Ministry of Defence

Defence Standard

03-24/Issue 3 5 September 1997

CHROMIC ACID ANODIZING OF ALUMINIUM AND

ALUMINIUM ALLOYS

Reprinted 23 June 1999

Incorporating Amendment No. 1

This Defence Standard supersedes

Def Stan 03-24/2
dated 14 September 1988
DEF STAN 03-24/3

AMENDMENTS ISSUED SINCE PUBLICATION

AMD NO DATE OF TEXT AFFECTED SIGNATURE &

ISSUE DATE
23/6/1999 Page 4 Section 4.2 and G McBride SPM4
1 Page 8 Section 12.1.5

Revision Note
This Defence Standard has been updated in order to bring method and procedures into line with
current requirements.

Historical Record
DEF-151 dated March 1965
Def Stan 03-24/1 dated 6 September 1984
Def Stan 03-24/2 dated 14 September 1988
 DEF STAN 03-24/1

CHROMIC ACID ANODIZING OF ALUMINIUM AND ALUMINIUM ALLOYS

PREFACE

This Defence Standard supersedes

Def Stan 03-24/Isssue 2
Dated 14 September 1988

i This Defence Standard specifies the requirements for Chromic Acid Anodizing of
Aluminium and Aluminium Alloys.

ii This Standard has been produced on behalf of the Defence Engineering and Equipment
Standardization Committee (DEESC) by the Corrosion Prevention of Metals Subcommittee
(E3).

iii This Standard has been agreed by the authorities concerned with its use and is intended to
be used whenever relevant in all future designs, contracts, orders etc and whenever practicable
by amendment to those already in existence. If any difficulty arises which prevents application
of the Defence Standard, the Directorate of Standardization shall be informed so that a remedy
may be sought.

iv Any enquiries regarding this Standard in relation to an invitation to tender or a contract in

which it is incorporated are to be addressed to the responsible Technical or Supervising
Authority named in the invitation to tender or contract.

v This Standard has been devised for the use of the Crown and its contractors in the
execution of contracts for the Crown. The Crown hereby excludes all liability (other than
liability for death or personal injury) whatsoever and howsoever arising (including, but without
limitation, negligence on the part of the Crown its servants or agents) for any loss or damage
however caused where the Standard is used for any other purpose.

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CONTENTS PAGE

Preface 1

Section One. General

1 Scope 3
2 WARNING 3
3 Related Documents 3
4 Definitions 4
5 Information to be Supplied to the Processor 5
6 Process Control 5

Section Two. Applications and Limitations

7 Applications 6
8 Compatibility with Explosives, Propellants or Pyrotechnics 6
9 Limitations 7

Section Three. Process Requirements

10 Surface Preparation 8
11 Anodizing 8
12 Washing 8
13 Sealing 9
14 Drying 9
15 Re-anodizing 9

Section Four. Inspection and Test

16 Processing 10
17 Frequency of Testing 10
18 Appearance 10
19 Test for Electrical Insulation (Sealed Coatings Only) 11
20 Corrosion Test 11
21 Sealing Quality 11

Annex A Chromic Acid Anodizing Process for Aluminium and A-1

Aluminium Alloys
Annex B Analysis of Chromic Acid Electrolyte B-1
Annex C Stripping Solutions for the Removal of Anodic Coatings C-1
Annex D Chromic Acid Anodizing for the Detection of Defects in D-1
Aluminium Alloy Bars, Extrusions, Sheet, Rolled Plate,
Forgings and Machined Items.
Annex E Procedure for Anodizing Hollow Items such as Tanks, Long E-1
Tubes and Extrusions
Annex F Approximate Conversion of Metric Units to Imperial F-1
Equivalents (Non-US)

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CHROMIC ACID ANODIZING OF ALUMINIUM AND ALUMINIUM ALLOYS

Section One. General

1 Scope

This Standard specifies the requirements for chromic acid anodizing of aluminium and
aluminium alloys.

2 WARNING

This Standard calls for the use of substances and/or procedures that may be injurious to health
if adequate precautions are not taken. It refers only to technical suitability and in no way
absolves either the designer, the producer, the supplier or the user from statutory and all other
legal obligations relating to health and safety at any stage of manufacture or use.

3 Related Documents

3.1 The following documents and publications are referred to in the text of this Standard:

BS 6161: Part 3 Methods of Test for Anodic Oxidation Coatings on Aluminium and Its
Alloys. Part 3: Assessment of Sealing Quality by Measurement of the
Loss of Mass after Immersion in Phosphoric-chromic Acid Solution.

BS 6161l Part 15 Methods of Test for Anodic Oxidation Coatings on Aluminium and Its
Alloys. Part 15: Determination of Electrical Breakdown Potential

BS 7479 Method for Salt Spray Corrosion Tests in Artificial Atmospheres.

