3rd ISSE National Conference on Complex Engineering Systems of National

Importance:Current Trends & Future Perspective (INAC-03), October 12-13, 2017

Advanced Materials

AM-0017 Corrosion Protection of Weldable AA2219

alloy Review & Case Study
Swarupendra Bhattacharyya1, a, Pravin Roy1, b, T.K.B. Kumaresh Babu1, c and Satish Chandra Kumar1, d*
a
[email protected], [email protected], [email protected], [email protected].
*corresponding author
1
Liquid Propulsion Systems Centre, ISRO, Bangalore, India

AbstractThestudy describes the corrosion protection was noticed that even minor pitting corrosion at the welding
of AA2219 alloys prior to welding of components for zone leads to porosity and crack defects in weld which
aerospace manufacturing applications. Different studies results in multiple weld re-work passes on the hardware.
conducted for protection of AA2219 alloy is discussed This in turn increases residual stresses on the weld, severely
briefly, thereby identifying the most suitable method affecting the reliability of the fabricated hardware in use.
with utmost effectiveness. The process elucidates the High residualstress in propellant tank weld observed during
anodisation of components with sulphuric acid for long Proof Pressure Tests (PPT) leads to possibility of hardware
term storage with subsequent scrapping / De- rejection. Hence pitting corrosion of parts as a result of long
anodisation of weld zone before welding of components. term storage before welding is a serious problem. Multiple
In order to validate effectiveness of the procedure, studies have been carried out previously to ascertain the
detailed case study is carried out.
pitting corrosion behaviour of AA2219 alloy [1][2].The
The specimens have undergone both destructive and non-
destructive evaluation techniques with
studies have shown that although the addition of copper in
satisfactory/encouraging results. AA2219 alloy increases its strength though precipitate/age
hardening process, it reduces the corrosion resistance of the
I. INTRODUCTION alloy. This is due to formation of CuAl 2 and CuAl2Mg
intermetallic phase which being more noble than Al phase
initiates pitting and enhances pitting growth.[3]-[5]
A A2219 ALUMINIUM alloy with copper as main
alloying element is a wonder alloy that meets all
requirements(like specific strength, weldability, Temper Condition Description
machinability, formability, compatibility, fracture F As Fabricated
toughness) of Earth storable as well as Cryo hardware of T4 Solution Heat treated
space industry and it is widely used for realization of T37 T4 + 8% Cold Work
propellant tank because of its high reliability due to absence T62 T4 + age 28h at 185oC
of stress corrosion cracking. However AA2219 is highly T87 T37 + age 24h at 165oC
prone for general corrosion and needs proper protection for Table 1.Temper and ageing treatments of AA2219 alloy.
long term storage which should also be suitable for critical
process like welding. The present study is for effective II. PREVIOUS STUDIES CONDUCTED
corrosion protection of AA2219 alloy for long term storage AA2219 is having the composition as given in Table 2. The
and assessing the effect of the protection process on welding distribution of second phase intermetallic particle and effect
based on systematic study. of copper content on the corrosion behaviour is well
Corrosion of space quality components made of AA2219 researched. [6]-[11].For the scope of the present study
can lead to simple problems like thickness loss, poor weld various corrosion protection schemes for AA2219 were
quality and serious problems like degraded performance / studied:
failure of mission due to blockage of propellants flow by
corrosion products. A. Oil Protection:
The present study is carried out to resolve the issues The simplest technique which is presently being
ascertained as a result of corrosion/ pitting corrosion noticed followed for components is Oil application. SAE 30 oil is
during fabrication of propellant tankages and internal sub- applied to the fabricated parts and they are covered and kept
systems (earth storable and cryogenic tankages and sub- for future usage. However oil application is extremely
systems) to be used in Indian launch vehicles viz. Polar cumbersome process. Oil gets dried up over a period of time
synchronous launch vehicle (PSLV) and Geo-stationary and thus has to be reapplied at regular interval (every 3
launch vehicle (GSLV) and GSLV MKIII launch vehicle for months). Furthermore, due to dust settlement on the surface
Indian Space Programme. The machined/formed parts of the of hardware, the protective barrier is damaged resulting in
tank/internal systems made of AA2219 in T62/T87 temper pitting corrosion.
condition [Table 1] are fabricated in bulk quantity and
B. Chromate Conversion Coating [CCC]:
stored as inventory, for welding with the propellant tank and
components. In this process pitting corrosion was seen on Chromate conversion coating is one of the most
hardware leading to rejections of the same. Furthermore it predominantly used method of corrosion protection of

