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 Mild Steel by Hydrogen

Peroxide—Oxalic Acid Mixtures

A. Hickling & A. J. Rostron

To cite this article: A. Hickling & A. J. Rostron (1954) The Chemical Polishing of Mild Steel
by Hydrogen Peroxide—Oxalic Acid Mixtures, Transactions of the IMF, 32:1, 229-261, DOI:
10.1080/00202967.1954.11869676

To link to this article: https://doi.org/10.1080/00202967.1954.11869676

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 229

Paper presented at the Spring Conference of the Institute

oi Metal Finishing, at Torq~.Wy, on 19th May, 1955.
Re/erenc,__Trans. lnst. Met. Finishing, 1955, ll, 229-261

THE CHEMICAL POLISHING OF MILD STEEL BY HYDROGEN PEROXIDE-

OXAUC ACID MIXTURES •
By A. HICKLING, D.Sc., Ph.D., F.R.I.C.,t and A. J, RosTRON, B.Sc.t

SYNOPSIS.
An experimental study has been made of the reactions of mild steel
with hydrogen peroxide/oxalic acid mixtures and the conditions under
which chemical polishing takes place have been defined. Polishing
occurs when the metal is alternating between active and passive states,
and it is accompanied by a periodic variation in the rate of dissolution
and the potential of the specimen. The phenomena are in conformity
with the view that the metal is partly covered by oxide under these
conditions and that its dissolution is electrochemical in nature, there
being set up local voltaic couples in which current flows from oxide-
covered hollows to hare metal peaks in the sudace. This theory has
been developed so as to give a detailed interpretation of the kinetic
and potential phenomena exhibited, and it provides a general approach
to the problem of the mechanism of chemical polishing.

INTRODUCTION.
It has been reported that certain aqueous solutions of oxalic acid
and hydrogen peroxide exert a pronounced smoothing action on
various types of steel. Evidence of periodicity of reaction was
noted and this was later shown by E. R. Buckle to be accompanied
by periodic variation of potential. The polishing action seemed to
be directed primarily to the smoothing of the fine texture in the sur-
face, and after this chemical treatment it was found 2 that an oxide
film of a very thin and tenacious character was spontaneously formed
on the metal and exerted some protective action. The reaction is of
interest since it affords an example of very good chemical polishing
and also an easily reproducible case of electrochemical periodicity,
and the investigation which is now reported was undertaken with a
view to discovering its fundamental mechanism.

ExPERIMENTAL TECHNIQUE.
The interaction of mild steel with hydrogen peroxide/oxalic acid
mixtures of widely ranging compositions has been investigated with
reference to three main features : -
{a) the potential exhi'bited by the metal,
(b) its rate of dissolution, and
(c) the effect on its surface.

• MS. received 18th December, 1954.

t Department of Physical Chemistry, Liverpool University.
230 CHEMICAL POLISHING OF MILD STEEL

MATERIALS.
Steel.-For the potential and kinetic experiments cylindrical mild
steel specimens cut from 6 in. nails were employed, each presenting
an apparent surface of 10 sq.cm. For experiments in which a close
examination of the surface was desirable, rectangular mild steel
specimens cut from steel bar of dimensions 1 X ! x fin. were
employed; these specimens were rubbed down on 0 grade emery
paper before treatment. The analyses of the two varieties used are
given below :
C Si Mn S P Ni Cr V Mo
cylindrical 0·06 <O·Ol 0·32 0·034 0·015 0·13 0·06 0·03 0·04%
rectangular 0·15 0·15 0·87 0·039 0·018 0·05 0·03 nil <0·01
Before use, all specimens were degreased in trichlorethylene vapour,
cathodically cleaned in alkali, and given a momentary anodic etch
in 30% (w/w) sulphuric acid to produce a uniform matt surface.
Reagents.-The oxalic acid and hydrogen peroxide used were
Analar grade and mixtures of the two 'Xere generally prepared
immediately before each experiment. Oxalic acid solutions were
prepared directly by weight, and h}'Jdrogen peroxide solutions by
diluting the stock reagent (either 20 or 100 vols.) after it had been
standardised by titration with permanganate.

POTENTIAL MEASUREMENTS.
The specimen was suspended by a thin iron wire in the sOlution
under investigation which was connected to a saturated calomel
reference electrode by a siphon of sodium sulphate solution; this
latter was necessary to obviate the introduction into the experimental
solution of traces of chloride which were found to have a marked
effect. The e.m.f. produced by the combination of the specimen and
reference electrode was applied in series with a standard cell to a
valve-voltmeter which could be read directly to a centivolt; the
standard cell eliminated the necessity of changing connections when
the experimental combination reversed its polaritY'. In general it
was desired to ascertain how the potential of the specimen varied
with increasing hydrogen peroxide concentration in an oxalic acid
solution of constant concentration. This was achieved by taking a
definite volume ( 130 ml.) of a given oxalic acid solution as the
working medium and running into it a mixture of oxalic acid of the
same concentration and concentrated hydrogen peroxide from a
burette, the potential being determined after each addition; for the
highest hydrogen peroxide concentrations the procedure was reversed
and a working mixture of oxalic acid and hydrogen peroxide was
progressively diluted by the addition of oxalic acid solution. By
working at reasonable speed, it was possible to keep the amounts of
reagents consumed small compared with the amounts present in the
medium, and the curves obtained of potential against concentration
 A. HICKLING AND A. J. RosTRON 231

of hydrogen peroxide (1r/[H 2 0 2 ]) were found to be very charac-

teristic and reproducible. All potentials quoted are expressed on the
hydrogen scale.
KINETIC MEASUREMENTS.
For measurement of rates of metal dissolution, six weighed cylin-
drical specimens were suspended vertically by thin iron wires in
l litre of reaction mixture which was maintained at l8o -+-1 oc.; it
was found desirable to have the specimens electrically connected and
this was accomplished by hanging them from a single brass bar.
Specimens were withdrawn at 10 minute intervals, and were washed,
dried, and re-weighed; a graph was then constructed of the losses in
weight against times of immersion. Initially the rate of dissolution
was often high and somewhat irregular, but it usually settled down
to a steady value after a short time as the surface of the specimens
became more uniform. The quantity of reaction mixture employed
was such that no appreciable change in its concentration occurred
during the course of one experiment. No attempt was made to
obtain great precision in measuring the rate of dissolution since
interest rested mainly in the order of magnitude of these quantities.
The values quoted are expressed in mg. of metal dissolving per
sq.cm. of surface per hour, and they could, in general, be repro-
duced in any set of conditions with an accuracy of ± 5%.
SURFACE FINISH.
In all preliminary work surface finish was judged simply by
visual inspection. Where a more precise measure was required the
rectangular specimens were used and the reflectivity of the surfaces
examined and recorded photographically. For obtaining some rough
quantitative assessment of the surfaces produced, use has been made
of the Halling reflectometer' in which the specular reflection from
the surface is examined while the inclination of the incident light
to the surface is varied from 0° to 90°. The angle at which the
reflected image just disappears is greater the smoother the surface
and, for ground surfaces, can be correlated with the surface texture
as revealed by Talysurf records. In the present work the instrument
has been used primarily for comparative purposes and it has been
most useful in discriminating between surface finishes.

ExPERIMENTAL REsuLTS.
GENERAL FEATURES OF THE SYSTEM.
'11" /[H 2 0 2 ] curves were obtained for solutions of oxalic acid varying
from O·Ol to 0·5 M and some typical graphs are shown in Figs. 1a
and b. Four main regions of potential are clearly distinguishable
although their extent varies with oxalic acid concentration : -
(A) The potential at very low hydrogen peroxide concentrations
is in the region - 0·3 to - 0·2 v. In this range the iron
232 CHEMICAL PoLISHING OJ! MILD STEEL

appears to dissolve very slowly, its surface is dull or filmed,

and there is very little gas evolution.
(B) As the hydrogen peroxide concentration is increased the
potential rises rapidly to ca. 0 v. and then remains fairly
steady. The metal seems to dissolve rapidly; in this region
with vigorous evolution of gas (oxygen containing a little
carbon dioxide) and the surface of the specimen is clean.
(C) When the ratio [H 2 0 2]/[H 2C 20 4 ] is somewhat greater than l,
the potential starts to oscillate between ca. + 0·5 v. and a
lower value approaching that for stage (B). The rate of
dissolution is high and polishing of the surface occurs; the
gas evolution is periodic.
(D) At a sufficiently high concentration of hydrogen peroxide the
periodic variation of potential ceases and the steady value
rises to about + 0·6 v. The metal appears passive, its sur·
face is unchanged on immersion, and there is very little gas
evolution.

ro...
·IM-H.a.-z.
·6 0

·4
n ·2
.. ...

·2

·4
Fig. la.-Characteristic curve of potential against hydrogen
peroxide concentration.

