Ministry of Defence

Defence Standard 03-24

Issue 5 Publication Date 11 April 2008

Chromic Acid Anodizing of

Aluminium and Aluminium Alloys
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Contents

Foreword............................................................................................................................................................v
0 Introduction .........................................................................................................................................vi
1 Scope ....................................................................................................................................................1
2 Warning.................................................................................................................................................1
3 Normative References .........................................................................................................................1
4 Definitions.............................................................................................................................................2
4.2 Process control schedule ...............................................................................................................2
4.3 Purified water ...................................................................................................................................2
4.4 Significant surface...........................................................................................................................2
5 Information to be Supplied by the Purchaser ...................................................................................2
6 Process Control ...................................................................................................................................2
7 Applications and Limitations..............................................................................................................3
7.1 Applications......................................................................................................................................3
7.2 Compatibility with explosives, propellants and pyrotechnics ....................................................3
7.3 Limitations ........................................................................................................................................3
8 Process Requirements ........................................................................................................................4
8.1 Surface Preparation.........................................................................................................................4
8.2 Anodizing..........................................................................................................................................4
8.3 Washing ............................................................................................................................................4
8.4 Sealing ..............................................................................................................................................4
8.5 Drying................................................................................................................................................4
8.6 Re-Anodizing ....................................................................................................................................5
9 Inspection and Test .............................................................................................................................5
9.1 Processing........................................................................................................................................5
9.2 Frequency of testing........................................................................................................................5
9.3 Appearance.......................................................................................................................................5
9.4 Tests for electrical insulation (sealed coatings only) ..................................................................5
9.5 Corrosion test ..................................................................................................................................6
9.6 Sealing quality..................................................................................................................................6
Annex A Chromic Acid Anodizing Process for Aluminium and Aluminium Alloys...................................7
A.1 Electrolyte.........................................................................................................................................7
A.2 Cathode.............................................................................................................................................7
A.3 Suspension or Jigging ....................................................................................................................7
A.4 Anodizing Procedure.......................................................................................................................7
A.4.1 Standard process..........................................................................................................................7
A.4.2 Alternative process for castings .................................................................................................7
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A.4.3 Alternative process for high zinc aluminium alloys in the overaged condition.....................8
Annex B Analysis of Chromic Acid Electrolyte.............................................................................................9
B.1 Analysis of Chromic Acid Electrolyte............................................................................................9
B.2 Analysis for Total Chrome ..............................................................................................................9
B.2.1 Reagents........................................................................................................................................9
B.2.2 Procedure ......................................................................................................................................9
B.2.2.1 Standardisation of ferrous ammonium sulphate.....................................................................9
B.2.2.2 Determination of total chrome...................................................................................................9
B.2.2.3 Calculation...................................................................................................................................9
B.3 Analysis for Free Chromic Acid (Used Electrolyte) ...................................................................10
B.3.1 Reagent........................................................................................................................................10
B.3.2 Procedure ....................................................................................................................................10
B.3.3 Calculation...................................................................................................................................10
B.4 Analysis for Free Chromic Acid (Fresh Electrolyte) ..................................................................10
B.4.1 Reagents......................................................................................................................................10
B.4.2 Procedure ....................................................................................................................................10
B.4.3 Calculation...................................................................................................................................10
B.5 Analysis for Chloride.....................................................................................................................10
B.5.1 Reagents......................................................................................................................................10
B.5.2 Procedure ....................................................................................................................................10
B.5.3 Calculation...................................................................................................................................11
B.6 Analysis of Chromic Acid Electrolyte..........................................................................................11
B.6.1 Reagents......................................................................................................................................11
B.6.2 Procedure ....................................................................................................................................11
B.6.3 Calculation...................................................................................................................................11
Annex C Stripping Solutions for the Removal of Anodic Coatings ..........................................................12
C.1 Preferred Solution..........................................................................................................................12
C.2 Alternative Solutions.....................................................................................................................12
Annex D Chromic Acid Anodizing for the Flaw Detection of Defects in Aluminium Alloy Bars,
Extrusions, Sheet, Rolled Plate, Forgings and Machined Items...................................................13
D.1 Applications ...................................................................................................................................13
D.2 Special Requirements ...................................................................................................................13
D.3 The Characteristics of Defects Revealed by Chromic Acid Anodizing....................................13
D.3.1 Guidance......................................................................................................................................13
D.3.2 Cracks or exfoliation corrosion.................................................................................................14
D.3.3 Cracks or folds not detectable by a yellow brown stain.........................................................14
D.3.4 Laps or folds in forged items ....................................................................................................14
D.3.5 Intercrystalline corrosion...........................................................................................................14
D.3.6 Machining damage......................................................................................................................14
D.3.7 Incipient melting at grain boundaries.......................................................................................14
D.4 Re-Anodizing for Inspection Purposes .......................................................................................14

