Paper 57 - Presented at 9th MECC, Bahrain, February 12-14th 2001

Properties of Metallic Materials for LNG Service

Liane Smith, Consultant to Nickel Development Institute
Intetech Ltd,
37, Mount Way, Waverton,
CHESTER, CH3 7QF, UK
Fax: +44-1244-336809
Email: [email protected]

Bruce Craig, Consultant to Nickel Development Institute

METCORR
4600 S. Ulster ST., Suite 700,
Denver, Colorado 80237, USA
Fax: +1-303-694-0613
E-mail: [email protected]

ABSTRACT
This paper presents the key physical and mechanical properties of 9% Ni steel, AISI 304L
stainless steel, 36% Ni low expansion alloy and aluminium alloys which are all used for low
temperature engineering, specifically for the handling of liquefied natural gas (LNG). Typical
values for all key properties are given. A theoretical explanation is given for why the alloys have
certain properties, particularly covering the origin of toughness in different kinds of crystal
structures, and also explaining the phenomenon of the interaction of magnetic properties and
thermal expansion which results in the low expansion coefficient of the 36% Ni material.
Practical information on the use and fabrication of the alloys is included.
1. INTRODUCTION
Engineering systems for handling liquefied natural gas are designed for an operating temperature
of 163C. Metals for use at such cryogenic temperatures have to comply with exacting demands
with respect to their mechanical and physical properties. The tensile strength of metals tends to
increase at lower temperature. Metals have to have sufficient strength in service, but also have to
be strong enough to be formed and fabricated at ambient temperature. In terms of mechanical
properties, the need for adequate toughness is of primary concern. Whether a metal is tough at a
given temperature depends upon whether it is able to plastically deform and that depends directly
upon the crystal structure of the metal. This issue is described in more detail below.
The physical properties, such as the thermal conductivity, also have to be considered in the
design. The value of the coefficient of expansion will influence the amount of thermal strain
induced during cooling to the operating temperature and this influences the detailed design
approach for various components.
The aim of this paper is to present certain metal properties pertinent to low temperature
application and to give some of the theoretical background to explain the properties. The paper
draws together many of the critical properties to provide a useful reference resource for design
engineers and metallurgists.

2. CRYSTALLOGRAPHIC NATURE OF PLASTIC DEFORMATION

In considering metals, that are suitable for pressure containment at -163C, the key property that
limits the application of many of the most common metals (including most steels) at such
temperatures is toughness. Toughness is the ability of a metal to deform in a ductile, rather than
brittle, manner when exposed to loads or strains with decreasing temperature. Toughness can be
measured using compact tension and crack-tip opening displacement testing at slow strain rates
or by Charpy testing at high strain rates (impact loading).
It can be shown theoretically that to get ductile behaviour in toughness tests a metal has to have 5
active slip systems. Face centred cubic (f.c.c.) metals, such as nickel and aluminium have a total
of twelve possible slip systems which can take part in the deformation. Moreover, this behaviour
persists in solid solutions with f.c.c. structure (i.e. alloys behave in a similar way to pure single
metal systems). It is this fundamental existence of a multiplicity of slip systems, each of which
offers a low shear stress limit (just about 11 MPa for nickel), which means that f.c.c. materials
behave in an inherently ductile fashion. Face centred cubic crystals do not show brittle
behaviour. They do not show a ductile to brittle transition with temperature and are fully ductile
over the full temperature range.
The other main crystal structure is the body centred cubic (b.c.c.) structure which is found in iron
(typical carbon steel structure). However, at lower temperatures (below the transition
temperature), there are typically only two or three slip systems available in b.c.c. metals and they
are therefore brittle.
The great benefit in toughness properties of the f.c.c. crystal structure is exploited in the 9Ni
steels. These steels contain sufficient nickel so that the microstructure consists of the normal
ferritic (b.c.c.) crystals, or grains, with a small proportion of fully austenitic (f.c.c.) grains. Whilst
the volume fraction of austenite is fairly small (about 4%), it is sufficient to ensure that the steel
has a high toughness even at 163C.
3. METALS FOR APPLICATION AT CRYOGENIC TEMPERATURE
There are four metals practically established in various applications for handling LNG. These are
listed in Table 1 along with examples of components required in LNG systems.
3.1. Chemical Composition
Typical chemical compositions of the metals used in LNG systems are given in Table 2.
3.2. Heat Treatment Condition
A list of the typical standards for 9Ni steel is given in Table 3. These show that 9Ni steel can be
used in two standard heat treatment conditions: Quenched and Tempered (QT) and Double
Normalised and Tempered (NNT). The metallographic structures usually formed in the steel after
water quenching or air cooling from the austenitising temperature (around 800C) are martensite
or bainite with a maximum hardness dependent on the carbon content but rarely more than 400
HV. The final tempering treatment heats the steel just above the austenite reformation
temperature (around 580C) to reform a small amount of austenite. This tempers the martensite