Measurements of the rate of iron dissolution were made at nine

different hydrogen peroxide concentrations using 0·3M-oxalic acid;
with this concentration of acid each of the potential regions is
reasonablY' extensive. The results are summarised in Table I and
are graphed along with the '1T' j[H202] curve in Fig. 2.
 A. HICKLING AND A. J. RosTRoN 233

TABLE I.-RATES OF DISSOLUTION OF IRON IN 0·3M-H2C20.

+ H202 mixtures at 18°C.
H202 Rate of dissolution Region of
M I mg.fcm. 2/hour I potential
0·05 1·0 A
0·2 14·0 I B
0·3 30·0 B
0·4 11·6 c
0·5 17·0 c
0·6 17·5 c
(}7 18·3 c
1·0 18·6 c
1·3 0 D

·6

·4

n
1·0 I·

·4
Fig. lb.-Characteristic curve of potential against hydrogen
peroxide concentration.

It is clear from these results that in region A the rate of dissolution

of metal is very small; in region B it becomes fast and increases
with increasing hydrogen peroxide concentration; in region C where
the potential is oscillating, the rate of dissolution is high but some-
what less than the maximum in B, and it is largely independent of
hydrogen peroxide concentration; in region D the metal is passive
and has ceased to dissolve.
234 CHEMICAL PoLISHING OF MILD STEEL

,- .... -- .. -------· .
,•
.,•'

32

..:
24
..<:
~
Ei 16
"
......
oil
e
.
~
cc:

Fig. 2.-Rates of dissolution in different potential regions.

To check the effect produced on the metal surface by reaction in

the different regions, eight rectangular specimens were taken and
while one was reserved as a control, the remaining seven were treated
for 30 minutes at l8°C. with reaction mixtures of 0·3M-H 2 C2 0, con·
taining respectively 0·03, 0·15, D-3, 0·35, 0·6, 0·95 and l·6M-H 2 0 2 •
The specimens were then withdrawn, washed, and dried with acetone.
They are '>hown photographed in Fig. 3 along with the 7r/[H 2 0 2 ]
curve, and their angles for specular reflection as measured by the
Halling reflectometer are listed in Table II.
 A. HicKLING AND A. J. RosTRON 235

·6

·4
n ·2

Fig. 3.-Surface finishes produced by reaction in different

potential regions.

TABLE 11.-REFLECTIVITY OF TREATED SPECIMENS.

No. of H202 Potential Angle on

specimen M region reflectometer
Control 13°
1 0·03 A 71
2 0·15 B (beginning) 7
3 0·30 B (end) 3
4 0·35 C (beginning) 44!
5 0·60 C (middle) 36
6 0·95 C (end) 28
7 1·6 D 13
236 CHEMICAL PoLISHING OF MILD STEEL

It is apparent from these results that all polishing is confined to

region C where the potential is oscillating; in other sections of the
curve, the surface either deteriorates (A and B) or is unchanged (D).
Polishing sets in quite abruptly with the onset of region C and the
reflectometer results suggest that it is at its best at the beginning
of this stage.
The general nature of the reactions occurring in regions (A), (B)
and (D) now appears to be fairly clear and it has been possible to
identify them.
The initial potential in stage (A) is approx. -0·3 v. and this is
practically identical with the static potential of iron in oxalic acid
solutions saturated with ferrous oxalate; thus the equilibrium poten-
tial for Fe in 0·3M-H 2 C2 0 4 saturated with ferrous oxalate was found
experimentally to be -0·33 v. This would suggest that the initial
reaction of iron with oxalic acid is
Fe + H2C20• = FeC204 + H2 ........................ (l)
followed by
Fe + H2C20• + H202 = FeC204 + 2 H20 .................. (2)
at appreciable but low concentrations of hydrogen peroxide. Owing
to the sparing solubility of ferrous oxalate, the metal surface will
be filmed during reactions ( l) and {2), and the rate of dissolution
of metal would be expected to be low.
At higher concentrations of hydrogen peroxide, oxidation of
ferrous oxalate will take place
2 FeC20• + H2C20, + H202 = Fe2{C20•)a + 2 H20 ......... (3)
accompanied by a rise in potential as the [Fe+++]/[Fe++] ratio
increases, and this reaction will be followed by direct dissolution
of iron in the ferric state
2 Fe + 3 H2C20• + 3 H202 = Fe2 ( C20•)a + 6 H20 ......... (4)
It would appear that this reaction (4) is the predominant reaction
in region (B). Thus the potential exhibited in thi!' region is in the
vicinity of 0 v. and is close to the calculated standard Fe/Fe+++
potential of - 0·04 v.; this potential is unstable and should tend
towards more negative values owing to the interaction of ferric ions
with metallic iron and it was found experimentally that the potential
of iron in 0·3M-H 2 C2 0 4 saturated with ferric oxalate was initially
- 0·03 v. and fell to -0·09 v. in the course of 15 minutes. In view
of the high solubility of ferric oxalate, the rate of metal dissolution
in region (B) is high and is governed primarily in any particular
oxalic acid solution by the concentration of hydrogen peroxide in the
reaction mixture. The metal is undergoing a normal etching
reaction, and while the surface is left clean, there is no polishing.
As soon as the hydrogen peroxide is in slight excess for reaction (4)
there is a transition to region (C).
In the presence of high concentrations of hydrogen peroxide in
region (D) the iron is passive and unattacked. This suggests that
 A. HICKLING AND A. J. RosTRON 237

it is covered by an oxide layer which is insoluble in acids of the

strength used. Some light was cast on the potentials manifested
in region (D) by making potential measurements on iron in mixtures
of acids with various oxidising agents under conditions such that
passivity ensued and comparing the results with potential measure-
ments on an inert platinum electrode in the same mixtures. The
results are summarised in Table III.
TABLE III.-OxmATJON·REDUCTION PoTENTIALS.

Mixture Potential
Fe Pt
0·3M-H 2C20, + 1·5M-H202 + 0·6 + 0·81 v.
0·25N-H 2SO, + 0·5M-Cr03 + 1·0 + 1·26
N-H 2SO, + 0·3M-K.Mn0, + 1·3 + 1·59

It is seen that the potentials at iron run parallel to, but somewhat
lower than the redox potentials measured at a platinum electrode.
This suggests that the positive potential manifested in region (D)
is essentially the redox potential of hydrogen peroxide, the iron
behaving as a somewhat imperfect inert electrode.
The above interpretation would suggest that in region (C) the iron
must be alternating between passive and active states, and it is note-
worthy that it is only in this region that any polishing occurs. It
seems possible therefore to arrive at the preliminary conclusion that
the essential condition for chemical polishing is that the metal shall
be alternating between the passive and active condition, and attention
has therefore been concentrated on a study of the reaction occurring
in region (C).
NATURE OF THE PERIODIC REACTION.
General Kinetics.-The dependence of the average rate of disso-
lution upon experimental variables in region (C) was investigated
using in general a standard mixture of 0·3M-H2C20 4 + 0·6M-H20 2.
Increase of temperature accelerated the dissolution as shown in
Table IV.
TABLE IV.-INFLUENCE OF TEMPERATURE.
Temperature 10 18 30°C.
2
Rate mg./cm. /hour 9·5 17·5 28·0
From these results an energy of activation can be calculated in the
conventional way and gives an average value of 10 ± 1 k.cal.
The average rate of dissolution was greatly increased by stirring
the reaction mixture as shown by the figures in Table V; the stirred
solution was moderately agitated by a mechanical stirrer of the screw
type.
 238 CHEMICAL POLISHING OF MILD STEEL

TABLE V.-INFLUENCE OF STIRRING.

Unstirred Stirred
2
Rate mg.jcm. /hour 17·5 78
Polishing occurred in the stirred solution, but the amplitude and
period of the potential oscillations were greatly reduced.
The average rate of dissolution was substantially independent of
hydrogen peroxide concentration but varied with oxalic acid con-
centration. This was investigated by keeping the [H 20 2 ]/[H 2C20 4 ]
ratio constant at 2 while the oxalic acid concentration was varied
from 0·05 to 0·5M. The results are listed in Table VI.

TABLE VI.-INFLUENCE oF OxALIC Acm CoNCENTRATION.

H2C 20, M 0·05 0·08 0·15 0·3 0·4 0·5

2
Rate mg./cm. /hour 1·8 3·4 7·5 17·5 28·8 38·0
The rate of dissolution depends upon a power of the oxalic acid
concentration rather greater than 1, and it can be approximately
represented as: Rate ex: [H:z(: 2 0,] 1 "3 •

VARIATION IN RATE OF DISSOLUTION DURING POTENTIAL CYCLE.

