Indian Journal of Chemistry

Vol. 27A, May 1988, pp. 387-389

Composition of Chromate & Chromate-Phosphate Conversion Coatings on

Aluminium using Rutherford Backscattering Spectroscopy
MOKI
Department of Chemistry, University of Port Harcourt, P.M.B. 5323, Port Harcourt, Nigeria
Received 8 June 198}; accepted 8 September1987

Compositions of chromate and chromate-phosphate conversion coatings formed by natural immersion of alu-
minium specimens in the respective coating baths have been studied by Rutherford backscattering spectroscopy
(RBS). The chromate coating consists mainly of chromium oxide whereas the coating formed from the chromate-
phosphate bath consists essentially of chromium phasphate.

Conversion coatings on aluminium and other me-
tals provide an adherent base for subsequent
paint application 1. In addition, the coatings afford
some degree of corrosion resistance on the sub-
strate metaF.
The chromate or chromate-phosphate coatings
are usually developed in solutions containing fluo-
ride ions which activate the metal followed by ca-
thodic reduction of Cr(VI) species in solution, in
addition to hydrogen evolution reaction.
The present Rutherford backscattering spec-
troscopy investigation seeks to know the composi-
tion of these coatings in order to formulate a gen-
eral mechanism for their formation. An under-
standing of the mechanism of formation of the
coatings may lead to the formulation of better
corrosion resistant coatings.
Materials and Methods
Spade-like electrodes, made of 99.999% pure
aluminium (0.002% Cu; 0.004% Fe; 0.003% Si)
were electropolished at - 5°C and 20-22V in
perchloric acid- ethanol mixture for 5 min. After
electropolishing, the specimens were rinsed in dis-
tilled water and dried by passing a cold stream of
aIr.
The two conversion coating baths employed
had the following compositions: Chromate: 4g
Cr03, 3g NazCrz07 and 0.8g NaP, and chromate-
phosphate: 100g H3P04, 4g Cr03 and Ig NaP.
The coating baths were made up to 1 litre with
distilled water. Conversion coating procedure was
performed by fully immersing the electropolished
specimens in the individual coating solution for 2
min at 25°C. The specimens were then rinsed in
distilled water and dried in air.
Rutherfordbackscattering spectroscopic (RBS)
examination of the two specimens was carried out
with a6 MeV Vail de Graaff accelerator at the
University of Manchester, UK.
The RBS arrangement and calculations of the
elemental compositions of the coatings closely fol-
lowed those described by Skeldon3.4. However,
4He + ion beams were employed to obtain the
spectra in the present study. The specimens were
tilted at an angle of 30° to the incident beam in
the system with a background vacuum level of ap-
proximately 10 - 4Pa. Scattered particles from the
targets were detected at an angle of 165° to the
incident beam direction by an annular silicon sur-
face barrier detector. The operating current em-
ployed was in the range of 1-15 nA
Results and Discussions
The RBS spectra for the chromate and chrom-
ate-phosphate conversion coated specimens are
displayed in Figs. 1 and 2 respectively.
For the chromate specimen (Fig. 1) the major
peaks identified are from chromium and oxygen,
whereas oxygen, chromium and phosphorous are
identifiable from Fig.2. The oxygen to the other
atom atomic ratios, calculated from the peak
yields are: oxygen to chromium ratio 0.53 + 0.03
(Fig.1) and oxygen to chromium ratio 0.160 ±
0.005 (Fig.2) and oxygen to phosphorous ratib
0.187 ± 0.005. In both cases, the ratios are con-
stant throughout the bulk of the coatings, i.e. from
the coating! environment interface to the metal!
coating interface. The ratios indicate that the
atomic compositions of the coatings are:
Cr1.59±O.09'03 for the chromate specimen and
CrO,64±O,OZ' PO,75±O.OOZ'
04 for chromate"'phosphate
specimen. For both the coatings the approximated
atomic ratios will be CrZ03 and CrP04 respect-
ively.
In a similar studys, XPS investigation revealed
that the chromate conversioncbating was com-
posed mainly of hydrated Cr(m) oxide, with
about 10%' ofthedlfomitim content' being in' + 6
oxidation state~ The same investigation showed'