and the carbon diffuses into the small austenite grains to stabilise them. After final tempering the
microstructure consists of ferrite with a fine distribution of carbides and approximately 4 vol%
retained austenite. This results in a steel of high strength and excellent toughness.
The QT route tends to produce a steel with higher yield strength (YS) and high yield strength to
tensile strength (YS:TS) ratio. The choice of heat treatment route depends principally upon the
choice of design code. Where a TS-based design code is chosen there is little incentive to select
the QT grade. The opposite is true where a YS based design code is used. In that case there is also
incentive to select high yield strength weld consumables, even if there is a cost penalty.
The other alloys (304L, 36NiFe and Al alloys) are used in the annealed condition with all the
alloying elements in solution. They do not require further heat treatment prior to fabrication. In
fact heating below the annealing temperature can be detrimental to stainless steels if it is
prolonged sufficiently to cause chromium carbide precipitation. The microstructure is then
sensitised and has reduced corrosion resistance. Similarly, aluminium alloy 5083 should not be
subjected to heating below the annealing temperature as Mg5Al3 or Mg 5Al8 precipitates can form
with resulting risk of stress corrosion cracking.
3.3. Physical Properties
Some physical properties of the metals used for LNG handling are presented in Table 4.
The remarkably low coefficient of expansion of 36NiFe arises because of the superposition of
two phenomena, one related to thermal expansion and the other related to the ferromagneticparamagnetic transformation. Charles-Edouard Guillaume was awarded the Nobel Prize in 1920
for his discovery of, and explanation of, the low coefficient of expansion of 36NiFe alloy. He
observed the contraction of this alloy on cooling and found that its length remained virtually
unchanged when cooling from the Curie Point (the temperature corresponding to the
paramagnetic-ferromagnetic transformation, about 260C for this alloy). The change in length
was least when the rate of change of magnetic transformation from para- to ferro- magnetic
behaviour was at a maximum1. The increase in ferromagnetism at lower temperatures results in
an increase in atomic spacing, which counteracts the normal contraction due to the reducing
temperature.
The thermal conductivity of the aluminium alloy is very much higher than the other materials.
This is advantageous for its use for a cryogenic heat exchanger.
The varying physical properties of the different alloys result in differing levels of thermal stress
as the metals cool. The last rows of Table 4 calculate an approximate stress level for the
contraction of a restrained length of metal from zero to 163C. The thermal stress, = E = E
T = 163 E , where E is the Youngs Modulus, is the strain, is the coefficient of expansion
and T the temperature range. The absolute value is given in MPa and the value as a percentage
of the minimum yield strength (from Table 5).
The stress is lowest in 36NiFe because of its extremely low coefficient of expansion. Whilst the
stress is high in 9Ni, its high strength prevents this alloy from yielding because of the thermal
strain of contraction. The low Youngs modulus of the aluminium alloy keeps the stress fairly
low but still above the yield strength of the alloy. The high elastic modulus and expansion
coefficient of the stainless steel result in the highest stress levels, also well above the yield
strength of the material. As a result of the physical properties, both stainless steels and aluminium
alloys have to be designed with expansion loops or with structures of inherently low modulus

