The Electrodeposition of Ternary Fe-Cr-Ni Alloys

Electrodeposition and Surface Treatment 367
Elsevier Sequoia S.A., Lausanne - Printed in Switzerland
T H E E L E C T R O D E P O S I T I O N OF T E R N A R Y I R O N - C H R O M I U M - N I C K E L
A L L O Y S - - A C R I T I C A L REVIEW
C. U. CHISHOLM
School of Mechanical Engineering, Robert Gordon's Institute of Technology, Aberdeen (Gt. Britain)
and R. J. G. CARNEGIE
Department of Mechanical and Production Engineering, Dundee College of Technology, Dundee
(Gt. Britain)
(Received December 17, 1972)
SUMMARY*
The potential properties of thin and thick deposits of nickel-chromium-

iron alloys are discussed. Codeposition from the baths investigated is reviewed and
results compared. The role of addition agents in the various baths is considered in
relation to deposit composition and quality. It is shown that thickness is the critical
limiting factor in all baths. The review shows that alloy compositions over a large
range are possible from the main baths. Corrosion resistance, microhardness and
structure of the more successful alloys are examined. The various deposition
mechanisms are investigated and it is shown that films on the cathode represent
the main mechanism. It is shown that the limiting factor in all baths is failure to
sustain deposition, which is associated with deterioration of deposits owing to
internal stresses and absorption/adsorption of gases. The thin alloys obtained from
the baths reviewed, in some cases, could be of considerable industrial value, but
require further development studies.
INTRODUCTION
In this highly advanced technological age, man is continually striving to

extend the frontiers of science. One major area of activity has been the development
of new materials, particularly alloys, with superior properties and better perfor-
mances than existing materials, to meet the demands of modern technology. In
particular, the development of electrodeposited alloy coatings is of great practical
interest in decorative, protective and engineering applications, mainly from the
point of view of providing an economical alternative to thermally produced wrought
and cast alloys.
This paper deals with attempts to obtain electrodeposits of ternary F e - C r -
* R6sum6 en fran~;ais b. la fin de l'article. Deutsche Zusammenfassung am SchluB des Artikels.
Electrodepos. Surface Treat., 1 (1972/73)

368 c . u . CHISHOLM,R. J. G. CARNEGIE
Ni alloys. These alloys in the wrought and cast form, in particular the stainless and
heat-resisting steels, are well recognised for the diverse combination of physical,
chemical and mechanical properties which they possess. It is quite feasible that
electrodeposited coatings of these alloys would offer similar and possibly improved
properties.
However, it is evident from a survey of previous research that the main
effort has been directed towards the production of alloy deposits having a composi-
tion approaching that of the classic highly corrosion resistant 18/8 Cr-Ni stainless
steels to the complete exclusion of other important classes of Fe-Cr-Ni alloys,
which possess other important properties such as scaling resistance and high
mechanical strength at elevated temperatures and could possibly find a wider range
of applications than the 18/8 Cr-Ni composition. In this paper, it is intended to
consider the full range of Fe-Cr-Ni alloys deposited and to critically assess the
potential value of the deposits obtained. The cast and wrought Fe-Cr-Ni alloys
can be classified accordingly to three basic groups:
1. Fe-rich alloys
This is the most important group and has two main sub-divisions, the austeni-
tic stainless and heat-resisting steels. The former contain 10-30~ Cr and 7-25%
Ni and include the widely used 300 series of austenitic stainless steels including the
basic 18/8 Cr-Ni grade. Their main attribute is their excellent corrosion resistance
in a wide variety of chemical media at room or moderate temperatures, up to
approximately 300°C. They have good mechanical and physical properties, such
as high strength and ductility, exellent wear resistance and hardness, high impact
strength, high electrical resistivity, fairly high reflectivity and possibly favourable
magnetic properties. The stainless steels find extensive applications including
corrosive service in chemical processing equipment, the food industry, the pressure
vessel industry, general engineering and the aircraft industry.
The heat resisting steels have as their most important properties high scaling
or corrosion resistance in gaseous or liquid media, either oxidising or reducing,
combined in many cases with high creep resistance at elevated temperatures in the
range 500-600 ° C. Their mechanical and physical properties are similar to those of
the stainless steels and in general these are retained to a considerable degree at high
temperatures. These steels cover a wide range of compositions, generally containing
approximately 5-30~o Cr and 7-35% Ni.
2. Cr-rich alloys
These constitute alloys with a Cr content of greater than 60~o and they
possess properties comparable with those of pure Cr. They may possibly have
improved properties over those of Cr since it is recognised that alloys usually
possess superior properties to those of the individual constituent metals owing to
favourable changes in structure. These alloys are still adequate to withstand fairly

ELECTRODEPOSITION OF F e - C r - N i ALLOYS 369
severe service conditions and find similar applications up to moderate temperatures

of 300 ° C.
3. Ni-rich alloys
The most important group of these alloys is that of the heat-resisting alloys
which contain 35-80 % Ni, 10-20 % Cr, remainder Fe. They are important because
of their superior scaling and creep resistances over the Fe-rich steels with lower Ni
contents. Their remaining mechanical and physical properties are basically equiva-
lent to those of the Cr-Ni steels, hence their applications are similar but with the
additional advantage of even higher temperature service.
The major limitation of all the above alloys in the cast or wrought iron form
is their high cost. Thus it would be highly desirable to deposit thin alloy coatings
on a cheap substrate to impart their favourable properties to the base metal and,
in so doing, provide an economical substitute for the cast and wrought alloys
without prejudice to the functional advantages.
It is interesting to note that in the absence of carbon, these electrodeposited
alloys are not expected to have an austenitic structure similar to the thermally
produced cast and wrought alloys since the austenite-stabilising action of the car-
bon would be missing. Instead a ferritic structure is anticipated, which would be
highly ferromagnetic.
Therefore such alloy deposits could have excellent potential as thin films
for use in the electronics industry for such applications as data storage in computer
memories and magnetic tapes for sound recording. The cast and wrought alloys
could not be used for such thin film applications.
Another benefit to be accrued from the absence of carbon in the alloy
deposits is the prevention of sensitisation to intergranular corrosion associated
with the austenitic steels and caused by carbide participation at and in the neigh-
bourhood of grain boundaries.
One other imt~ortant facet of the establishment of Fe-Cr-Ni codeposition
could be a single-stage plating process which would obviate the need for the two-
stage 'duplex' nickel/chromium process used at present. In addition, the mecha-
nism of deposition may be changed by such a process so that the occurrence of
cracking, associated with high internal stresses in chromium deposits, would be
prevented. Higher current densities and cathode efficiencies than those realised in
Cr deposition might also be possible.
This paper reviews and discusses previous experimental work relating to the
electrodeposition of ternary Fe-Cr-Ni alloys from aqueous electrolytes.
REVIEW
The electrodeposition of ternary Fe-Cr-Ni alloys has been reported in

reviews on Cr alloy deposition by Levy1, Spencer 2 and Brenner a. It has also been

370 c. u. CHISHOLM, R. J. G. CARNEGIE
m e n t i o n e d in general reviews on alloy deposition and electrodeposition by Saro-

j a m m a and R a m a C h a r 4, R a m a C h a r s, and K r o h n and Bohn 8. M o r e recently, a
paper by S a r o j a m m a and R a m a C h a r 7 has appeared, reviewing the electrodeposi-
tion o f 18-8 C r - N i stainless steel.
A s u m m a r y o f baths used by previous investigators is shown in Table 1, with
the o p t i m u m results obtained.
TABLE 1
THE MAJOR PLATING BATHS INVESTIGATED TO OBTAIN IRON--CHROMIUM--NICKEL ALLOY DEPOSITION
Investigators Ref. Electrolyte Operating Results

composition (g/I) conditions
Lainer and 8 Not specified. Not specified Nickel-based alloy

Kudryavtsev Based on green deposits; no informa-
modification of chro- tion on composition
mium sulphate
Kalocsay 9 Not specified. 4 Volts; 3.5 A/dm2; Stainless iron alloy

Includes addition soluble stainless iron deposits; composition
agents, in particular alloy or steel anodes not specified
citric acid
Skalozubov and 10 Chromic acid 250; 50 A/dm2; Range of alloy

Goncharova nickel sulphate 250; 60° C deposits:
ferrous sulphate 175; 44-57 ~o Ni;
boric acid 25 2 8 ~ 7 ~ Cr;
10-14~o Fe.
Poor quality plate
Brenner, 11 Not specified. Not specified. Alloy deposits. No