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3rd ISSE National Conference on Complex Engineering Systems of National
Importance:Current Trends & Future Perspective (INAC-03), October 12-13, 2017
Advanced Materials

Aluminium.CCC is chromium/chromic acid based coating study showed that the increase in corrosion resistance is due
for the aluminium metal where the part surface is converted to cerium and lanthanum deposits at the site of CuAl 2
to a coating for corrosion protection.CCC for Copper rich intermetallic inclusions.
alloys of Aluminium which are prone to pitting corrosion Conversion coating based on Ce and La are available for
have been studied in details. Hugeset.al. studied CCC on corrosion resistance and are not hazardous like CCC.
AA2024-T3 to find the coating to be heterogeneous [12]. However these being special coated with unknown
Vasquez et. al. also found the CCC on AA2024 to be compounds, their compatibility with various propellants vis
heterogeneous and Cu enrichment were found on the outer a vis LH2, LOX, N2O4, UDMH, RP-1 have to be studied in
most layer of CCC [13]. Hence it is understood that the details before qualifying for use in propellant tankages.
coating will have Cu enriched regions which will initiate Out of the various methods discussed, Sulphuric acid
localized corrosion in exposure to anodizationis chosen for the present study due to its known
environment.MoreoverCCC is carcinogenic and is effectiveness for AA219 and easiness in implementation.
hazardous to nature.
III. CHALLENGES FACED
C. Anodization: Sulphuric Acid anodization is chosen for protection of
Anodization is another most predominantly used method AA2219 alloy from corrosion and its effectiveness is studied
of corrosion protection in Aluminium and its and results obtained are encouraging. However the welding
alloys.Anodization is a electrolytic passivation process of aluminium with oxide film has many challenges. The
which increase the thickness of natural oxide layer on the oxide layer has high melting point and low conductivity. So
surface of metal parts. Chromic Acid anodisation developed welding with oxide layer leads to failure of arc initialization
by Benbough& Stuart [14] and Sulphuric acid anodisation at the required voltage. In case of partial oxide layer the arc
developed by Kallenborn& Emmons [15] are the two most stabilization issues are faced. Improper cleaning of
commonly used process of anodization for Aluminium. oxidelayer is associated with weld defects like high porosity,
Previous studies have shown that Chromic Acid anodization lack of fusion and oxide film entrapment. Hence anodisation
is not recommended for high copper aluminium alloy [16]. layer must be removed at the weld edge either by scrapping
Sulphuric acid anodisation method is more suitable for high or deanodisation process.
copper aluminium alloy like AA2219 which produces a
oxide coating for 6-8m. [17] IV. EXPERIMENT DESIGN

D. Alclad: The base material (bare plate) AA2219 was received in

Alclad is the method in which aluminium alloy is
metallurgically bonded on all sides to pure aluminium thin
sheet. Pure aluminium is anodic to aluminium copper
intermetallic phase and thus helps in corrosion resistance.
However this process has its limitation for complex shaped
parts (as in isogrid pockets, complex machined parts, thin
channels, etc.) Furthermore for AA2219 the temperature and
time of thermal treatment should be very carefully Case 1
controlled as prolonged exposure leads to diffusion of
copper to the cladding itself thus making it less anodic and
prone to pitting corrosion [18].
E. Copper Removal:
CuAl2 is removed through AC Anodic Polarization
technique. Thus aluminium surface is corroded protecting
Case 2
the inner metal from corrosion. Copper removal from the
surface of AA2219 has shown good results in increasing the
corrosion resistance of AA2219 [19]. SrinivasRaoet. al.
have studied that Copper Removal along with CCC have
lead to significant increase in pitting corrosion resistance of
AA2219 [20]. However during the same study it is
concluded that the CuAl2removal has no effect on the
Case 3
corrosion resistance of sulphuric acid anodized AA2219.
F. Use of rare earth metal chloride Inhibitors: Fig. 1.Different cases for experimentation.

