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The Removal of Electrodeposits of Nickel From Steel

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Transactions of the IMF

The International Journal of Surface Engineering and Coatings

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

The Removal of Electrodeposits of Nickel from


Steel

G. E. Gardam

To cite this article: G. E. Gardam (1938) The Removal of Electrodeposits of Nickel from Steel,
Transactions of the IMF, 14:1, 13-16, DOI: 10.1080/00202967.1938.11869346

To link to this article: https://doi.org/10.1080/00202967.1938.11869346

Published online: 09 May 2017.

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13
Paper relld. bt'/'JI'i' the J~'le«·lrotleposilorx·
Technical Society at the Northarn)>ton Pol1Jiech11ir
Inatitute, 0/erkenweU, London, R.O.l, on Wednesday,
22nd September, 1937.

THE REMOVAL OF ELECTRODEPOSITS OF NICKEL


FROM STEEL.*
By G. E. GARDAM.

SYNOPSIS.
Nickel coatings can be completely removed from steel articles
without appreciable attack on the steel by anodic treatment in
50 per cent. (by volume) sulphuric acid solution with an applied
potential not exceeding 2·0 volt.
The method is suitable for the removal of thick nickel coatings
as an alternative to machining, which is expensive ;!nd removes
some steel. It can also be used to determine the avera;,::! thickness
of nickel or of composite nickel-copper coatings on : ~·I by loss
in weight.
INTRODUCTION.
In the repair of worn or undersized steel parts by the electro-
deposition of nickel it is sometimes necessary to remove an existing
deposit, which partially or completely covers the surface, prior to
further deposition. Such deposits can be removed by machining,
but this method is tedious and expensive, particularly if the shape
of the article is complex; complete removal of all the nickel can
also only be assured by removal of some steel. An electrochemical
method has been developed and is described below. When suitably
controlled, this process has a negligible action on steel and can,
therefore, be also applied to remove thin coatings for determination
of their thickness by loss in \Veight.
DESCRIPTIO~ OF THE METHOD.
The method consists essentially in subjecting the nickel coated
article to anodic action at air temperature in a mixture (S.G. 1·545)
of equal volumes of concentrated sulphuric acid and water, the
potential difference between the anode and cathode being controlled
so that it does not exceed 2·0 volts.
The solution may be conveniently contained in a lead-lined tank,
the lining being used as cathode; alternatively separate cathodes of
lead or nickel may be used.
Control of the applied voltage may be attained by connection to
a generator whose open circuit voltage is 2·0 volts or to a single
lead accumulator cell. Where the available supply is at a higher
voltage, the applied potential can be adjusted by manual control
of a series resistance. Since the current falls and finally ceases
when the nickel is completely removed, satisfactory control is more
easily achieved if a further resistance is connected in parallel with
the stripping bath. Alternatively a resistance carrying a sufficiently
*Communication from the Research Department, Woolwich.
MS. received 8th September, 1937.
14 THE REMOVAL OF ELECTRODEPOSITS OF NICKF.L FROM STEEL.

large current may be connected across the available supply and


the stripping bath supplied from two tappings, the open circuit
voltage between which is 2·0 volts. Articles placed in the bath
connected in this manner may be left for long periods and removed
when convenient, but the time of stripping is longer and the con-
sumption of current is higher than by either of the previous methods.
The completion of removal of nickel is indicated by cessation of
current in the stripping bath; agitation of the solution or removal
and inspection of the article is undesirable as the unavoidable
disturbance of the protective film results in further attack on the
steel. The current density on the nickel surface is limited by the
applied voltage to a low value and the time of stripping is in
general greater than the time of depositing.
NOTES ON THE METHOD.
The concentration of sulphuric acid used is not critical; however,
in more concentrated solutions, e.g., 60 per cent. by volume,* anodic
dissolution of nickel at low voltage is extremely slow, apparently
owing to the formation of viscous or gelatinous nickel compounds
on the surface, which do not readily disperse in the solution. In
less concentrated solutions, e.g., 40 per cent. by volume, attack on
the exposed steel is increased. The addition of 200 g. per litre of
nickel sulphate (NiS04 . 7H 2 0) to 50 per cent. {by volume)
sulphuric acid solution appeared to be without influence on its use
for stripping nickel; it therefore appears possible to operate the
solution at least until the nickel content reaches a high value.
Before insertion into the bath, articles should be degreased and
dried. Methods of degreasing as used prior to electroplating may
be employed, but wiping with a cloth soaked in organic solvent
followed by rubbing with a paste of magnesium oxide or precipitated
chalk is also satisfactory.
The process has been found to operate satisfactorily on articles of
complex shape, e.g., a nickel-plated sheet bent into the form of a
long relatively narrow tube.
ATTACK ON THE STEEL.
The selective action of the process appears to be due to formation
on the steel surface of a protective film, possibly of sulphate. If
this is not disturbed by agitation of the solution or by oxygen
evolution, further dissolution of steel is prevented. The overall
voltage at which oxygen evolution commences depends on a number
• The volume of concentrated sulphuric acid S.G. 1'84 is expressed as a
percentage of the total volume of acid and water before mixing. When
equal volumes of acid and water are mixed, the cooled mixture occupies
only 1'83 volumes, hence calculations of strength of acid in percentage
by weight or in g. per litre must be carried out with care. A SO per
cent. by volume solution has a specific gravity of 1·545, and contains
990 g. per litre or 64 per cent. by weight of acid.
G. E. GARDAM 15