The above kinetic experiments refer to the average rates of disso-
lution observed over appreciable periods of time during which many
alternations of activity and passivity have occurred. It was obviously
of great importance to study the variation of the rate of reaction
during a single cycle. This was ultimately accomplished in the
following way. An early observation had shown that the addition
of 1% pyridine to the reaction mixture eliminated gas evolution and
greatly increased the period of the potential oscillation without,
however, affecting its general form or interfering with the polishing
action. By com·bining this addition with a lowering of the tempera-
ture to ca. 14°C. it was possible to extend the period from about
4 to some 30 seconds duration, which afforded a reasonable time in
which to make several observations of the rate of dissolution. Con-
tinuous observation of the apparent weight of a specimen while dis-
solving in the reaction mixture seemed to offer the best method of
following the rate of dissolution, and preliminary experiments
showed that, with a specimen of sufficient surface area, this oould
be done by suspending it from the beam of a direct-reading heavily
damped balance. Finally by connecting this specimen and a reference
electrode to a valve-voltmeter simultaneous observations of potential
could be made; the specimen was connected electrically to the
external circuit without hindering the movement of the balance by
a coil of very thin copper wire which exerted no appreciable
anchoring action.
 A. HicKLING AND A. J. RosTRON 239

Fig. 4.-Measurement of variation in rate of dissolution during

potential cycle.

The experimental arrangement is shown in Fig. 4. The specimen

was a piece of mild steel sheet of 40 sq.cm. area which was sus-
pended from the beam of an Oertling aperiodic direct-reading
balance by a fine iron wire so that it hung vertically and was com·
pletely immersed in the reaction mixture. This was 0·3M-HzC 2 0 4
+ 0·5M-Hz02 + 1% pyridine and it was contained in a small beaker
mounted on a bridge over the balance pan. The specimen was con-
nected through a very fine copper wire coil to one side of the valve-
voltmeter, and the circuit was completed by a calomel electrode
dipping into the reaction mixture. The time was called out at
5-second intervals, and by using two observers, simultaneous obser-
vations of the weight and potential of the specimen were recorded.
Numerous series of runs were carried out and a typical set of
results is graphed in Fig. 5. The upper graphs show the weight and
potential of the specimen against time, while the bottom graph shows
the decrease in weight each 5 seconds plotted against time; this last
approximates to the desired variation of the instantaneous rate of
dissolution with time.
The results show that following the rise of potential to + 0·5 v.,
the rate of dissolution sinks to a minimum value; this then hegins
to increase and does so with progressive acceleration until it attains
a maximum very high value as the potential drops suddenly to about
240 CHEMICAL PoLISHINC OF MILD STEEL

.....u"
rfl

""·3
n.2
•I

0
roo 3

TIME (sees.)
Fig. 5.-Variation in rate of dissolution and potential during
polishing.

0 v. The metal is apparently dissolving throughout the whole cycle,

the rate varying from a minimum at the high potential when the
metal is approaching the passive state, to a maximum at the low
potential when the surface is presumably free from protective oxide.
Some slight uncertainty in the correlation of the rate measurements
 A. HICKLING AND A. J. RosTROl!i' 241

and potentials is inevitable owing to the time lags introduced by the

inertia of the balance and valve-voltmeter, but the general conclusion
outlined seems to be unequivocally established.
RELATION BETWEEN RATE OF DISSOLUTION AND FREQUENCY OF
POTENTIAL OSCILLATION.
Early observations had suggested that there might be some
relation between the average rate of dissolution and the frequency
of the potential oscillations. To investigate this, a series of
experiments was carried out in which four weighed cylindrical
specimens were suspended from a single brass har in the reaction
mixture under various conditions, and a specimen was withdrawn
and re-weighed after 100, 200, 300 and 400 potential oscillations as
counted on the valve-voltmeter. The time was also noted and from
these o·bservations the average period (t) of the oscillations in any
given set of conditions could 'be obtained, together with the amount
of reaction in each cycle, and the average rate of dissolution of
metal. To obtain reproducible results it was found necessary to
polish the specimens in the usual reaction mixture (0·3M-H 2 ~0,
+ 0·6M--H20 2) before use, and to connect the specimens electrically
so that all oscillations were in phase. Experiments were carried out
in this way with a wide range of experimental conditions so that the
period and frequency of the oscillations varied considerably, and
the results are summarised in Table VII.
TABLE VII.-INFLUENCE oF PERIOD oF PoTENTIAL OsciLLATION
UPON RATE OF DISSOLUTION.

Solution Temp. Period

·c. sec.
I Amount of reaction
mg./cm. 2/cycle
Rate of reaction
mg./em. 2/hour
-
0·3M-HzC20,

+ 0·6M-Hz0z 11 9·3 0·021 8·1

18 3·7 ()-017 16-5
30 1·4 0·014 36·0

.._ 0·4M-Hz0z 18 5·7 0·021 13·3

+ 0·6M-Hz0z 18 3·7 0·017 16·5
+ 0·8M-H202 18 3·2 0·014 15-8

+ 0·6M-Hz0z
+ 1% pyridine 18 10·5 0·017 5·8
+ 0-5% sucrose 18 16 0·025 5·6
+ 0·025% KC1 18 1·2
I
0·013 39·0

A significant result clearly evident from Table VII is, that while
the period and rate of reaction can ·be varied very considerably by
B
242 CHEMICAL PoLISHING oF MILD STEEL

altering the experimental conditions, the amount of reaction per

cycle remains substantially constant. Thus for conditions in which
the period varies from 1•2 to 16 seconds and the rate from 39 to
5·6 mg.jcm. 2 /hour, the amount of reaction per cycle is always
between 0·013 and 0-()25 mg.jcm. 2 ; furthermore what variation there
is in the amount of reaction is always in the sense that the longer
the period the greater the amount of reaction. This strongly sug·
gests, therefore that the cycle is determined by the local exhaustion
of some substance which is present in the solution in constant
amount, and during long periods, some diffusion of this substance
up to the surface of the metal can occur with some small increase
in the amount of reaction per cycle. Now the only substance of
constant concentration in Table VII is the oxalic acid, and it would
seem, therefore, that it is this or some close derivative of it which
determines the periodicity and the amount of reaction per cycle. To
check this the concentration of oxalic acid was varied from 0·2 to
0·4M in a reaction mixture containing 0·6M-H 2 0 2 at 18°C. and the
amount of reaction per cycle determined. The results are given in
Table VIII.

TABLE VIII.-INFLUENCE OF OxALIC Acm CoNCENTRATION UPON

.AMoUNT OF REACTION PER CYCLE.
[H,C.O,J Period Rate of reaction Amount of reaction Amount/[H,C,O,]
M sec. mg./ em. 2 /hour mg./cm.2/cycle
0·2 4·1 9·7 0·011 0·055
0·3 3·7 16·5 0·017 0·057
0-4 3·7 21-4 0·022 0·055
It is seen that the amount of reaction per cycle is proportional to
the oxalic acid concentration.
From the figures in Table VIII the average amount of reaction
per cycle in D-3M-H,C2 0• + 0·6M-H202 at 18°C. is 0·017 mg.jcm. 2
This corresponds to a dissolution of 0·017 X 6 X 1020 /56 = 1·8 x 1017
atoms of Fe. The diameter of the Fe atom as calculated from den·
sity measurements is approximately 2·3 x 10-s em. and hence there
are about 1·9 x 1015 atoms of Fe per sq.cm. in a perfectly smooth
iron surface. Hence if the surface of the metal is flat, i.e. the real
and apparent areas are approximately the same, about 100 atomic
layers must be removed during each period; even if the surface is
very rough, so that the real area is much greater than the apparent
area, it is obvious that a relatively large number of atomic layers
must still be involved in reaction during each cycle. The amount
of oxalic acid used up per sq.cm. of metal in each period in forming
ferric oxalate will be 0-()17 x 1·5 x I0-3 /56 g.moles, and in the usual
reaction mixture this will be contained in 1·5 x 10-s c.c. Thus in
each cycle the oxalic acid in a layer a·bout O-OD15 em. thick adjacent
to the metal surface is used up.
 A. HICKLING AND A. J. RosTRON 243

Fig. 6.-Typical oscillograms.

OSCILLOGRAPHIC STUDY OF POTENTIAL OSCILLATIONS.

For the investigation of the exact form of the potential variation
with time, use was made of a special cathode ray oscillograph unit.
For the present purpose the electron beam was deflected horizontally
by an electronic time base the period of which could be varied from
about one minute downwards, and the potential between the specimen
under investigation and a calomel reference electrode was applied
to a linear D.C. amplifier the output from which deflected the elec-
tron beam vertically; the resultant oscillogram was displayed on the
7 in. screen of a cathode ray tube and photographed when desired.
The typical oscillograms in Fig. 6 show some of the principal
features observed with the usual reaction mixture of 0·3M-H 2C2 0,
+ 0·6M-H 20 2 at 10, 18 and 30°C. The form and amplitude of the
oscillation is the same throughout but the period decreases with rise
of temperature.· At 18°C. each cycle occupies about 4·0 seconds of
which 3·8 seconds are spent close to the high potential state of
244 CHEMICAL PousHINC oF MILD STEEL

+ 0·5 v. and about 0·02 seconds in the low potential state at 0 v.