Due to the carcinogenic nature of chromium used in T87 temper condition having 6mm thickness. The chemical
CCC, its use is expected to be banned in the near future. composition of the bare plate as per Table 2 as reported by
Hence a viable alternative is rare earth metal inhibitors. Chemical Analysis. The sheet was cut and machined into
Studies by G. Venkatasubramanianet. al. have shown multiple pieces of size 400mm x 120mm x 6mm each. The
improved corrosion resistance of AA2219-T87 by use of Square Butt joint was machined and prepared for DCSP TIG
chloride of Cerium (Ce) and Lanthanum (La) [21]. The Welding.

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3rd ISSE National Conference on Complex Engineering Systems of National
Importance:Current Trends & Future Perspective (INAC-03), October 12-13, 2017
Advanced Materials

Mn Si V Fe Ti Cu Mg Zn Zr Al E. Non Destructive Testing

0. 0. 0. 0. 0. 6 0. 0 0 B The welded plates are tested by X-ray using GE
231 082 068 096 038 .33 005 .01 .10 al
9 8
(USA)make radiography machine. The optical density of the
film is maintained within 2.2+15%
Table 2. Chemical Composition of AA2219 alloy The Ultra Sonic Analysis is doneusingKrautkramer
Branson make Ultrasonic Testing Machine. Angle beam
In order to ensure the integrity of the process
ultrasonic A-Scan examination is done on the weld using
experiments/trials with different combinations of the
ultrasonic pulse echo method. AMS 2632 standard is
weldmentsbriefedin Fig 1. Three plates were welded for
followed for the analysis.
each Case and various Non destructive testing and
Dye Penetrant Test is carried out on the weld as per
destructive testing were carriedout.
ASTM-E165.
A. Anodisation
F. Destructive Testing
The plates were cleaned/ degreased with
trichloroethylene. Then the plates were cleaned in Nitric The plates are then cut and machined to prepare Tensile
Acid base de-oxidized solution (Con-5% by volume: De- Strength Specimen for Room Temperature and Cryogenic
oxidizer-6 and Nitric acid 10 to 15%v/v) until no scales Temperature [Fig. 2] as per ASTM B557M and ASTM E8M
were visible on the surface. Then the plates were washed to respectively. The specimens have been taken from the start,
remove any residue of de-oxidizer. The parts were then middle and end of the weld. Room Temperature tensile test
cleaned with De-mineralized water. Complete removal of is carried out on MTS System Corp.,USA make electro-
acid/alkaline was confirmed with litmus paper test. Then the mechanically controlled universal testing machine. Cryo
plates were connected to the anode and inserted in the Temperature tensile test is carried out in LN2 bath.
Sulphuric Acid bath (15% 1% by wt) at a temperature of
202oC. pH of the bath was maintained between 1-3. The
voltage used is 17-18V. The plates were anodized for
45mins. After bringing out, the plates were rinsed with De-
mineralized water to ensure ion free surface. Then sealing of
porous oxide film was done in boiling DM water followed
by De-Masking in acetone. Fig. 2(a) Flat Type Tension Test Specimen (for room
specimen)(ASTM B557M)
B. De-Anodisation of weld edge
The plates undergoing De-Anodization were dipped in nitric
acid based solution used for De-Oxidizer cleaning until no
scales of grey oxide layer is visible. Then the plates were
washed to remove any residue of de-oxidizer. The parts
were then cleaned with De-mineralized water.
C. Welding
For welding the weld edge preparation is done to avoid
Fig. 2(b) Pin Type Tension Test Specimen (for cryo specimen)
the problems associated with improper cleaning discussed
(ASTM E8M)
above. The weld edge are degreased with trichloroethylene
and cleaned with acetone. Then the edge is scraped to
Metallurgical Analysis is done to analyse the metallurgical
remove any oxide or dirt. Difficulty was observed in
structure and finer scale defects which are not detected in
removal of sulphuric acid anodized layer. However with
radiography. Theweldments are cut in transverse section.
second round of scrapping, oxide layer was completely
The samples for macro and micro examination were
eliminated. The surface is checked with Ultra Violet Light
prepared & analyzed in accordance with ASTM E340 &
to find any small trace of Aluminum oxide or dirt left on the
ASTM E112 respectively.The samples arepolished.Macro
surface. The weld joint is positioned with acceptable
samples are etched usingNaOH solution and Micro Samples
mismatch and root gap. The Humidity & Temp is also
are etched using Keller's reagent for metallographic
ensured to be within acceptable range. Auto GTAW is
examination. Microstructural studies were carried out at
carried out in DCSP Mode using Hobart Welders, USA
Weld Zone, Fusion Zone, HAZ and Parent Metal Zone.
make machine according to qualified weld parameters used
for propellant tank welding. AA2319 filler wire is used for G. Corrosion Resistance Test
the welding. Corrosion Resistance is verified with salt spray test. As part
D. Visual Inspection of salt spray test, the test specimen is washed in distilled or
de-ionized water, dried with a soft cloth and then subjected
Visual Inspection of the crown and penetration side of the
to a 5 percent salt spray in accordance with ASTM B 117
weld is to be done to ensure the joint is free from defects
for 336 hrs. [23]
like Undercut, collapse, lack of thickness etc. Weld joint
colorwasalso to be checked.