Def Stan 03-2 Cleaning and Preparation of Metal Surfaces.

Def Stan 03-25 Sulfuric Acid Anodizing of Aluminium and Aluminium Alloys

3.2 Reference in this Standard to any related documents means in any invitation to tender or
contract the edition and all amendments current at the date of such tender or contract unless a
specific edition is indicated.

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3.3 Related documents are obtainable from:

DOCUMENT SOURCE
British Standards (BS) British Standards Institution
Sales Department
389 Chiswick High Road
London W4 4AL
Tel: 0181 996 9000
Fax: 0181 996 7400
Defence Standards (Def Stan) Directorate of Standardization
Ministry of Defence
Kentigern House
65 Brown Street
GLASGOW G2 8EX
Tel: 0141 224 2531
Fax: 0141 224 2503

4 Definitions

For the purpose of this Standard the following definitions apply.

4.1 Process Control Schedule. The document which specifies/defines:

The sequence of manufacturing operations and processes.

The control parameters and their tolerances for each individual process within the total
sequence.

4.2 Purified Water. Water which has been produced by distillation, deionization or reverse
osmosis, having a conductivity measurement not greater than 30 µS/cm at 20°C and a silica
content not greater than 5 ppm w/w (as SiO2).

4.3 Significant Surface. That area of the item covered, or to be covered, by the coating and for
which the coating is essential for serviceability and/or appearance.

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5 Information to be Supplied to the Processor

The following information shall be given on the drawing, contract or order.

(a) The number of this Defence Standard.

(b) The specification, heat treatment and surface condition of the aluminium alloy.

(c) The sealing requirements (see clause 13).

(d) The Significant Surface. This may be indicated on the drawing or by a marked
sample.

(e) Any special conditions of service, eg contact or close proximity to explosives,

Propellants or pyrotechnics.

(f) Any special condition of service, eg Aerospace Applications requiring

Mandatory Process Control Schedules (see clause 6).

(g) Any preference for position of contacts.

(h) Any requirement for test of electrical insulation (see clause 19).

(i) Whether the anodizing is for the detection of defects (see annex D).

(j) Any limit on the number of retreatments (see clause 15).

(k) Additional test requirements.

6 Process Control.

6.1 A Process Control Schedule suitable for achieving the requirements of this Standard shall
be prepared by the processing contractor(s) prior to the commencement of production.

6.2 Details of the coating process, including all preparatory treatments, post-coating treatments
and processing, thickness of the coating, significant surface, tests and all other treatments shall
be included in the Process Control Schedule.

6.3 All stages in the complete schedule shall follow each other without delay.

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Section Two. Applications and Limitation.

7 Applications

7.1 The chromic acid anodizing process yields relatively thin coatings (of the order of
2 µm) that may be dyed and which are normally suitable for general protective purposes and for
subsequent painting or adhesive bonding.
NOTE: This process can be followed by other anodizing processes.

7.2 For castings of suitable composition (see 9.2), this is the preferred process for treatment
and shall be specified where anodizing is required and one or more of the following
considerations is paramount.

7.2.1 Minimizing loss of fatigue strength due to anodizing.

7.2.2 The treatment of items containing crevices or small blind holes from which electrolyte
may be difficult to remove.

7.2.3 The treatment of material less than 250 µm thick.

7.3 Information and special requirements concerning the use of chromic acid anodizing as an
aid to the detection of defects in aluminium alloy semi-finished products and machined items is
given in annex D. Where a penetrant method of flaw detection is additionally to be used it shall
precede anodizing.

7.4 Information on the procedure for anodizing hollow items such as tanks, long tubes and
extrusions is given in annex E.

8 Compatibility with Explosives, Propellants or Pyrotechnics

8.1 Whilst anodizing is not essential to render aluminium or aluminium alloys compatible with
explosives, propellants or pyrotechnics, anodized surfaces may be expected to be compatible
provided that all residues of reagents used in anodizing and sealing are removed by the final
washing process

8.2 After chromic acid anodizing, any electrolyte remaining after inadequate washing, or due
to seepage from flaws in the metal, will leave an easily detected yellow stain. For this reason
this process is mandatory for anodized items which will be in contact with explosives,
propellants or pyrotechnics and is preferred for anodized items which are to remain in close
proximity to explosives, propellants or pyrotechnics.

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8.3 Advice regarding the choice of process for applications where compatibility with
explosives, propellants or pyrotechnics is a requirement may be obtained from the responsible
Technical or Supervising Authority named in the tender, contract or order.

9 Limitations

9.1 The standard process (annex A) may not provide optimum corrosion resistance when
applied to high zinc aluminium alloys, especially in the overaged condition, and an alternative
process may be considered. A suitable alternative process is given at A.4.3.

9.2 The process is not normally suitable for use on aluminium alloys containing a specified
maximum total of 7% (copper + nickel + iron), or more than 6% of copper. A silicon content
of greater than 7% in castings may adversely affect the properties of the film.