(such as the waffle design of membrane used for the stainless steel tanks) in order to keep the
contraction stresses below yield value.
3.4. Mechanical Properties
The mechanical properties of the metals used for LNG handling are presented in Table 5.
Most mechanical properties are taken from typical values for annealed material. In some cases
different sources give different values. In such cases the mid-range of values is reported here.
Specified minimum values at room temperature vary depending upon the specification but are
generally much lower normal values in terms of strength, toughness etc.
The rise in strength which is noted in the 304L stainless steel and 36NiFe alloy as the temperature
drops are a result of the effect of interstitial elements (typically nitrogen or carbon) in the crystal
lattice as it cools down. The aluminium alloy does not have any interstitial alloying elements (all
elements are fully dissolved) and so there is little change in the strength as the temperature drops
from zero.
The aluminium alloy shows low Charpy Impact toughness values in the parent metal, with almost
identical values also found in the weld zone, and little change in cooling to cryogenic
temperature. This reflects the low shear strength of this alloy.
A potential factor to consider in the case of type 304L stainless steel and 36NiFe would be the
stability over long period to exposure to temperatures of -163C as some metals can undergo
(partial) transformation to martensite at these temperatures. This is a strong microstructural
constituent but it tends to reduce the metal ductility and toughness. However, long term past
performance of these materials in cryogenic applications indicates that this is not a practical
concern.
3.5. Fabrication Aspects
The different metals are available in different forms (Table 6). 9Ni steel is made only as plate,
geared to its main application for storage tanks. In some cases it has been formed into pipe and
longitudinally welded but this product form is not often used.
The other alloys are available as plate or as strip, which is easily formed into tubing or pipe.
Welding of stainless steels and 9Ni steel is described in detail elsewhere2,3. Some general points
are described below.
3.5.1. 9Ni steel can be prepared for welding by flame cutting and grinding. Weld
preparations need to be slightly wider than for conventional steels to ensure good root access.
Welding methods used include GMAW, GTAW and SMAW, although some fabricators have
used SAW. The strong magnetic nature of 9Ni can lead to problems of arc blow, which can be
minimised by avoiding direct current welding and by de-magnetising on site. Pre-heating of the
weld zone is not necessary. The maximum interpass temperature is 150C.
Three categories of welding electrode can be used4:
1) Ni/15-22Cr/ Fe type with additions of Mo, Nb etc.
2) 50Ni/13Cr/Fe/Mo type

3) 16Cr/13Ni/Mn/W modified austenitic type

The weld consumable usually selected is the first type, Ni 22Cr 9Mo 3.5Nb (Alloy 625), which
gives an as-deposited yield strength of about 450 MPa and tensile strength of about 700-800 MPa
minimum. Because the weld metal is slightly undermatching the parent metal in strength, the wall
thickness of the tanks is usually increased to compensate. Nevertheless, cross-weld tensile
specimens tend to yield first in the gauge region, and then work harden, with ultimate yielding
in the surrounding parent metal once the TS of the work hardened weld has exceeded the parent
steel yield strength. The normally applied design guides tend not to exploit the tensile properties
of the weld region to the full.
There is a tendency for the HAZ to show higher hardness than the weld deposit but the hardness
can be controlled by limiting the parent metal carbon content to 0.08% max. With that carbon
level the maximum hardness falls below 350Hv and so no post-welding stress relief heat
treatment is required.
The very fine microstructure in the HAZ results in good toughness with Charpy impact values
throughout the weld zone tending to be in excess of 100J at 196C. Extensive critical defect
length tests have been carried out on 9Ni structures indicating quite long critical defect sizes
(dependent upon the precise crack tip location) typically between 19-47 mm. Tests with preexisting defects have proven that 9Ni tanks will leak-before-break. Decommissioned 9Ni tanks
have also been extensively inspected after many years in service, and show no deterioration in
properties or tendency for slow crack extension5,6.
3.5.2. Welding of stainless steels for LNG service requires the same weld preparation
and controls as would be found for any conventional stainless steel welding. Many welding
techniques are applied, although there is a preference for GTAW for thin sections. The welding
consumables selected for 304L stainless steel are E308L (rod) and ER 308L (wire), with adjusted
chemical compositions for Low Temperature application.
The key difference in welding procedures, compared to fabrication of stainless steels for use at
ambient conditions, is to aim for a low volume of delta ferrite in the weld. Whereas conventional
welding would allow 5-12% delta ferrite (to assist in reducing hot cracking), it is normal practice
for LNG service to limit the ferrite to lower values (0-2 Ferrite Number according to IIW
Document II-C-871-91) in order to maximise the toughness. Resistance to hot cracking in these
low ferrite welds depends upon keeping the S and P to a minimum in the weld consumable and
having sufficient Mn to react with the S to form MnS inclusions.
Weld toughness is also optimised by keeping the weld oxygen content low (e.g. basic rather than
rutile coated electrodes) and nitrogen content low e.g. by good gas shielding with Ar or Ar-He
mixtures. Minor additions of CO2 or O2 may be used in GMAW shielding gas to improve the arc
characteristics.
The presence of some delta ferrite in the weld zone increases the strength relative to the parent
metal and reduces the toughness.
3.5.3. 36NiFe is normally in the form of thin sheets and is generally welded by GTAW.
The matching filler wire has very low levels of trace elements (S, P, Al, B, N) to minimise
porosity and re-heat cracking. The wire is also alloyed with 0.5-1.0% Ti and up to 3% Mn which
react with contaminant elements to form inclusions. These help to nucleate a fine dendrite
structure in the weld zone. Alternatively 36NiFe can be welded by resistance seam welding