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3rd ISSE National Conference on Complex Engineering Systems of National
Importance:Current Trends & Future Perspective (INAC-03), October 12-13, 2017
Advanced Materials

V. RESULTS AND DISCUSSIONS

A. Visual Inspection Weld Specimen
UTS 0.2% Proof
% Elongation
(MPa) Stress (MPa)
No undercut, collapse or lack of thickness is noticed in
all the welds. The weld is grey in colour which shows good Anodized Plates
353-357 191-208 4.8-5.2
quality of weld. (Case 1)

B. Non-Destructive Testing DeAnodised Plates

352-361 193-208 4.9-5.0
Non-Destructive Evaluation Techniques (NDE) viz. (Case 2)
radiography, dye penetrant tests and ultrasonic tests were
performed. All discontinuities seen in radiographic analysis Bare Plates
367-373 230-231 6.6-7.0
(Case 3)
[Table 3] are minor in nature and acceptable as per standard
followed for ISRO propellant tank fabrication. Ultrasonic
test was carried out by calibrating the instrument using Table 4(b). Mechanical Properties at Cryo Temperature [LN2].
standard rectangular F-notch. No significant defect echo
above 80% was observed. This ensured sound weld quality. D. Metallurgical Analysis
Dye Penetrant test was carried out on both top and under The Macroexamination of weld zone, fusion zone &heat
bead side of the weld and was found satisfactory. affected zone (HAZ) revealed satisfactory fusion and
penetration. The weld is seen to be free from defects like
porosities, lack of fusion and crack. Since it is known that
Radiography Report the AA2219 weld generally fails at the bead edge or weld,
Plate Type
Fine Pores these region was closely studied. Copper rich films are seen
within HAZ of the weld. Grain size in the parent metal,
Anodized Cluster Pores (2.5x2mm) HAZ and width of the HAZ are shown in Table 5. The
Plates
Cluster Pores microstructure of the anodized plate, at various locations
(Case 1)
(1.0*0.7,1.2*1.0,0.5*0.5mm) (Fusion, HAZ & Parent Metal) is given in Fig. 3. Thus it is
clear that there wasno defect in the microstructure as the
Fine Pores
grain recrystalization could be seen in the fusion zone
Cluster Pores (0.5x0.5mm) clearly.
De-Anodized
Plates Cluster Pores (1.0*1.0, Grain Size
Grain
(Case 2) 0.5*0.2,0.8*0.7mm) in parent Approx
Size in HAZ
metal . width of
Fine Pores Weld Specimen (ASTM
(ASTM HAZ
Grain Size
Grain Size (mm)
Bare Plates Fine Pores No.)
No.)
(Case 3) Anodized Plates
Cluster Pores (0.5*0.5,1.0*1.0, 2
(Case 1)
0.5*0.5mm)
De-Anodised
6-7
Plates 5-6 2
(Case 2)
Table 3.Radiography Report of welded specimens
Bare Plates
2.5
Thus the discontinuities observed as a result of (Case 3)
inspection were minor in nature and acceptable.
Table 5: Grain Size & HAZ width
C. Tensile Testing
Tensile test was done at room and cryo temperature to
evaluate the mechanical properties. The values obtained
[Table 4 (a & b)] for Case 1 & 2 meet the requirement and
are equivalent to the bare metal (specimen) welding. The
percentage elongation showed little reduction (2%) for
anodized and de-anodized specimen w.r.t. bare plate
specimen. The loss in ductility may be attributed to presence
of micro oxide particles in the lower surface of the
specimen, which was not removed during scrapping/de-
anodisation process. However the mechanical properties are
well within the acceptable limits with respect to the design
requirement of the hardware.
UTS 0.2% Proof %
Weld Specimen
(MPa) Stress (MPa) Elongation
Anodized Plates (Case 1) 245-254 130-147 5-5.6
De-Anodised Plates (Case 2) 258-268 137-148 4.4-5.0
Bare Plates (Case 3) 248-253 129-137 6.4-6.6
Fig. 3. Microstructure of weld specimen.
Table 4(a). Mechanical Properties at Room Temperature.

