Transactions of the IMF

The International Journal of Surface Engineering and Coatings

ISSN: 0020-2967 (Print) 1745-9192 (Online) Journal homepage: http://www.tandfonline.com/loi/ytim20

The Chemical Polishing of Aluminium

E. A. Culpan & D. J. Arrowsmith

To cite this article: E. A. Culpan & D. J. Arrowsmith (1973) The Chemical Polishing of Aluminium,
Transactions of the IMF, 51:1, 17-22, DOI: 10.1080/00202967.1973.11870258

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 The Chemical Polishing of Aluminium
E. A. Culpan* and D. J. Arrowsmith
University of Aston in Birmingham

MS received 2 November 1972

SuMMARY-The chemical polishing of aluminium in phosphoric-sulphuric-nitric acid mixtures with controlled

additions of copper was studied by electron microscopy. Changes in specular reflectivity were correlated with
aluminium dissolution rates and the surface structure which changed through an etching stage to a· polishing
stage and then to a coarsening stage. The results furthered discussion of chemical polishing mechanisms.

INTRODUCTION were etched in Lacombe and Beaujard's reagent,3 which

CHEMICAL polishing (or chemical brightening) prior to
anodizing is widely used to produce a bright finish on
aluminium. Phosphoric-sulphuric-nitric acid mixtures,1 such
as Phosbrite 159, are commonly employed. The nitric acid
content, water content, aluminium content and the addition
of copper all influence the degree of brightening obtained.
Brace and Kape 2 studied these variables and reported
working ranges for optimum brightness. They discussed
the mechanism of chemical polishing in chemical and
electrochemical terms. Their work was re-examined and
extended, as detailed below, by using electron microscopy
to study the changes in surface structure that occur during
the chemical polishing of aluminium.
EXPE~NTALPROCEDURE
CHEMICAL POLISHING
Aluminium in the form of annealed sheet 1·2 mm thick
with a nominal purity of 99·99% was used. Samples
I 0 x 5 em were degreased in acetone and stored in a desic-
cator before chemical polishing. The basic chemical polish-
ing solution used was a mixture of 77·5 parts (by volume)
orthophosphoric acid (SG 1·74), 16·5 parts sulphuric acid
(SG 1·84), and 6·0 parts nitric acid (SG 1·42). The follow-
ing polishing mixtures were made up, each comprising the
basic solution with copper added as copper sulphate.
A Basic solution
B Basic solution +0·25 g/1 copper
C Basic solution +0·5 g/1
D Basic solution +0·75 g/1
E Basic solution + I·O g I 1 ..
Chemical polishing was carried out in three litre beakers
controlled at a temperature of too• ±I ·c. using moderate
agitation with a magnetic stirrer. Each polishing condition
investigated was carried out in duplicate at least.
After chemical polishing the specular reflectivity of each
specimen was measured using an Evans Electroselenium
Metspec to British Standard Specification BS 1615: 1961
and the loss in weight per unit area during polishing was
determined gravimetrically.
ELECTRON MICROSCOPY
The surfaces of the chemical polished specimens were
examined by electron microscopy using a two stage
cellulose-triacetate/carbon replica technique. The carbon
repli::as were shadowed at an angle of 45• with a gold/
palladium alloy. Before replication some of the specimens
• Admiralty Underwater Weapons Establishment,
Portland, Dorset.
produced etch pits of cubic form suitable for orientation
determination without attacking the general surface.
Some specimens were also examined directly by
Stereoscan scanning electron microscopy.
TRANSMISSION ELECTRON MICROSCOPY
Thin foil specimens were produced to examine the sites
of copper deposition and surface morphology during
polishing in relation to the internal structure of the
aluminium.
Specimens of 99·99% aluminium foil 25 x 25 x 0·050 mm
were chemically polished, carefully rinsed and dried, and
then one side coated with lacquer. The foil was electro-
polished using the window method, in a solution (cooled
with liquid ni.trogen) of one part perchloric acid and four
parts absolute alcohol. After perforation of the foil the
lacquer was dissolved from the back of the specimen by
immersion in acetone.
WEIGHT OF DEPOSITED COPPER
Aluminium samples were removed from the chemical pol-
ishing solution and the copper deposited on the surface
was dissolved in 50% nitric acid. The weight of copper in
each nitric acid solution was determined using colorimetric
analysis with a 0·01 % solution of zinc dibenzyldithio-
carbamate in carbon tetrachloride. 4 A blank specimen was
used for each batch of copper determinations. This was an
aluminium specimen which had not been chemically pol-
ished but was immersed in 50% nitric acid and the solution
obtained analyzed for copper. The carbon tetrachloride
layer obtained from this specimen was taken as zero copper
deposited on the surface and the other specimens were
compared with this solution. This method ensured that
any copper dissolved from the bulk aluminium, or any
copper in the analysis solutions used, did not affect the
results obtained.
RESULTS AND INTERPRETATION
SPECULAR REFLECTIVITY
The specular reflectivity results obtained from chemically
polished specimens are plotted in Fig I (a). The degree of
specular reflectivity clearly depends on the time of pol-
ishing and on the concentration of copper in the solution.
The results indicate that the polishing cycle can be
divided mto three stages. The initial stage involves a rapid
etching of the aluminium and a low specular reflectivity
is recorded. During the second stage the etched structure
is replaced to give a polished surface. The specular re-
flectivity rises to a peak at the end of the second stage