Burkhardt and Based on chromic Lead anodes; information on actual
Jennings acid. Ni and Fe copper deposit compositions
introduced mainly cathodes but deposits con-
in the form tained mainly Cr with
of metal very small percentages
dichromates of Ni and Fe present as
basic inclusions rather
than free metals
Machu and 12, Chromic sulphate 9-30 A/dm 2; Alloy deposits with
E1-Ghandour 13 (violet modification) 30-80 ° C; range of compositions.
265; nickel sulphate pH 2.1-2.4; 1 2 7 ~ Cr; 4 2 9 ~ Ni;
112, ferrous insoluble platinum 69-74~ Fe; including
sulphate 56; anodes; various compositions approxi-
boric acid 25; cathodes: copper, mating to 18/8 Cr-Ni
urea 180 brass, nickel, stainless steel. Good
zinc, aluminium and quality deposits up
iron to 6/~m thick

ELECTRODEPOSITION OF Fe-Cr-Ni ALLOYS 371
Table 1 (continued)

composition (g/I) conditions
Kalyuzhnaya 18 Chromium potassium (a) 15-16 A/dm2; Alloy deposits over

and alum (violet modifi- 25°C; range of composi-
Pimenova cation) 400; (b) 18-20 A/dm2; tions: 19-40~ Cr;
nickel sulphate 56; 40°C; 6 - 7 ~ Ni; 52-72~ Fe;
ferrous ammonium pH 1.6-1.8; including compositions
sulphate 39; soluble Cr 18 ~, approaching 18/8
trisubstituted sodium Ni 9 %, Ti steel Cr-Ni steel. Good
citrate 70; sodium anodes; copper and quality plate up to
fluoride 8 iron cathodes 6 #m thick
Ray and 25 Chromium sulphate 21-29 A/dm2; Alloy deposits.

Banerjee (green variety) 250; 40-58°C; Range of composi-
nickel sulphate pH 1.3-1.4; tions: 6-24% Cr;
50-120; soluble stainless 6-21 ~ Ni;
ferrous sulphate 30; steel anodes; 67-89~ Fe; including
disodium salt of brass cathodes compositions close to
EDTA 50-100; that of 18/8
boric acid 25-35 stainless steel
Takahashi, 26 Chromium trichloride 10-30 A/dm2; Alloy deposits.

Sugiyama and (green form) 133; 20-30°C; pH 2.0; Composition range:
Hayakawa nickel chloride insoluble platinum 7-25~ Cr; 5-30~ Ni;
24-71 ; ferrous anodes; copper and 63-70~ Fe. Good
chloride 20~0; nickel plated quality plate up
ammonium copper cathodes to 10~m thick
chloride 200
Mutafchiev 28 Chromic sulphate 5-60 A/dm2; Alloy deposits of

and 240-260; nickel 20-60 ° C; composition:
Marinkov sulphate 50-60; pH 1.8-2.0; 17-25 ~ Cr;
ferrous sulphate soluble 18/8 stainless 5-11~ Ni;
50-60; urea 160-180; steel anode 68-72 ~ Fe;
aluminium sulphate including composition
20-30; magnesium close to 18/8 type
sulphate 10-15 ; stainless steel
nickel chloride 10-15 ;
ammonium sulphate
35~10; ethyl alcohol
3540 ml/l
Saimanova and 32 Chromic acid 270; 8-12 A/dm2; Chromium-rich alloy

Drobantseva nickel sulphate 20-25 ° C; deposits of composi-
150-200; ferrous pH 0.2~.5; tion 9 3 ~ Cr;
sulphate 50; calcium lead or nickel anodes; I% Ni; 6 ~ Fe.
carbonate 40-60; copper and steel Good quality de-
calcium sulphate 4-10 cathodes posits up to 40btm

372 C.U. CHISHOLM, R. J. G. CARNEGIE
Table 1 (continued)

composition (g/1) conditions
Zytner, 34 Chromic chloride 35--40 A/dmZ; Alloy deposits of

Rotinyan and (green form) 250; 60-80 ° C; composition:
Fedot'ev nickel chloride pH 0.1-0.3; 5-8~o Cr; 20-25 ~ Ni;
92; ferrous soluble Cr 18 ~, 70-72 ~ Fe. Good
chloride 30; Ni 9 ~o, Ti stainless quality coatings of
trisodium steel anodes; copper 12-15/zm
citrate 70 and steel cathodes
Sarojamma 35 Chromic sulphate 4-13 Volts; Alloy deposits over

and Rama Char 132-330; 5-40 A/dm 2; range of compositions :
nickel sulphate 25-60°C; 2-30~ Cr; 3 20~ Ni;
28-168; ferrous pH 2.0; insoluble 49-85 ~ Fe; including
sulphate 14-56; platinum anode; 18/8 Cr-Ni steel
triethanolamine 149; copper-coated composition
boric acid 25 platinum cathode
Gowri, Elsie 37 Chromium sulphate 18.6 A/dm2; Alloy deposits of

and Shenoi (violet modification) 30-35°C; composition:
255-287; nickel pH 1.7-2.0; 30-35 ~ Cr;
formate 47-63; insoluble platinum 8-10 ~ Ni;
ferrous sulphate and soluble stainless 58-60 ~ Fe.
25-40; trisodium steel anodes; Satisfactory deposits
citrate 100; various cathodes: up to 15pm
ammonium sulphate copper, brass, nickel,
50-70 boric acid; 30 mild steel,
glycine 7-10; aluminium, etc.
sodium fluoride 6-8
Kudryavtsev, 40 Chromium potassium 5-12 A/dm2; Alloy deposits

Smirnova and alum 333; nickel 20°C; pH 2.0-2.2; within composition
Volkova sulphate 84; insoluble graphite range: 15-34 ~ Cr;
ferrous sulphate 56; anodes enclosed in 5-10~o Ni;
glycine 150 ceramic diaphragms 61-75 ~ Fe;
containing 0.1 N including Cr 18 ~o,
sulphuric acid Ni 9 ~ type alloy.
solution; Good quality deposits
platinum cathode up to 2-3/zm
Rotinyan, 45 Chromic chloride 25-30 A/dm2; 30°C; Alloy deposits of

Zytner and (green modification) pH 0.2-0.3; composition close
Fedot'ev 150-200; nickel nichrome (20-30~ Cr, to that of 18~ Cr,
chloride 25-50; 50-60 700Ni, 9 ~ Ni stainless
ferrous chloride 12-20; 25-30~ Fe) anode; steel, viz:
trisodium citrate copper, steel, and 20-22 ~ Cr,
50-70; aluminium copper-plated 8-10~ Ni,
chloride 130 steel cathodes 68-72 ~ Fe.
Good quality deposits
up to 25/zm

Table 1 (continued)

composition (g/l) conditions
Katser, 47 Chromic sulphate 5-10 A/dm2; Alloy deposits over

Petrova and (green modification) 20-30 ° C; range of
Vitkin 160; nickel sulphate pH 1.4-1.6; compositions:
56-84; ferrous graphite anode 18-35 ~ Cr;
sulphate 29-43; (insoluble); copper 4-12~ Ni;
sulphamic acid and steel cathodes; 61-70 YoFe.
220-250 anode separated from Satisfactory deposits
cathode space by a up to 25 btm
ceramic diaphragm
Vitkin, 49 Chromium sulphate 5-10 A/dm~; Satisfactory alloy

Katser and 222; nickel 20-30° C; deposits in composi-
Petrova sulphamate 50-76; pH 1.4-1.9 tion range:
ferrous sulphamate 16-36 ~ Cr;
26-39; glycine 20--40 4-12~ Ni;
6o-72 % Fe
Kudryavtsev, 50 Chromium fluoroborate 25-30 A/dm 2; Alloy deposits

Tsupak, 217-260; nickel 45-47 oC; range of
Rashinskaya fluoroborate 47-70; insoluble anodes compositions:
and Gulyaeva ferrous fluoroborate in IN hydrofluoroboric 12-18% Cr;
29-34; free acid solution 8-18~ Ni;
hydrofluoroboric acid separated from 60-74 ~ Fe
189-198; aluminium cathodic compartment
chloride 40-45 by a porous
diaphragm
Chisholm 51 Chromium fluoroborate 8-60 A/dm2; Alloy deposits:

40-100; nickel 25-75°C; composition not
fluoroborate 100-300; pH 1.0-3.0; specified
iron fluoroborate insoluble anodes of
100-500 platinum-group metals:
titanium, graphite or
platinum;
copper cathode
Firoiu and 52 Chromium 10-20 A/dmZ; Alloy deposits in

Ionescu ammonium sulphate 45°C; pH 2.5; composition range:
350; nickel platinum anode; 36~8% Cr;
sulphate 50; copper cathode 13-18% Ni;
ferrous sulphate 50; 36-49 % Fe.
boric acid 30; Satisfactory deposits,
glycine 5; EDTA 4-5 btm thick
(disodium salt) 250