9.3 Composite items which include non-aluminium materials which would be attached by the
process, or would prevent satisfactory formation of the anodic coating on the aluminium alloy,
or would cause attack of the aluminium alloy, shall not be anodized as assemblies unless the
non-aluminium surfaces are effectively masked.

9.4 This process shall not be used on items which are liable to be used in contact with
concentrated hydrogen peroxide (HTP).

9.5 All heat treatment procedures shall be completed prior to anodizing.

9.6 Dyed film have an inferior light fastness when compared to sulfuric acid anodized films
(see Def Stan 03-25).

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Section Three. Process Requirements

10 Surface Preparation

Surfaces shall be cleaned and free from grease, oil, oxide, scale or other foreign matter. All
items shall be degreased prior to commencement of a cleaning sequence which shall be in
accordance with Def Stan 03-2 to produce a chemically clean surface. Items to be anodized
for flaw detection shall not be abrasive blasted (Def Stan 03-2, Method D).

11 Anodizing

One of the processes described in Annex A shall be used. The method of analysis of the
electrolyte is indicated in annex B.

12 Washing

12.1 Immediately after removal from the anodizing bath all items shall be washed to remove
electrolyte as follows:

12.1.1 Items which have been anodized other than for flaw detection, painting or adhesive
bonding shall be washed in clean cold running water. They shall then be finally rinsed in
purified water at a temperature not exceeding 60°C. Items shall then be sealed in accordance
with clause 13.

12.1.2 Items which have been anodized for painting or adhesive bonding shall be washed in
clean cold running water. They shall then be finally rinsed in purified water at a temperature
not exceeding 60°C.

12.1.3 Items which have been anodized to detect surface discontinuities, eg cracks or laps,
shall only be given a brief rinse in cold water, in order to avoid removal of chromic acid from
defects. Inspection shall be carried out not less than 8 hours after anodizing. It is not necessary
to wait 8 hours if inspection is for defects other than surface discontinuities (see D.2.2). After
inspection for surface discontinuities, satisfactory items shall be treated in accordance with
12.1.1 or 12.1.2 as appropriate.

12.1.4 Particular attention shall be given to the thorough washing of castings and of items to
be used in contact with, or in close proximity to, explosives, propellants or pyrotechnics.

12.1.5 Water used for final rinsing shall be discarded or retreated when the conductivity
exceeds 100 µS/cm and/or when the silica content becomes greater than 5 ppm w/w (as SiO2).

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13 Sealing

13.1 Items shall be sealed by immersion in a solution made up from purified water at not less
than 96°C for a minimum period of 10 minutes, at pH of 5.5 – 7.0 (corrected to 20°C),
adjusted by the addition of one of the following: acetic acid, sodium hydroxide, or ammonium
hydroxide as necessary.

13.2 Items anodized as a pre-treatment for painting or adhesive bonding shall not be sealed.

14 Drying

14.1 Drying by means of chlorinated solvents containing surface active agents shall not be
used.

14.2 Items anodized for flaw detection shall be allowed to dry naturally.

14.3 Items to be subsequently painted or adhesive bonded shall not be sealed but shall be dried
at a temperature not exceeding 60°C. Suitable precautions shall be taken to prevent
contamination.

14.4 If the items are to be dried at elevated temperatures, the temperature shall not exceed
110°C. The duration at this temperature shall not exceed 10 minutes.

15 Re-anodizing

15.1 Items which are to be re-anodized shall have the anodic coating removed before
retreatment.

15.2 The use of stripping solutions for the removal of anodic coatings may result in an attach
on the substrate which, in finished items, may adversely affect their fatigue strength. Suitable
chemical methods are described in annex C.

15.3 Attention is also drawn to the desirability of abrasive blasting (Def Stan 03-2, Method D)
before re-anodizing. Some measure of compressive stress is introduced into the surface by this
method.

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Section Four. Inspection and Test

16 Processing

The processing methods employed shall comply with the Process Control Schedule where
specified (see clause 6).

17 Frequency of Testing

17.1 Visual examination shall be applied to all items. The test for electrical insulation (see
clause 19) and, where specified, any of the tests in clauses 20 and 21, which may be applicable,
shall be carried out on not less than 2% of the items represented, with a minimum of one item
per anodizing batch. A batch shall consist of items of the same material specification
processed together in the same anodizing bath.

17.2 In exceptional circumstances, eg the treatment of a small number of large items or large
number of small items, the frequency of such tests may be modified. Coupon samples coated
together with the items may be used, due consideration being given to their shape, size and
material. The treatment of the coupon samples shall be representative of that applied to the
items being coated.

