlonar

Sume au "ulthout Yes(SOi)a


except t h a t 30 ppn iron us
Fur(SOr)a uaa added for
Has abatement.

TABLE A-9 (Continued)


CORROSION STUDY IN THE BAROMETRIC CONDENSERS AT TIM GEPSERS, CA

Without Ire'(80b)r
Pittin8
; r m h of
repeat p i t
i n DPY)

Addition'

C-nt

&aments'

Alloy Iron h a c
Hild S t e e l (lalo)
Gray iron
c(r.l
im

DV

a
mlctile

iron,

> 6.2
< 3.6
< 3.8

5.8

< 2.7

--

Typa 2-Ellresist
Cor-fen

--

26.5

--

4.0

Bpaol~engone
Orrphitlrud
O l r p h lt i z e d
Brord p i t a
B r d shellw deyresaioas

h p l e t o l y &raphitiad
E h t r l x deatroyed ( g r a p h i t i z e d
Partially graphitired

Lainless S t e e l s

W P 304

<0.1

Type 304 ( s e n s i t i z e d )

CO.1

nOue

0.1

0.3
5.3
9.5
perf.

0.1

< 1.0
< 0.1
< 0.1

none

< 0.1

none
none

(0.1

--<
c 0.5

0.1

----

1.8
< 1.6
c

c5

586 day.
'bpoaura = 1378 days
'Exposure

3.2

<0.1
c 0.1

w
w

1.1
P i t s on edee
L-erice p e r f o r a t e d sample
Numerous p e r f o r a t i o n a

verrorattd
Perforated

1.6

---

Broad p i t a t t a c k
P e r f o r a t e d , broad p i t a t t n c k
Broad p i t a t t a c k
Brood p i t a t t a c k

6.6
1.32 .

----

Jeneral a t t a c k

'Obscrvation sate at end of t e a t

S p e c l u n s expoaed t o uashing-alsting condition. near t o p o f b a r m e t r i c condenaer. No


q u a n t i t a t i v e d a t a on t h e test media is a v a i l a b l e * but c o n a l a t a o f a t e m condensate and
aurated cooling voter. It c o n t a i n s C o t , flr8, 00,. and t r n c e a of Cl-.

Reference:

S i a i l n r t o " u l t h o ~ i t i r o n Hddition" except t h a t 30 ppm i r o n as Pea(SOb), una added for


1129 abatement.

CE-119

A. 3.2

D i s cus s i o n o f Resul t s

Type 316, Carpenter Alloy 20Cb-3, and 17-4 PH s t a i n l e s s


steels experienced minimal c o r r o s i v e a t t a c k . S e n s i t i z e d Type
316 showed some p i t t i n g i n r e c i r c u l a t i n g a e r a t e d condensate
w i t h Fe2 (SO4) a d d i t i o n . Type 304 e x h i b i t e d s i g n i f i c a n t p i t t i n g
i n both t h e s e n s i t i z e d and s o l u t i o n annealed c o n d i t i o n s . Both
t h e g e n e r a l c o r r o s i o n r a t e and r a t e of p i t p e n e t r a t i o n of Type
304 i n c r e a s e d s i g n i f i c a n t l y with t i m e . F e r r i t i c s t a i n l e s s
steels such as Types 403, 409, 410, and 430 had such high p i t t i n g rates t h a t they were n o t s a t i s f a c t o r y i n The Geysers condensate system. The c o r r o s i o n r a t e of Type 430 i n c r e a s e d w i t h
time.
The d u c t i l e , g r a y , and Ni-resist cast i r o n s and high
c o r r o s i o n r a t e s . The matrix tended t o g r a p h i t i z e and/or d i s s o l v e . The remaining material looked sound b u t could n o t withs t a n d any load.
Carbon s t e e l (1010) had ap extremely high corrosion
r a t e andwas n o t s u i t a b l e f o r use i n c o n t a c t w i t h The Geysers
condensate.
Aluminum a l l o y s were u n s u i t a b l e f o r u s e i n condensate
because o f excessive p i t t i n g , e s p e c i a l l y when Fez (SO,)
was
added.
Copper a l l o y s s u f f e r e d severe s u l f i d e a t t a c k b e f o r e
F e 2 ( S 0 4 ) 3w a s added. Addition of i r o n tended t o reduce corros i o n of copper a l l o y s when t h e specimens were completely submerged and i n c r e a s e d c o r r o s i o n when they were n o t completely
submerged.

A-34

A. 3.3

Turbines

Design Change

T h i r t e e n o f t h e f i f t e e n power units a t The Geysers


w e r e provided by Toshiba Turbines. Turbine b l a d e s , shrouds,
and s t a y s are Type 410 s t a i n l e s s s t e e l . Early t u r b i n e blade
problems i n d i c a t e d erosion-corrosion o f t h e b l a d e s and cracking
o f t h e .stays.
The t u r b i n e s were redesigned mechanically. Blade
p a s s i n g v e l o c i t y w a s reduced and t h e blade r o o t w a s thickened
f o r i n c r e a s e d s t r e n g t h . Problems w e r e s i g n i f i c a n t l y reduced by
t h e s e changes w i t h no change i n materials ( p e r s o n a l communicat i o n w i t h PG&E personnel). Corrosion f a t i g u e , p o s s i b l y induced
by c h l o r i d e p i t t i n g , was c i t e d as t h e probable cause o f t h e s e
problems (SH-334).
A.3.4

E l e c t r i c a l Equipment

Attack on copper and s i l v e r switch c o n t a c t s by atmos p h e r i c H2S has been a major problem a t The Geysers, This problem i s b e i n g solved by r e p l a c i n g a l l copper, copper a l l o y , o r
s i l v e r c o n t a c t s w i t h c o r r o s i o n - r e s i s t a n t c o n t a c t s as they are
due f o r s e r v i c i n g . Terminals are dipped i n s o l d e r and switch
c o n t a c t s , r e l a y p o i n t s , e t c . a i e b e i n g cadmium p l a t e d . This
approach seems t o be s a t i s g a c t o r y a t The Geysers (personal communication w i t h PG&E personnel).