17
 Transactions of the Institute of Metal Finishing, 1973. Vo/51

1001..--.-~-,---,.------~----...,-----~ 1·0.------r---.-----,.----,

• No copper
' 0·25 copper qf!
o 0·5 copper qfl
a 0·75 copper qfl
0·8 + 1·0 copper qfl

OQ 1 1 50s 1 2 4
Immersion lime, mon .....,..
.&:::
(a) ·~
~
.5

.5"' 0'4

0·2

2 3 4
Immersion time, min
(b) Fig 2. Variation of loss in weight with immersion time in
Fig 1. Variation of specular reflectivity with immersion time chemical polishing solutions with additions cf between 0 and
in chemical polishing solutions with between 0 and 1·O g /1 1·0 g I 1 copper.
copper added.
(a) Etching, polishing and coarsening stages.
(b) Reflectivity of aluminium chemically polished in solution surface features in each of the solutions investigated. There
C containing 0·5 g/1 copper; time in solution, left to right,
10 s, 30 s, 50s, 3 min. were three stages: etching, polishing and coarsening. The
surface structure of each stage was characteristic. The in-
fluence of copper additions was to increase the growth
rates of each stage (Table 1).
and thereafter decreases, with a marked deterioration of
the surface in the third stage. Electron micrographs obtained of replicas taken from
The addition of copper to the basic solution increases surfaces after 1. 2, 4, 15, 30, 60 and 180 seconds in the
the specular reflectivity obtainable during polishing. The solution which contained 0·5 g/1 are shown in Fig 3.
addition of copper also shortens the time of the polishing
cycle. With the composition of basic solution used, the ETCHING STAGE
amount of copper to give maximum specular reflectivity Figs 3 (a-d) show that in the first few seconds extremely
during chemical polishing is between 0·25 and 0·5 g/1 Cu. small, randomly nucleated, hemispherical etch pits are
Greater quantities of copper shorten the polishing cycle formed around defects such as scratches on the original
even more and reduce the level of the maximum specular surface. Wi.th increasing time in the solution the pits grow
reflectivity obtainable. hemispherically, impingeing laterally on each other to pro-
duce a cellular pattern (Fig 3 (d) ). The cells are depres-
WEIGHT Loss sions or scallops in the surface: the cell boundaries stand
The weight lost by aluminium specimens chemically pol- proud.
ished in the solutions investigated is plotted in Fig 2. The
curves show the rapid loss in weight of specimens polished TABLE I. INFLUENCE OF COPPER ADDITIONS
in .the solutions containing the high copper contents. How-
1
ever, the losses in weight of specimens polished in the Time for Time for Time for onset
solutions containing 0·25- 0·50 g/ 1 copper are less than Solution Copper, etch pattern, polishing of coarsening,
those polished in the solution with no copper. gjl s pattern, s min
------
REPLICA ELECIRON MICROSCOPY A 0 21 100 2
Replicas were taken from aluminium specimens after im- B 0•25 15 60 3
mersion in the chemical polishing solutions for a range c 0·5 10 50 2
of times from one second to four minutes. The electron D 0·75 8 40 1
micrographs obtained showed a similar development of E 1·0 5 20 t

