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Zinc alloy plating - General Considerations

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Zinc Alloy Plating –
General Considerations
By B. Chatterjee
The technology of zinc alloy plating is reviewed which includes both the early
work and current state of affairs. A comparative study of the various zinc alloy
plating systems is presented in terms of mechanism of deposition, corrosion
behaviour and susceptibility to hydrogen embrittlement.

1 Introduction trolytes has been one obvious progress in the main

stream of surface finishing [1–7]. This approach
There has been an ongoing activity in the zinc plat-
was pursued, mainly because the open-circuit poten-
ing technology to meet the increasing demand of
tial of zinc is not only more electronegative than
customers, particularly the automobile industry as
steel but also cadmium [2, 7]. Any tendency for the
well as the aerospace and fastener fields among others,
steel to corrode is counteracted by the flow of elec-
for higher standards of performance in corrosive
trons from the corroding zinc to the steel surface
atmosphere. The stimulus has been to develop the
(cathodic protection). As a result, zinc would be
technology to achieve higher levels of cost-effective
sufficiently sacrificial to a steel substrate to undergo
productivity with better quality.
preferential corrosion like cadmium, to protect the
In the past, electroplated cadmium played an impor- functional steel components. The life of zinc elec-
tant role as a functional coating in many branches trodeposit, and hence the substrate can be further
of industry, and is particularly known as an excel- improved by following the plating operation with
lent corrosion resistant finish for steel by providing various chemical treatments producing conversion
sacrificial protection and other desirable physical coatings which slow down the effect of corrosive
characteristics. However, the high degree of toxic- atmosphere.
ity and carcinogenic nature of cadmium metal and However, a drawback of zinc plating has been its
its compounds along with the consequent damage corrosion products, which are voluminous and can
to the environment have forced the users to look for cause seizure and wedging of parts, such as fasten-
alternative coatings. In fact, many countries are now ers. Furthermore, kinetics of galvanic corrosion of
prohibiting the use of cadmium, or even the import zinc is faster i.e. zinc is consumed more rapidly
of goods containing cadmium-plated parts. A fur- than cadmium under corrosive conditions. As a
ther drawback has been the use of cyanide baths for result, zinc plating in order to be effective, needs
cadmium plating which is undesirable from a health to be relatively thick and thus becoming expensive.
and safety viewpoint. Also, scarcity and cost of cad- Also, the effect of thick plating can cause problems
mium metal at the end of World War II was another during the forming and welding stages of the body
factor in the commercial development of alterna- panels, and may require alterations of dimensions
tive coating. The need for an alternative technol- of relevant components in order to accommodate
ogy was, therefore, sought which would offer the the increased thickness. Taking all these criteria
potentials for eliminating the use of two chemical into consideration and adding the obviously impor-
hazards, namely cadmium and cyanide, so that it tant question of cost, one is left with perhaps one
will be easier to achieve the increasingly stringent competitor to zinc which besides cadmium, might
environmental regulatory compliance. be aluminium. However, aluminium is not easy to
Among the various degrees of successes of a host of apply which militates against it. It is thus apparent
metal finishing treatments for corrosion protection that when factors such as cost, health hazard, effi-
of steel, the development of less toxic and cheaper cacy and ease of application are taken into consid-
zinc plating technology using non-cyanide elec- eration, zinc emerges as an unchallenged leader.
32 Chatterjee: Zinc Alloy Plating – General Considerations