A-35

APPENDIX B
CORROSION IN SEAWATER
DESALINATION PLANTS

B-1

-_
CORROSION IN SEAWATER DESALINATION PLANTS
Geothermal fluids are similar in many ways to seawater.
Therefore, corrosion experience from desalination plants may
be useful when actual geothermal corrosion data are not available. There are two major restrictions on the applicability
of desalination experience to geothermal corrosion problems.
First, the maximum temperature used in most desalination plants is around 120C. This is considerably lower than
geothermal inlet conditions.
Secondly, the chemical compositions of seawater and
geothermal fluid may differ in several ways. Seawater for desalination near 120C is normally pretreated to remove CO2 and
then adjusted to about pH 7 . Many geothermal fluids have high
C02 concentrations and pH less than 7. Geothermal fluids may
also contain ammonia and hydrogen sulfide which are not found
in seawater. The presence of hydrogen sulfide causes severe
corrosion of some alloys which give good service in its absence. Some geothermal fluids also contain larger concentrations
of heavy metal ions, especially copper and mercury ions. A
typical analysis for the major constituents which account for
the chemical behavior of seawater is given in Table B-1.
TABLE B - 1
-NGRMAL SEAWATER
Concentration
Component
ppm
gm/liter
Sodium (Na)
10768
11.035
1298
1.330
Magnesium (Mg)
408
0.418
Calcium (Ca)
388
0.394
Potassium (K)
19.841
19361
Chloride (Cl)
2702
Sulfate (SO,,)
2m769 Reference GE-117
0.146
143
Bicarbonate (HC03)
Total Solids
35175
36.047
B-2

B. 1

Corrosion Results

The results of corrosion tests in desalination facilities are discussed below for several metals.
B.l.l

Aluminum

Geothermal experience indicates that the usefulness


of aluminum in contact with geothermal fluids is limited. Though
it did well in corrosion tests at Cerro Prieto, aluminum failed
rapidly in service as oil and hydrogen cooling heat exchangers
exposed to aerated cooling waters. Aluminum a'lso performs
poorly in desalination environments. The tendency to pit is increased by heavy metal ions. Also, galvanic coupling is a problem; aluminum is anodic to most other metals and must be insulated from all contact (GE-117).
B. 1.2

Copper-Based Alloys

Uniform corrosion data for 12 copper alloys tested at


the OSW Materials Test Center are presented in Table B-2. These
results are for seawater controlled at pH 7.4; corrosion increases
rapidly at pH less than 7.0. Other types of corrosion were also
noted for copper alloys, Table B-3 shows the results of impingement corrosion. Destruction of the CuO film will cause all copeposits or where the seawater velocity
per alloys to pit unde
+) greatly increase
is greater than 8 fps. H2S and N H 3 (or "I,
the pitting of copper alloys. Alloys 433 and 687 undergo stress
corrosion cracking and become major hazards if exposed to "3,
or Hg. Alloy 706 is a minor stress corrosion cracking ha"I,+,
zard under these conditions. Brasses with more than 15 percent
zinc must be inhibited with arsenic or antimony to prevent dealloying (GE-117).

w
B-3

TABLE B-2
CORROSION OF COPPER BASED ALLOYS AT THE OSW MATERIALS
TEST CENTER AT FREEPORT, TEXAS

'I

45.c

mcwd

S
S
S

Mad4

.
I

2 . ~ s . 2 1.0-2.0

A
A
A

1.4-7.9

0.74.7

1.94.0

0.5-0.7

rn

Mdd

m
L

su

0.1

Io
h

hfucv*
rmpr

6
S

75 ppb

0.

Of

~
D

wI1)

Ill

2.4-3.3

0.44.7

R
S
S

A
A
A
A

1.7-S.3
-

0.7-1.2
-

S
S

A
A

.
I

0.12
0.50

0.42

77%

1m.c

LI2-l

30 n
b 200 prb
0.U
0.49
0.50

"0:

0.26

0.34
0.42
0.30

0.31

Lo
4.0

1.3
1.4

-1-.8

1.2

1.4

i
2.0

1.6

0.8

1.4

1.1

TABLE B-3
IMPINGEMENT CORROSION OF COPPER ALLOYS
AT THE OSW TEST CENTER

Copper Alloy
Designation
Arsenical Admiralty Brass
Arsenical Aluminum Brass
90/10 Cu/Ni
70/30 Cu/Ni (.4-.7

B.1.3

Fe)

Impingement Corrosion (mpy)

Alloy No.

10 fps

15 fps

433
687
706
715

84
28

112
60
48

12

44

40

Low Alloy Steels

The c o r r o s i o n behavior of some low a l l o y s t e e l s and


pure i r o n i n seawater a t 121C i s presented i n Table B-4.
I
jflJ P i t t i n g and crevice c o r r o s i o n of t h e low a l l o y s t e e l s w e r e sev e r e , but t r a c e s 'of oxygen ( ~ 5 0ppb) were p r e s e n t i n t h e flowi n g seawater and t h i s would f a c i l i t a t e t h e s e types o f c o r r o s i o n .
B.1.4

S t a i n l e s s Steels

A u s t e n i t i c s t a i n l e s s steels have good g e n e r a l corros i o n resistance t o nonaerated seawater. Many have good p i t t i n g
and crevice
c o r r o s i o n r e s i s t a n c e i n nonaerated media. When
,
seawater i s a e r a t e d , p i t t i n g and c r e v i c e c o r r o s i o n become major
concerns, as does stress c o r r o s i o n cracking. Table B-5 p r e s e n t s
t h e results of p i t t i n g tests on 19 s t a i n l e s s s t e e l a l l o y s t e s t e d
a t t h e OSW Materials T e s t F a c i l i t y a t F r e e p o r t , Texas. These
results apply t o s t a i n l e s s steels i n seawater with varying d i s solved oxygen c o n c e n t r a t i o n s .
B-5

TABLE B-4

CORROSION OF LOW LLOY

r
kterial

Exposure
(days)

STEELS IN FLO~INGSYNTHETIC SEAWATER

elocity
(fp)

i t t i n g Mtack*

Ultra High p u r i t y i r o n

10

0.3

5.3

slight

A-104 (pure iron)

10
20
30

3-4
3-4
3-4

11.1
8.9
11.1

severe
severe

10
20

8.6
5.0
4.9

very s l i g h t

30

0.3
0.3
0.3

10.8
21.1

0.3
0.3

6.5
3.7

slight
wderate

31.1

0.3

3.1

8.7
9.7
19.5
29.1
42.3
82.3

0.3
0.3
0.3
0.3
0.3
0.3

4.3
7.3
3.2
2.4
1.9
2.0

9.7
19.5
29.1
51.0

0.3
0.3
0.3
0.3

5.5
3.3
2.2
2.1

very s l i g h t

10

0.6
0.6
0.6
3-4
3-4
3-4

4.4
3.7
2.6
7.0
3.7
3.2

moderate
moderate
slight
slight
severe
moderate

0.6
0.6
0.6
3-4
3-4
3-4

4.9
3.8
3.1
6.1
3.8
3.0

moderate
moderate
slight
small b l i s t e r s
severe
severe

A-104 (electron beam


melted as r o l l e d )
A-104 (induction melted
as r o l l e d )

A-104 (induction melted.