The decrease of potential appears to be continuous although ulti·
mately very rapid, but in the recovery stage, a point of inflexion
appears• at a potential of ca. + 0·15 v. The identification of the
characteristic potentials displayed presents a pwblem of some
interest. The lower limiting potential of 0 v. obviously corresponds
to region B in the 7r /[H 20 2] curve and suggests that at this potential
the metal is bare and is dissolving in the ferric state, while the upper
limiting potential of ca. + 0·5 v. is approaching that of region (D)
and at this potential the metal would seem to be largely covered by
a protective oxide film. The point of inflexion at + Q-15 v. in
the passivation stage seems to correspond to the beginning of ferric
oxide formation on the metal surface. Thus studiesa of the anodic
polarisation of iron in N--lNaOH have shown that ferric oxide
formation begins in this electrolyte at - Q-62 v., and making the
usual allowance for variation of an oxide potential with hydrogen
ion concentration, this would correspond to about + 0·13 v. at the
pH of 0·3M-H2~0.. Iron specimens which had been superficially
oxidised by rusting were found on immersion in 0·3M-H 2C20 4
invariably to give a potential in the region of + 0.15 to + 0·25 v.,
passing to negative values as the oxide layer dissolved away;. It
would thus appear that when the lower potential in an oscillation
is in the vicinity of + 0·2 v., as happens at very high concentrations
of hydrogen peroxide and in stirred solutions, this implies that the
surface is never completely stripped of oxide.
The general picture which the oscillograms suggest is that at the
beginning of the high potential state the metal is covered by a pro·
tective ferric oxide film; this undergoes some process of dissolution
and/or reduction and the potential drops usually to the value for
the bare metal, and sometimes to that for the metal in contact with
a porous oxide coating; re·oxidation of the surface then leads again
to the formation of the protective film and the cycle repeats itself.
The phenomenon of potential periodicity is one which is
notoriously susceptible to the influence of foreign substances6 , and
Couper 7 in experiments with hydrogen peroxide/oxalic acid mixtures
noted that the addition of substances such as hydroquinone and
dipyridyl reduced or eliminated gas evolution and increased the
period of the potential oscillations. An observation early. in the
course of the present work showed that pyridine had a similar effect.
A survey was therefore made of the influence of a wide range of
additives on the 7r j[H202] curve and the oscillograms in the usual
0·3M-H 2C20 4 + 0·6M-Hz02 reaction mixture. The results obtained
were complex, but in the following account an attempt has been
made to elucidate the main significant features.
Chloride ions at very low concentrations were found to decrease
the period and amplitude of the potential oscillations and to increase
gassing; the polishing action of the solution greatly deteriorated,
and with concentrations of 0·01 g.ion Cl-jlitre the potential remained
 A. HICKLING AND A. J. RosTRON 245

steady in the region of 0·2 v. and the metal rusted instead of

polishing. Bromide ions were found to act similarly but higher
concentrations were required. These observations agree with the
general influence of halide ions in hindering passivity and suggest
that in their presence, the formation of the protective oxide layer
which is essential to polishing, can no longer take place properly.
A num·ber of organic substances including cane sugar, pyridine,
teepol, formaldehyde, and gelatin, with no very obvious property in
common except the possession of a mild reducing action and a
general probability of adsorption at an interface, were found at low
concentrations to increase the period of the potential oscillation and
to reduce or in•hibit gas evolution, the metal still polishing satis-
factorily. At low concentrations there was frequently a linear
relation between the period of the potential oscillation and the con-
centration of additive. At higher concentrations (usually of the
order of l-2%) potential oscillations ceased and polishing stopped;
the metal in some cases then become passive (pyridine), dissolved
at a low potential (fonnaldehyde, cane sugar), or rusted (gelatin).
The very miscellaneous nature of these additives which produce
similar effects at low concentrations makes any explanation of their
action somewhat difficult. Their main effect is undoubtedly to
diminish the rate of metal dissolution, and it is noteworthy that
many of these substances have been used as inhibitors in metal
pickling baths. In some cases the change of colour of the reaction
mixture indicates that the additive is forming a complex with the
dissolved iron, and the diminution of gas evolution is probably
bound up with the removal in this way of an active catalyst for
hydrogen peroxide decomposition.

DISCUSSION.
The main features of the periodic reaction between iron and
hydrogen peroxide/oxalic acid mixtures have been established above
and it now seems possible to construct a theory of the mechanism
of the reaction which will account for these features and for the
polishing action.
In the high potential state it has been shown that the metal is
covered by a film of pmtective oxide which is probably ferric
oxide. This film will almost certainly not he of uniform thick-
ness and it seems not unreasonable to suppose that it will he weakest
at any asperities in the metal surface. Now, as may be shown by
direct experiment, oxalic acid in the concentration range 0·3 to
0·05M has a slight solvent action on ferric oxide at room tempera·
ture, which may he represented purely formally as
Fe20a + 3 H2C20, = Fe2 (C20,)a + 3 H20 ............... (5)
and by virtue of this action the peaks in the metal surface will
become exposed. As soon as this occurs their potential will drop
to about 0 v. in contrast to the potential of ca. + 0·6 v. at the
246 CHEMICAL POLISHINC OF MILD STEEL

oxide-covered portions of the surface. A number of voltaic couples

will therefore be set up in the surface*, current flowing through
the metal fwm the oxide-covered hollows to the bare metal peaks.
and two electrode reactions will occur : -
at exposed metal (anode) 2 Fe - 6 e = 2 Fe+++ ............... (6)
at oxide-covered metal (cathode) 3H 2 0 2 + 6 H+ + 6 e = 6 H 2 0 (7)
Now it should be particularly noted that in reaction ( 6) no hydrogen
ions are used up, but in reaction (7) hydrogen ions are consumed
and the acidity in the oxide-covered hollows must diminish. Thus
the electrochemical dissolution mechanism itself serves not only to
direct corrosion to the exposed metal peaks, but to ensure that
further removal of oxide takes place in their immediate vicinity,
and it is clear that we have here a self-maintained differential dis-
solution effect which must tend towards a smoothing of the surface.
The actual current flowing at any instant between the oxide-covered
and exposed metal surfaces, which determines the rate of dissolution,
will depend in the first instance upon the difference of potential
and the electrical resistance of the local cells formed, but where
the resistance is very low the rate-determining process may become
the diffusion away of ferric ions from the anodic areas 8 • As the
ferric oxide is gradually dissolved, the area of exposed metal will
increase so that for a constant anodic C.D. the actual current and
corresponding rate of dissolution will rise progressively. As the
oxide-covered area diminishes the cathodic C.D. will rise and even-
tually will attain a limiting value for the reduction of hydrogen
peroxide by reaction (7); any further increase in C.D. can then only
take place by reduction of ferric oxide
Fe 2 0 3 + 6 H+ + 6 e = 2 Fe + 3 H20 .................. (8)
and the entire surface will then be suddenly stripped of its remaining
oxide and the potential of the metal as a whole will drop to ca. 0 v.
If sufficient acid then remains in the vicinity of the surface, the metal
may undergo a normal chemical etching (non-polishing) reaction
2 Fe+ 3 H2C20, + 3 H202 = Fe2(C204)s + 6 H20 ......... (9)
but eventually, when sufficient acid is used up, the pH value imme-
diately adjacent to the surface must rise to a point at which ferric
oxide is not appreciably soluble, and the hydrogen peroxide, which
is always in excess for reaction (9), will then re-oxidise the surface,
and the whole cycle can then begin again.
Some direct evidence in favour of the above theory was obtained
by study.ing cells made up of two iron electrodes under different
oxidising conditions and observing their behaviour when current was
taken from them. With one electrode in region B (active) and the

• U. R. Evans (J. Chern. Soc., 1930, 478) demonstrated that the dissolution in
acids of initially passive iron was largely electrochemical and proceeded via
local cells set up in the sudace,
 A. HICKLING AND A. J. RosTRON 247

other in region D (passive) the cell had an e.m.f. of about 0·6 v.