18
 Culpan and Arrowsmith: The Chemical Polishing of Aluminium
(a) (b)
(e) (f)
Fig 3. Replica electron micrographs showing the change in surface structure with time in chemical polishing solution
C containing 0·5 g/1 copper.
(a) I s. Etching stage.
(b) 2 s. Etching stage showing etch nucleation on scratches.
(c) 4 s. Etching stage.
(d) 15 s. Etching stage, cellular network complete.
When the network of cells is complete the aluminium
surface is covered with fine equiaxed cells, 0·5- 1·0 J.tm in
size. The shape and distribution of the cells are independent
of crystal lat.tice orientation and grain size of the alum-
inium. This was established by comparing the cell struc-
tures formed on grains of different orientation which had
been identified by the shape of etch pits produced by the
Lacombe-Beaujard reagent as in Fig 3 (d).
POLISHING STAGE
The etching stage is followed by a polishing stage. Orien-
tation dependent polishing patterns are formed. The
development of the surface structure after 30 and 60
seconds is shown in Figs 3 (e-g).
On the {100} grains, identified by cubic etch pits, small
approximately hemispherical pits nucleate on the ridge
boundaries of the equiaxed cells, particularly at triple
points. As polishing proceeds .these depressions grow later-
ally, with the elimination of the original cells (Figs 3 (e)
and 3 (g).
On the {110} grains, new ridge boundaries are produced
within the equiaxed cells by local dissolution. As polishing
proceeds, more dissolution of the aluminium takes place
around the new ridges until they are as pronounced as the
original cell boundaries. The ridges are formed preferen-
tially in the <110> direction; thus the overall appearance
of the polished structure is that of elongated cells (Fig
3 (/) ).
On the {Ill } planes, dissolution takes place in certain
areas on ·the ridge boundaries leaving isolated asperities.
COARSENING STAGE
After the cellular network produced in the etching stage
has been replaced by the characteristic patterns of the
polishing stage, this pattern coarsens with increasing time
(c) (d)
(g) (h)
(e) 30 s, (100) plane. Polishing stage.
(/) 30 s, (II 0) plane. Polishing stage.
(g) I min. Polishing stage.
(h) 3 min. Coarsening stage.
in the chemical polishing solutions. The orientation de-
pendent form of the pattern does not change appreciably
but there is a marked coarsening of the structure which
occurs very rapidly in the solution with the highest copper
content. Fig 3 (h) shows the electron micrograph of the
replica of the surface after 3 minutes in the solution with
0·5 gjl copper. It can be seen that the depressions on the
{ 100} planes enlarge and merge to cover most of the
grain: there is also pitting of the surface within the de-
pressions. The same figure shows the coarsened ridge
structure characteristic of the {110} planes. The ridges
and asperities on the [110} and {111} planes also become
enlarged and the surrounding surface pitted.
The same three stages, etching, polishing and coarsening,
were observed 5 when using the solution with no copper
present, only the reaction rates were much slower. There
were slight differences in the surface structures obtained
in that the etched structure was not completely removed.
The initial etching stage was similar but there was a
greater range of polishing patterns which were the same
as those described by Cuff and Grant 6 and others7 • 8 who
used chemic_,al polishing solutions with no additions of
copper or any other metal.
TRANSMISSION ELECTRON MICROSCOPY
The technique used was to prepare aluminium foil thin
enough for transmission electron microscopy by electro-
polishing after chemical polishing by immersing prepared
foils in the chemical polishing solutions for a range of
times from l second to 4 minutes. Examples of the trans-
mission electron micrographs obtained are shown in Fig 4.
It can be seen that there is random nucleation of hemi-
spherical etch pits and no preferential attack at the grain
boundaries (Fig 4 (a)). Pits are formed more readily at
defects such as scratches in the original surface. Copper
19
 Transactions of the lnstitllte of Metal Finishing, 1973, Vol 51