Crevice Attack

very s l i g h t
slight
slight
moderate

severe

annealed)

Armco i r o n (as r o l l e d )

Armco iron (annlaled)

ASZM

A-212 ( r o l l e d and

20
30

ground)

10

20
30
ASRI A-285 ( r o l l e d and

10

20
30
10
20
30

ground)

slight
very s l i g h t
alight
slight
-derate
moderate

BA-539

B-6

moderate
alight

slight
moderate

*Qualitative d a t a only. lo d e f i n i t i o n of descriptors.


T e s t conditions: f l w i n g s y n t h e t i c sea water, 121C. pE 6.4-7.9, (50 ppb 0
Source:

slight

slight
severe
severe
moderate
moderate
slight
severe
severe

TABLE B-5
P I T T I N G CORROSION OF STAINLESS STEEL ALLOYS I N THE AIS1

.. .

DESALINATION PLANT AT FREEPORT, TEXAS

P i t t i n g Corrosion of H e a t Exchanger TubH e a t Rec.overy U n i t


43-93OC
Length of
Exposure

Brine Rester
113-121C

Growth of
Deepest P i t

Length of
Exposure

25 mpy
perforated'
1.5 mpy
no p i t s
no p f t s
perforated'

12 mo
24 mo
18 mo
24 mo
6 mo'

Growth of
Deepest P i t

U S 1 Standard Grades

Type
Type
Type
Type
Type
Type

202

304
309

316
317
430

k h e r Grades
Allegheny 216
Allegheny 304N
Allegheny 329
Allegheny 329X
Allegheny 409
Allegheny 444L
Incoloy 800
E - B r i t e 26-1
18121.25 CrlMolTi
1811812 CrlNilMn
~
C 22-13-5
O
Armco 20-45-5
Carpenter 2 0 4 3 3
Allegheny 6X

12
24
24
24
30
6

mc
mo
mo
mo
mo

mo

36 mo
18 mo
36 mo
6 mo
6 mo

12

w,

30 mo
24 mo
6 mo
6 mo
24 mo
18 mo
36 mo
24 mo

no p i t s
perforated2
no p i t s
no p i t s
perforated'
perforated2
no p i t s
no p i t s
50 mpy
50 mpy
4 mpy
no p i t s
no p i t s
no p i t s

l2mo

36 mo
18 mo

Mmo
6 mo
6 mo

12 mo
24 ma
24 mo
6 mo
6 mo
24 mo
18 mo
36 mo
24 mo

(walls 49 mil thick)

Brine Recycle Loop


105OC
Length of
Exposure

mo

5 mPY
5 mPY
1 0 mpy
1 3 mpy
no p i t s
40 mpy

30
12
24
36
24
12

4 mPY
7 mw
0.5 mpy
no p i t s
80 mpy
4 mPY
2.5 mpy
7 mPY
1 0 mpy
30 mpy
a . 5 mp9
17 mpy
a . 3 mpy
1.5 mpy

36 mo
1 8 mo
36 mo
6 mo
12 mo
l2 mo
24 mo
24 mo

mo

mo
mo
mo

mo

6 m
12 mo
24 mo
18 mo
36 mo
24 mo

Vertical Tube Evaporator

Growth of
Deepest P i t
2.2 mpy
4 mPY
2 mPY
1.1 mpy
no p i t s
30 mpy
no
4
no
no
30
20
no
no
2
no
no
no
no

Length of
Exposure

Growth of
Deepest P i t

--

18 mo

17 mpy

18 mo
12 mo
6 mo

3 m
w
2.5 mpy
40 mpy

30 mo

1 mPY

pits
pits

30 mo

--

1 mPY

mpy

12 mo
12 mo

12 mpy

pits

W Y

mpy
pits
pits
mPY
pits
pits
pits
pits
no p i t s

--

-18 mo
--

20 mpy

6 mo
6 mo
18 mo
30 ma
18 mo

70 mpy
6 mPY
3 mPY
1 mPY
2 mPY

mw

APPENDIX C
PRELIMINARY COMPARISON OF GEOTHERMAL
FOSSIL FUEL GENERATING PLANT AVAILABILITY

c-1

PRELIMINARY COMPARISON O F GEOTHERMAL


FOSSIL FUEL GENERATING PLANT AVAILABILITY

_
I

Power p l a n t downtime o r outage may r e s u l t f r o m - e i t h e r


scheduled preventive maintenance o r f a i l u r e of a c r i t i c a l component. Estimating outages f o r a geothermal power p l a n t i s
highly u n c e r t a i n because t h e number of o p e r a t i n g geothermal
f a c i l i t i e s i s s m a l l and t h e r e i s no s i g n i f i c a n t s t a t i s t i c a l
b a s i s f o r making such p r o j e c t i o n s . An outage r e p o r t i n g system
similar t o those f o r f o s s i l and nuclear f u e l power p l a n t s has
n o t been e s t a b l i s h e d s p e c i f i c a l l y f o r geothermal p l a n t s . Geothermal power p l a n t s r e p o r t t h e i r problems and s o l u t i o n s through
t h e open l i t e r a t u r e , b u t are n o t s p e c i f i c on a unit-by-unit
b a s i s . Although general t r e n d s a r e becoming a v a i l a b l e , exact
d a t a from t h e geothermal i n d u s t r y a r e n o t a v a i l a b l e . U n t i l a
l a r g e r d a t a base i s accumulated f o r geothermal power p l a n t s ,
some l i m i t e d comparisons can be made with f o s s i l f u e l p l a n t s .
C o r r e l a t i o n of e x i s t i n g geothermal d a t a with s t a t i s t i c a l experience from f o s s i l f u e l p l a n t s should h e l p t o determine
operations and problems of f u t u r e geothermal power p l a n t s .
The most frequent outage i n a f o s s i l f u e l power p l a n t
i s due t o b o i l e r - r e l a t e d problems. F o s s i l f u e l b o i l e r s r e q u i r e
cleaning and inspection and are t h e leading cause of major
power p l a n t f a i l u r e s . However, t h i s type of outage does n o t
apply t o geothermal power p l a n t s s i n c e they do n o t r e q u i r e b o i l e r s .
Turbine-related problems a r e t h e second most frequent
cause of outages i n a f o s s i l f u e l p l a n t b u t are t h e major cause
of outages i n geothermal p l a n t s . Turbine outage i n f o s s i l f u e l
p l a n t s i s g e n e r a l l y f o r i n s p e c t i o n o r c o n t r o l system maintenance. The major causes of t u r b i n e outages i n geothermal p l a n t s
are blade corrosion, e r o s i o n , o r f a i l u r e . Geothermal power
p l a n t s t h a t use a binary c y c l e w i l l t r a n s f e r many of t h e s e