without any filler material. This welding technique has been applied for the fabrication of LNG
containment tanks made with the membrane design.
No pre- or post- welding heat treatment is used. Surfaces should be clean before welding and any
oxidation removed by grinding. The heat input should be kept low with a low interpass
temperature of 180C to prevent any grain growth in the weld or HAZ.
3.5.4. Aluminium alloys are welded using gas shielded processes (GTAW and GMAW)
with Ar or Ar-He gas. Filler metals for welding alloy 5083 include 5183, 5356 and 5556A. The
welds have tensile and toughness properties very similar to the parent metal, both at ambient and
cryogenic temperature.
Where the 6000 series of alloys are selected (e.g. for flanges) suitable filler metals include the AlSi grades which are resistant to weld metal solidification and HAZ liquation cracking, or Al-Mg
filler metals which produce more ductile welds. These alloys show a loss in strength of the HAZ
after welding. Whilst this can be recovered by heat treatment, that is rarely practicable and so the
allowable design stress for welded 6000 series has to be reduced to account for the loss in
strength on welding.
4. CONCLUSIONS
A range of alloys, 9% Ni steel, AISI 304L, 36% NiFe and Aluminium alloys, with diverse
mechanical and physical properties has been applied for handling liquefied natural gas since the
start of the LNG business over the last 40 years. Certain specific properties have been shown to
derive fundamentally from the atomic and crystalline structure of the metals concerned which
thus limits the number of suitable alloys for LNG applications. Correct use of these alloys,
allowing for the impact of their specific properties on the design, allows the correct material to be
used for each application.
REFERENCES

Lambret E. and Saindrenan G., The discovery of Invar and the Metallurgical Works of Charles-Edouard
Guillaume, The Invar Effect, A Centennial Symposium, Ed. J. Wittenauer, TMS 1997
2
Avery, R.E. and Tuthill, A.H., Guidelines for the Welded Fabrication of Nickel Containing Stainless
Steels for Corrosion Resistant Service., NiDI Publication 11007
3
Avery, R.E. and Parsons, D., Welding of Stainless and 9% Nickel Steel Cryogenic Vessels, NiDI
publication 14037
4
Guide to the Welding and Weldability of Cryogenic Steels, pub IIW 1987, ISBN 0 85300193 6
5
Lewis J.P. and Williams, T.A., Evaluation of Decommissioned LNG storage Tanks at Chula Vista,
California, NiDI Publication 10067
6
Mounce, W.S., Nine per cent nickel 28 years of reliable service in liquefied natural gas containment,
NiDI Technical Series No. 10030
5
Scott MT & Gittos MF, TWI Research Report 163/1981 Oct 1981

Table 1 Typical Applications of Metals Used for LNG Systems

Alloy
9Ni
304L

TYPE
9% Ni steel
Stainless steel type AISI 304L

36NiFe

Low expansion, 36%Ni-Fe alloy

Al

Aluminium alloy type 5083 (Al-4.5%Mg)

Alloy 5154 (Al-3.5%Mg)
Alloy 6000 (Al Si)

APPLICATION
Storage tanks
Piping; Small vessels.
Some designs of large storage tanks.
Some large storage tank designs.
Piping in critical applications.
Spherical or prismatic storage tanks for ship transportation of LNG.
Tubing for the main cryogenic heat exchanger.
Forgings such as flanges.

Table 2: Typical Chemical Compositions of Metals Used in LNG Systems.