and was able to supply considerable currents with the active electrode
dissolving at a steady potential. The potential of the passive elec-
trode decreased somewhat as current was taken from the cell, but
the metal was not attacked until a critical current density was
attained. Its potential then dropped suddenly and began to oscil-
late; metal passed into solution and the specimen became polished.
The critical current. density was determined by the concentration of
hydrogen peroxide around the passive electrode. These experiments
seem definitely to establish that cells between bare and oxide-coated
metal can exist in the reaction mixture and that they have the proper-
ties which the theory postulates. The theory furthermore requires
that, as oxalic acid is used up, the pH at the surface of the metal
shall ultimately rise abruptly so that ferric oxide is no longer
soluble. That this can in fact take place was shown by measuring
pH values with the glass electrode in samples of reaction mixture
in which various amounts of oxalic acid had been used up by
reaction with iron. During the removal of two-thirds of the oxalic
acid the pH remained in the vicinity of l, but it then began to rise
rapidly as further acid wa.s used up. Qualitative experiments on
powdered ferric oxide suggested that it was just attacked by
O·OSM-H2C 20 4 (pH 1·4) at room temperature but O·OlM-H 2 C20t
(pH 2) had no apparent action. It seems clear, therefore, that with
the concentrations of oxalic acid normally used in the reaction mix-
tures, the acidity is carefully poised so that any protective ferric
oxide layer can be gradually dissolved, hut that when the oxalic
acid near the metal surface is largely used up the pH rises suffi-
ciently for the oxide film to he re-formed under oxidising conditions.
It appears useful now to examine in some detail the implications
of the theory which has been outlined with reference to the main
features of the reaction.
The complete mathematical treatment of the kinetics of the
reaction scheme suggested is a very formidable problem which has
not yet been solved, but a partial solution reveals many foints of
interest. If () is the fraction of each sq.cm. of the meta surface
which is bare at time t from the beginning of the cycle, then the
rate of increase of () will depend upon the fraction of surface which
i~ still covered by oxide and upon some function of the acidity of
the reaction mixture, and as a first approximation

.............................. (i)

If the anodic C.D. in amp./cm. 2 at the bare metal areas (1.) is con-
stant under a given set of conditions, then the current I flowing in
all the local cells at time t will be given by
I= I •. o .................................... (ii)
248 CHEMICAL PousmNG or MILD STEEL

Hence the rate of dissolution of metal by the electrochemical

mechanism at any instant may be defined as

Rate = F
I = Ia.(Jr- g.eqt. / em. 2 / sec. .................. (iii)

Assuming [H+] to 'he constant, which is approximately true over the

greater part of a cycle, equation (i) may be integrated and gives
I
t = - k [H+] log.(l - 0)
1

whence (J =I - e-k,[H+Jt ..................... (iv)

Substituting this value in equation (iii) gives

Rate of dissolution = ~ (1 - ek,[~+]J .................... (v)

This expression predicts that starting with zero velocity the instan·
taneous rate of dissolution of iron by the electrochemical mechanism
will increase progressively with time towards an ultimate constant
value. In practice the electrochemical dissolution will be terminated
when the cathodic C.D. (lc) for reaction (7) reaches a limiting value,
and this may happen in either of two ways:-
(a) At moderate concentrations of hydrogen peroxide, Ic will
depend primarily upon this factor, and when the limiting
value is exceeded the metal will be stripped of its remaining
oxide by reaction (8).
(b) At very high concentrations of hydrogen peroxide, the
limiting value of Ic will be determined by the exhaustion of
hydrogen ions near the surface, and dissolution may stop
while the metal is still partly covered by oxide.
Both these conditions are encountered practically; (a) is the common
one when the potential oscillations are of full amplitude, but (b)
occurs when the potential drops only to ca. + 0·2 v. before
re-passivation. If the limiting value of the cathodic C.D. is lc, then
the limiting rate of metal dissolution by the electrochemical
mechanism will be given by
T. (1- 0) T. e -k,[H+]t •
Limiting rate
F
F ................... (v1)
and it must also be given by
. .. Ia (1 - e -k,[H+l~) ••
Limiting rate = - ........................ ( vu)

where t is the time from the initiation to the termination of the

 A. HICKLING AND A. J, RosTRON 249

electrochemical mechanism, i.e. approximately the period of an

oscillation. On equating (vi) and (vii)
- I lc
t = k1 [H+] Iog.(I + T.) ........................ (viii)

Equation (viii) predicts the way in which the period of the oscil·
lations should be affected by experimental variables. Any increase
in the rate constant k1, e.g. by rise of temperature, or of the hydrogen
ion concentration near the metal surface, e.g. by stirring or by
increasing the acid concentration in the reaction mixture, should
decrease the period and this is in conformity with what has been
found. Halide ions tend to penetrate oxide films and to render them
porous, which wiH be equivalent to an increase in k1 and a con·
sequent diminution in the period; at sufficiently high halide concen-
trations the oxide film will be unable to exert any protective action
and the electrochemical mechanism will break down. Any additive
which can be strongly adsorbed at the bare metal will markedly
decrease Ia by blocking part of the surface and the period will thus
be increased; this is pmbably the fundamental effect of substances
such as pyridine, gelatin, sugar, etc.
The actual amount of reaction per cycle in an unstirred solution
has been found experimentally to be proportional to the oxalic acid
concentration. If this empirical result is combined with the period
as defined by equation (viii) the average rate of dissolution under
polishing conditions is given by
15
Average rate ex: k1[H+][H2C20.] ex: kl[H 2C20.] ' ............... (ix)
log. (I + lc/Ia) log. (I + lc/1.)
if it is supposed that the hydrogen ion concentration near the metal
surface is proportional to its concentration in the bulk of the reaction
mixture. Thus the average rate of dissolution in an unstirred solu-
tion should be mainly: dependent on the temperature, which affects
k 1 , and upon [H:~C 2 0.] 1 ' 5 ; this is similar to what has been found
experimentally. Additives which decrease Ia markedly will diminish
the average rate of dissolution.
On the theory outlined, the electrochemical dissolution mechanism
will automatically lead to smoothing and polishing of the metal
surface, but the actual quality of the polish produced in any given
set of conditions will depend upon the extent to which the electro-
chemical dissolution predominates over other reactions which tend
to etch the metal surface. The present explanation of the polishing
action would account for the efficacy of the process in smoothing the
microtexture in the surface since it can obviously operate against
inequalities of dimensions less than the thickness of the oxide layer
and this ma}'l be of the order of IOO A. It seems very likely that
the polishing mechanism considered here may also 'he a fundamental
factor in electrolytic polishing. It has ·been shown 9 that electrolytic
polishing occurs when the limiting C.D. for the anodic dissolution
250 CHEMICAL PoLISHING OF MILD STEEL

of a metal has been attained, and this normally coincides with the
formation on the metal surface of an oxide film which is continually
being dissolved; it is apparent, therefore, that conditions are very
suitable for the setting up of local cells as postulated in the present
theory with consequent differential dissolution and polishing. Hoar
and co-workers have drawn attention 10 to the importance of the oxide
film in anodic polishing and suggest that cations pass from the metal
surface into vacant sites in the oxide lattice which is dissolving at
the outside as fast as it is formed at the metal; the random distri·
bution of vacant sites is then considered to account for the a·bsence
of etch figures. While this view accounts for the absence of etching,
it provides no real explanation of positive smoothing as does the
electrochemical theory; furthermore, as applied to polishing by
hydrogen peroxide/oxalic acid mixtures, Hoar's oxide film
mechanism would not predict the remarkable kinetics which are
observed.
Two minor features of the periodic reaction between iron and
hydrogen peroxide/oxalic acid mixtures are worth brief mention.
It has frequently been observed that, towards the end of each cycle,
a pulse of gas occurs at the surface of the metal. This appears to
coincide with a maximum local concentration of ferric ions at the
metal surface and a rise in the local pH value, both these conditions
favouring the catalytic decomposition of hydrogen peroxide. The
suppression of gas evolution by additives such as pyridine probably
involves several factors. Such additives diminish the rate of metal
dissolution and frequently form complexes with ferric ions, both
these factors tending to reduce the local concentration of the effective
catalyst for hydrogen peroxide decomposition; and in some cases the
additive may exert a specific chain-breaking action on the catalytic
decomposition of hydrogen peroxide by ferric ions. At the end of
each cycle under favourable optical conditions a " blinking " of the
metal surface can sometimes be observed in which a shadow seems
to pass rapidly across the specimen. This does not seem to be due
to any film which is normally visible, since the metal in the passive
state and in the bare state may appear equally ·bright, and it seems
likely that it is an interference effect accompanying the sudden
removal or growth of an invisible ferric oxide film.
According to the theory which has been described the primary
function of the oxalic acid in the reaction mixture is to maintain
a certain critical pH value at which the ferric oxide film on the
passive metal can just dissolve, and this function might be performed
by other acids of appropriate dissociation constants. There are,
however, certain secondary properties which the acid component in
the reac.tion mixture must have and which oxalic acid possesses in
a rather exceptional way. Thus the corrosion product formed with
the metal must be freely soluble and it is very desirable that a stable
complex ferric ion should be formed so that the etching reaction
Fe++++ Fe = 2 Fe++ •.•............... (10)
 A. HrcKuNc AND A. J, RosTRON 251