c-2

corrosion problems to heat exchangers; the turbines in these


systems will more closely parallel those in fossil power plants.
Condenser-related problems are the third most frequent
cause of downtime at a fossil power plant. Cleaning is the
most prevalent reason for outage, but it is of a short duration
of about 6 to 8 hours. Condenser problems can be expected to
be higher in geothermal power plants because of the chemical
composition of geothermal fluids versus fossil fuel steam.

Exciter generator maintenance is the fourth major


reason for outages at fossil power plants. Exciter generator
maintenance can be expected to increase in a geothermal power
plant, particularly when the geothermal fluid contains gaseous
sulfur species.
The quality of steam in a geothermal power plant is
the key to the amount of downtime incurred by that plant.
Based upon experience at The Geysers and Cerro Prieto,.less maigp
tenance is required on major equipment items as the geothermal
fluid becomes cleaner. Equipment such as turbines, generators,
condensers, pipes, and heat exchangers that are exposed to geothermal fluid should experience more downtime than comparable
systems exposed to clean steam in fossil power plants, but downtime will not be lost to boiler problems, More direct correlation between fossil and geothermal power plants is not possible
because the predominance of outages is due to boiler problems
in fossil plants and because outage data specific for geothermal
plants are limited.
The cost of maintenance versus capital costs for equipment is a driving force toward more frequent maintenance outages

e-3

c,
to detect incipient problems before they become major problems.
Better materials may be necessary in many geothermal plant applications; best available materials should be considered for critical applications where maintenance and replacement costs could
become prohibitive.

c-4

Appendix D

GEOTHERMAL ELASTOMERIC MATERIALS

D-1

GEOTHERMAL ELASTOMERIC MATERIALS

The Department of Energy i s conducting r e s e a r c h t o


develop elastomers f o r geothermal use. Five r e s e a r c h programs are involved i n various phases of t h e development and
t e s t i n g o f elastomers f o r use i n geothermal w e l l s . The goal i s
t o seek new materials and t e s t s which w i l l serve i n geothermal
a p p l i c a t i o n s . O f p a r t i c u l a r i n t e r e s t are packer seals and d r i l l
b i t c u t t e r cone seals. The approaches range from b a s i c r e s e a r c h
t o a p p l i e d development and i n c l u d e s y n t h e s i s o f new polymers,
i n v e s t i g a t i o n of new but a v a i l a b l e ( a t high c o s t ) elastomers,
modification o f commonly known materials and development and
e v a l u a t i o n o f t e s t methods.
Results of t h e s e ongoing r e s e a r c h programs are described
below. Each program, conducted by an i n d i v i d u a l c o n t r a c t o r , has
d i f f e r e n t goals and t e s t methods ; t h e r e f o r e , r e s u l t s are grouped
according t o r e s e a r c h program.
D. 1

Elastomer 0-Ring Seal Program

The o b j e c t of t h i s study w a s t o t e s t commercial e l a s t o m e r i c materials f o r p o t e n t i a l a p p l i c a t i o n as O-ring s e a l s i n


geothermal environments. The O-rings w e r e e i t h e r r e e d o v a l
c o n f i g u r a t i o n s o r #2-329 types. The c r i t i c a l p r o p e r t i e s d e s i r e d
i n t h e elastomers w e r e :
1)

low compression s t r e n g t h of less than 20%,

2)

good abrasion r e s i s t a n c e and high t e a r


strength,

3)

r e s i s t a n c e t o a t t a c k from petroleum-based

D-2

l u b r i c a n t s , common mud a d d i t i v e s , H2S, and


moderate s h i f t s i n pH, and
4)

D. 1.1

r e t e n t i o n of t h e above p r o p e r t i e s a t e l e v a t e d
temperatures.

T e s t Program

The t e s t program i n v e s t i g a t e d t h e i n f l u e n c e o f t h e
f o l l.owing v a r i a b l e s on t h e performance o f elastomers i n geothermal
d r i l l i n g operations :
1) temperature o f geothermal formation and from
friction,

D.1.2

2)

r o t a t i o n a l e c c e n t r i c i t i e s o f d r i l l c u t t e r cones
("wobbling" on t h e l u g ) ,

3)

a b r a s i v e p a r t i c l e s , and

4)

chemical composition o f t h e geothermal b r i n e ,


e s p e c i a l l y H 2 S which causes b r i t t l e n e s s i n
elastomers by c r e a t i n g unwanted c r o s s - l i n k s .

Materials Tested and Results

1) Buna-N (Parker JlN4187) performed w e l l between


10O"C-20O0C w i t h 'no a b r a s i v e s p r e s e n t . The temperature l i m i t
w a s approximately 225C. Preheating o f t h e seal t o 50C before
use i n c r e a s e d l i f e s p a n , but p r e h e a t i n g t o 240C and 260C, then
cooling t o 175C p r i o r t o d r i l l i n g r e s u l t e d i n e x t e n s i v e seal
damage and poor performance. Test t i m e : 4 hours simulated
d r i 1l i n g .