374 C. U. CHISHOLM~ R. J. G. CARNEGIE
Table 1 (continued)

composition (g/l) conditions
Chisholm and 53 Chromic chloride 10-50 A/din'2; Alloy deposits over

Carnegie (green form) 75; 40°C; pH 0.5-1.0; range of compositions:
nickel chloride 25; anodes: platinum 0-20~ Cr;
ferrous chloride 20; 18~o Cr, 8~o Ni 5-51 ~ Ni;
disodium salt of stainless steel, and 45-90.5 ~ Fe.
EDTA 25 Brightray B alloy including composi-
(65~ Ni, 15-20~ Cr, tion approaching
remainder Fe) 18 ~o Cr, 8 ~ Ni
cathodes: copper, steel. Good quality
steel, and copperplated deposits up to
steel 20/~m thick
Ternary F e - C r - N i alloy deposition was first reported as late as 1938 by

Lainer and Kudryavtsev s but the results presented were of a very vague nature.
A year later, Kalocsay 9 patented a bath to produce stainless iron deposits.
Only an abstract of this work was available and this lacked detail. No in-
formation was given on bath composition or the quality and composition of the
resultant deposits.
Skalozubov and Goncharova 1° reported results of a more fundamental
nature. They obtained alloy deposits from a chromic acid based bath, Information
was given on the effects of operating conditions on deposit composition and bath
performance. An increase in current density was alleged to increase the Cr and
decrease the Ni and Fe contents of the deposit. A rise in electrolyte temperature
resulted in a decrease in Cr. The cathode efficiency decreased with increasing
temperature and current density. The deposits were found to be of poor quality
and the electrolyte was reported to be unstable in operation at the working tem-
perature. No information was given on the thickness of deposits but the maximum
current yield was reported as 1 5 ~ and with optimum operating conditions only
approximately 10~o. Brenner et a l. l l also claimed deposition from a chromic acid
bath. The results were of limited value since deposits were obtained with only very
small percentages of Fe and Ni present as basic inclusions rather than as free metals.
The first detailed investigations in this field were conducted by Machu and
El Ghandour in 1960 when they published three papers 1z--14. Although their
particular interest was in alloys of the 18/8 C r - N i stainless steel composition, they
succeeded in depositing a wide range of alloy compositions from a complex metal
sulphate bath containing urea and boric acid t2. Urea was added to promote
complex formation and suppress the formation of metal oxides and hydroxides.
Boric acid prevented or at least greatly reduced cracks and flaws in the deposits.
Citric acid gave similar results. It can be seen from Table 1 that uniform deposits
of satisfactory appearance, showing some signs of pitting, were obtained up to a
Electrodepos. Surface Treat., I (1972/73)

thickness of about 6#m, but deposits could be obtained up to 20/zm. The maximum
current efficiency was around 2 5 ~ . Fundamental studies on the influence of work-
ing conditions on deposition 13 showed that the composition of the alloy deposits
was affected by changes in the concentration of the bath constituents. An increase
in Cr concentration in the bath led to a slight increase in theCrcontentinthedeposit
but decreased current efficiency. If the Fe concentration was reduced, the Fe
content of the deposit became less, while the Ni and Cr content increased but the
current efficiency dropped. If Ni concentration was increased, the Ni content rose
sharply while the current efficiency remained constant. An increase in temperature
caused a decrease in the amount of Cr in the deposit, an increase in Ni, little change
in Fe and a rise in current efficiency. At current densities of 33 A / d m 2 cracks
appeared in the deposits as well as individual 'burnt' spots and oxide formation.
At temperatures of 70-80°C smoothing of the deposit took place and led
to the disappearance of cracks and defects. Hence a high temperature and low
current density of 10 to 15 A / d m 2 were the most suitable for the formation of a
uniform deposit free from defects. The duration of electrolysis was stated to have
no effect on alloy composition but the current efficiency and brightness of the
deposits were found to decrease somewhat with increasing time. The cathode
material had no effect on the alloy composition but caused a variation in current
efficiency. Fundamental studies were also made of the mechanism of deposition 12
and it was suggested that deposition could be directly attibuted to the formation
of a chromium hydroxide diaphragm on the cathode surface which was particularly
sensitive to variations of current density, temperature and pH and that the low
current efficiency and the composition of the alloy were largely determined by this
diaphragm. It was also proposed that the three metals, Fe, Cr and Ni, mutually
impeded, or polarised, each other during their codeposition; thus the current yields
were much smaller than might be expected from the deposition of the three metals
individually. This mutual impedance was reduced if the temperature and current
density were increased. A study of the current density-cathode potential curves 12
revealed that the strongest polarisation occurred in the deposition of Cr and at
50°C with pH 2.1; the deposition potentials of the three metals and the alloy were
found almost to coincide indicating the possibility of codeposition of the three
metals.
Various organic and inorganic brightening agents were also tested 14 and in
all cases the brightening effect was much smaller than that for the individual
metals. In addition, where brightening agents were effective, current efficiencies
were reduced.
These same researchers subsequently published two further reports 15 and
filed three patents 16 on the basis of this work. The patents gave the additional
information that the metal salts could also be present as chlorides and that an
acceptable and desirable brightening agent was pyridine.
A further improvement on this bath was patented by Amchem Prods., Inc. 17,

376 C. U. CHISHOLM, R. J. G. CARNEGIE
which constituted the use of soluble hydrazine in the bath to improve the quality
and corrosion resistance of the coatings produced.
A sulphate bath containing trisodium citrate was used by Kalyuzhnaya and
Pimenova is for the deposition of a range of Fe-Cr-Ni alloys. However, although
their investigation was of a fairly fundamental nature, their main interest was in
producing alloys of the 18/8 stainless steel type. It was found, through a comparison
of soluble and insoluble anode systems, that soluble 1 8 ~ Cr, 9~o Ni, 0.68~ Ti
anodes gave the best results in regard to performance and stability of the electrolyte
and alloy quality and composition. The current efficiency obtained under the
optimum conditions reported in Table 1 was about 4 5 ~ . Alloy coatings were
claimed up to a thickness of 20-25 #m, but only uniform, and adherent, up to
6/~m. At greater thicknesses, the coatings exhibited cracking and porosity, lost
their adhesion, and peeled off the cathode surface, owing to the presence of appre-
ciable tensile stresses in the deposits. After heat treatment under vacuum at
1000°C for 5 hours, these deposits became more uniform and adhered to the
cathode. The microhardness of the deposits was found to be of the same magnitude
as that of ordinary Cr 18~, Ni 9 ~ , Ti sheet steel. Coatings up to 6 #m thick had
higher corrosion resistance in 5 ~ H2SO4 solution at 20°C than coatings 20-25/zm
thick, owing to the presence of cracks in the latter. Fundamental information was
provided on the dependence of alloy composition and current efficiency on the
operating conditions. Enrichment of the electrolyte raised the Fe content of the
alloy, but had an adverse effect on deposit quality and current efficiency. Increases
in current density caused the Cr content in the alloy to increase and the Fe content
to pass through a maximum, while the Ni showed no change. The Ni and Fe
contents increased while the Cr content dropped sharply when the temperature
was increased. Experiments were also conducted on the same electrolyte using a
diaphragm cell where the cathodes were shielded by a copper wire frame. Insoluble
lead anodes were used, with sulphuric acid. Similar deposits were obtained but the
cathode efficiency was only 18~. This work was reviewed by Domnikov 19 two
years later.
Three further papers z0-22 were published extending this basic research
work is.
In the first of these papers 20, internal stress in the deposits was studied. It
was thought that one of the probable causes of stress was the influence of hydrogen
included in the deposit and basis metal. Alternating current superimposed on d. c.
current reduced the stresses but decreased the current yield. The formation of a
thin oxide film on the cathode using sodium hydroxide solution improved deposit
quality by the oxygen in this film reacting with the hydrogen discharged at the
cathode, thus preventing hydrogen penetration into the cathode metal. The deposits
on anodised cathode surfaces had considerably lower internal stresses and satis-
factory adhesion to the basis metal. Deposits on passivated steel surfaces also
showed lower internal stresses.