can be inhibited. When iron dissolves in the ferric state in the

presence of excess oxalic acid the v~ry stable trioxalatoferric ion
Fe (C 2 0 4 )a--- is produced and this condition is satisfied. It has been
found possible to produce some measure of chemical polishing of
iron with various acid/hydrogen peroxide mixtures, but in general
the polish produced is inferior -to that obtained with mixtures con·
taining oxalic acid for the above reason.
The electrochemical theory of polishing which has been developed
. here has arisen from the study of a particular reaction-that of iron
with hydrogen peroxide/oxalic acid mixtures. It would seem, how-
ever, to have some important implications for the mechanism of
chemical polishing generally. Pinner 11 has reviewed very compre-
hensively the essential features of chemical polishing and has
shown that on general grounds it is best regarded as electrochemical
in nature and is analogous to electrolytic polishing with the oxidising
agent playing the part of a depolariser in the local cells set up;
he has furthermore emphasised the importance of film formation
and periodic passivity in some cases. The present theory provides
a detailed formulation of these general ideas. It suggests that some
chemical polishing of any metal might be brought about if a com-
patible mixture of an acid and an oxidising agent can be realised
such that the oxidising agent can render the metal passive by oxida-
tion of its surface and the acid is such that this oxide layer can be
slowly dissolved. Under these conditions directed electrochemical
dissolution should occur with consequent levelling of the surface,
and if direct chemical attack on the metal can he kept small,
polishing should also result. Periodic variation of the potential of
the metal as a whole is likely to occur if the electrical resistance of
the local cells formed is sufficiently low; where this is not so the
voltaic couples set up may no longer keep in phase and the potential
of the specimen as a whole may show no regular periodicity although
the same type of mechanism is operating.
REFERENCES.
(1) W. A. Marshall, J. Electrodepositors' Tech. Soc., 1952, 28, 27.
(2) A. Hickling, W. A. Marshall and E. R. Buckle, ibid., 1952, 28, 47.
(3) J. Halling, J, Sci. Instruments, 1954, 31, 318.
( 6) First noted by E. R. Buckle (private communication).
(5) A. Hickling and D. Taylor, unpublished results; D. Taylor, Thesis, Liver-
pool University 1948.
(6) See, for example, E S. Hedges and J, E. Myers, "The Problem of
Physico-Chemical Periodicity," Arnold, London, 1926.
(7) A. Couper (private communication).
(8) Thus A. Hickling and J, K. Higgins have shown this to be the case for
many metallic anodes in aqueous electrolytes; see Trans. lnst. Met.
Finishing, 1953, 29, 274
(D) A. Hickling and J, K. Higgins loc.cit. ref. 8
( 10 ) T. P. Hoar and J. S Mowat, Nature, 1950, 165, 64; J. Electrodepositors'
Tech. Soc., 1950 26, 7S; T. P. Hoar and T. W. Farthing; Nature, 1952.
169, 324.
( ) R. Pinner, Electroplating, 1953, 360, 401, 444; 1954, 127.
11
252

DISCUSSION ON " THE CHEMICAL POLISHING OF MILD STEEL BY

HYDROGEN PEROXIDE-OXALIC ACID MIXTURES "

DR. J. EDWARDS (British Non-Ferrous Metals Research Association).

-Dr. Hickling and Mr. Rostron have put forward some novel views
a:bout the mechanism of chemical polishing hut, perhaps equally
important, they have also made a valua!ble contrihution to the
development of experimental techniques suitable for the study of
this type of process.
There are many points in the Paper which, I am sure, will stimu-
late discussion but I should like to concentrate on what the authors
call the "electro-chemical dissolution mechanism." There are certain
difficulties about it on which I should welcome the authors' views. In
the first place, it seems that the theory presupposes a continuously
oscillating system; otherwise, the self-maintained dissolution effect
to which the authors refer would he expected to produce discontin-
uities as between anodic and cathodic areas, while removing the
original roughness. If the system is oscillating, these areas can
possibly be imagined to he shifting about sufficiently rapidly to avoid
this. In the reaction between iron and oxalic acid/hydrogen peroxide
mixtures, oscillations appear always to accompany polishing 'but
there is no evidence that this is so with other chemical polishing
systems and it is certainly not so with electropolishing. Yet one very
interesting feature of this work is that it shGws so clearly the simil-
arity between chemical and electcrolytic polishing. The shapes of
the rate and potential versus concentration curves are very similar to
those of current/voltage curves of electropolishing systems. Oscil-
lations occur in both cases, and in electropolishing they can take
forms closely similar to those shown in the Paper. In electropolish-
ing, however, the polishing action can persist under perfectly steady
conditions. It is true that this only applies on the high voltage side of
the oscillating region and perhaps there is a continuous film under
these conditions, so that the differential dissolution mechanism can-
not take effect. If so, the mechanism cannot he important since there
is no obvious deterioration in polishing ection when oscillations
cease. I suspect that the authors were preparing the ground for this
question when they wrote at the end of their Paper that, where the
electrical resistance is high, voltaic couples may no longer keep in
phase. However, this seems unlikely, in view of the fact reported in
the Paper that making an electrical connection between two separate
specimens synchronises the oscillations. It seems even more unlikely
in electropolishing.
Another difficulty concerns etching. One of Dr. Hoar's valuable
contributions to the theory of electrolytic and chemical polishing
was his drawing attention to the fact that the removal of initial rough-
ness is not sufficient for polishing; it is also necessary that crystallo-
graphic etching should he suppressed. The authors ·appear to accept
 DISCUSSION 253

Dr. Hoar's view that the random distribution of vacant sites in the
oxide lattice accounts for rhe absence of etch patterns, at any rate in
electropolishing. In the present case, however, the authors suggest
that most of the metal which dissolves comes from anodic areas which
are free from oxide. How, then, is crystallographic etching sup-
pressed? It is stated in the Paper that for at least a portion of each
cycle, when the surface is entirely. free from oxide, etching will take
place, ·but why does it not take place the whole time? As a possible
explanation it occurs to me that more metal might dissolve through
the film than the authors allow. For example, if any appreciable part
of the metal removed is oxidised to form the film, then this must be
taken into account in interpreting Fig. 5, since the loss in weight will
not truly represent the rate of dissolution of metal. However, if one
frames an explanation of the suppression of etChing along these lines,
the electrochemical dissolution mechanism must become relatively
less important.
I notice that the authors say in the Paper that an oxide film is
likely to be weakest at asperities on the metal surface so that the
film is removed first at these points. In view of the fact that the
asperities are commonly only very gently rounded protuberances, I
think it is more reasonable to assume that the film as formed is prob-
ably fairly uniform, but is attacked more readily at projections owing
to the structure of the diffusion layer outside it, allowing a greater
rate of arrival of solvent molecules at projections. I was interested in
the evidence for control of metal dissolution by oxalic acid concen-
tration shown in Table VIII and my own inclination would be to
pursue further this question of diffusion control. A few years ago I
reported some work which showed that, in certain electrolytic and
chemical polishing systems, the rate of smoothing was equal to, or
certainly not more than, the calculated rate, assuming diffusion
control. It would be useful to repeat that excperiment with iron in
oxalic acid/hydrogen peroxide mixtures. Presumably, if the authors'
views are correct, a higher rate of smoothing would be observed.
MR. R. PrNNER (Electroplating and Metal Finishing).-! have been
much impressed by this Paper, which covers many aspects of chem-
ical polishing of metals. The authors suggest that SJD()othing takes
place in that part of the cycle at which film dissolution is beginning,
that is, when the peaks are bare and the hollows are covered. How-
ever, smoothing may also be due to the fact that oonditions for
passivity are reached sooner in the recesses than at the peaks, so that,
in each cycle, metal dissolves for a little longer at the peaks than in
the recesses. This explanation seems more plausible as it is similar
to that for other systems, for example, rhe polishing of silver in
cyanide solutions, in which similar fluctuations occur. In this case,
we do not get polishing either before or after the potential fluctua-
tions in the current/potential diagram. Another, slightly different,
example is that the brightening of aluminium, reported on by Dr.
1
254 DISCUSSION