1)-3

'

2) Ethylene-Propylene (Parker #34183-80A) gave poor


performance at 200C (only temperature t e s t e d ) . D e t e r i o r a t i o n
r e s u l t e d when petroleum-based l u b r i c a n t s were used. Time: 4
hours.
3) Fluorocarbon elastomers from DuPont's Viton and
3M's F l u o r e l (Parker #V747-75A) were t e s t e d . Pre-warming of t h e
seal t o 50C w a s b e n e f i c i a l . Ultimate usable temperature was
235C. Results were good with o r without t h e presence of
abrasives. F a i r r e s u l t s were obtained when s e a l s were h e a t e d ,
then cooled, t o simulate "tripping" i n t o a h o t w e l l . Time:
4
hours.
4 ) Fluorosilicone Rubber (Parker #L4216-70A) severe
breakdown occurred between 175C-2000C. B r i t t l e f a i l u r e occurred

via deep cracks and p i t t i n g of t h e running s u r f a c e s . Molecular


degradation was i n d i c a t e d throughout t h e m a t e r i a l . Time : 4
h o u r s a t 200"-260C with no a b r a s i v e s ; 1 hour a t 175C w i t h
abrasives.
5 ) Test r e s u l t s were incomplete f o r F i r e s t o n e PNF-200,
a fluoronated polyphosphozene rubber. F a i l u r e occurred a f t e r
t e s t i n g a t 200C with no abrasives. Molecular degradation was
i n d i c a t e d . Time: 4 hours.

6) Test r e s u l t s were incomplete f o r Kalrez #1050-70A,


a perfluorelastomer. Compression s e t r e s u l t e d i n f a i l u r e t o
maintain a seal. There was no apparent molecular degradation a t
200OC. Time 4 hours.
7) Modified Buna-N gave poor r e s u l t s . Excessive
f r i c t i o n a l h e a t i n g r e s u l t e d i n breakdown of t h e elastomer a t t h e
s e a l s u r f a c e . T e s t s were conducted a t 200-225"C. Time: 4-6
hours.

D-4

T e s t r e s u l t s are summarized i n Table D-1.

D. 2

Downhole Packer Seal Program

The o b j e c t i v e w a s t h e development of elastomers f o r


downhole geothermal seals. The a p p l i c a t i o n s are f o r use as casi n g packer seals.

D.2.1

Test Program

Simulation (SIM) Tests w e r e designed t o provide a good


simulation of t h e c a s i n g packer seal o p e r a t i o n a l environment i n
t h e l a b o r a t o r y . The SIM apparatus a p p l i e s a l l environmental
stresses simultaneously, i . e . , f l u i d p r e s s u r e , d f f f e r e n t i a l
p r e s s u r e , temperature, mechanical f o r c e s , and b r i n e chemistry, t o
a f u l l s c a l e packer seal. The s y n t h e t i c geothermal f l u i d w a s f o r mulated t o c o n t a i n : H2S-300 ppm; NaC1-25,000 ppm; CO2-1,OOO ppm;
XZO-balance. Elastomers were t e s t e d i n t h i s s y n t h e t i c goethermal
f l u i d a t 260C and up t o 5000 p s i g . T e s t d u r a t i o n w a s 24 hours
o r u n t i l seal f a i l u r e .

D.2.2

Materials Tested and Results

Five companies s u p p l i e d t h e following t y p e s of e l a s t o mers : Buna-N ( N i t r i l e ) , Ethylene Propylene Terpolymer (EPDM) ,


Viton , and Epochlorohydrin. Several d i f f e r e n t formulations o f
each were t e s t e d . The r e s u l t s are summarized i n Table D-2.
,

D. 3

Casing Packer Development Program

The o b j e c t i v e o f t h e program was t o develop a material


as a c a s i n g packer f o r use a t 260C, 1500 p s i a , f o r 24 hours i n
a geothermal environment. The casing packer should be thermally

D- 5

TABLE D-1
HIGH-TEMPERATURE ELASTOMER SEAL MATERIALS

Product
L

Name

Producer

Haterlal Class

Probable
Temp L i m l t

Cost/Lb

~~

~~

Potcnt Ia 1
'hys 1ca 1 Propert1es
Potentlal
Problems
Conpatability Problems.
~

temp l l m i t

LOW

High temp water and


steam

LOW

E t h y lene-propy 1ene 180C (350F)

Lon

Petroleum base f l u l d s

Yone

Fluorocarbon

260C (500F)

LOW

High temp water and


steam

rear resls tance

Don Coming

Fluorosll icone

260C (500'F)

LOW

S i 1icone lubes water


and steam

Tear 8 abrasion
resistance; etc.

PNF-200

F1res tone

Phosphonltrll IC 200C (400F)


Fluoroelastomer

$100

14one expected

Unknown

K a l rez

Du Pont

Perfluoroelastomer 260C (500F)

$2000

wO n e

Unknown

5AD-7004

Custom Rubber
Products

Hodlfled Buna N

230C (450F)

Lon

None

Unknown

V I ton, PeroxldeCurred

DuPont/Parker

F1uorocarbon

260C ( 500F)

LOW

High temperature water


and steam

Tear reslstance

TR-70

Don Corning

Fluorosll Icone
(clear)

260'C

LOW

S i 11cone 1ubes , water


and steam

Tear reslstance

Buna N ( W i t r l l e )

A t least 6 Co.'s

Butadlene 6
acrylonl t r l l e

Lthylenepropylene

A t least 5 Co.'s

V i ton

Du Pont

Fluorosll icone

150C (300F)

(500F)

From Hendrickson, R . R . et al. "Annual Report. Support Research for Development


of Improved Geothermal Drill Bits." ERDA Contract #(lo-1)1546, Terra Tek, Inc.
S a l t Lake City, Utah (June 1977).

c
TABLE D-2
SIM TEST SUMMARY

Sequence
flo

Speclmen
NO.

215-3
215-2

Duration
1irs:Min

compound

5:52

VT-A-4590,Aus t i n 70 pkr
VT-R-45!lO ,Aus t in 70 phr

Ni 1

260

13

Flat

Configuration

N i1

260

13

Flat

Nil
Nil

149
149

Flat
Flat

Nitrile
Vi-R-4590,Asbestine

11:

0.5

260

13
25
175
175
175

Flat
Flat
Flat

:07

220- 3
216-2

VT-R-4590,Austin 65 phr
VT-R-4590,Kevlar

:05

105-11-1

Viton GH. AustinIMT

216-1
A- 5

VT-R-4590
Nitrile

12

105-11-2

Viton GH, Austin/MT

3X

, Kevl ar

:oo
24 :

:47
24 :
24 :

13
14

18
19

Diamet.
Gap, M i l s

24 :
24 :

:oo
:oo
:oo

0-3

Nitrile
Epochlorohydrin

222-3

V i ton
VT-R-4590,Austin 40 phr

17

Set,
Temp. C

Nitrile
Nftrlle

10
11

15
16

Inches
Extrusion

1:13
I

I
1
1

:oo
3:44
:03
:38

N i1
Ni1
N i1

260
260
260

N i1

260
260

1.75

Flat

,175
175
175

Flat
Chamfered

260

175

Chamfered

Nil

260

175

Chamfered

3.75
2.5

260
260

4.5

260

NIA
No fleas.
0.75

260
260
260

0.75

260

CO.