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D.5 Comparison With Penetrant Methods of Flaw Detection...........................................................15

Annex E Procedure for Anodizing Hollow Items such as Tanks, Long Tubes and Extrusions .............16
E.1 Cleaning ..........................................................................................................................................16
E.2 Small Tanks ....................................................................................................................................16
E.3 Other Tanks ....................................................................................................................................16
E.4 Combination Tanks........................................................................................................................16
E.5 Hollow Items ...................................................................................................................................16
E.6 Repairs ............................................................................................................................................16
E.7 Flow of Electrolyte .........................................................................................................................17
E.8 Auxiliary Cathodes ........................................................................................................................17
E.9 Cathode Material ............................................................................................................................17

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Foreword
AMENDMENT RECORD

Amd No Date Text Affected Signature and Date

REVISION NOTE

This standard is raised to Issue 5 to update its content and incorporate the latest MoD / DStan policy.

HISTORICAL RECORD

This standard supersedes the following:

Def 151 dated March 1965

Def Stan 03-24 / Issue 1 dated 6 September 1984

Def Stan 03-24 / Issue 2 dated 14 September 1988

Def Stan 03-24 / Issue 3 dated 5 September 1997

Def Stan 03-24 / Issue 4 dated 16 December 2003

a) This standard provides requirements for the Chromic Acid Anodizing of Aluminium and Aluminium
Alloys.

b) This standard has been produced on behalf of the Defence Material Standardization Committee (DMSC)
by the Corrosion Prevention and Metallic Materials Standards Production Group (E3).

c) 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,
UK Defence Standardization (DStan) shall be informed so that a remedy may be sought.

d) 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.

e) Compliance with this Defence Standard shall not in itself relieve any person from any legal obligations
imposed upon them.

f) This standard has been devised solely for the use of the Ministry of Defence (MOD) and its contractors
in the execution of contracts for the MOD. To the extent permitted by law, the MOD hereby excludes all
liability whatsoever and howsoever arising (including, but without limitation, liability resulting from
negligence) for any loss or damage however caused when the standard is used for any other purpose.

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0 Introduction

0.1 This standard specifies the requirements for the chromic acid anodizing of aluminium and aluminium
alloys. It includes details of electrolyte analysis and methods of flaw detection using chromic acid anodizing.

0.2 Anodizing of aluminium and aluminium alloys is a well established surface engineering process based
on the use of extremely toxic hexavalent chromium chemicals. The toxicity of these hexavalent chromium
chemicals has led to the imposition by national and international legislation of progressively greater
restrictions on their use due to concerns over Health & Safety and Environmental Protection.

0.3 Users of this standard should refer to Def Stan 03-38 - Guidance for the Use of Alternatives to Hard
Chromium Plating, Chromium Conversion Coatings and Anodizing for the Protective Coating of Defence
Equipment – for possible alternative processes.

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Standards for Defence - Chromic Acid Anodizing of Aluminium

and Aluminium Alloys

1 Scope
This standard specifies the requirements for chromic acid anodizing of aluminium and aluminium alloys.
Chromic acid anodizing is the preferred process when treating items that may come into contact with
explosives. See Def Stan 07-85 clause 10.5.9.3.3.

2 Warning
The Ministry of Defence (MOD), like its contractors, is subject to both United Kingdom and European laws
regarding Health and Safety at Work. All Defence Standards either directly or indirectly invoke the use of
processes and procedures that could be injurious to health if adequate precautions are not taken. Defence
Standards or their use in no way absolves users from complying with statutory and legal requirements
relating to Health and Safety at Work.

3 Normative References

3.1 The publications shown below are referred to in the text of this standard. Publications are grouped and
listed in alpha-numeric order.