Evans and Mr. Whitham in 1947, in which the metal was anodically
passivated and the passivity then destroyed by taking the specimen
out of the electroly.te, the cycle being repeated several times, and
similar, too, to the results of recent German workers who found that
aluminium can be brightened by repeatedly anodising and dissolving
the oxide film.
In all these examples, we have very much the same type of system
as in the chemical polishing of steel by oxalic acid/hydrogen perox·
ide solutions except that, in the case of the repeated anodising of
aluminium, the periodicity was achieved somewhat clumsily by hand,
while with the other two systems the process is, as it were, mechan-
ised. However, I do not wish to be too emphatic about the question
of when the smoothing occurs for there seems to he no reason why it
should not occur at both ends of the cycle.
I would, 'however, like to emphasise that at this stage it does not
seem possible to advance a general overall theory of chemical polish-
ing. There appear to be at least two distinct types of chemical
polishing processes. In one, periodicity occurs and the process is
akin to the electropolishing of silver. Such systems usually. use
dilute solutions having rather slow dissolution rates and the mech-
anism is more or less that described by the aut'hors. The other type
of process includes the chemical poli8hing of copper or aluminium
in phosphoric acid based solutions-which have much higher dis-
solution rates and where the mechanism is much more akin to the
phosphoric acid electropolishing, on which Dr. Edwards reported two
years ago and on which Dr. Hickling has also worked. In this oase
the mechanism ·has been shown to depend on diffusion control, to-
gether with suppression of etching by the formation of a solid film,
according to the theory of Hoar and Mowat.
The whole problem is far from being solved. I have heard recently
of the chemical polishing of 'high purity zinc in nitric acid, in which
Dr. Hoar's mercury wetting test showed no oxide film present. Per-
haps Dr. Hoar would like to comment on this.
DR. K. SACHS (G.K.N. Group Research Laboratory).-The authors
of this Paper are to be congratulated on their very valuable study of
the mechanism of chemical polishing in these mixtures. I am partic-
ularly interested in the postulated mechanism because I think it helps
to interpret some interesting results which we have obtained at the
G.K.N. Group Research Laboratory.
In general, chemical polishing tends to have a brightening rather
than a flattening effect; it smooths out the micro-texture which affects
the optical properties of the surface rather than the main texture as
indicated, say, by the Talysurf trace. This conclusion was reached by
Schmid and Spahn in their exhaustive study of the chemical brighten-
ing of copper alloys in the Battelle solution; a similar conclusion
can be drawn from the Talysurf traces shown in Marshall's origina·l
Paper in 1952, ·and from the observation in llhe present Paper (p. 22)
 DISCUSSION 255

that the polishing mechanism "can obviously operate against in-

equalities of dimensions less than the thickness of the oxide layer,
and this may be of the order of 100 A." If my arithmetic is correct,
this amounts to about 0·4J.I. in.; at the highest magnification a vailahle
on the Talysurf instrument we have been using, x 20,000, a surface
uneveness of this order would deflect the trace by 0·008 in. Although
this estimate of less than 100 A refers to one cycle, and there are
about 900 cycles per hour, it seems reasonable to expect that the
electroohemical mechanism will have only a slight effect on the
Talysurf trace.
Our own experiments have shown that immersion in the still
solution has a slight smoothing effect as indicated by the appearance
of the Talysurf trace, but that there is no profound decrease in the
centre-line average, and that a slight increase in C.L.A. value is in
fact often observed. Ohemical polishing tends to increase both the
wave length and the amplitude of the surface roughness; prolonged
immersion leads to pitting, probably because the solution gets stale.
We have 'also done some experiments in which small mild steel
specimens were tum•bled in a barrel for ·half and hour. The surface
remains bright throughout and the treatment can be repeated in-
definitely without pitting. The surface of a coarsely ground surface
of texture approximately 200J.I. in. is progressively smoothed to give
an ultimate texture of about 201-£ in.; the number of treatments re-
quired depends on the original ground texture. In my opinion the
electrochemical mechanism cannot account for this gross effect
because the surface irregularities which are flattened out in a single
half hour treatment are about 1,000 times larger than the postulated
thickness of the oxide film.
We have found that, in barelling, the surfaces do not remain
absolutely flat, and that specially prepared surfaces can undergo very
complex changes in contour; the results suggest that the polishing
action at any point depends to a considerable extent on the rate of
flow of the solution relative to the surface at that point. Now Table
V in the Paper shows that the rate of solution and presumably the
frequency of the polishing cycles increases if the solution is stirred,
and I would suggest that this is the key to mechanism of gross
smoothing in barrelling. Coarse asperities on the surface interrupt
the flow of solution over the surface, produce eddies, and general•ly
increase the agitation, so ·that the mechanism postulated by Hickling
and Rostron operates with higher frequency at the asperities than
elsewhere; the rate of solution is increased locally and the asperities
are smoothed out. In depressions the rate of·solution is much slower;
nevertheless some material is removed from the depression and by
the time the mean level of the surface has been brought down to
smooth out the depressions, a substantial amount of material has been
dissolved. This is confirmed in practice; in the course of 20 half-hour
tumbling treatments at least 0·009 in. was dissolved off each surface
of the specimen.
256 DISCUSSION

MR. A. W. BRACE (Aluminium Development Association).-It is

difficult for me to add to the remarks by earlier speakers in con-
gratulating the authors on their most valuable Paper and, although
my remarks may appear a little critical of their explanation of the
mechanism of the process, my appreciation is none the less sincere.
In work we have carried out on chemical mixtures, a progressive
decrease in the rate of reaction to a constant value has been observed.
Thus, using a mixture consisting of 75% phosphoric acid, 20/~
sulphuric acid, 5/'0 nitric acid (by vol.) at l00°C, the time/weight-
loss curve for commercial purity aluminium flattens out after 4-5
minutes immersion, although it is nearly linear in the first minute.
The periodicity observed by the authors was not found in our
work and seems to me not to be an essential feature of a chemical
polishing bath. Various investigators have shown that the harrier
layer thickness obtained on anodising in non-oxide solvent electro-
lytes is a product of the potential x 14 A, and a value smaller than
the above in oxide solvent electrolytes such as sulphuric acid, the
barrier layer tends to develop to the thickness expected from a non-
solvent electrolyte, but the solvent effect comes into action and the
film thickness decreases, to level out at a value of 10 Ajvolt.
In chemical •polishing it appears likely that the thickness of the
film formed is dependent on rhe product of the potential of the
system and a constant, dependent on the solutions employed. Investi-
gations on anodic coatings on aluminiumjroduced in oxide solvent
electrolytes show that they are porous an the porosity increases as
the forming potential decreases. This suggests that diffusion of metal
ions through the oxide film enters into the mechanism. Further, local
potential differences such as at the peaks in the surface could result
in variations in film thickness over the surface.
It is possible that we are in sight of a general theory for chemical
polishing. It appears that initially in all chemical polishing baths
there are two mechanisms proceeding-the linear dissolution of the
metal and the growth of an oxide film. If the film is stahle, then the
anodic and cathodic current densities are in equilibrium and the
reaction proceeds at a steady rate as is the case with the chemical
polishing of aluminium. If, however, the oxied film is not very stable
and the electrolyte is strongly oxide solvent, it should be possible
to reach a cathodic current density at which rapid dissolution of the
film occurs and the process then recommences, as with mild steel in
oxalic acid/hydrogen peroxide solutions. It seems probable that in
chemical polishing of thigh chromium iron or stainless steel, or
possibly even pure iron, in such solutions, this periodicity may not
occur.
Finally, I would make a plea regarding terminology. The terms
" smoothing," " polishing " and "·brightening" are used somewhat
indiscriminately in the literature. With aluminium it is possible to
produce smoothing in a 75/'0 phosphoric acid, 25/'0 sulphuric acid
mixture at 100"C., although the surface is 'bright but diffused.
 DISCUSSION 257

Addition of 5% nitric acid produces smoothing and a bright surface

having mainly specular reflectivity. These terms should be oonsidered
by investigators in the field to see if agreement could be obtained in
their definitions.
DR. T. P. HoAR (Department of Metallurgy;, University of Cam-
bridge).-Dr. Hickling and Mr. Rostron ingeniously interpret the
results of their elegant experiments to provide an explanation of
smoothing in terms of local cell ·action between anodes on asperities
and cathodes elsewhere. They also ascribe the periodicity of potential
and of dissolution rate to the local cells. However, I understand that
when the surface has become smooth it remains smooth, yet the
periodicities persist. Consequently, I believe that the smoothing can
be better explained on rhe lines developed by Edwards for anodic
smoothing.
Periodicity has been Dbserved in many cases of anodic passivity
and of anodic polishing, and although the full mechanism of all
cases are not yet understood, explanations not involving local cells
are often plausible; I think the same may be true of the present
case of chemical polishing. When iron or steel is made anodic
in certain concentrations of aqueous phosphoric acid, with increase
of voltage a typical 'plateau ' in the current/voltage curve is reached
and anodic brightening occurs with dissoluion of the metal as
ferrous ions. At slightly higher voltages, the current falls to a
second, very low, plateau, the metal dissolving extremely slowly to
ferric ions. (This latter stage is sometimes considered one of pas-
sivity, but the very slow dissolution dDes in fact lead to anodic
brightening after a very long time-perhaps the authors would care
to confirm this). If the anodic current in such a S}'!Stem is controlled
(by any factor other than the anodic processes themselves) some-
where between the values o.f the two plateaux, anodic potential oscil-
lations are to be expected. The potential and dissolution-rate oscil-
lations in the present case of chemkal polishing may, I believe, be
oscilllltions between similar ' brightening ' and ' near-passivating '
ranges-not between brightening and etching ranges : the brighten-
ing dissolution would perhaps be to ferrous ions and the very slow
brigqtening dissolution to ferric ions. Local ceJ.l action is certainly
not a necessary concept to explain this kind of oscillation.
Dr. Hickling and Mr. RDStron do nDt specifically explain the
brightening action except to imply that if no compact non-metallic
film were present on the metal, etching would occur. Do they agree
that a compact film is the positive cause of brightening, as I have
argued for anodic brightening in the papers with Mowat and Farthing
that they mention? Farthing and I showed that mercury dropped on
to a copper or brass anode during dissolution under brightening
conditions does not wet the metal, whereas it immediately. does so
when the metal is dissolving under conditions giving etching. In as
yet unpublished work, Dr. M. Cole and I have applied the mercury
test to a large number of systems giving anodic brightening and
8
258 DISCUSSION