The second paper 21 considered the rates of discharge of Fe, Cr and Ni ions
during their joint reduction through a basic study of the cathode polarisation
curves for the deposition of the alloy and the separate metals at various tempera-
tures. It was found that the rate of discharge of the ions was dependent on whether
the violet or green chromium complex was present. Electrodeposition of the alloy
from the violet modification of the Cr took place at potentials more positive than
from solutions of the green modification.
The results indicated that in solutions of the violet modification of chrome-
alum, the total polarisation curves for the deposition of the alloy were situated at
more positive potentials than the polarisation curves for the individual metals.
Deposition of Cr in the alloy was observed to take place more easily than in its in-
dividual deposition.
The third paper ~2 studied the effect of sodium citrate concentration in their
previous electrolyte la on alloy composition and quality. At very low citrate con-
centrations, a hydroxide film formed on the cathode surface, the composition and
properties of which affected the metal ion discharge. An optimum citrate addition
of about 140 g/1 decreased the Cr content, increased the Fe and Ni contents in
the alloy and also led to better quality deposits and stabilisation of the alloy com-
position.
Kvachkov and Stoicheva 2a succeeded in obtaining good, decorative, protec-
tive alloy coatings, resistant to corrosion up to 400 °C, similar in composition to
18/8 Cr-Ni stainless steel. They used the same bath and optimum operating
conditions as did Machu and EI-Ghandour lz, 13. A soluble steel anode of 18~o
C r - 9 ~ Ni permitted prolonged use of the bath without correcting its composition.
Ray published a preliminary paper 24 and later, with Banerjee, a more de-
tailed paper 25 on a successful attempt to deposit F e - C r - N i alloys from a sulphate-
EDTA (disodium salt) bath, with particular emphasis on obtaining an alloy compo-
sition approximating to 18/8 stainless steel. EDTA was added to the bath as a
complexing agent. The deposition of Cr was facilitated by its presence. Boric acid
had a particularly beneficial effect on the uniformity of the deposits by preventing
or at least reducing cracks and discontinuities in the deposits. The maximum
current efficiency obtained was 13~o for the deposition of the 18/8 Cr-Ni alloy.
A chloride electrolyte was employed by Takahashi et al. 26 for the production
of flat and continuous alloy deposits up to 10 # m thick. A chloride solution was
selected for its high electrical conductivity, high anodic dissolution efficiency, and
its capability of plating Fe-group metals at high current densities. Microscopic
cracks occurred in deposits from l0 to 15/~m thick. Heat treatment at 1000°C for
one hour followed by quenching considerably increased the corrosion resistance
of the coatings in solutions of 5 ~ HC1, 5 ~ H2SO4, and 2 0 ~ NaCl. The cathode
efficiency was maintained in the range of 30 to 4 0 ~ under the optimum conditions
shown in Table 1. A study of the effects of plating conditions on deposition showed
that the higher the chromium chloride concentration in the solution, the lower was

378 c.u. CHISHOLM, R. J. G. CARNEGIE
the current efficiency. As the current density increased, the Cr content of the de-
posits increased but the Ni content decreased. At increased temperatures, the de-
posits contained more Ni and less Cr. The Fe content remained fairly constant with
increasing current density and increased with rise in temperature. The current
efficiency remained fairly constant with current density increase and decreased with
rise of temperature. At a pH greater than 3.0, a white colloidal film formed on
the cathode surface. A decrease in current efficiency was evident after 10 minutes
plating.
Various base metals were tested. Nickel-plated copper gave good adhesion,
while wrought iron and high carbon steel led to cracks in the deposits. It was shown
that the system behaved as a regular codeposition system characterised by the
diffusion control of Fe and Ni ions. In this electrolyte, an anode of 1 8 ~ Cr, 8 ~
Ni steel was dissolved with an anode efficiency of 100~. A patent 27 was subse-
quently filed on the basis of this research.
Mutafchiev and Marinkov 28 introduced ammonium, magnesium and
aluminium sulphates, and ethyl alcohol, as additives in the basic bath described
earlier by Machu and El-Ghandour 12, a3. They obtained alloy deposits from 20
to 100 # m thick, with a network of microcracks, over a range of compositions close
to the 18/8 stainless steel composition. The average cathode efficiency was 25-30~o.
Higher amounts of ammonium sulphate improved the quality of the plate, but
caused precipitation of nickel. The presence of nickel chloride was required to
activate anode dissolution, thus maintaining a stable electrolyte composition.
These authors showed in a later paper 29 that the dissolution rates of 18/8 stainless
steel anodes was greatest at 45-55°C with an optimum chloride concentration
giving the anodic dissolution rate as equivalent to the cathodic deposition rate. The
effect of varying pH showed that the cathode efficiency reached an optimum value
at 2-2.7, with a correspondingly high anode efficiency.
Another paper 3° was published by these researchers in which they determined
a throwing power of 26.2°~, for the deposition of an F e - C r - N i alloy at 16 A/dm ~,
40°C and pH 1.8, after 15 minutes.
Saimanova and Drobantseva 31, 32 reported the deposition of a chromium-
rich alloy from a self-regulating tetrachromate electrolyte. Smooth, bright, com-
pact, non-porous deposits showing good adhesion and no cracking were deposited
up to 40 # m thick, with a microhardness of 712 kg/mm 2 compared with 480
k g / m m 2 for pure chromium deposited under similar conditions. The deposits were
compact and resistant to the action of dilute acids. A coating, 20/zm thick on steel,
showed no corrosion after 300 hours in a salt mist chamber. It was therefore
stated that the direct deposition of Cr Fe Ni alloy on steel was possible
without the use of Cu and Ni underlayers. A maximum cathode efficiency of
30~,~, was achieved but under the optimum conditions reported in Table 1 this
dropped to 16-18~. A subsequent report o n this research work was made by
Domnikov 33.

ELECTRODEPOSITIONOF Fe-Cr-Ni ALLOYS 379
The production of alloy coatings from a chloride-citrate bath was claimed

by Zytner, Rotinyan and Fedot'ev a4. A chloride solution was chosen because of
the high limiting currents for Fe and Ni deposition, which are also required for the
deposition of Cr. Trisodium citrate was employed as a complexing agent for Ni
and Fe. Good quality coatings which adhered well to the substrate, with a thick-
ness of 12-15 #m, were produced with a cathode efficiency of 2 5 - 2 7 ~ . X-Ray
diffraction showed the deposits to consist of a solid solution. Information was given
on the dependence of deposit composition and quality on plating conditions.
In 1968, a study was made by Sarojamma and Rama Char a5 of the electro-
deposition of alloys from complex sulphate-triethanolamine solutions. The boric
acid served to maintain the pH and to promote the production of adherent and
satisfactory deposits. It was found possible to obtain good deposits, varying from
dull to bright grey in appearance, over a wide range of compositions, particular
emphasis again being on the 18/8 Cr-Ni stainless steel composition. However, the
total metal content of the deposits was found to be less than 100~o, the proportion
of non-metallic constituents being approximately 3~o. The cathode efficiency
varied from 2 to 2 8 ~ . The cathode efficiency increased with increase in current
density, temperature and Fe concentration in the electrolyte. Various other addi-
tion agents were tested but in general they did not afford an improvement in the
properties of the deposits.
A subsequent paper by Rama Char and Sheth 36 reported on alloy deposi-
tion from two baths, a sulphate-urea one which was basically Machu and EI-
Ghandour's earlier bath 12, lz and the sulphate-triethanolamine bath z5 previously
described under almost the same operating conditions. The results of these studies
verified the earlier work.
Gowri, Elsie and Shenoi 37 succeeded in obtaining adherent alloy deposits
from a sulphate-citrate bath with a current efficiency of 26/0~. The hardness of the
deposit was found to be 322 kg/mm 2 compared with stainless steel at 245 kg/mm 2.
Its corrosion resistance in 5 ~ H2SO4 and 3 ~ NaCI was good. Ageing the bath for
24 hours increased the current efficiency for Cr reduction and also for the alloy.
The functions of the various addition agents were studied. Ammonium sulphate
increased the solution conductivity and improved the deposit appearance. Tri-
sodium citrate increased the pH of chromium hydroxide formation, complexed Fe
and Ni, keeping the Fe in the ferrous state in which the deposition efficiency is
high, and helped in obtaining adherent deposits. Boric acid had a profound influence
on the useful life of the bath. Glycine helped to maintain the bath pH and prevented
the pitted deposits, while sodium fluoride acted as a stress reliever. Detailed studies
were made of the effect of such variables as current density, pH and temperature
on the quality and composition of the alloy deposits. Agitation was found to in-
crease the deposit brightness, current density range and thickness. Additions of
sodium, magnesium or aluminium ammonium sulphates to the basic bath were
reported to improve the throwing power of the bath slightly, and to increase the