C hamf ered

175

Chamfered

175
175

Chamfered
Chamfered
Chamfered

175
175
175

II

Chamfered
Chamfered

From Hirasuna, A.R., et al. "Geothermal Elastomeric Materials. Twelve Month


Progress Report." Contract #EG-77-03-1308, L'Garde, Inc. , Newport Beach, CIA, 1977.

s t a b l e i n a geothermal environment with 400 p s i t e n s i l e s t r e n g t h


and a t least 50% elongation.
D. 3.1

T e s t M e t h o ds

S t r e s s r e l a t i o n measurements, s o l - g e l determinations
swollen s t r e s s - s t r a i n measurements, weight-loss t e s t s , and
t e n s i l e tests w e r e conducted a f t e r exposure t o t h r e e s o l u t i o n s
a t e l e v a t e d temperatures. The t h r e e s o l u t i o n s w e r e s a l i n e
carbon dioxide s o l u t i o n ( s o l u t i o n f l ; 2.5% N a C l , 1000 ppm C O P ) ,
s a l i n e hydrogen s u l f i d e ( s o l u t i o n #2; 2.5% NaC1, 300 ppm HPS),
and deionized water ( s o l u t i o n f 3 ) .

D.3.2

Materials Tested and Results

The materials t e s t e d w e r e :
1)

Viton 10, 10K, 10G (du Pont)

2)

Kalrez 3065, 3050 (du Pont)

3)

AFLAS 150H (Asahi Glass, Yokohama, Japan)

Table D-3 summarizes t h e mechanical p r o p e r t i e s of aged


elastomers, and Figure D - 1 shows t h e e f f e c t of aging on t h e
t e n s i l e s t r e n g t h o f t h e elastomers. R e s u l t s of t h e elastomer
classes are given below.
1 ) Viton - Viton-1OG underwent less o x i d a t i v e degene r a t i o n during s t r e s s - r e l a x a t i o n t e s t s than t h e o t h e r Viton f o r mulations. S u b s t a n t i a l c r o s s - l i n k i n g w a s observed i n a l l formu. l a t i o n s . Cross-link d e n s i t i e s d i d n o t decrease n o t i c e a b l y i n
any formulation when s o l - g e l measurements were made. Weight-loss

D-8

TABLE D-3
MECHANICAL PROPERTIES OF AGED ELASTOMERS
TENSILE STRENGTH PSI, Aft0 (ELONGATION X) AT 260C

20h a t 252%

Unaged

40h at 252%

60h a t 252%

Viton 10

Viton 10 K

vi ton

'io G

Kalrez 3050

Kalrer 3065

A nA S 150H

Sol. 1

2.5% NaCl

loo0 ppm COP; Sol. 2 = 2.5% NaCl

300 ppm HZS; Sol. 3 = Deionized water

Measured at room temperature; I less than 10% elongation a t break;

- not measured.

From Mueller, et al. "Development and Evaluation of Geothermal Materials. Progress


Report I. l A G Contract #E(49-27)-1011, Jet Propulsion Laboratory, Pasadena, CAD

October, 1977 (Draft Copy).

400

300
n

*
v)
n

I
I-

z2

200

t;;
W
v)

z
W
I-

100

Figure D-1. Effect o t Aglng In arrne [ D O L . 11 ~ I I U


,---. -,
on
_ _ Elastomer Compositions
From Meuller , et al. "Development and Evaluation of Geothermal Environmental Materials. Annual Progress Report. 1AG-#(49-27) -1011, Jet Propulsion Laboratory,
Pabadena, CA, Oct. 1977. (Draft Report).
S J G A W L L ~ - ~

measurements a f t e r aging i n b r i n e s o l u t i o n #l f o r 60 hours a t


250C w e r e :
Viton 10
Viton 10K
Viton 10G

9% l o s s
13% l o s s
17% l o s s

Mechanical p r o p e r t i e s ( t e n s i l e / e l o n g a t i o n s t r e n g t h ) w e r e low f o r
t h e Vitons a f t e r 40 hours i n each of t h e t h r e e test s o l u t i o n s .
2 ) Kalrez - In stress r e l a x a t i o n s t u d i e s , Kalrez
3050 and 3065 behaved s i m i l a r l y t o Viton 10G, except t h a t both
w e r e more thermally s t a b l e than t h e Vitons. Cross-link densit i e s d i d n o t appreciably decrease when s o l - g e l measurements were
made. Weight-loss measurements i n s o l u t i o n 81 f o r 60 hours at
250C w e r e :
Kalrez 3050
Kalrez 3065

- 2% l o s s
- 8% l o s s

A f t e r 40 hours i n s o l u t i o n #3, Kalrez 3065 r e t a i n e d 50% of


i n i t i a l t e n s i l e s t r e n g t h and 100% o f i n i t i a l e l o n g a t i o n . In
o t h e r s o l u t i o n s Kalrez 3050 and 3065 were s t a b l e f o r 60 hours.

3) AFLAS-15OH - This polymer w a s a v a i l a b l e only i n


s m a l l q u a n t i t i e s and w a s n o t t e s t e d e x t e n s i v e l y . No stress
r e l a x a t i o n o r s o l - g e l measurements were performed on AFLAS-15OH.
Weight l o s s i n b r i n e s o l u t i o n #l w a s 1%. T e n s i l e s t a b i l i t y i n
a l l t h r e e b r i n e s o l u t i o n s w a s g r e a t e r than t h a t o f t h e Vitons
b u t less than t h a t of Kalrez 3050 o r 3065.
A f t e r one y e a r ' s work, no candidate elastomer appeared

t o s a t i s f y t h e o b j e c t i v e requirements of t h e p r o j e c t .