In some environments, the corrosion resistance of deposits start to corrode, there will be less genera-
pure zinc coating as barrier, is not sufficient to pro- tion of voluminous corrosion products compared
vide a long term protection. This problem was over- with zinc.
come by alloying zinc with relatively noble metals, Based on electrochemistry, the corrosion potential
such as cobalt, nickel, iron, manganese, chromium of an alloy is always different from those of the
and tin. With the demise of cadmium, zinc has been constituent alloying elements. Accordingly, alloys
able to make inroads into speciality areas with the of zinc are found to be more passive by being less
introduction of zinc alloy plating to industry. The electrochemically active than pure zinc, and yet suf-
earliest alloy electrodeposits containing a signifi- ficiently electronegative to steel [7–12] to provide the
cant proportion of zinc were those of tin-zinc alloy, necessary anodic protection (Tab. 1). A post plating
typically 10 % tin and 90 % zinc alloy. Despite chemical treatment involving chromate conversion
interest in the high performance zinc systems, there coatings would provide further protection of the
was little development in this field until zinc-iron electrodeposits. It is, however, necessary to point
and zinc-nickel coatings were described as a means out at this juncture that the conventional method
of improving the corrosion resistance of steel body of applying conversion coating involves use of hex-
panels for automotive. Interest was shown for zinc- avalent chromium (Cr6+) ion which is carcinogenic
cobalt electrodeposit with its significantly improved in nature, and therefore, not favoured by many
corrosion resistance on items previously protected organisations. Efforts are thus being made world -
by bright zinc plating. It is worth mentioning here wide to replace hexavalent chromium with non-haz-
that copper-zinc (brass) deposits are valuable coat- ardous trivalent chromium (Cr3+) ion or non-chro-
ings for decorative, protective and bonding applica- mium chemicals.
tions. But because they are not anodic to steel, pro-
tection of steel substrates is not accomplished and Tab. 1: Open-circuit potential in sea water
is thus outside the interest of the present context. (3.5% NaCl) [7–12]
Much of the recent research work on the electro- Metal Potential (mV vs. SCE)
plating processes for zinc alloys was carried out in Zinc –1030 to –1060
Europe and Japan where cadmium was effectively
Cadmium –820
outlawed in the 1970s. The alloying elements suc-
cessfully used with zinc have been mostly the iron Mild steel –610
group metals, namely iron, cobalt, nickel, manga- Aluminium alloys –600 to –850
nese, chromium as well as tin. Except for the tin, Zinc – 0.6% Cobalt –981 to –998
which is typically used to provide an alloy of 70 % Zinc – 12% Nickel –996
tin, and 30 % zinc, most of the alloy deposits con- Zinc – 10 to 30 % Iron –920 to –980
tain between 85 and 99 % zinc.
Zinc – Manganese –920 to –960
The basic reason for plating from an alloy bath is
to produce some desired change in the electrode-
posit, such as corrosion resistance, which can not Increasingly, zinc alloys are finding their way into
be achieved from a pure metal bath. It was thus applications previously held by cadmium, and the
possible to make the electrodeposited pure zinc automotive industry leads the charge in its effort to
coatings more corrosion resistant by co-depositing provide increased service life to various components.
with small amounts of alloying elements such as the As a result, zinc alloy plated components may be
iron-group metals, for longer service life in harsher found in chasis hardware, fuel and brake systems,
environments or to attain a given service life with and heating and air conditioning parts. Engineers
reduced coating thickness. Since alloy deposits are beginning to specify zinc alloy coatings as their
are associated with reduced corrosion rates, there deposit of choice to replace zinc on fasteners, appli-
would be no need to have too thick electrodeposit as ance and bicycle parts, lighting fixtures as well as
required for pure zinc. As a consequence, once such furniture, plumbing and window hardware.
 Chatterjee: Zinc Alloy Plating – General Considerations 33