18 Appearance

18.1 The undyed coating is usually light grey but may be dark grey or black on some alloys
and is opaque white on some aluminium-magnesium alloys. The presence of processing
residues on items shall be cause for rejection. Slight yellow staining due to chromic acid
absorption during anodizing and not due to inadequate washing may not be cause for
rejection. Surfaces which are to be in contact or near contact with explosives propellants or
pyrotechnics shall be free from yellow staining. Examination for staining shall take place not
less than 72 hour

NOTE: Yellow stains of this type may indicate the presence of material defects.

18.2 When internal cathodes are used, the internal surface of the treated items shall be
carefully examined for evidence of ‘anodic burn’ caused by inadvertent contact between the
item and the cathode. Surfaces which cannot readily be examined by the unaided eye, eg the
bores and internal surfaces of long tubes and hollow spars, shall be systematically explored by
a visual aid such as an intrascope.

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19 Test for electrical Insulation (Sealed Coatings Only)

Items may be subjected to the appropriate test method in BS 6161: Part 15, carried out at a
relative humidity not exceeding 60%, when the breakdown voltage shall be not less than 50
volts or such other value as may be specified on the drawing or order. The coatings, when
tested, shall be dry and the test shall not be applied on edges unless these have been rounded,
or on wire less than 0.5 mm diameter. For tests on anodized wire, the contact electrode shall
be a 3 mm diameter polished hard metal cylinder.

NOTE: The surface finish of items to be anodized for breakdown voltage will influence the
electrical resistance of the coating required.

20 Corrosion Test

Where the Process Control Schedule requires a corrosion test, a test panel (minimum
dimensions 120 mm x 60 mm) of the same material specification as the components, shall be
anodized and sealed along with the components. The test panel shall be subjected to the salt
spray method as described in BS 7479. Where the components are of a form other than plate
or sheet, the actual component shall be subjected to the test. The duration of the test shall be
for 300 hours.

21 Sealing Quality

When the Process Control Schedule requires an assessment of sealing quality, the test method
described in BS 6161: Part 3 shall be used. The mass loss shall not be more than 3 g/m2.

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COLLATION PAGE

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 DEF STAN 03-24/3
ANNEX A

Chromic Acid Anodizing Process for Aluminium and Aluminium Alloys

A.1 Electrolyte. The electrolyte shall consist of an aqueous solution containing 30 to 100 g
Of chromium trioxide (chromic acid – CrO3) per litre. Chloride in the electrolyte shall not
exceed the equivalent of 0.20 g NaC1 per litre and the sulfate shall not exceed 0.50 g Na2 SO4
per litre. The free chromic acid content shall not be allowed to fall below 30 g per litre. The
electrolyte may be regenerated by the addition of chromic acid providing that the total
chromium in solution does not exceed 100 g per litre calculated as CrO3. The electrolyte shall
be agitated by air or mechanical means sufficiently to maintain a uniform temperature
throughout the bath.

A.2 Cathode. The cathode shall be mild steel or stainless steel in the form of plates or the
Tank itself. The anode-to-cathode area ratio is not critical but less chromic acid is consumed at
the higher ratios. Values varying from 5:1 to 10:1 are generally suitable. Where the tank acts
as the cathode, the sides and bottom may, if desired, be partially covered by glass or other
chemically inert insulating material to reduce the cathodic area.

A.3 Suspension or Jigging. The items to be anodized shall be suspended by such means
that good electrical contact is maintained throughout the treatment. Any metallic parts of a
suspension device which makes contact with the electrolyte shall be of aluminium or titanium.
Suspension devices with spring or screw contacts are recommended. Where possible items
shall be suspended in the bath so that air or evolved oxygen cannot become entrapped, causing
incomplete coating. Rigid items which are too small to be held in jigs may be packed in
perforated aluminium or titanium canisters which shall incorporate means for maintaining
electrical contact between the items and shall permit adequate circulation of the electrolyte
through their interiors. Items with flat faces, such as washers, tend to nest together and cannot
normally be effectively treated in canisters unless adequately dispersed by treating them with
other items. Care shall be taken that items undergoing treatment do not come into contact
with the tank, stirrer, heating or cooling pipes or cathodes, as this may cause breakdown of the
film and damage to the items.

A.4 Anodizing Procedure

A.4.1 Standard process. The operational temperature of the electrolyte shall be within the
range of 38 to 42°C. The items to be treated shall be immersed in the electrolyte and connected
as the anode to a suitable electrical source. The voltage across the bath shall be then increased
in steps of not more than 5 volts, from 0 to 40 volts in the first 10 minutes, maintained at 40
volts for 20 minutes and gradually raised to 50 volts during the next 5 minutes and maintained
at 50 volts for 5 minutes. These times shall be regarded as minima.

A-1
DEF STAN 03-24/3
ANNEX A
A.4.2 Alternative process for castings. As the temperatures and voltages given in A.4.1 may
be unsuitable for anodizing certain aluminium casting alloys, the following alternative
conditions may be used where necessary.