10,000

c"'::s
8 5,000
:=.
·;;
c
0>

....c
(a) (b) (c)
Fig 4. Transmission electron micrographs of aluminium foils
chemically polished for 2, 10 and 120 seconds in chemical
polishing solution C containing 0·5 g/1 copper.
(a) 2 s. Etching stage. (b) 10 s. Etching stage. 0
(c) 120 s. Coarsening stage.
Energy, keV
Fig 6. Energy dispersive X-ray microanalysis of aluminium
particles can be observed after 10 seconds immersion (Fig chemically polished in solution C containing 0·5 g/1 copper.
4 (b)) and appear on the cell boundaries (which stand AI 1·5 keV Cu 8·0 keV
proud of the surface). It is clear that the sites of copper
deposition and ·the cell pattern of the etching stage are
unrelated to the underlying crystal structure. After two
minutes (Fig 4 (c) ) the etch stage cellular pattern has
WEIGHT OF DEPOSITED COPPER
been replaced by the characteristic polishing patterns.
Copper is present on the ridges of (110) grains (identified The weight of copper deposited on aluminium specimens
by electron dit:fraction) and the peripheries of the cells on immersed for various times in the polishing solutions in-
the (100) grains. There are also large agglomerations of vestigated is shown in Fig 7. The results indicate that, for
copper in the enlarged depressions. all solutions, no copper is deposited on the specimens
during the first few seconds of polishing. However, as
SCANNING ELECTRON MICROSCOPY polishing continues there is a build-up of copper on the
specimen, the rate of which is determined by the concen-
Scanning electron microscopy enabled direct examination
tration of copper in the polishing solution.
of the surface and confirmed the nucleation of pits in the
etching stage and the deposition of copper on the ridges
of the polishing pattern (Fig 5). The resolution of the
scanning electron microscope and the development of
image contrast are not well suited to the study of polished 20
surfaces. The copper particles appear bright owing to
atomic number contrast between copper and aluminium.
The etched surface structure is shown in Fig 5 (a)
together with fine globular deposits of copper 0·1 - 0·2 J.tm 18
in size, situated at the ridge boundaries. In Fig 5 (b) the
copper deposits appear as stringers along the polishing
patterns and occasionally as larger irregular shaped par- 16
ticles.
Fig 5 (c) shows a specimen polished for 3 minutes. The
copper particles are now large agglomerates about 5-10 J.tm 14
in size and are associated with deep depressions in the
surface. ~
><
Energy dispersive X-ray analysis* of selected areas on
the surfaces of these specimens showed that the deposits
-
eu
c::r
12

. ./j
are copper and that no copper was detected on the alum- ....
inium surfaces adjacent to the deposits. Fig 6 is an Edax ~ 10
0
analysis trace taken from a deposited particle, showing a u

copper line at 8 keV and lines from the underlying alum- 0

-B
II ././-·
inium at 1·5 keV. .c
c::r
'6;
3

4 lc'/ / /
/;&:../• • 0·25 copper qfl
1
I. "o ~,...... o 0·5 copper qf!
(a) (b) (c)
2
I
1 ~/
.~.......... a
1
0·75 copper qfl
1·0 copper qJt
Fig 5. Scanning electron micrographs of aluminium chemically
polished for 10, 90 and 180 seconds in chemical polishing %~----~------~----~3~----~4
solution C containing 0·5 g/1 copper.
(a) 10 S. X 5000 (b) 90s. X 5000 (c) 180 S. X 500 Polishinq time, min
Fig 7. Weight of copper deposited with immersion time in
• Carried out at Fulmer Research Institute. chemical polishing solutions.