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Cr
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> 6144 "
Ul
:::
cr
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I II
2048
100
CHANNEL
Fig. I - Rf3S spectrum for chromate conversion coating deve-
, loped on aluminium for 2 min
that the: composition of the specimen treated in
the chtomate-phosphate bath was hydrated
CrPO 4' ifhese results are in agreement with the
findings fof Traverton and Davies6 who employed
XPS te¢hniques with argon etching to study
chromat~ and chromate-phosphate conversion
coatings Ion aluminium. In the present study, there
is no in~ication for the presence of water of hy-
dration. ifhis may be due to the age of the coating
- two t'eeks, prior to analysis. During this peri-
od the qoatings would have dried up completely.
In additibn, the water of hydration may have dri-
ed up in the high vacuum operating in the Van de
I,
Graaff aqcelerator before analysis was completed.
In Figf 1, a small peak from aluminium is ob-
servable! at channel number 210. Whereas, in
Fig.2, it ,S not clear whether aluminium is present
in the cdating. The edge corresponding to scatter-
ing fro~ aluminium is overlapped by the phos-
phorous peak, indicating, the phosphorous yield
I,
includes some contribution due to aluminium if
!
the latte~ were present in the coating. However, in
both cases the aluminium yield may be derived
from wi~n the coatings and/or from the sub-
strates a~ spalled or cracked regions. 'Mud-crack-
ing' is a i characteristic feature of both coatings7.
388
INDIAN J. CHEM., VOL. 27 A, MAY 1988
'" ~
ac
w , \
"l
I
~~C
AI
200' '300
NUMBERS
100 400
Fig. 2 - RBS spectrum for chromate-phosphate conversion
coating developed on aluminium for 2 min
From investigations using Scanning electron Mic-
roscopy (SEM) and ultramicrotomy/ Transmission
etectron Microscopy (TEM) techniques 8, some of
the cracks present in the coatings are observed to
penetrate to the metal/coating interface. It is like-
ly that the aluminium yield is partly derived from
such cracked regions. In addition, during the acti-
vation of aluminium substrate by the complexing
action of the fluoride species present in the coat-
ing baths, cathodic reduction of Cr(VI) to Cr(III)
species is accompanied by hydrogen evolution.
The liberation of hydrogen, obviously, leads to in-
crease in the pH of the solution. The theory9,IO
which supports the hydrogen evolution reaction
also indicated the deposition of hydrated alumini-
um oxide-from AP + generated during the activa-
tion of the substrate by F-. Such hydrated alumi-
nium oxide may be trapped within the growing
coating and this will partly account for the alumi-
nium yields observed.
If the aluminium yield is derived from the coat-
ings and its distribution within the coating thick-
ness assumed to be constant, the aluminium oxy-
gen ratio (from Fig.1) comes out to be
0.074.± 0.005. This leads to the composition of
AlO,22±0.Q2· CrI.59±009' 03' On the other hand, the
 OK!: COMPOSITION OF CHROMATE & CHROMATE-PHOSPHATE
aluminium oxygen ratio in the chromate-phosph-
ate specimens is < < 0.01. The presence of alu-
minium species in the coatings agrees with the
findings of Abd Rabbo et apt and that of Traver-
ton and Davies6 who respectively employed SIMS
and XPS techniques to study conversion coatings
on aluminium. Such aluminium species a{e either
AlP3 or AlOE
From the atomic composition obtained by the
RBS technique, the formation of the coatings can
proceed through the following steps.
(i) Activation of aluminium substrate achieved
by the complexing action of fluoride in the coat-
ing baths (Eqs 1 and 2),
F-
Al203 --+ AlOF (soluble) ... (1)
or
... (2)
It has been shown by potential-time measure-
ments for electropolished aluminium 1911itre NaF
solution that fluoride maintains aluminium substr-
ate active at a potential of about -0.9Y. This is
consistent with activation of substrate by fluoride
species in the solutions.
(ii) The exposed, reactive aluminium surface
acts as a source of electrons for the reduction of
Cr(VI), in contact with it, to Cr(III) species (Eq.3).
... (3)
When the solubility product for Cr 203 is ex-
ceeded, it deposits on the metal via the quilibri-
urn reaction (Eq.4).
... (4)
However, in the presence of PO 43 - in the
chromate-phosphate bath, CrP04 is deposited in
preference to Cr203. the solubility product of the
CONVERSION COATINGS ON ALUMINIUM
former is lower than that of the latter. Thus, reac-
tion (5) becomes predominant.
... (5)
The presence of Cr203 in chromate-phosphate
coating' was reported by Traverton and' Oavies6•
However, they further stated that it might have
been generated from CrP04 during argon sputter-
ing prior to XPS analysis. It is likely that reaction
(4) takes place as well; however, the product,
Cr203, is largely converted into CrP04 in the
presence of excess phosphate ions.
Acknowledgement
The author wishes to thank Dr M Skeldon of
UMIST, UK, for the provision of time during
RBS analysis and Dr G E Thompson for his guid-
ance .
References
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