A.4.2.1 The temperatures of the electrolyte shall be in the range 25 to 30°C. Bath voltage
shall be increased in steps of not more than 5 volts from0 to 40 volts in 10 minutes and the
voltage maintained at 40 volts for 30 minutes.

A.4.3 Alternative process for high zinc aluminium alloys in the over aged condition. The
temperature of the electrolyte shall be (35 ± 2) °C. The bath voltage shall be raised to (19-22)
volts and held at that level for a minimum of 30 minutes. The rate of voltage increase shall be
3 to 4 volts per minute. All other anodizing conditions shall be as in A.1, A.2 and A.3.

A-2
 DEF STAN 03-24/3
ANNEX B

Analysis of Chromic Acid Electrolyte

B.1 The electrolyte shall be analysed by any reputable method which shall be comparable
with or better than the following referee method.

NOTE: The reagents used shall be of recognized analytical quality. Purified water shall be
used throughout.

B.2 Total Chromium

B.2.1 Reagents

B.2.1.1 Sulfuric acid (SG = 1.84) diluted 25% (v/v).

B.2.1.2 Ferrous ammonium sulfate, 0.1M solution.

Dissolve 80 g ferrous ammonium sulfate in 600 ml of the diluted sulfuric acid and dilute to 2
litres.

B.2.1.3 Potassium dichromate, M/60 solution.

Dissolve 9.807 g potassium dichromate in 500 ml water and dilute to 2 litres.

B.2.1.4 Silver nitrate, 3% (m/v) solution.

B.2.1.5 N-phenylanthranilic acid indicator.

0.1% (m/v) in 0.1% (m/v) solution of sodium carbonate.

B.2.2 Procedure

B.2.2.1 Standardization of ferrous ammonium sulfate. Measure exactly 25 ml of the

potassium dichromate solution into a 500 ml conical flask containing 200 ml water and 45 ml
of the diluted sulfuric acid. Add 5 drops of the indicator and titrate with the ferrous
ammonium sulfate solution until the reddish-purple tint turns to green. Towards the end-point
the ferrous ammonium sulfate solution should be added drop-wise allowing a few seconds to
elapse between additions. Let (a) ml be the amount of ferrous ammonium sulfate required.

B.2.2.2 Determination of total chromium. Dilute 20 ml of the electrolyte to 250 ml in a

calibrated flask. Measure exactly 25 ml of the diluted solution into a 500 ml conical flask,
containing 150 ml of water and 45 ml of the diluted sulfuric acid. Add 10 ml of the silver
nitrate solution and 2 g of ammonium persulfate. Heat the solution to boiling for 20 minutes to
decompose the excess ammonium persulfate. Cool to room temperature and add 5 drops of
The indicator. Titrate with the ferrous ammonium sulfate solution as in B.2.2.1 above. Let (b)
ml be the amount of ferrous ammonium sulfate required.

B-1
DEF STAN 03-24/3
ANNEX B
B.2.2.3 Calculation. Total chromium, calculated as CrO3, in grams per litre.

= 125 x (b)
31 (a)

B.3 Free Chromic Acid (Used Electrolyte).

B.3.1 Reagent. Sodium carbonate, 0.25 M solution.

B.3.2 Procedure. To 100 ml of water in a 250 ml conical flask add 10 ml of the electrolyte
and titrate with the 0.25M sodium carbonate solution to the first appearance of a distinct
permanent turbidity. Let (c) ml be the amount of sodium carbonate solution required.

B.3.3 Calculation. Free chromic acid, calculated as CrO3, in grams per litre = 5(c).

B.4 Free Chromic Acid (Fresh Electrolyte).

B.4.1 Reagents

B.4.1.1 Sulfuric acid (SG = 1.84) diluted to 25% (v/v).

B.4.1.2 Ferrous ammonium sulfate, 0.1M solution, prepared as described in B.2.1.5

B.4.2 Procedure. Dilute 25 ml of the electrolyte to 250 ml in a calibrated flask. To 45 ml of

the diluted sulfuric acid and 200 ml of water contained in a 500 ml conical flask, add 50 ml of
the diluted electrolyte and 5 drops of the N-phenylanthranilic acid indicator and titrate with the
ferrous ammonium sulfate as described in B.2.2.1 above. Let (d) ml be the amount of sodium
carbonate solution required.

B.4.3 Calculation. Free chromic acid, calculated as CrO3, in grams per litre

= 50 x (d)
3 (a)

B.5 Chloride

B.5.1 Reagents

B.5.1.1 Nitric Acid (SG = 1.42).

B.5.1.2 Nitric acid wash water, 2% (v/v).

B-2
 DEF STAN 03-24/3
ANNEX B

B.5.1.3 Silver nitrate, 1% (m/v) solution.