D-11

Kalrez

3050 appeared t o be
i n casing packers.
mercially available
elastomers f o r high
being synthesized.
D .4

t h e b e s t , but i t i s t o o expensive t o be used


AF'LAS w a s b e t t e r than Viton. Since no comproducts appear t o be s a t i s f a c t o r y , new
temperature geothermal a p p l i c a t i o n s are

Elastomer Synthesis and Development Program

The o b j e c t i v e o f t h i s program w a s t h e i n v e s t i g a t i o n of
materials and techniques f o r production of high temperatureand h y d r o l y t i c a l l y r e s i s t a n t rubber. Three materials w e r e i n v e s t i g a t e d : 1 ) carborane-siloxane (Union Carbide), 2) "FASIL",
a f l u o r i n a t e d elastomer being synthesized by Hughes A i r c r a f t , and
3) an ethynyl s u b s t i t u t e d p e r f l u o r o a l k y l e n e e t h e r elastomer being
s y n t h e s i z e d by Hughes. The materials were t o be used as seals,
cable t e r m i n a t i o n s and cable i n s u l a t i o n s i n geothermal w e l l
logging instrumentation. Materials t e s t e d thus f a r have been i n
t h e developmental s t a g e s and have n o t been formed i n t o anything
but 1/4" x 1/8" "buttons".
D.4.1

Results

Various polymers o f carborane-siloxane w e r e formulated


(Table D-4) and t e s t e d f o r compression s e t , durometer hardness
(an i n d i c a t i o n of c r o s s - l i n k i n g ) , t e n s i l e s t r e n g t h / e l o n g a t i o n ,
and h y d r o l y t i c s t a b i l i t y under p r e s s u r e . Results of compression
set t e s t s f o r t h e most promising formulations are shown i n
Table D-5, along with hardness t e s t s r e s u l t s . Hydrolytic s t a b i l i t y t e s t conditions were 24 hours a t 275C and 800 p s i . Comp l e t e d i s i n t e g r a t i o n of t h e polymer w a s n o t e d , r e g a r d l e s s of
formulation used o r type of w a t e r ( t a p o r d i s t i l l e d ) . F u r t h e r
work on t h i s compound has been suspended u n t i l information
regarding i t s h y d r o l y t i c i n s t a b i l i t y can be found.

D-12

e
TABLE D-4
CARBORANE-SILOXANE FORMULATION DATA

&imp.
Nu.

rwm

-29

Data
6-27

Type

CIS
F hto re1

w
-

TYPC

50
50

Tullawx
M P

75
25

fallamix

LVS-76
30

6-28

CIS
Fluorel
LVS-76

nti

M 6)

ani

Stabilizer

Cure

T vP
'.

tent
gm

--Cure Schedule
Temp up

Min.

nt.t

Ternpol

H r.
-

Ha rdneoe

Orig.

I%at Cured

15
35

None

Nnne

34ou

30, 60,
90, I 2 0

did nut cure

15

None

None

34ou

30, 60,

did not c u r e

35

31

7-7

C RS

100

T U ~ ~ ~ I M IDS X
20
Md)

V a lytx

2.0

340

30

45

Silt and
etlcky

32

7- 7

CIS

100

Tullanox

Va mix

2. 5

340

30

40-SO

Stickv

15

MfP
33
34
35

36

37

8- I

n- I
0-9

8-9

8-9

c OS

io0

COS

CN:
CRS

c DS

100

IO0

LOO
lo0

- --

lullanux

t3.3

M e

31.9

Tullanox

5.17
14.3

Vurox

MgO
Tullanox
Mfl

5.87
14.3

Vulcup

Tullanox
Mi9

20

Vulcup

Tullanox

20
50

MIrO

\ ulcup

3. 13

340

30

12. 5

340

30

3. 75

340

30

Varux

12.5

575OF

53. 3

70

79

48
48

52. 6

61

72

4soO
5 25

40

42. 5

45

49

45B
525

3. 75

40 h r

525F
48
48

5 25

48

340

30

450"
S25

48
48

48. 2

60

63

340

30

450
525

48
48

56

67

70

50

&ioo

48 hr

--

TABLE D-5
COMPRESSION SET TESTS

Filler

Curing Agent
Formulation

Type

%*
Tullanox
MgO

33

Vulcup

34

Varox

35

Vulcup

3. 75

Tullanox
MgO

36

Vulcup

3, 75

37

Varox

3. 75
12.5

12. 5

13
32

Flnal
Hardness
5 25O
575O

Compo
S e t 70

70

79

61

72

98

5, 07
14, 3

45

49

122

T ullanox
MgO

20
50

60

63

81

T ulla nox
MgO

20
67

70

100

T ullanox
MgO

50

93-100

*Percent by weight of base polymer

Hughes synthesized a f l u o r i n a t e d elastomer ("FASIL") ,


but no materials t e s t i n g has been done on t h i s m a t e r i a l ; work
has stopped i n t h i s a r e a because of t h e h y d r o l y t i c i n s t a b i l i t y
of siloxane-type polymers.
Synthesis of perfluoroalkylene e t h e r elastomers i s cont i n u i n g , but no s a t i s f a c t o r y material has yet been developed
D. 5

Program t o Develop and Evaluate Elastomers

The o b j e c t i v e s of t h e program were 1 ) t o develop and


e v a l u a t e c o a t i n g processes f o r elastomers t o be used i n deep
w e l l s , and 2) t o e v a l u a t e commercial elastomers f o r use i n a
geothermal borehole logging t o o l . Application p o t e n t i a l s w e r e
f o r e l a s t o m e r i c m a t e r i a l i n g e n e r a l , but Kalrez O-rings received
specific attention.
Kalrez, a p e r f l u o r b n a t e d elastomer from DuPont has
good p o t e n t i a l f o r deep w e l l a p p l i c a t i o n because of i t s high
thermal s t a b i l i t y and chemical r e s i s t a n c e . I t s usefulness
( e s p e c i a l l y i n packer manufacture) is l i m i t e d by i t s high c o s t :
$2000/lb.
D.5.1

T e s t Program
0

The following elastomers were coated w i t h a 400 A-thick


c o a t i n g of c r o s s - l i n k e d poly ( t e t r a f l u o r o e t h y l e n e ) using an RF
Glow Discharge apparatus : 1 ) Kalrez (DuPont)l 2) Fairprene
BS-5565 (Buna-N, DuPont); 3) Buna-N (Parker) ; 4) Viton V-747-75
(Parker). Samples were aged i n a s o u r gas (composition n o t provided) environment f o r one month a t 200C.