20
 Culpan and Arrowsmith: The Chemical Polishing of Aluminium
(a) (b) (c)
Fig 8. Replica electron micrographs of etched aluminium.
(a) Etched in 1 % HF.
(b) Etched in 10% NaOH.
(c) Etched in Brytal electropolishing solution at an applied
potential in the etching range.
DISCUSSION
RELATIONSHIP BETWEEN SURFACE FINISH AND
STRUCTURE
The aluminium exhibits a low specular reflectivity during
the initial etching stage of chemical polishing. This is due
to the very rapid formation on the surface of a relatively
coarse cell structure, which is apparently independent of
the crystallographic orientation of the underlying alum-
inium. During -the first seconds immersion in the polishing
solution the metal appears unattacked and there is only
a small decrease in specular reflectivity. However, electron
micrographs taken at this stage indicate that extremely fine
etch pits are produced at defects in the original oxide films
on the aluminium. The reflectivity falls rapidly as polishing
proceeds, as the initial etch pits grow hemispherically until
the etched cell network is complete.
It is interesting at this point to note the similarity between
the surface etched structure produced in the first stage of
chemical polishing and the structures produced in mild
etching solutions, such as dilute 1 % hydrofluoric acid, Fig
8 (a}, 10% sodium hydroxide solution, Fig 8 (b), and the
etching region of the Brytal electropolish, Fig 8 (c). The
similarity indicates that during the etching stage the chemi-
cal polishing solution acts like any anodic dissolution
process to remove the original oxide film and to give a
uniform mildly etched surface. The polishing solution then
replaces this etched structure with a finer polished struc-
ture. In the polishing stage -the specular reflectivity of the
alummium reaches a maximum. This increase is due to
the gradual removal of the coarse cell structure and its
replacement by a fine structure which appears to be de-
pendent on the crystallographic orientation of the alum-
inium. By comparing the shadowing on the replica electron
micrographs, it can be seen that polishing not only pro-
duces a finer structure but also there is less difference in
height between the elevations and the depressions. The
surface, therefore, has been smoothed, as shown schematic-
ally in Fig 9.
By comparing the results of specular reflectivi-ty vs
polishing time and the electron micrographs, it is clear
that maximum reflectivity is attained when the etched cell
structure has just been replaced by the polished structure.
Prolonged polishing results in a gradual decrease in
specular reflectivity, which is due to a coarsening of the
surface structure. This appears as an enlargement of the
structural features on the surface and pitting attack on the
remaining areas.
It was observed that specimens polished in the solution
containing no copper did not give such high specular re-
flectivity results. This was ascribed to the further obser-
vation that the etched cell structure was not completely
removed from the surface of these specimens.
INITIAL ETCH PIT, APPROXIMATELY 5.000 l DEEP
COMPLETE ETCH NETWORK, APPROXIMATELY 2.000 l DEEP
.. .. .. . . . . . . ..
,
POLISHED STRUCTURE, APPROXIMATELY 500 l DEEP
Fig 9. Schematic view of the difference in height of elevations
during the polishing process.
INFLUENCE OF COPPER IN THE CHEMICAL POLISHING
SOLUTIONS
It has been stated 2 •9 • 10 • 11 that additions of heavy metals to
polishing solutions improve the surface finish obtained, and
most patented chemical polishing reagents contain heavy
metal additions, 12- 15 although the reasons for such addi-
tions have not been clear. In fact it is well known that the
presence of copper, either alloyed or in contact with alum-
inium, generally favours pitting attack.
The present investigation has shown that the copper in
the chemical polishing solutions promotes the formation
of a fine structure characteristic of a polished surface to
obtain a surface with a high specular reflectivity. The
larger the amount of copper in the solution the shorter
the polishing time required to produce maximum reflec-
tivity and also the shorter the polishing time before surface
deterioration.
By comparing Figs 1 and 7 it is apparent that during
the initial etching of the surface very little copper is
deposited on the specimens. However, as polishing con-
tinues the amount of copper increases, with a corresponding
increase in specular reflectivity. As further polishing takes
place it is apparent that the amount of copper deposited
is in excess of that required for the polishing process and
coarsening of the surface occurs which reduces the specular
reflectivity.
High specular reflectivities were not obtained with the
solution containing no copper, confirming that a minimum
amount of heavy metal is necessary on the specimen sur-
face for optimum polishing.
Electron microscope examination indicates that during
the etching stage the copper is deposited at the cell boun-
daries in the form of fine particles, 1000 - 2000 A in size.