B.5.2 Procedure. To 100 ml of the electrolyte contained in a 300 ml flask add 10 ml of the
nitric acid. Heat the solution to boiling point, add 50 ml of the silver nitrate solution and
agitate the solution vigorously to coagulate the precipitate. Allow the silver chloride to settle,
filter on a weighed Gooch crucible, transferring the precipitate completely. Wash with the hot
nitric acid wash water, at a temperature not less than 60°C , dry and weigh. Let (e) be the
amount of silver chloride.

B.5.3 Calculation. Chloride, calculated as NaC1, in grams per litre = 4.1(e).

B.6 Sulfate

B.6.1 Reagents

B.6.1.1 Hydrochloric acid (SG = 1.16).

B.6.1.2 Glacial acetic acid.

B.6.1.3 Barium chloride, 10% (m/v) solution.

B.6.1.4 Ethanol (pure ethanol, methylated spirit or iso-propanol).

B.6.2 Procedure. To 100 ml of filtered electrolyte in a 400 ml beaker (squat form) add 10 ml
of the hydrochloric acid, 25 ml of the glacial acetic acid and 20 ml of the ethanol and boil the
solution gently for 15 minutes to expel aldehydes and excess ethanol. Dilute to about 200 ml
and raise the solution to boiling point. Add slowly 10 ml of the barium chloride solution, boil
gently for about 15 minutes and allow the precipitate to settle overnight. Filter the precipitate
on a weighed Gooch crucible transferring the precipitate completely. Wash well with warm
water, dry and re-weigh. Dry at 100°C until a constant weight of barium sulfate is achieved.
Let (f) be the amount of barium sulfate.

B.6.3 Calculation. Sulfate, calculated as Na2SO4, in grams per litre = 6.1(f).

B-3
DEF STAN 03-24/3
ANNEX B

COLLATION PAGE

B-4
 DEF STAN 03-24/3
ANNEX C

Stripping Solutions for the Removal of Anodic Coatings

C.1 Preferred Solution

Phosphoric acid (SG = 1.75) 3.5% (v/v)

Chromic acid 2.0% (m/v)

Stripping is most effective when the solution is used at or near boiling point.

C.2 Alternative Solutions.

C.2.1 Sulfuric acid (SG = 1.84) 15% (v/v)

The solution should be used at about 50°C .

C.2.2 Sulfuric acid (SG = 1.84) 10% (v/v)

Potassium fluoride 4% (m/v)

The solution should be used at room temperature.

C.2.3 Sulfuric acid (SG = 1.84) 10% (v/v)

Hydrofluoric acid, commercial (50/60% HF) 1% (v/v)

The solution should be used at room temperature.

NOTE: The solutions listed in clause C.2 will cause slightly greater attack of the base metal
than that given in clause C.1

C-1
DEF STAN 03-24/3
ANNEX C

COLLATION PAGE

C-2
 DEF STAN 03-24/3
ANNEX D

Chromic Acid Anodizing for the Detection of Defects in Aluminium Alloy Bars, Extrusions,
Sheet, Rolled Plate, Forgings and Machined Items.

D.1 Applications

D.1.1 Chromic acid anodizing permits inspection for:

D.1.1.1 Cracks which give rise to yellow brown stains.

D.1.1.2 Cracks or crack like defects which do not give rise to a stain but to a black line (eg.
very fine fatigue cracks, forging laps or folds,

D.1.1.3 Grain flow and grain size.

D.1.1.4 Corrosion.

D.1.1.5 Segregation

D.1.1.6 Machining damage, eg overheating or smearing.

D.1.1.7 Incipient melting caused by overheating during forging.

D.1.2 Chromic acid anodizing is not to be used as an aid to inspection on tanks or other items
which are to be used in contact with concentrated hydrogen peroxide (HTP).

D.2 For the satisfactory inspection for cracks and fissures revealed by stains, particular
attention must be paid to the washing after treatment which is to consist of a brief rinse in cold
water (see 12.3) (prolonged washing or the use of hot water may render the test abortive by
washing all the acid out of the defect). For the examination of these defects it is necessary
to wait not less than 8 hours after anodizing to allow chromic acid retained in the defect to
reach the surface. There may be a reduction in detection time when items are etched
beforehand to allow ingress of searching agent but this pre-treatment should only be used when
it can be demonstrated that any reduction in fatigue strength can be accommodated.

D.2.2 It is not necessary to wait 8 hours if inspection is for defects other than cracks. In the
event that a short delay time between anodizing and inspection is required, the component may
be dye or fluorescent penetrant examined for the presence of cracks and then, after suitable
washing, anodized and visually examined for other defects at D.1.1.2 and D.1.1.3.
D.2.3 When chromic acid anodizing for inspection is carried out under sub-contract order, the
order shall specifically refer to this requirements (see 5(i)). Searching of defects, as revealed
by anodizing, is not the responsibility of the anodizer.