current density range. Aluminium ammonium sulphate also gave a better deposit
by preventing the formation of slight cracks obtained in deposits from the basic
bath. Increasing time of deposition had the detrimental effect of increasing the
cracking of deposits.
The development of these alloy coatings indicated that internal stresses were
important in relation to the cracking tendencies observed in the deposits. As a
result, these same experimenters, together with Cleghorn, conducted further work 3s
in which stress measurements were made on the alloy deposits and then correlated
to the observed cracking and spalling. The deposits showed an initial compressive
stress followed by the rapid development of a tensile stress which reached a maxi-
mum at a deposit thickness of about 0.5 to 1.0/zm and then decreased up to the
termination of electrolysis. It was suggested that this characteristic initial shape of
the stress curves might be attributed to the evolution and diffusion of hydrogen at
the substrate-deposit interface. Cracking and spalling occurred in all deposits once
the peak stresses had been reached. The stresses in the deposits were lower on electro-
polished Cu and steel than on brass and Ni substrates. Various addition agents
were tested which produced a reduction in stress without deterioration of the deposit.
The stress characteristics and crack patterns found in the deposits were similar
to those found in Cr deposits. It was suggested that if cracking problems continue,
the development of a two-layer coating system such as that used with 'duplex' Cr
deposits might be necessary.
In 1970, a slightly modified version of their earlier bath 37 was patented 39.
The main difference between the two baths was the substitution of hexamine or
formaldehyde in the later bath a9 for ammonium sulphate. The deposits obtained
after 5 minutes plating were 4 to 5 btm thick, free from basic inclusions, and
resistant to 5 ~ H 2SO4 and 3 ~ NaCI over a period of time. Their composition was
stated as 3 0 ~ Cr, 10~ Ni and 60~o Fe.
An extensive investigation by Kudryavtsev, Smirnova and Volkova 4° was
reported in which they claimed successful deposition from a sulphate-glycine bath,
their particular interest, however, being in the deposition of an alloy of the Cr
18~, Ni 9 ~ type. Smooth, bright, compact deposits of 2-3/~m were obtained,
followed by dull and matte layers of up to 50 #m, with current efficiencies of 20
to 2 6 ~ . When the coating thickness exceeded 50 btm, however, a dark precipitate
of chromium hydroxide was formed at the edges of the plates. Deposits with a Cr
content greater than 1 8 ~ showed a tendency to crack. This was suggested to be due
to a change in the nature of the internal stresses in the deposit from compressive
to tensile. The microhardness of the deposits increased with their Cr content and
reached 650 kg/mm z in a deposit containing 3 5 ~ Cr, 5 ~ Ni and 6 0 ~ Fe. The
addition of glycine to the electrolyte was reported to increase the buffering capacity
of the electrolyte, to increase the pH for the formation of chromium hydrate and
to increase the thickness of the coatings. Detailed information was given on the
influence of various factors on the deposition process. The mechanism of deposi-

ELECTRODEPOSITIONOF Fe-Cr-Ni ALLOYS 381
tion was studied using cathodic polarisation curves. From the cathodic polarisa-
tion curves it was observed that in the codeposition of the three metals, the deposi-
tion of Cr increased while that of Fe and Ni decreased. This was related to the
potential of hydrogen evolution on the F e - N i - C r alloy being more positive than
on Fe or Ni, thus causing a larger part of the current to be consumed in the evolu-
tion of hydrogen and thereby decreasing the amount of current expended in the
deposition of Fe and Ni. Increase in the glycine concentration in the electrolyte
shifted the overall polarisation curves towards more positive potentials sharply
retarding the discharge of Fe and Cr ions and facilitating theevolution of hydrogen,
with a rapid drop in cathode efficiency. This was explained by the fact that when the
glycine concentration in the electrolyte exceeded the value corresponding to the
formation of a complex cation, the presence of free glycine causes an increase in
the concentration of hydrogen ions at the cathode. This bath was subsequently
reported by Domnikov 41 and later patented 42.
Later these experimenters extended this work in two papers 4a which in-
vestigated the causes of cracking in their alloy deposits. These papers were only
available in the form of abstracts. It was discovered that internal tensile stresses
were generated in deposits with a dense network of fractures formed immediately
after electrolysis. The main cause of cracking and brittle coating formation was
proposed to be the hydrogenation of the deposit, which increased with the Cr
content in the alloy. This was verified by the fact that the amount of hydrogen in
deposits without fracture was three-fold smaller than in deposits which cracked
during electrolysis. Addition of various stress reducing agents to the bath as well as
the superposition of a.c. current on the d.c. current did not result in elimination of
deposit cracking.
A paper 44 was presented by these scientists at an international conference in
Germany in 1968. It discussed all their earlier work 40, 42, 43 and also provided
some additional information. Experiments with rotating disc electrodes showed that
the presence of chloride ion in the electrolyte was required for anode dissolution.
It was also claimed that deposits free from porosity were obtained at thick-
nesses near to 30/~m if crack-free, but the corrosion resistance of these deposits
was found to be poor.
Rotinyan, Zytner and Fedot'ev 45 attempted to improve the quality of their
earlier alloy deposits a4 using lower temperatures. Their previous work 34 had given
coatings with reduced Cr contents but of good quality at 80°C and coatings con-
taining 2 0 ~ Cr of markedly improved quality at lower temperatures. The effect of
aluminium chloride in the bath was studied using polarisation curves, X-ray
analysis and microstructural studies. They obtained high quality bright alloy
deposits showing good adhesion with compositions close to 18/9 Cr-Ni and thick-
nesses of up to 25/tm. Aluminium chloride was found to increase the quality and
Cr content of the deposit at ordinary temperatures, improve throwing power and
increase the current yield. The structure was a solid solution of a-iron type which

382 C. U. CHISHOLM, R, J. G. CARNEGIE
was magnetic. Annealing at 1100°C followed by air quenching produced a stain-

less steel structure in the electroplated alloy. The alloy possessed considerable
wear resistance with a microhardness of 580-600 kg/mm 2 and could be used as a
protective, decorative coating in corrosive atmospheres.
Annealed alloys gave, on testing, similar corrosion resistance to a Cr 18,
Ni 9, Ti-stabilised stainless steel.
The polarisation curves showed that the introduction of A1CIa to the elec-
trolyte displaced all the curves towards more negative potentials. Its addition also
retarded the discharge of hydrogen to a greater extent than the discharge of the
alloy components, thus considerably increasing the current yield.
This bath was subsequently reported by Domnikov 46.
A sulphamic acid bath was employed by Katser, Petrova and Vitkin 47 in
an attempt to reduce internal stresses in deposits. G o o d deposits of up to 25 ~m
were claimed with a current efficiency of 18 to 2 5 ~ . Temperature was found to
have a marked effect on the metal content of the alloy and the current yield. An
increase in temperature caused a rise in the Ni, but a drop in the Cr.
An increase of sulphamic acid from 50 to 250 g/l was reported as giving
higher quality deposits with no metal hydroxides. Domnikov 48 also reported on
this work.
Another paper 49 by these same scientists reported the production of deposits
of satisfactory quality from a sulphamate electrolyte at current efficiencies varying
from 17 to 2 8 ~ . Only an abstract of this work was available. The addition of gly-
cine was reported to give higher quality deposits.
A patent was filed by Kudryavtsev et al. 5o in 1969, covering the deposition of
alloy coatings from a fluoroborate electrolyte containing aluminium chloride.
Deposits up to 30 # m thick were obtained with a current yield of 30 and 5 0 ~ . The
microhardness of the deposits was reported to be 600 k g / m m 2.
Another fluoroborate bath was patented by Chisholm 5t in which 100-500
g/l of iron fluoroborate was added to a basic electrolyte for producing binary
N i - C r alloy deposits. Grey, adherent deposits were reported, with thicknesses
varying from 2.5 to 76 #m. This patent was only available in abstract form and no
other details were given.
A recent report by Firoiu and Ionescu 5~discussed the effects of current density,
temperature and pH on current yield, appearance and composition of electrode-
posited F e - C r - N i alloys obtained from a sulphate-EDTA bath with additions of
boric acid and glycine.
Using the optimum conditions reported on Table 1, deposits 4-5 # m thick,
with good adhesion, were obtained over a range of compositions at current effi-
ciencies of from 14 to 19~. The Cr content of the deposit attained a maximum
while the Fe content reached a minimum at a definite current density. Thereafter
the Cr decreased while the Fe and Ni increased. The total and partial polarisation
curves for the deposition of the alloy were also studied.