Element (Maximum weight%)
Alloy UNS
C
Si
Mn
S
P
Ni
Cr
Fe
Al
9Ni
K81340 0.13* 0.15- 1.00 0.040 0.035 8.00Bal
0.35
10.00
304L S30403 0.03
1.00 2.00 0.030 0.040 8.018.0- Bal
12.0
20.0
36Ni K93600 0.04
0.25 0.2- 0.012 0.012 35Bal
0.4
36.5
Al
A95083 0.40 0.40- 0.05- 0.40 Bal
5083
1.0
0.25
Al
A96061 0.40- 0.15 0.04- 0.7
Bal
6061
0.8
max.
0.35
max.
* lower carbon content, e.g. 0.04 - 0.08%, reduces the risk of excessive HAZ hardening.

Cu
-

Mg
-

Zn
-

0.10

4.0- 0.25
4.9
0.15- 0.8- 0.40 1.2

Table 3 Specifications for 9Ni steel Indicating Heat treatment Conditions Covered
Country
Specification
Heat Treatment
Condition
Belgium
NBN 630-70
France
AFNOR A36-208
Germany
Werkstoffblatt 680-70
NNT or QT
Italy
UNI 5920-66
NNT or QT
UK
BS1501 509
NNT or QT
BS1501-510
QT
USA
ASTM A353
NNT
ASTM A553
QT
NNT = Double normalised and Tempered
QT = Quenched and Tempered
Table 4 Physical Properties of Metals Used for LNG Systems
Property
T
9%Ni
C
Steel
3
Density, kg/m
7860
Elastic Modulus E, GPa
+20
186
-196
207
Thermal Conductivity, W/mC
+20
28.5
-196
13.0
Mean Coefficient of thermal
0 to
9.5
expansion, , 10-6/C
-196
Theoretical thermal stress in
304
contracting a rigid length from
0 to -163C, MPa
= E = E T = 163 E
Theoretical thermal stress in
51-69%
contracting a rigid length from
0 to -163C, MPa as a
percentage of yield strength

AISI 304L
Stainless Steel
7900
193
205
13.4-15.1
9
14.4 15 (at 0C)
11.7 - 13.5 (at -196C)
440

36% Ni Fe
Alloy
8120
148
138
10.5
5.7
1.5

Al alloy
5083
2660
70
81
117

34

228

176%

12.6%

157%

17.5

Table 5 Mechanical Properties of Metals Used for LNG Systems (Typical values unless stated to be specified)
Property
T
9%Ni
AISI 304L
36% Ni Fe
C
Steel
Stainless Steel
Alloy
Yield stress, MPa
0
441-587 min. specified
250
270

Al alloy
5083
145

650 (NNT), 690 (QT)

Ultimate tensile stress, MPa

-196
0

680 (NNT), 840 (QT)

637-834 min. specified
840 (NNT)

400
590

650
490

165
290

Elongation to break, %

-196
0

1100 (NNT), 940 (QT)

17-20 min.specified
30

1525
60

900
40

405
16

Impact energy, J

-196
0

23
125

40
200

40
150

36
247

-196

42

100-150 parent
70-90 HAZ
50-70 GMAW
40-100 SMAW

>100

20

Table 6 Fabrication Aspects of Metals Used for LNG Systems

9%Ni
Steel
Availability in:
- thin sheet, strip
- plate
- tube
- bar/rod
- wire
Welding methods*

Welding consumable

No
Yes
No
No
No
GMAW,
SMAW,
GTAW,
SAW
70Ni type
(alloy 625)
50Ni type
16Cr type

* GTAW = Gas Tungsten Arc Welding

GMAW = Gas Metal Arc Welding
SMAW = Shielded Metal Arc Welding
SAW = Submerged Arc Welding

AISI 304L
Stainless Steel

36% Ni Fe
Alloy

Al alloy
5083

Yes
Yes
Yes
Yes
Yes
GTAW or GMAW

Yes
No
No
Yes
Yes
Resistance seam
welding or GTAW

Yes
Yes
Yes
Yes
No
GTAW or
GMAW

Use 308L stainless

steel electrodes
giving max. ferrite
number 2 in the
weld zone

Use filler with 0.51.0%Ti and up to

3%Mn

Alloys 5183,
5356, 5556A