D.3 The Characteristics of Defects revealed by Chromic Acid Anodizing.

D.3.1 The following information is given as a guide to inspection. Brown stains due to
chromic acid shall not be removed by chemical means unless part of a re-anodizing process.

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ANNEX D

D.3.2 Cracks or exfoliation corrosion. These appear as a yellow brown stain. Because the
electrolyte becomes darker during the operation of the bath, a solution near the end of its
useful life is more effective than a new one. As the stains may be difficult to distinguish in
yellow light, light of a bluish colour (mercury vapour lamps are suitable) shall be used if it is
not possible to examine in full daylight which is to be used in instances of doubt. The apparent
colour of the stain will vary with the colour of the light used for viewing.

D.3.3 Cracks or folds not detectable by a yellow brown stain. Experience has shown
instances where very fine fatigue or stress corrosion cracks are not detected by a brown stain
and were also beyond the limit of detection by conventional NDT methods. Detection in these
instances as a black line can be made at a magnification in the order of X300. See also D.5.2.

D.3.4 Laps or folds in forged items. Laps or folds in the surface of forgings may be so tight
that they are not revealed by penetrant methods of crack detection. After anodizing they can
appear as very fine dark grey/black lines often only readily seen with the aid of a magnifying
glass and which may be accentuated by a variation in the grain flow around it. Occasionally
after a suitable period a brown stain may also appear, possibly as isolated spots where ingress
of chromic acid has been possible. It is especially necessary to inspect for such defects in the
highly stressed areas of forgings subject to fatigue stresses. A good surface finish is essential
for the satisfactory detection of crack-like defects.

D.3.5 Intercrystalliner corrosion. Areas of intercrystalline corrosion often appear in the form
of dark grey blotches of which finger marking is a special case. Severe intercrystalline
corrosion gives rise to chromic acid staining in the area attacked. The high strength aluminium
alloys in the cold-worked condition, eg tubes, are particularly prone to intercrystalline
corrosion.

D.3.6 Machining damage. Overheating or smearing of the surface during machining is often
rendered visible by anodizing. Overheating shows as a darker area, frequently of about the
diameter of the cutter used, or following the track of the cutter. Smearing appears usually as
lighter circular swirls on the surface, again following the cutter tracks. Smearing marks can
usually be polished away without permanent damage to the part, but overheating indications
are normally too deep to be removed.

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ANNEX D

D.3.7 Incipient melting at grain boundaries. This will appear as fine discontinuous dark lines
at grain boundaries frequently accompanied by brown stains.

D.4 If corroded items are to be re-anodized for inspection purposes, all evidence of
corrosion shall first be removed by machining or any method which will not cause smearing of
the surface; rough corroded areas may house cracks from which the exuded chromic acid can
spread over the corroded surface instead of yielding the more usual positive outline which
cracks normally give rise to on clean surfaces.

NOTE: This is not to say that every item should be so treated. It is generally impracticable to
remove evidence of corrosion from threaded items by machining or abrasive blasting and,
furthermore, few items are equally and highly stressed all over. These factors must therefore
be considered when deciding on the procedures to be adopted for renovation and repair
schemes on individual items. It is also important to remember that repeated anodizing can
eventually give rise to surface pitting which may contribute to fatigue failure and this should
be balanced against the ability of anodizing to detect intergranular corrosion when items are
re-examined after serving in a hostile corrosive environment.

D.5 Comparison with Penetrant Methods of Flaw Detection.

D.5.1 It is generally accepted that where cracks are present, particularly tight cracks which
nonetheless permit ingress of the searching agent, then the post-emulsified fluorescent
penetrant is superior to anodizing both in sensitivity and speed of detection. This would not
necessarily be true if the lesser sensitive dye penetrant methods are used.

D.5.2 There is experience, however, to show that some very fine fatigue cracks of a size in
the order of 25 to 50 mm in length and possibly half that in depth are only visible by
examination at a magnification in the order of X300 after chromic acid anodizing. The cracks
are detectable as black lines and their detection is beyond the capability of penetrant methods.

D.5.3 The best inspection technique for forging defects is to use both chromic acid anodizing
and fluorescent penetrant, since anodizing can detect very light forging folds which may
remain undetected by the most sensitive penetrant. An additional advantage is that the
metallurgical features of a forging are also revealed, including intergranular corrosion which is
not shown by any other etching process with the same degree of clarity or reliability.

D.5.4 Where dual inspection is carried out either for the reasons in D.5.3 or to reduce
inspection time, then penetrant should be used first for three main reasons.

D.5.4.1 The crack may be closed by the anodic film.

D.5.4.2 The anodic film may absorb some penetrant and reduce contrast.

D.5.4.3 Any trapped anodic solution may reduce the effectiveness of the penetrant and
prevent a penetrant indication.