The most recent work in this field has been recorded by Chisholm and
Carnegie 5~ in which they investigated three baths, a sulphate-glycine bath based on
that of Kudryavtsev et ai.4o, a chloride--citrate bath based on that of Rotinyan et
al. 45, and a new chloride-EDTA bath.
The first bath differed from that of Kudryavtsev and his co-workers 40 in the
respect that a normal cell utilising platinum anodes was employed rather than a
diaphragm cell with graphite anodes. The electrolytes employed were identical.
Smooth, fine textured, bright deposits showing good adhesion and ductility were
obtained with similar compositions to those claimed by Kudryavtsev et aL 4o,
including the 18~ Cr, 8 ~ Ni stainless steel composition. All the deposits exhibited
microcracking and a spherical nodular growth which resulted in a coarsening of
surface texture. The alloys were satisfactory up to thicknesses of 10 #m but at
greater thicknesses the deposits became highly stressed and cracked.
Cathode current efficiencies did not change significantly with electrolysis
time and remained constant at around 2 0 - 2 2 ~ over the first 30 minutes of deposi-
tion.
A Brightray B alloy anode ( 6 5 ~ Ni 15-20~ Cr, remainder Fe) gave alloy
deposits up to thicknesses of 28/~m before the quality of the deposits deteriorated,
and cathode efficiencies of 19-24~. These results were of practical interest, since
such coatings were obtained directly on mild steel, thus providing a possible
corrosion-resistant coating.
Studies made on the chloride-citrate bath based on the work of Rotinyan
et al. 45 revealed a lack of reproducibility of the results. Wide variations in deposit
compositions were obtained over the narrow range of current densities employed
and although their adhesion and ductility were fairly good, only thin deposits up
to 12.5 #m thick were obtained exhibiting large amounts of microcracking.
The chloride bath containing the sodium salt of EDTA gave fine-textured
deposits showing no pitting, porosity or microcracking. The deposits exhibited a
nodular growth structure on their surface which became more severe with increased
current density.
Soluble anodes of 18~ Cr, 8 ~ Ni steel and Brightray B alloy gave rise to
satisfactory deposits, but a constant deposit composition could not be maintained
owing to differences between the anode and cathode efficiencies.
Pilot plant tests were carried out on a continuous flow plating system. This
system involved continuous circulation of a bulk quantity of electrolyte from a
central reservoir through a cylindrical plating cell.
The sulphate-glycine and chloride-EDTA electrolytes were studied and the
deposits appeared to be affected by the flow pattern of the fluid through the plating
cell.
Tests using very slow electrolyte circulation rates resulted in deposits similar
to those obtained under static conditions in the small-scale tests but no greater
thicknesses of deposit were obtained.

384 C . U . CHISHOLM, R. J. G. CARNEGIE
Initial tests using the chloride-EDTA bath at a very low circulation rate
gave rise to thicker deposits than could be obtained in the static tests. Thicknesses
of about 35 to 40/tm were possible and although the deposits exhibited coarse nodular
surface textures, they were ductile, showed good adhesion to the substrate and, in
general, exhibited no microcracking. The deposits had an average composition of
86~o Fe, 7 ~ Ni and 7~o Cr.
The tests conducted using EDTA in a chloride bath were considered to
show promise for future commercial development since microcracking appeared to
be eliminated in the deposits.
DISCUSSION
The codeposition of chromium with metals of the iron group has always
been difficult owing to the simultaneous discharge of hydrogen as a result of the
low hydrogen overpotential associated with the deposition of chromium and
chromium alloys. The low pH at which chromium hydroxide is formed also limits
the process. These factors make elucidation of the mechanism of the deposition
process difficult. Consequently, no practical commercial process exists today for
the electrodeposition of ternary iron-chromium-nickel alloys despite the many
investigations made into this system, as summarised in Table 1.
Most investigations reported success in obtaining alloy deposition, although
in much of the earlier work s, 9, 1 t the information presented was of a very vague
nature and no information was given on the composition or quality of the deposits
obtained. Several patents have been filed but only two of these 16, 17 were available
in full, giving detailed information on the processes; the remainder were only
available as abstracts 9, 27, ag, 42, 50, 51
The plating baths studied can be divided into two main groups: those based
on hexavalent chromium and those based on trivalent chromium. In the hexa-
valent baths, the chromium was present in the form of chromic acid. Two of the
chromic acid-based bathslO, 11 yielded unsatisfactory deposits but the self-regulat-
ing tetrachromate bath of Saimanova and Drobantseva 32 produced satisfactory
chromium-rich alloy deposits. However, these deposits can hardly be classed as
constituting an iron-chromium-nickel alloy because of their extremely low nickel
content. The tetrachromate electrolyte was used for its high stability in operation,
simplicity in use, and high cathode efficiency.
The trivalent baths were widely studied and gave the most successful results.
These baths were based on sulphates 12, 18, 28, 25, zs, 35-37, 40, 47, 52, 53, sulpha-
mates 49, chlorides 26, 34, 45, 5a and fluoroborates 5°, 51. Although sulphate baths
were the most frequently used, chloride baths 2~, 34, 42, ~z were sometimes preferred
for the advantage of their high electrical conductivity, high efficiency of anodic
dissolution and high limiting current densities for iron and nickel deposition. A
sulphate bath containing sulphamic acid 47 and a sulphamate bath 49 were employed

in attempts to reduce internal stresses in the deposits. Fluoroborates 50, 51 were

used to give increased rates of deposition at fairly high current efficiencies.
Addition agents
The plating solutions generally contained various complexing and addition
agents in addition to the metal salts. The complexing agents used were urea 12,23,2s, 36,
trisodium citrate is, 23, 34, 37, 45, EDTA25, 52, 53, ammonium chloride 26, triethanol-
amineaS, 36, glycine40, 53, sulphamic acid 47 and hydrofluoroboric acid 5°. In
addition to promoting complex formation of the metal ions in the plating baths,
the complexing agents were beneficial from such aspects as promoting bath
stability, favourable buffering properties and improving deposit quality. Since
complexing of metal ions is recognised as a powerful method of bringing the deposi-
tion potentials of metals closer together, it is quite conceivable that this particular
mechanism was partly responsible for codeposition of the three metals in most of
the baths examined.
The most common addition agents employed were boric acid 10, 12, 25,35-37,52,
sodium fluoride TM 23, 37, ammonium sulphate 2s, 37, nickel chloride 2s, gly-
cine37, 49, 52 and aluminium chloride 45, 50
Boric acid served as a buffer and hence had a profound influence on the
useful life of the plating bath. Sodium fluoride generally acted as a stress reliever.
Ammonium sulphate increased the conductivity of the plating solution and im-
proved the quality of the plate. Nickel chloride was reported to activate anode dis-
solution, thus maintaining a consistent electrolyte composition and allowing
prolonged electrolysis. Glycine prevented pitting of the deposits and made the
deposits more uniform and compact. The introduction of aluminium chloride
improved deposit quality and increased current efficiency. Additions of sodium
sulphate, magnesium sulphate and aluminium ammonium sulphate to the sulphate-
citrate bath improved the throwing power, increased the current density range and
gave better quality crackfree deposits.
Machu and Ei-Ghandour tested various organic and inorganic brighteners
and found the most effective ones to be saccharin, pyridine, saccharin plus pyridine
and pyridine plus glucose, citric acid or tartaric acid 14. In all cases where brighten-
ing was effective, cathode efficiencies were decreased.
Thickness of deposits
The main obstacle encountered in most of the researches is the existence of a
limiting thickness of good quality deposits. In many cases, it has been shown that
good quality thin deposits can be obtained but few attempts have been made to
establish conditions for sustained deposition and the build-up of thick deposits.
Generally, this limiting thickness has a value of the order of 6/~m 13, is, 52 or
10-15/zm 26, 34. Exceptions are, however, to be found where satisfactory coatings
of up to 20-25 btm were obtained 45, 47, 53. The tetrachromate bath gave uniform,
Electrodepos. Surface Treat., l (1972/73)

pore-flee and crack-flee deposits up to 40 #m thick 32 while the sulphate-glycine

bath produced compact deposits up to 50#m thick 4°. However, these latter deposits
were smooth and bright in thin layers of 2-3/zm but dull and matte in thicker layers.
The maximum thickness of deposit reported was 100/zm but these deposits ex-
hibited a network of microcracks 2s. Kudryavtsev et al. claimed that deposits could
be obtained up to 50/~m thick and were only cracked if their chromium content
was more than 18~ 4° whereas Chisholm and Carnegie 5z found that deposits could
only be obtained up to 28 btm thick and were always microcracked regardless of their
chromium content 53. Rotinyan et al. obtained deposits of reproducible quality and
composition up to thicknesses of 25 btm without microcracking 45 while Chisholm
and Carnegie claimed a lack of reproducibility in their results and produced
cracked deposits up to only 12.5 #m thick. These contradictions are probably due
to differences in the experimental conditions employed in these researches.
The basic problem, as revealed from an examination of the literature,
appears to be the build-up of internal stresses in the deposits in the early stages of
deposition, leading to deposit embrittlement, microcracking and ultimately loss
of adhesion, spalling and exfoliation of the deposits. In this way, the thicknesses of
good quality deposits have been limited to low values.
However, this problem was solved in one instance by carrying out suitable
heat treatment on the deposits in order to reduce the stresses and improve their
adhesion to the base metal is. After this treatment, the cracked deposits were
reported to become uniform and homogeneous and adhered firmly to the substrate.
Another limitation to the build-up of thick deposits is the low cathode effi-
ciencies at which most of the baths operated. The majority of baths attained
efficiencies which did not exceed 30%. In the chloride 26, ~5 and fluoroborate 5°
baths, high efficiencies of 30 to 40~o and 30 to 5 0 ~ respectively are expected since
these types of electrolyte are well known for their high deposition efficiencies. A
sulphate Is bath gave 45 to 5 0 ~ when operated with soluble anodes.
The problem of low cathode efficiencies was further aggravated by the lower-
ing of efficiency after short deposition times. In one instance the efficiency was
reported to rise with increasing electrolysis time 18.
Internal stresses
Although most of the previous researches were of an extensive and funda-
mental nature, most of them have been restricted to theoretical studies of the
dependence of deposit quality and composition on the plating conditions, and of
the cathode polarisation curves. Few, however, have attempted to extend the exist-
ing work or endeavoured to solve the aforementioned practical problems in an
effort to develop a plating process operating at high current densities and efficien-
cies, which would give thick, crack-free deposits of good quality. These practical
aspects have, nevertheless, received some attention.
Internal stresses and cracking tendencies in deposits were studied in detail by