D-15

u.5.2

Results

Both coated and uncoated samples o f Kalrez were s t a b l e


under t h e t e s t conditions. Coating o f t h e Buna-N rubbers w i t h
c r o s s - l i n k Teflon d i d n o t prevent o r minimize degradation which
may have been caused by h e a t alone. Chemical r e s i s t a n c e of Viton
rubber appeared t o be enhanced by t h e plasma coating. An a i r
l e a k during t h e t e s t may have been r e s p o n s i b l e f o r t h e poor
Buna-N performance.
A Kalrez O-ring seal w a s exposed t o steam f o r 100
hours at 275C and 4800 p s i . Experimenters r e p o r t only t h a t it
"failed catastrophically"

D-16

APPENDIX E
COMPARATIVE ALLOY COSTS

E-1

COMPARATIVE ALLOY COSTS


Table E-1 lists the comparative costs of ten common
C
truction alloys. The costs of the alloys are normalized and
compared to AIS1 Type 304L stainless steel, a widely-used alloy.
All values in Table E-1 are comparative values ratioed to 1.00
for Type 304L and do not represent actual dollar values. The
comparative costs in Table E-1 were assembled after examining
available information and talking to alloy suppliers.

The alloy cost comparisons in Table E-1 are based on


the same dimensions of bulk metal sheet for each alloy. This
does not take into account the factors involved in fabricating
an alloy for a particular application. Some corrosive environments may require such a thicker plate of lower cost, less resistant alioy that using a normally more expensive but resistant
alloy will actually result in lower initial costs because a much
thinner plate can be substituted.

E-2

TABLE E-1
COMPARATIVE COSTS OF-SOME ALLOYS

Approximate Relative
Cost per sq ft of %
inch plate*

Alloy

0.25
1.00
1.25
2.13
2.50
2.50
3.00
3.50
3.88
5.00

Carbon Steel
AISI Type 304L
AISI Type 316L
90-10 Cupronickel
Ti-50A (Grade 2)
70-30 Cupronickel
TiCode 12
Monel 400
Inconel 600
Ti-0.2 Pd (Grade 7)

*Cost relative to cost of 1 sq ft of %-inch Type 304L plate.


Based on late 1976 prices.

E-3

APPENDIX F PRELIMINARY LIST OF AVAILABLE GEOTHERMAL


POWER EQUIPMENT

PRELIMINARY LIST OF AVAILABLE GEOTHERMAL


POWER EOUIPMENT

Table F-1 i s a preliminary l i s t of s u p p l i e r s of geothermal equipment. The l i s t includes firms t h a t responded a f f i r matively t o an i n i t i a l survey d i r e c t e d toward i d e n t i f y i n g firms
t h a t manufacture equipment s p e c i f i c a l l y f o r geothermal a p p l i c a t i o n s . This l i s t i s n o t intended t o be a l l - i n c l u s i v e and i s f o r
t h o s e groups who may need to know p o t e n t i a l manufacturers but who
do n o t have access t o such vendors through normal channels. The
l i s t is only a s t a r t i n g p o i n t i n i d e n t i f y i n g t h e equipment t h a t may
be needed t o u t i l i z e a geothermal resource.

F-2

c
TABLE F-1
PRELIMINARY PART-SUPPLIER LIST OF GEOTHERMAL EQUIPMENT
P a r t s or Services

Manufacturer*

Specialty

compressors

The Nash Engineering Co.

Instrument a i r , 0-300 CFM. 125 p s i

Controls and Instruments

Fox Valve Lkvelopm,cnt Co.


M n w e t r i c s Inc.
Leeda and Northrup Co.

Venturi c o n t r o l s and fl-ters


Seismic monitoring instruments
Controls and instruments f o r power generation

E l e c t r i c a l Equipment

C u t l e r H a s c r , Inc.
The I d e a l E l e c t r i c Co.
The Lima E l e c t r i c Co. Dept TC
Louis Allis
Marathon E l e c t r i c
WCGrtr-Edison
Reulaad Electric Co.
TUDCO, The E l e c t r i c Materiala Co.

Motor c o n t r o l s and .witchboards


Large motors, generators, c o n t r o l s

h e r i c a n b a t I& Pipe CO.


National Tank and Pipe Co.
Northwest Pipe and Casing Co.
Wolf Ridge P l a s t i c s
P l a n t Derign. Construction
sad I n s t a l l a t i o n

Specialty motors t o 11.000 Bp


1800 RPPI generators, 50 60 1100 Irv
S t a t i o n step-up transformers
Specialty r o t o r s . c o n t r o l s , packaged d r i v e s
Bus systems. s p e c i a l l y f a b r i c a t e d p a r t s
Polybond-lined d u c t i l e i r o n piping
wood piping

S t e e l pipe, 2-120" d i a
P l a s t i c piping and v e s s e l s
Complete turnby power p l a n t , a l l components on non-turnkey b a s i s
T o t a l flow skid mounted sntems. 2-4 me

Brown h e r i Corp.
Research-Cottrell Inc.
Technical Enterprises, Inc.
DeDietrich (USA). Inc.
m Company, Inc.
BhW
C-E Iummw
D E Natco
C e i l c o t e Company
Croll-Reynolds
DeDietrich (USA), hrc.
Ecrm-Then Energy Sy6te0e Corp.
Poly Processing Co.
Steam-Roger, Inc.
Themchanger Inc.
Wyatt I n d u s t r i e s

E l a t e type h a t exchangers in s t a i n l e s s s t e e l s , titanium. Incolloy


Heat exchangtr equipment
Heat srchangtr equipment
S e p a r a t o r s and water f i l t e r s
Pressure veseels. piping, a i r p o l l u t i o n c o n t r o l equipment
F i l t e r systems
Glass-lined steel vessels. pipes and f i t t i n g s
X e a t exchangers from carbon s t e e l and s t a i n l e s s a l l o y s
Large v e s s e l r and s t r u c t u r e s of high d e n s i t y polyethylene
Mediuwlarge p l a t e f a b r i c a t i o n s . heavy machine work
Tube and s h e l l heat exchangers
Pressure v e s s e l s and heat exchangers. a l l weldable metals

Allis-Chahers Corp.
The Rash Engineering Co.
Uorthingtoa Pump Corp. (USA)

Large c e n t r i f u g a l punpa
Vacuum pumps, 0-9000 CFM, 3-27" Bg
Downhole, jet, hydraulic d r i v e r pump6

Turbine Generators

E l l i o t co.
Turbodyne Corp.

S t e m a d binary vapor t u r b i n e generators


Steam generators

Valves

Kamyr Valves. Inc.


R4clmll International,
Flow Control Division

Severe service b a l l and b u t t e r f l y valves

Wellhead Equipment

R4C Corp.
WIM-Wellhead Systems

Wellhead systems
Wellhead systems

Pressure Vessels

*Affirmative responaes

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