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COLLATION PAGE

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ANNEX E

Procedure for Anodizing Hollow Items such as Tanks, Long Tubes and Extrusions

E.1 Cleaning. Scrupulous care is to be taken to ensure that all swarf and loose metal is
removed from both the exterior and interior surface of such items before they are placed in the
anodizing bath. The presence of even minute loose particles may lead to serious pitting.

E.2 Small tanks. These may be anodized in the same manner as other items provided that:

E.2.1 They are entirely of welded construction.

E.2.2 The apertures are sufficiently large to ensure an adequate supply of cool electrolyte to
the interior.

E.2.3 The gas evolved during anodizing can escape from the interior without forming
stationary bubbles.

E.3 Other tanks. Where they are of entirely riveted or bolted construction, they shall be made
from items which have been previously anodized.

E.4 Combination tanks. Many tanks are of combined welded and riveted construction. Unless
items made from metals other than aluminium alloys are embodied, these are best anodized
after assembly. Tanks and tubular shaped items of large length-to-bore ratio frequently require
the use of auxiliary cathodes to ensure satisfactory coverage of the internal surface.

E.5 Hollow items. These should be so orientated in the bath that the accumulation of gas in
recesses cannot occur. Tanks can usually be racked in such a manner that all internal baffles
are vertical. By immersing tanks to slightly more than half their depth, anodizing may be
carried out without danger of gas accumulation, the process being repeated with the tanks
inverted.

E.6 Repairs. If repairs or other considerations require the welding of items previously
anodized, the coating may be removed from the areas to be welded by means of an application
of one of the stripping solutions described in annex C, followed by thorough washing in water.
Areas which have not taken a satisfactory coating owing to unsatisfactory cleaning or the
formation of a gas bubble, are to be cleaned with one of these solutions, thoroughly washed
and re-anodized.
E.7 Flow of electrolyte. During the anodizing of partially enclosed vessels, long tubes, etc, an
adequate flow of electrolyte is to be maintained to the internal surfaces.

E.8 Auxiliary cathodes. If internal auxiliary cathodes are employed, these should be well
insulated and so designed that contact between them and the items being treated cannot occur
during processing. Such cathodes are to be examined at frequent intervals during their life to
verify that the efficiency of the insulation has not suffered due to wear or accidental damage
during use.

E.9 Cathode material. No metals other than aluminium, aluminium alloy or titanium anodes
and steel cathodes shall be allowed to come into contact with chromic acid electrolyte.

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ANNEX E

COLLATION PAGE

E-2
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ANNEX F

Approximate Conversion of Metric Units to Imperial Equivalents (Non-US)

SI IMPERIAL IMPERIAL SI Context Used

1 MPa 145 lbf/in2 1 lbf/in2 0.006895 MPa Tensile Strength

1 MPa 20886 lbf/ft2 1 lbf/ft2 0.000048 MPa Tensile Strength

1 kgf/m2 0.205 lbf/ft2 1 lbf/ft2 4.88 kgf/m2 Tensile Strength

1 g/ml 62.43 lb/ft3 1 lb/in3 0.016017 g/ml Density

1 g/l 0.161 oz/gal 1 oz/gal 6.225 g/l Concentration

1 µm 0.000039 in 1 thou 25.4 µm Thickness

(mil in US)

1 A/m2 0.0929 A/ft2 1 A/ft2 0.1076 A/m2 Current Density

1 A/dm2 9.29 A/ft2 1 A/ft2 0.1076 A/dm2 Current Density

1g 0.0353 oz 1 oz 28.349 g Weight

1 kg 2.205 lb 1 lb 0.454 kg Weight

1 ml 0.035 fl oz 1 fl oz 28.41 ml Volume

11 0.220 gal 1 gal 4.5461 Volume

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ANNEX F

COLLATION PAGE

F-2
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DEF STAN 03-24/3

© Crown Copyright 1997 This Standard may be fully reproduced

except for sale purposes. The following
Published by and obtainable from: conditions must be observed:
Ministry of Defence 1 The Royal Coat of Arms and the
Directorate of Standardization publishing imprint are to be omitted.
Kentigern House 2 The following statement is to be inserted
65 Brown Street on the cover:
GLASGOW G2 8EX 'Crown Copyright. Reprinted by
(name of organization) with the
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Stationery Office.'
Fax No: 0141-224 2503
Requests for commercial reproduction should be
addressed to MOD Stan 1, Kentigern House,
65 Brown Street, Glasgow G2 8EX

The following Defence Standard file reference relates to the work on this Standard -
D/D Stan/313/2/1

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Defence Standards are revised when necessary by the issue either of amendments or of revised
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Index of Defence Standards and Specifications published annually and supplemented
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Standard encounters an inaccuracy or ambiguity is requested to notify the Directorate of
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action taken.

94/50012