three groups of researchers 2°, as, 43. The importance of this particular problem is
emphasised by the fact that many earlier attempts to electroform stainless steel for
structural items ended in failure because the deposits became too highly stressed
and cracked 54. Kalyuzhnaya et al. reported that the most probable cause of stresses
was the occlusion 2° of hydrogen in the deposit and base metal.
Kudryavtsev et al. attributed the main cause of internal stresses and cracking
to the hydrogenation of the deposit, which increased with increase in the chromium
content of the alloy 4a.
In the chloride bath of Takahashi et al., microcracking was ascribed to
the inclusion of minute amounts of oxides in the deposits 26.
Chisholm and Carnegie suggested that the most likely reason for the failure
to sustain good quality deposition over prolonged periods of electrolysis was the
instability of the solid state film on the cathode surface associated with the deposi-
tion of chromium 53. This film may break down after deposition has progressed for
some time and thereafter the current would drive off large amounts of hydrogen
which become absorbed in the deposits, leading to a rapid drop in cathode effi-
ciency and resultant deterioration in deposit quality through the formation of
highly stressed, powdery and cracked deposits.
It was suggested that subsequent heat treatment removes hydrogen absorbed
in deposits 16 thus avoiding hydrogen embrittlement. The addition of many stress
reducing agents and the superimposition of a.c. on the d.c. current were not re-
ported to eliminate deposit cracking, although in most cases the internal stresses
were reduced 20, 38, 45
Aluminium ammonium sulphate was reported 37 as preventing the formation
of cracks in the deposits.
Chisholm and Carnegie 53 considered that the use of the sodium salt of EDTA
in their chloride bath showed promise for future commercial development in that
it ted to alloy deposits showing no microcracking.
Future development
From an examination of the literature, the most successful plating baths in
terms of obtaining thicker alloy deposits of good quality and without microcrack-
ing at good current efficiencies appeared to be the chloride-citrate-aluminium
chloride 45 and chloride-EDTA 53 baths. These two baths, therefore, offer promise
for future commercial development.
Alloy compositions
The compositions produced vary over a wide range despite the fact that the
main objective of many investigations has been to obtain alloy coatings correspond-
ing in composition to 18~ Cr, 8 ~ Ni stainless steel.
Most of the deposits obtained are iron-rich alloys with compositions ap-
proaching those of austenitic stainless steels.

388 c. u. CHISHOLM,R. J. G. CARNEGIE
Deposits were produced with a lower chromium content and higher nickel
content than the 1 8 ~ Cr 8 ~ Ni alloy 34, 53. These lower chromium contents gave a
reduction in hardness and their corrosion and heat-resistant properties compared
with those of the 1 8 ~ Cr 8 ~ Ni compositions. Improved mechanical properties,
in the form of strength and ductility, were obtained with the higher nickel contents.
Alloys were also produced with higher chromium contents than those of the
18~o Cr 8 ~ Ni alloys. These deposits possessed improved corrosion resistant
properties and increased hardness. However, one of the adverse effects of the high
chromium content was the increase in the brittleness of the deposits.
Alloys with high chromium and iron and low nickel contents were also
obtained 5z giving considerably improved corrosion and heat resistance and in-
creased hardness but also a tendency to embrittlement and cracking.
It would seem from the work completed that there is need for an investiga-
tion into the properties of the deposits. Although some work has been done on
testing of deposits, it is mainly in the fields of corrosion resistance and hardness
and information on the engineering properties is severely limited.
Corrosion resistance o f alloys

Considerable information was presented on the corrosion resistance of
deposits. Corrosion tests were conducted in dilute solutions of sulphuric acid,
hydrochloric acid, nitric acid, sodium chloride and copper sulphate. Tests were also
carried out in a salt-spray chamber.
It was found that thin coatings of 6/~m possessed higher corrosion resistance
in dilute sulphuric acid solution than 20-25/zm thick coatings 18. The latter coatings
separated from the basis metal owing to attack on the base occurring through the
fine cracks in the deposits.
Heat treatment of the deposits considerably increased the corrosion resis-
tance coatings and improved their protective properties z6, 45. After heat treatment
the corrosion resistance of the deposit approached that of 18°/O Cr, 9% Ni, Ti-
stabilised stainless steel in the same corrosive media 45.
The chromium content of the deposit was found to be an important con-
sideration by Gowri et al. 37 since an alloy coating containing 30-35% Cr and
8-10°~ Ni exhibited satisfactory corrosion resistance compared with lower chro-
mium contents.
The tetrachromate bath 32 gave 20/zm thick deposits on steel substrates which
satisfactorily withstood corrosion after 300 hours in salt-spray tests. This raises the
possibility of direct deposition of an alloy on steel as a protective/decorative coat-
ing and could obviate the need for undercoats of copper and nickel.
Microhardness studies
The hardness attained a minimum value of 322 kg/mm z for deposits obtained
from the sulphate-citrate bath 37 and a maximum of 712 kg/mm z for deposits from

the tetrachromate bath 32. Sheet steel of 18 ° / C r , 9 ~ Ni, Ti grade is reported to have
a hardness value of 321 kg/mm 2 18. The exceptionally good hardness possessed by
the latter deposits 3z was due to the high chromium content. Microhardness
increased with increasing chromium content of deposits reaching 650 kg/mm z for
an alloy containing 3 5 ~ Cr and 5 ~ Ni 4°.
Throwing power
Three attempts were made to examine throwing power 30, 37, 45. This prop-
erty becomes a very important consideration when plating objects of complex
shape and has obviously received little study.
Mutafchiev and Marinkov 3° devised a method to evaluate the throwing
power and obtained values of 26.2~ for their bath.
Addition of sodium, magnesium or aluminium ammonium sulphates to the
sulphate-citrate bath 37 and of aluminium chloride to the chloride-citrate bath 45
was found to improve the throwing power.
Structure of alloys
Deposits from the tetrachromate bath were reported to have a micro-
crystalline structure 32.
X-Ray diffraction analysis showed that the deposits consisted of a solid
solution over the entire composition range 34, 45. In the deposited condition, the
alloy was a solid solution of the three component metals with a body-centred lattice
of the a-iron type. After suitable heat treatment the deposits attained the structure
of an austenitic 18~ Cr, 8~o Ni stainless steel. The a-iron phase structure is what
could be predicted for an electrodeposited alloy as opposed to a thermally-formed
alloy a-iron phase.
Microscopic examination of the deposits from the sulphate-glycine and
chloride-EDTA baths of Chisholm and Carnegie 53 revealed a spherical nodular
growth structure on the deposit surfaces which became more pronounced with
increase in electrolysis time and current density 5a. This suggested a growth struc-
ture of the field-oriented type where the deposit grows outwards from the cathode
surface in the direction of current flow.
Deposition mechanisms
An examination of the trends obtained in the literature revealed that the
majority of the baths studied were controlled by complex plating mechanisms which
appear to be a compromise between normal and abnormal codeposition systems.
The deposition of the metals iron and chromium in the ternary alloy system follows
the trends of normal alloy deposition while nickel deposits by an abnormal plating
mechanism.
Consequently, an accurate assessment of any particular system is difficult
and can only be based on which plating mechanism predominates according to