This is different from an earlier suggestion 2 that the alum-
inium surface is uniformly covered with copper to a
thickness of several atomic layers. The etch pits or cells
are anodic sites while the cell boundaries standing proud
of the surface are cathodic sites. When copper is present,
copper is deposited on the cell boundaries. The copper
nuclei grow and promote film formation as was shown by
potential measurements. 5 Localized high potential differ-
ence between the copper on the cell boundaries and the
aluminium of those boundaries results in high dissolution
rates of aluminium through the solid film. This localized
dissolution of the cell boundaries smooths the surfacr
during the polishing stage, resulting in increased reflec-
tivity. The effect of this dissolution on ·the { 100} and { 110}
planes is shown schematically in Fig 10.
It can be seen that there will be a decrease in scale of
the submicro dissolution figures, together with a smoothing
of the asperities, both of which are observed by electron
microscopy and specular reflectivity results.
21
 Transactions of the Institute of Metal Finishing, 1973, Vo/51
e COPPER PARTICLE
100 PLANE 110 PLANE
Fig I0. Schematic diagram of copper deposition on (I 00)
(110) planes.
The localized dissolution discussed above will produce
undercutting of the deposit ; and further deposition will
occur at other asperities. Each deposit will enlarge during
polishing as the amount of copper on the aluminium sur-
face increases and metal is preferentially deposited on
existing nuclei. At the same time, the spacing of the sur-
face structure is reduced by the dissolution at the asperities.
A stage is reached when the size of the deposited copper
particles approaches the dimensions of the surface features,
whereupon the copper particles on neighbouring asperities
will touch and agglomerate. Electron microscopy indicates
that this occurs when the copper particles are about 0·4 I-'m
in size. This agglomeration prevents any further decrease
in scale of the dissolution features and a deterioration of
the surface quality occurs if polishing is continued.
The film formed in the polishing stage is promoted by
the potential difference between anodic and cathodic sites
(increased by copper when present) and ·the oxidizing power
of the chemical polishing solution used. Brace and Kape 2
have demonstrated that a certain amount of nitric acid is
nece'!sary for brightening to take place. They concluded
that below the optimum nitric acid content etching occurs
probably because insufficient oxygen ions reach the surface
to maintain a stable film. Above the optimum content the
coarsening stage of the chemical polishing sequence is
reached in too short a time for the development of maxi-
mum brightness in the preceding polishing stage.
CONCLUSIONS
The results of this investigation show that there are three
stages in the chemical polishing of aluminium in etching,
polishing and coarsening. Maximum brightness is obtained
22
after development of the polishing structure and before the
onset of coarsening. The presence of deposited copper on
the surface of the specimen is necessary for maximum
brightening to take place. Below the optimum amount the
etching stage is not completely replaced by the polishing
structure before the onset of coarsening, so maximum
brightness is not developed. Above the optimum amount
of copper, large agglomerated particles of copper build up
and on the surface and produce high current densities in
localized areas ; the onset of coarsening is very rapid. It
was observed that specimens chemically polished in the
solution containing 0·25 - 0·5 gjl copper had a lower rate
of metal removal than those polished in the solution with
no copper. The above results indicate that the presence of
the copper in these solutions is to promote the formation
of a solid film on the metal surface. The film is formed
at an optimum rate to give a compact structure that reduces
the rate of metal dissolution.
REFERENCES
l Brit Pat 675,444.
2 A. W. Brace and J. M. Kape, Theoretical Aspects of Elec-
trolytic and Chemical Polishing, Proc ADA Conf on
Anodizing Aluminium, Nottingham l%1, 167.
3 C. J. Sm1thells, Metals Ref Bk, Butterworths, Third Ed,
1962, and also:
P. Lacombe and L. Beaujard, Rev Met, 1947, 44, 71;
1 lnst Metals, 1948, 74, l.
4 E. Johnson, Organic Reagents for Metals, Vol I, Hopkins
and Williams, 1955.
5 E. A. Culpan, PhD Thesis, University of Aston in Bir-
mingham, 1970.
6 F. B. Cuff and N. J. Grant, J lnst Metals, 1959, 87, 248.
7 M. S. Hunter and D. L. Robinson, Trans AIMME, 1953,
197, 717.
8 H. Bischel, Metal Treatment and Drop Forging, 1%0, 27,
319.
9 A. W. Brace, Alum Dev Ass, Tech Memo 212, 1955.
10 H. Fisher and L. Koch, Metal/, 1952, 6, 305.
II R. Pinner, Proc ADA Conf on Anodizing Aluminium,
Nottingham, 1961, 203.
12 Brit Pats 687,774; 958,499 and 1,145,881.
13 German Pats 804,054 and 814,984.
14 Light Metals, 1954, 15, 348.
15 W. K. Bates and C. D. Coppard, Met Fin 1, 1958, 4, 5.