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 3rd ISSE National Conference on Complex Engineering Systems of National
Importance:Current Trends & Future Perspective (INAC-03), October 12-13, 2017
Advanced Materials

E. Corrosion Resistance anodisation method locally by incorporating a bath with

In order to ensure the integrity of the specimen with groove of required dimension (as per the dimension of the
respect to corrosion protection, salt spray test was carried weld area for cir-seam and L-seam welds).
out for 336 hrs in the salt spray bath. The results [Table 6] The above study gives the solution for effective protection
shows no corrosion spots were developed (after 336 of AA2219 components for long term storage and method of
hours)on the anodized surface of the weldment as shown in TIG welding for meeting the quality requirements of space
Fig 3. application standards which will ensure the success of
launch missions and improve the reliability of the hardware
Sl Type of for Indian Space program.
Remarks
No. specimen
1 Corrosion spots developed after 24
Anodized Plates hrs at the weldment, however no
REFERENCES
(Case 1) corrosion spots noticed at the anodised [1] W. R. Pinner and P. G. Sheardy: The surface treatment of
zones after 336 hrs of test aluminium& its alloys, 194; 1987, Teddington, Finishing
2 DeAnodised Corrosion spots developed after 24 [2] L. L. Sheir, R. A. Jarman and G. T. Burstein: Corrosion, 3rd edn,
Plates hrs at different zones, the spots 123; 1994, Oxford, Butterworth-Heinemann.
(Case 2) developed further after 336 hrs of test [3] C. M. Liao, J. M. Olive, G. Gao and R. P. Wei: Corrosion, 1998, 54,
3 Corrosion spots developed after 24 451458.
Bare Plates [4] P. Traverso and A. M. Baccaria: Br. Corros. J., 1997, 32, 255261.
hrs at different zones, the spots
(Case 3) [5] W. A. Badawy, F. M. Al-Kharagi and A. S. Azab: Corros. Sci., 1999,
developed further after 336 hrs of test
41, 709727.
[6] Robinson, M. J. (1982): Mathematical modeling of exfoliation
corrosion in high strength aluminium Alloys, Corros. Sci., 22(8),
pp.775-790
[7] Meletis, E. I.; Weiji Huang. (1991): The role of the T1 phase in the
pre-exposure and hydrogen embrittlement of Al-Li-Cu alloys, Mater.
Sci. and Engg. A, 148(2), pp.197- 209
[8] Keddam, M.; Kuntz, C.; Takenouti, H; Schustert, D; Zuili, D. (1997):
Exfoliation corrosion of aluminium alloys examined by electrode
impedance Electrochim. Acta, 42 (1), pp. 87-97
[9] Williams Stewart, W; RajanAmbat; Debbie Price;
ManthanaJariyaboon; Alison Davenport, J.; Andrew Wescott. (2003):
Laser treatment method for improvement of the corrosion resistance
of friction stir welds, Mater. Sci. Forum. 426, pp.2855-2860
Fig 3(b) Bare specimen [10] Birbilis, N.; and Buchheit, R. G. (2005): Electrochemical
Fig 3(a) Anodised specimen after 24 hrs of salt spray test characteristics of intermetallic phases in aluminum alloys: An
weldment after 24 hrs of salt spray experimental survey and discussion, J. Electrochem. Soc., 152(4)
test pp.140-151
[11] Paglia, C. S; Buchheit, R. G. (2006): Microstructure, microchemistry