390 C. U. CHISHOLM, R. J. G. CARNEGIE
the trends observed between the alloy composition structure and bath para-
meters.
This approach has been used to identify to which plating system a particular
bath belonged. Takahashi et al. 28 classified their deposition process as a regular
alloy plating system controlled by the diffusion of iron and nickel ions 26. A critical
examination of the results of the investigations of most of the plating baths suggests
that this mechanism is predominant.
Exceptions to this behaviour do exist. The chloride-citrate 34 and sulphate-
EDTA 5z baths exhibited a predominant tendency towards irregular codeposition
which is controlled, not simply by diffusion, but by the effect of the cathode poten-
tials.
Abnormal codeposition was shown by the tetrachromate bath where the
less noble metal chromium was deposited preferentially with respect to the more
noble metals iron and nickel.
The chloride-EDTA bath, investigated by Chisholm and Carnegie 53, gave
an indication that chromium acts as a reluctant metal during its codeposition and
was deposited in association with some form of solid state film on the cathode
surface. This plating mechanism appeared to be of the abnormal type associated
with induced codeposition where the more noble metals iron and/or nickel induce
deposition of the reluctant metal chromium. In addition, thin deposits were obtained
with a fairly high reluctant metal, chromium present, such as are associated with
induced codeposition.
Examination of the literature shows that very few attempts have been made
to analyse the possible reasons for codeposition of the three metals, in particular,
the mechanisms responsible for bringing together the deposition potentials and
promoting codeposition. Complex formation is known to be a very effective method
of bringing the deposition potentials of meta|s closer together and it is quite feasible
that this particular mechanism was partly responsible for alloy deposition in most
of the baths studied. If the complexing agents are to be effective, however, their
action would have to be predominantly on the more noble metals iron and
nickel, since it is known that the complexing of a metal ion normally causes the
deposition potential of the metal to shift in an electronegative direction. Their
action was reported to be specific to only iron and nickel in some investiga-
tions18, 34, 37
Potentiostatic studies showed that during simultaneous deposition of the
three metals, the discharge of chromium was facilitated while that of nickel and
iron was retarded relative to their individual deposition 21, 40
Film mechanisms were proposed as being responsible for alloy deposition
in two investigations. Machu and El Ghandour claimed that successful codeposi-
tion in their sulphate-urea bath 12 was due to a chromium hydroxide diaphragm
formed on the cathode surface in solutions containing urea, the presence of which
was necessary for the deposition of chromium in metallic form.

Chisholm and Carnegie 5a postulated that chromium acts as a reluctant

metal during its codeposition with iron and nickel from their chloride-EDTA bath
and was deposited in association with some form of solid state film on the cathode
surface 53. The film mechanism suggested seems quite feasible since this type of
mechanism is generally accepted for the deposition of chromium and has also
been proposed for the deposition of chromium alloys.
Green and violet modifications of chromium salts

It is a known fact that the hydrated salts of chromium can exist as differently
coloured modifications. Thus the sulphate and chloride salts of chromium can
occur in both violet and green modifications. Studies showed that the violet
modification of chromium was the most widely preferred in the sulphate baths
whereas the green modification was reported for the chloride baths. The reasons
for these preferences were not always given. It was reported for the sulphate-
citrate bath 18 that cathode efficiencies were considerably higher using solutions
of the violet rather than the green modification. This was confirmed through a study
of the cathode polarisation curves which revealed that the alloy was electro-
deposited from solutions of the violet chromium salt at more positive potentials
than from solutions of the green salt ~1.
In violet solutions chromium was suggested as being a complex hydrated
ion. The green form was alleged to be a more mobile hexaquo ion which was hydrol-
ysed to a more stable and tightly bound complex chromium ion. Hence the green
form of chromium sulphate was more difficult to reduce than the violet form.
However, conflicting ideas were reported for the chloride bath where the
green form gave rise to easier reductions.
General conclusions
1. Satisfactory codeposition of ternary alloys of iron, chromium and nickel
can be obtained from a wide range of plating baths.
2. A wide range of deposit compositions, including the 18% Cr, 8% Ni
stainless steel composition, can be produced.
3. In general, only thin deposits of good quality could be produced, the
limiting factor being failure to sustain deposition regardless of the bath type.
4. Stressing and resultant deterioration of deposits appear to be associated
with the absorption and/or adsorption of gases, in particular hydrogen, into the
deposits and/or the base metal.
5. The development of functional deposits will involve elimination of internal
stresses and microcracking.
6. Microcracked deposits could be considered as functional deposits in con-
junction with underlayers of nickel and/or copper to obtain corrosion resistance.
7. Many of the deposits possess considerable wear resistance and could
therefore be developed as protective coatings on softer substrate materials.

392 c . u . CHISHOLM, R. J. G. CARNEGIE
8. Th e experimental results confirm the need for future studies towards the
d e v e l o p m e n t o f sustained deposition.
9. Certain c o m p l e x i n g agents offer promise for future c o m m e r c i a l develop-
ment by giving rise to thicker deposits showing no microcracking.
ACKNOWLEDGEMENTS
The authors wish to express their thanks to the G o v e r n o r s o f D u n d e e

College o f T e c h n o l o g y and R o b e r t G o r d o n ' s Institute o f T e c h n o l o g y for research
facilities provided.
Dr. C h i s h o l m wishes to express his thanks for bibliography research provided
by the staff o f the Library in R o b e r t G o r d o n ' s Institute o f Technology.
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19 L. Domnikov, Metal Finishing, 62 (1964) 61.
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21 P. F. Kalyuzhnaya, K. N. Pimenova and Z. P. Gavrilova, Ukr. Khim. Zh., 30 (1964) 1161.
22 K. N. Pimenova and P. F. Kalyuzhnaya, Zh. Prikl. Khim., 43 (1970) 2105; Chem. Abs., 73
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L¥1ectrod~position d'alliages ternaires f e r - c h r o m e - n i c k e l - Etude critique

Les propri6t6s potentielles de d6p6ts minces ou 6pais en alliages n i c k e l -
c h r o m e - f e r sont discute6s. On 6tudie la d6position ~t partir des bains consid6rfs et
c o m p a r a i s o n des r6sultats, et le r61e des agents d ' a d d i t i o n dans les diff6rents bains
et r a p p o r t s de ces agents avec la c o m p o s i t i o n et la qualit6 du d6p6t. D a n s t o u s l e s
bains, c'est l'6paisseur qui constitue le facteur limitatif critique. A partir des princi-
paux bains, il est possible d ' o b t e n i r une g a m m e 6tendue dans la c o m p o s i t i o n des
alliages. Les alliages les mieux r6ussis sont examin6s du p o i n t de vue r6sistance ~. la
corrosion, micro-duret~ et structure. On a 6tudi~ les diff6rents m~canismes de d6po-
sition, d o n t le principal est la f o r m a t i o n de films sur la cathode. D a n s t o u s l e s bains, le

394 C. U. CHISHOLM,R. J. G. CARNEGIE
facteur |imitatif est l'impossibilit6 de maintenir le processus de d~position, facteur

qui est associ6 h la dft6rioration du d6p6t due ~ des efforts internes et h l'absorp-
tion/adsorption de gaz. Les alliages minces obtenus ~ partir des bains 6tudi6s
pourraient dans certains cas avoir une valeur industrielle consid6rable, mais ils
n6cessitent encore d'autres 6tudes.
Die elektrolytische Abscheidung terndrer Eisen-Chrom-Nickel-Legierungen - Eine

kritische Ubersicht
Die wesentlichsten Eigenschaften diinner und dicker Abscheidungen aus
Eisen-Chrom-Nickel-Legierungen werden diskutiert unter besonderer Bertick-
sichtigung von verschiedenen Zusatzmitteln zu den Elektrolyten, durch die die
Anteile an Legierungskomponenten in der Abscheidung bestimmt und die Eigen-
schaften der Niederschl~ige beeinfluBt werden. Aus den meisten der untersuchten
Elektrolyte sind Legierungsabscheidungen innerhalb breiter Bereiche m6glich.
Korrosionswiderstand, Mikroh~irte und Struktur wurden bestimmt. Die erreich-
bare Schichtdicke ist das den ProzeB limitierende Kriterium. Bei der Untersuchung
der Abscheidungsmechanismen stellte sich heraus, dab der Kathodenfilm fiJr
diese von allergr61~ter Bedeutung ist. Es ist sehr problematisch, den dtinnen
Legierungsniederschlag st~irker auszubilden und dicker aufwachsen zu lassen. Dies
steht in Zusammenhang mit hohen inneren Spannungen in der Abscheidung sowie
mit Absorption/Adsorption yon Gasen. Die nur sehr diinnen Schichten, die aus
den untersuchten Elektrolyten resultieren, haben fiir gewisse Bedarfsf~ille bereits
industrielle Bedeutung erlangt, das Verfahren bedarf jedoch noch eingehenderer
Untersuchungen.

The Electrodeposition of Ternary Fe-Cr-Ni Alloys

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Electrodeposition and Surface Treatment 367

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The potential properties of thin and thick deposits of nickel-chromium-

In this highly advanced technological age, man is continually striving to

* R6sum6 en fran~;ais b. la fin de l'article. Deutsche Zusammenfassung am SchluB des Artikels.

Electrodepos. Surface Treat., 1 (1972/73)

Electrodepos. Surface Treat., 1 (1972/73)

severe service conditions and find similar applications up to moderate temperatures