3.2 Reference in this Standard to any normative references 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.

3.3 In consideration of clause 3.2 above, users shall be fully aware of the issue and amendment status of
all normative references, particularly when forming part of an Invitation to Tender or contract. Responsibility
for the correct application of standards rests with users.

3.4 DStan can advise regarding where normative references documents are obtained from. Requests for
such information can be made to the DStan Helpdesk. How to contact the helpdesk is shown on the outside
rear cover of Def Stans.

Designation Title

BS EN ISO 3696 Water for Analytical Use: Specification and Test Methods
BS EN ISO 9227 Corrosion Tests in Artificial Atmospheres. Salt Spray Tests
BS EN 12373-6 Aluminium and Aluminium Alloys. Anodizing. Assessment of Quality of Anodic
Oxidation Coatings by Measurement of the Loss of Mass after Immersion in
Phosphoric Acid / Chromic Acid Solution Without Prior Acid Treatment.
BS EN 12373-17 Aluminium and Aluminium Alloys. Anodizing. Determination of Electrical Breakdown
Potential.
Def Stan 03-2 Cleaning and Preparation of Metal Surfaces
Def Stan 03-25 Sulfuric Acid Anodizing of Aluminium and Aluminium Alloys

Def Stan 07-85 Pt 2 Design Requirements for Weapons and Associated Equipment. Supplementary and
Design Process Requirements

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4 Definitions

4.1 For the purpose of this Defence Standard the following definitions apply.

4.2 Process control schedule

The document which specifies / defines:

(a) The sequence of manufacturing operations and processes.

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

4.3 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 of not greater than 5 ppm w/w (as
SiO2).

4.4 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.

5 Information to be Supplied by the Purchaser

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 8.4).
(d) The significant surface. This may be indicated on the drawing or by a marked sample.
(e) Any special conditions of service, e.g. contact or close proximity to explosives, propellants or
pyrotechnics.
(f) Any special condition of service, e.g. 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 9.4).
(i) Whether the anodizing is for the detection of defects (see Annex D).
(j) Any limit on the number of re-treatments (see 8.6).
(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, coating treatment and processing,
significant surface, tests and all other treatments shall be included in the Process Control Schedule.

6.3 All stages of the complete Schedule shall follow each other without delay.

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7 Applications and Limitations

7.1 Applications

7.1.1 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.

7.1.2 For castings of suitable composition (see 7.3.2), 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.

7.1.2.1 Minimizing loss of fatigue strength due to anodizing.

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

7.1.2.3 The treatment of material less than 0.250 mm thick.

7.1.3 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.

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

7.2 Compatibility with explosives, propellants and pyrotechnics

7.2.1 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

7.2.2 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.

7.2.3 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.

7.3 Limitations

7.3.1 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.

7.3.2 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.

7.3.3 Composite items which include non-aluminium materials which would be attacked 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.

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

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

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

8 Process Requirements

8.1 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).

8.2 Anodizing

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

8.3 Washing

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

8.3.1.1 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 8.4.

8.3.1.2 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.

8.3.1.3 Items which have been anodized to detect surface discontinuities, e.g. 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 8.3.1.1 or 8.3.1.2 as appropriate.

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

8.3.1.5 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).

8.4 Sealing

8.4.1 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.

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

8.5 Drying

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

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

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8.5.3 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.

8.5.4 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.

8.6 Re-Anodizing

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

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

8.6.3 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.

9 Inspection and Test

9.1 Processing

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

9.2 Frequency of testing

9.2.1 Visual examination shall be applied to all items. The test for electrical insulation (see 9.4) and, where
specified, any of the tests in 9.5 and 9.6, 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.

9.2.2 In exceptional circumstances, e.g. 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.

9.3 Appearance

9.3.1 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 hours after anodizing.

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

9.3.2 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, e.g. the bores and internal surfaces of long
tubes and hollow spars, shall be systematically explored by a visual aid such as an intrascope.

9.4 Tests for electrical insulation (sealed coatings only)

Items may be subjected to the appropriate test method in BS EN 12373-17, 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

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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.

9.5 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 neutral salt spray test as described in BS EN ISO
9227. 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 336 hours with no corrosion spots or staining
evident following test.