of factors, e.g., cathodic and anodic overvoltages and resistance of


the solution: it may vary with conditions, but in experiments
using a steel anode and a lead cathode in SO per cent. (by volume)
sulphuric acid solution, the minimum voltage at which visible
oxygen evolution occurred on the anode was 2·4-2-5 volts.
When the voltage exceeded this figure, attack on the steel was
progressive and frequently localised. In the practical application
of the process, it is desirable to limit the applied voltage to a
maximum of 2·0 volts; at this voltage a satisfactory rate of removal
of nickel is obtained without danger of oxygen evolution.
The attack on the steel under the recommended conditions appears
to be confined to that necessary to form a protective film and is
not progressive. Thus in a number of experiments on mild steel
in which the time of anodic action was varied, but disturbance of
the protective film was avoided, the loss in weight was approximately
constant at 0·01 g. per sq. inch independent of the time. The
attack appeared uniform; a polished surface was rendered matt.
A number of ferrou!) alloys were subjected to anodic action in
SO per cent. sulphuric acid and the loss in weight determined; the
results are shown in Table I.
TABLE I.-Loss IN WEIGHT OF FERRous ALLOYs DURING ANomc
ATTACK FOR 64 HOURS IN SO PER CENT. (RY VOLUME)
SuLPHURIC Acm AT 2 VoLTs.

Loss in
Type of Alloy. weight Carbon Principal other metals.
g./sq. in. % %

Mild steel .. . 0'0108


Grey cast iron .. . 0'0101
High carbon steel .. . 0'0191 0'83 Mn 0·23%
Manganese steel .. . 0"0157 0'46 Mn 0'68%
Nickel steel .. . .. . o·o1 53 0'39 Ni 3'61%
, , ... ... o·0146 0'26 Ni 3'32% Cr o·36%
Nickel chromium steel 0'0178 0"61 Ni 2·0% Cr 2'25%
Nickel chromium 0'0119 0"25 Ni 2'8% Cr 0'48%
molybdenum steel Mo 0'41%
Ditto ditto ... 0'0132 0'32 Ni 2·37% Cr 0·63%
Mo o·70%
Immersion of steel or nickel-plated steel articles in the stripping
solution without current does not result in severe corrosion. Thus
a piece of mild steel and a similar piece coated with nickel over
half its area were immersed in SO per cent. (by volume) sulphuric
acid at air temperature for 7 days. The loss of weight was
0·023 g. per sq. inch in each case (calculated on the exposed steel
only), equivalent to a loss of approximately 0.0002 inch thickness.
DETERMINATION OF THE AvERAGE THICKNEss OF NICKEL
CoATINGS ON STEEL.
The recommended method may be used to determine the weight
16 TIIF. REMOVAL OF ELECTROOEPOSITS OF NICKEL FROM STEEL.

of relatively thin nickel deposits on steel applied for decorative and


protective purposes. The nickel-plated area is estimated; the
article is then degrcascd, weighed and made the anode in the
sulphuric arid solution, supported by an iron wire or strip. Current
is supplied from a single-cell lead accumulator or a potentiometer.
To minimise attack on the steel, it is preferable to use a 55 per
cent. instead of a 50 per cent. (by volume) solution of sulphuric
acid.. Care is taken to avoid disturbing the protective film and
anodic action is continued for some time (e.g., 15 minutes) after
current has ceased to pass through the solution. The article is
then quickly withdrawn, thoroughly rinsed, dried and reweighed.
The loss in weight is that of the nickel coating together with some
steel. The attack on the steel can be reduced by careful operation
to about 0·005 g. per sq. inch, equivalent to an error of + 0.00004
inch. The error may be partially eliminated in the following
manner, depending on the fact that attack on steel is confined to
the formation of a protective film : After reweighing, the steel
article is replaced and again subjected to anodic action under the
same conditions for a short period, e.g., half an hour, washed,
dried and reweighed. The loss in weight is deducted from the
previously obtained figure, the difference being the weight of nickel
coating alone.
Taking the density of nickel at 8·9, the weight of a coating
0·001 inch thick is 0·146 g. per sq. inch (0·01 mm. thick =
0·0089 g. per sq. em.).
CoMPOSITE CoATI:'IIGS.
Electrodeposits on steel, externally of nickel, arc sometimes
composite and consist of layers of nickel, copper and nickel or of
copper and nickel; the copper deposit is sometimes polished before
the application of the final nickel coating. Anodic solution of
copper by the method described above tends to be arrested after
solution of some copper has occurred, but the amount of the attack,
together with the possibility that the copper layer is not continuous
or is very thin locally, renders the method in general unsatisfactory
for estimation of the individual layers of a nickel-copper-nickel
coating. By slight modification, the method may be used to
determine the total weight of the coating and, in view of the small
difference of density of copper and nickel, the inaccuracy in the
calculated thickness is small. The procedure described above is
followed as far as the first reweighing; if copper is apparent the
article is made anode at a current density of 5-15 amps. per sq.
ft. in a solution of ammonium sulphate 50 g., ammonium hydroxide
(S.G. 880) 50 mi. per litre, until copper is removed. The surface
of the solution is preferably covered with a layer of oil to prevent
loss of ammonia. The article is removed, rinsed and dried, and if
nickel is still present it is replaced dry in the sulphuric acid solution
and treated as described for a nickel-plated article.

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