chemical brightening, including one very similar to that now being

discussed. We have never found a case of brightening (as distinct
from smoothing) in which wetting of the metal by mercury occurs
(except that of zinc in concentrated nitric acid, where the brightening
is associated with the quite exceptional rate of reaction). Have the
authors tried the experiment on the present s}'!Stem under their con·
ditions? I am oonfident that mercury will not wet the. surface.
showing that there is some solid compact non-metallic film, continu-
ous over the surface, not only on part of the surface for part of the
time; and if this is the case, I find the concept of local cell$ difficult
to visualize.
The very beautiful results of Fig. 5 seem to me not necessarily to
refer to the actual rate of arwdic attack on the metal. There can be
no loss of specimen weight if the metal cations merely pass from
the metal into the film, without dissolution; ·indeed there wiU be a
gain, owing to the deposition of anions equivalent to the cations. The
rate of loss of weight of the specimen at any instant must, in fact,
be equal to the rate of dissolution qf metal cations (from the film
or direct from the metal) plus or minus the rate of dissolution or of
deposition resptlCtively of anions. The observed weight changes must
also he subject to certain corrections for bouyancy depending on the
density of the metal and of the film substance. I think, therefore,
that care should be taken in the interpretation of the rate of loss
of specimen weight ·in terms of the operating potential; perha·ps the
authors would comment on this point.
As to the general process of chemical polishing, I believe that it
can best be pictured in many cases by the following extension of
current theories of anodic polishing. In chemical polishing, the
cathode, instead of •being remote, is at the surface of the film on the
metal: the anode is the metal/film interface. In anodic polishing,
the dissolution rate is often control·led almost entirely by the diffusion
away of anodic products or the diffusion up of anodic reactants: in
chemical polishing, the rate of diffusion of cathodic reactants to-
wards and resultants away from the film surface is also important.
I propose to elaborate this hypothesis elsewhere.
Mrss M. ODGERS (G.K.N. Group Research Laboratories).-! would
like to ask Dr. Hickling whether he has considered the effect of sul-
phuric acid on the rate of dissolution of metal. We in the G.K.N.
Group Laboratories have found that the sulphuric acid present can
be very critical, and for this reason we had to abandon the use of
B.P. 20 vol. hydrogen peroxide when using the oxalic acid smoothing
solution. (There was already an excess of acid in the reagent). -
We have noticed that although there is some slight reaction before
sulphuric is added, this is considerably greater after addition of the
acid ·and I venture to suggest that increase in acid might have con-
tributed to the initial sharp increase in the rate of dissolution shown
in Fig. 2.
 DISCUSSION 259

DR. A. HICKLING (in reply).-Dr. Edwards ·has suggested '!!hat the

mechanism we have put forward pre·supposes a continuously oscil·
lating system. This need not necessary imply, however, that the
potential of the specimen as a whole shows any regular periodicity
We have done much work on this, much of it not shown in the Pape1.
In the case of Marshall's solution we have a clock-like periodicity
which seems to link well with the ideas suggested, but I agree that
this is by no means generally the case in chemical polishing or
electrolytic polishing.
Suppose we take Marshall's solution and put in two iron rods and
measure their potentials separately. They "both oscillate quite in-
dependently of each other. If they are connected by a wire, they
immediately synchronise and oscillate together. If they; are connected
through a resistance box and the resistance varied, they osciHate
together if the resistance is sufficiently low. As the resistance is
raised, a point is reached at which they begin to get out of p'hase, and
for higher resistances they oscillate quite independently. It seems
that to get oscillation of a specimen as a whole, two things are
needed. Firstly a slow rate of reacti001 is necessary; if it is too quick
there is no chance .for reaction to be transferred from one point to
another in an orderly way. Secondly, the cells formed must have a
low internal resistance. With Marshall's solution these two con-
ditions are satisfied, but in many soluti001s they are not. Brightening
has been obtained in mixtures of hydrogen peroxide and phosphoric
acid, peroxide and sulphuric acid, and peroxide and hydrofluoric
acid. Not all give periodicity; some show random periodicity while
some wiH give a steady potential.
As for the relation to electrolytic polishing, I am tempted to think
that the two methods of polishing must be related and Mr. Pinner's
recent articles in " Electroplating " brought out the parallelism
between the two cases very clearly.
With regard to the suppression of crystallographic etching, it seems
to me that while the electrochemical mechanism is operating we shall
have directed corrosion and ordinary etching is not to he expected.
When the electrochemical mechanism ceases to operate, as is the case
if the specimens remain at the bottom of the 'Potential cycle for any
length of time, then crystaUographic etching sets in.
I had not considered whether the weight of the oxide film affects the
experimental results. I hope it will not grealty affect the interpreta-
tions we have drawn, but I will certainly consider this aspect. I have
seen many arguments about why oxide coatings should he weak at
points--it has, for example, ·been suggested that the oxide film will
not be compressed at asperities in the surface and will therefore break
more easily. Certainly diffusion will contribute in making the oxide
at the peaks more readily attacked. I have long held the view that
there are two factors in electropolishing-general diffusion which
leads to smoothing and another factor responsible for brightening.
For a long time I thought that Dr. Hoar's mechanism accounted for
260 DISCUSSION

the second factor, but now I am not so sure; most of Dr. Hoar's
experiments can be accounted for on the electro-chemical idea.
'.Dhe theory mentioned by Mr. Pinner, that film formation occurs
more easily in recesses than at peaks and the cavities remain passive
while the peaks are active, is quite old. Dr. U. R. Evans first sug-
gested it in 1936. In many cases there is, no doubt, a thick deposit in
the stagnant holes. The present view may ·he considered a develop-
ment of this original theory.; in the present case the film appears to
be very thin and the potential difference set up ·between peaks and
cavities is considered to be the primary factor which leads to
polishing.
I have been most interested in the series of experiments described
by Dr. Sachs which I find very i1luminating. I thoroughly agree that
in general, chemical polishing is effective against microtexture rather
than in general smoothing, and one of the advantages of the local cell
idea is that it would be expected to be effective against very small
irregularities in the surface.
Mr. Brace's remarks on the approach to a geperal theory of chem-
ical polishing seem to me to be both very relevant and stimulating.
I would emphasise that the mechanism which we have put forward
has arisen from a study of one particular case. It may not be
generally applicable at all, but it does seem worthwhile considering it
provisionally as a possible factor in many examples of chemical
polishing. I very much agree with Mr. Brace about the need for
definition of smoothing and brightening; this is a constant source of
trouble in the literature.
Dr. Hoar has pointed out that while the periodicities and smoothing
are attributed to local cell action, periodicity persists when the sur-
face has become smooth. This does not seem to me to be entirely un-
expected. Were it possible to produoe a completely flat and uniform
surface then the periodicity might be eliminated, but our best surfaces
are far from this ideal, and it seems inevitable that the oxide film
must break down at some points preferentially and periodicity will
then follow. The present theory does provide a specific explanation
of the brightening action in that the electrochemical mechanism
directs corrosion against the peaks in the microtexture of the surface,
and it is in the smoothing of this fine texture which is llhe positive
cause of brightening. In our opinion, the influence of the oxide film
which Dr. Hoar has ingeniously shown to be present in many cases of
electrolytic polishing may well arise by the setting up of local cells
as suggested in the present Paper rather than by a mechanism in
which metal ions pass into the film instead of the solution. Although
we have not tried the experiment, I have no doubt that mercury wil>l
not wet the surface of iron undergoing polishing in Marshall's solu-
tion, but this I think would be expected under the reaction conditions
we have described in which the surface is being cyclically oxidised
and stripped so that no spot is bare for an appreciable length of time.
 DISCVSSION 261

As already mentioned in my reply to Dr. Edwards, we did not con-

sider whether the weight of the oxide film would affect the results
in studying the periodic rate of dissolution. As Dr. Hoar points out,
this should undoubtedly be done, although I do not think it will
affect the general nature of the results very materially.
In reply to Miss Odgers, I can only say that we did not find the
sulphuric acid content in Marshall's solution to be very criticaL The
mixture would tolerate an appreciable concentration of sulp'huric
acid without the nature of the reaction being substantially changed,
and indeed we have produced brightening in hydrogen peroxid~
sulphuric acid mixtures alone.