9.6 Sealing quality

When the Process Control Schedule requires an assessment of sealing quality, the test method described in
BS EN 12373-6 shall be used. The mass loss shall not be more than 3 g/m2.

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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 NaCl per litre and
the sulfate shall not exceed 0.50 g NasSO4 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.4.2 Alternative process for castings

A.4.2.1 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.4.2.2 The temperature 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 from 0 to 40 volts in 10 minutes and the voltage maintained at 40
volts for 30 minutes.

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A.4.3 Alternative process for high zinc aluminium alloys in the overaged 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.

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Annex B
Analysis of Chromic Acid Electrolyte

B.1 Analysis of Chromic Acid Electrolyte

The electrolyte shall be analyzed by any reputable method. In cases of dispute the following referee methods
shall be used.

NOTE The reagents used shall be of recognized British Standard analytical quality. All laboratory equipment used
shall be of British Standard quality. Water complying with BS EN ISO 3696 Grade 3 should be used throughout.

B.2 Analysis for Total Chrome

B.2.1 Reagents

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

(b) 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.
(c) Potassium dichromate, M/60 solution. Dissolve 9.807 g potassium dichromate in 500 ml
water and dilute to 2 litres.
(d) Silver nitrate, 3% (m/v) solution.
(e) 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 Standardisation of ferrous ammonium sulphate

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 dropwise 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 chrome

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.2.2.3 Calculation

Total chromium, calculated as CrO3, in grams per litre = 125 x (b)

3 (a)

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B.3 Analysis for Free Chromic Acid (Used Electrolyte)

B.3.1 Reagent

(a) 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 Analysis for Free Chromic Acid (Fresh Electrolyte)

B.4.1 Reagents

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

(b) Ferrous ammonium sulfate, 0.1M solution, prepared as described in B.2.1.
(c) N-phenylanthranilic acid indicator 0.1% (m/v), prepared as in B.2.1.

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 ferrous ammonium sulphate solution required.

B.4.3 Calculation

Free chromic acid, calculated as CrO3, in grams per litre = 50 x (d)

3 (a)

B.5 Analysis for Chloride

B.5.1 Reagents

(a) Nitric acid (SG = 1.42).

(b) Nitric acid wash water, 2% (v/v).
(c) 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 dried, weighed Gooch crucible, transferring the
precipitate completely. Wash with the hot nitric acid wash water, at a temperature not less than 60°C, dry the
crucible and its contents in an air oven, maintained at 130-150°C, allow to cool in a desiccator and weigh.
Let (e) be the amount of silver chloride.

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B.5.3 Calculation

Chloride, calculated as NaCl, in grams per litre = 4.1(e).

B.6 Analysis of Chromic Acid Electrolyte

B.6.1 Reagents

(a) Hydrochloric acid (SG = 1.16).

(b) Glacial acetic acid.
(c) Barium chloride, 10% (m/v) solution.
(d) 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, (cool in a desiccator) 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).

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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

(a) Sulfuric acid (SG = 1.84) 15% (v/v)
Chromic acid 5% (m/v)

The solution should be used at about 50°C.

(b) Sulfuric acid (SG = 1.84) 10% (v/v)

Potassium fluoride 4% (m/v)

The solution should be used at room temperature.

(c) Sulfuric acid (SG = 1.84) 10% (v/v)

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

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.

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Annex D
Chromic Acid Anodizing for the Flaw 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:

(a) Cracks which give rise to yellow brown stains.

(b) Cracks or crack like defects which do not give rise to a stain but to a black line e.g. very fine
fatigue cracks, forging laps or folds,
(c) Grain flow and grain size.
(d) Corrosion.
(e) Segregation
(f) Machining damage, e.g. overheating or smearing.
(g) 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 Special Requirements

D.2.1 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 8.3.1.3)
(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 (b) and D.1.1 (c).

D.2.3 When chromic acid anodizing for inspection is carried out under sub-contract order, the order shall
specifically refer to this requirement (see 5(i)). Sentencing 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 Guidance

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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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 Intercrystalline 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, e.g. 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.

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 Re-Anodizing for Inspection Purposes

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.

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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 µm 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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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:

(a) They are entirely of welded construction.

(b) The apertures are sufficiently large to ensure an adequate supply of cool electrolyte to the
interior.
(c) 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.

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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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