and environmental cracking susceptibility of friction stir welded
2219-T87, Mater. Sci. and Engg. A, (429) pp.107-114
VI. CONCLUSION [12] Hughes A H, Taylor R J, and Hinton B R W, Surface and interface
analysis 25 (1997) p 223.
The present study reinstates that anodization with [13] Vasquez M J, Kearns J R, Halada G P, and Clayton C R, Surf
sulphuric acid electrolyte is successful in protection of Interface Anal 33 (2002) p 796.
AA2219 from pitting corrosion. It is further investigated that [14] G. D. Bengough and J. M. Stuart, British Patent, 223994 (1923).
the anodized parts can be welded as it is by following the [15] K. J. Kallenborn and J. R. Emmons, NASA Conference Publication,
1995, 3298 (Aerospace Environmental technology Conference 1994).
standard procedures followed during preparation of edge for 267 (Eng) (1995).
welding i.e. cleaning/degreasing and scrapping.The aim of [16] Davis J R, Surface engineering, ASM International, IOM
the study was also to qualify DCSP TIG welding process on Communications (2001) P 102
[17] K.SrinivasaRao, N.Sreedhar, B.MadhusudanaRao and K.PrasadRao,
anodized AA2219-T87 specimen in order to ensure better Trans. Indian Inst. Met. Vol.57, No. 2, April 2004, pp. 133-140
protection of AA2219 components from corrosion by [18] Davis J R, Corrosion of Aluminum and Aluminum Alloys, ASM
anodisation for long term storage. On the basis of repeated International, 1999, P 203
[19] K. SrinivasaRao and K. Prasad Rao: Trans. Indian Inst. Met., 2003,
welding trials criticalparameters for welding was optimized 56, 383390.
in order to achieve acceptableweldquality of the test [20] K.SrinivasaRao, N.Sreedhar, B.MadhusudanaRao and K.PrasadRao;
specimen. However since the scrapping process is manually Trans. Indian Inst. Met., Vol.57, No. 2, 2004, 133-140
[21] G. Venkatasubramanian, et al., Inhibitive effect of Ce(III) and La(III)
controlled, high level of uncertainty exists in meeting the
cations for AA2219 aluminium alloy corrosion in sodium chloride
quality requirements, prior to welding of the hardware. On medium, Materials Chemistry and Physics (2014),
the other hand, de-anodisation of the part before welding is a http://dx.doi.org/10.1016/j.matchemphys.2014.07.043
process controlled method with less dependence on skill of [22] P SrinivasaRao, K G Sivadasan and P K Balasubramanian; Bull.
Mater. Sci., Vol. 19, No. 3, June 1996, pp. 549-557
labour. Therefore de-anodisation process can be [23] MIL-A-8625F MILITARY SPECIFICATION ANODIC
incorporated over scrapping process for handling larger COATINGS, FOR ALUMINUM AND ALUMINUM ALLOYS,
components (viz. tankages of 2.8m and 4m in diameter) as 1993
these hardware would require long weldment, scraping of
which will be extremely ineffective. Alsode-anodising
locally on very large components / sub-assemblies (4000 x
2500 mm) is not possible by conventional method /
facilities. It thereby calls for innovative design of facilities
to provide weld preparation of larger components by de-

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