2 Early work in the deposit making it brittle with cracks develop-

It becomes apparent from a literature survey that ing, resulting in poor corrosion resistance.
most of the development work on zinc alloy plat- The problem was rectified later on by Roehl [18]
ing in the pre 1970s had been centred around alloys who reduced the metal contents of the bath from 60
containing nickel, cobalt, iron or tin [13]. The most to 35 g/L for both zinc and nickel to produce bright
widely investigated zinc alloy plating since the early alloy deposit with around 8 % nickel. The bath
part of 20th century has been, however, the zinc- composition was further modified to produce an
nickel system based upon a number of electrolytes alloy deposit containing 11 % nickel with improved
including the acid chloride, sulphate, sulphamate, corrosion resistance [19]. There had also been some
pyrophosphate baths and an alkaline cyanide bath. limited work in the 1950s and 60s to produce black
The majority of the work is of academic nature electrodeposition of zinc-nickel alloy from a chlo-
without much commercial viability. The formulae ride bath containing thiocyanate [20].
and operating parameters of different electrolytes
The least investigated of all iron group-zinc alloy
since 1940 till 1962 have been reviewed by Brenner
systems has been the zinc-cobalt plating from an
[14] and from 1962 to 1983 by Hall [15].
acid chloride bath [14], and yet it was the only alloy
The various plating systems to provide electrode- besides zinc-nickel, which was being actively mar-
position of zinc alloys with optimum corrosion pro- keted on a worldwide scale for bright plating in
tection to steel, include alloying with several iron those early days [13]. The deposit enhanced corro-
group metals, such as cobalt, nickel and iron using sion protection of the steel work considerably com-
both alkaline non-cyanide and acid baths. It has pared with zinc plating only.
been reported that commercial plating of nickel-
zinc alloy was carried out as early as 1905 using a Scarcity of zinc in the 1950s led to the work on
bimetallic anode system [13] which is likely to be zinc-iron alloy plating that was less thoroughly
soluble anodes of the same alloy to be plated rather studied than the zinc-nickel system. The objective
than a dual anode system of two metals to be plated was to reduce zinc content without sacrificing cor-
using separate rectifiers. The end product was co- rosion resistance. Both chloride and sulphate baths
deposition of nickel in the zinc deposit which could were developed [21], which, however, unfortunately
hardly be termed as an alloy deposit. It seems that required very high current densities (~ 80 A/dm2) to
the very first commercial process for clearly defined provide bright deposit, and was thus never taken up
zinc alloy plating was justifiably achieved in the by the plating industry. Additions of organic chemi-
early 1940s [16]. It involved electrodeposition of cals, such as derivatives of aminopropionic acid
separate layers (4 to 8 µm each) of zinc ad nickel seemed to reduce the high level of current densi-
from individual acid baths, which was subsequently ties to a normal level for producing bright deposit.
thermally diffused at 370 °C to form an alloy. The Such bath has been of academic interest because of
product demonstrated remarkable corrosion pro- apparent difficulty to control the composition.
tection to steel and marketed under the trade name High price and scarcity of cadmium in mid 1940s led
Corronizing. The process, however, failed to gain to the development of tin-zinc plating which pro-
popularity because the facilities required for heat vided improved solderability with elimination of
treatment of plated components, besides being not cadmium. Corrosion resistance of the deposit was
easily available, were expensive to install. better than zinc or cadmium, but required a mini-
Nevertheless, the potential of zinc-nickel deposits mum plating thickness ~ 12 µm. Typical formula-
to provide outstanding corrosion protection was tions of the plating bath included cyanide which
recognised, and one of the first patents was granted was to be operated at 65 °C for better cathode effi-
to Schantz [17] in 1947 for electrodeposition of ciency [14]. There has not been any commercial
zinc-nickel alloy from a mixed chloride-sulphate development of the technology for a long time due
bath. The bath did not, however, attract any com- to the unfavourable economics of the alloy and the
mercial interest because of the high internal stress use of cyanide.
34 Chatterjee: Zinc Alloy Plating – General Considerations

3 Current development times suggests that zinc-iron deposits (from a non-

Electrodeposited zinc alloy coatings introduced in cyanide alkaline bath) containing 0.3 to 1.0 % iron is
the last twenty years to improve corrosion resist- capable of providing high level of corrosion protec-
ance of zinc, have achieved an important position in tion. Zinc alloy electrodeposits formed with man-
the protection of ferrous substrate. Since the middle ganese (up to 50 %), tin (60 to 80 %) and chromium
of 1980s, there has been a large market growth for (4 to 8 %) are mostly under development with some
zinc alloy plating, particularly in the automotive commercial availability, and thus holdout the pros-
sector where the need for improved anti-corrosion pect of a wider range of zinc-base electrodepositions
warranties of automotive parts became progres- being available to the designer in future. Table 2 sum-
sively more demanding from the customers. The marises the various zinc alloy electrodeposits men-
trend continued from early days to develop less haz- tioned above that would offer solutions to problems
ardous deposit alternative to cadmium, and plating with respect to environmental safety and economic
baths which do not contain cyanide. viability. In Table 3, typical process parameters of
Both acid and alkaline baths have been developed
for zinc alloy plating. Although commercial electro- Tab. 2: Composition ranges
lytes are available in both acid and alkaline condi- of zinc alloy deposit
tions for electroplating zinc-nickel and zinc-cobalt Alloy element Alloy content (wt %) 
alloys, it is only the alkaline process developed for   Acid bath Alkaline bath
zinc-iron electroplating. As with conventional zinc, Cobalt 0.3–1.2 0.3–1.2
the acid processes exhibit higher cathode efficiency, Nickel 6.0–15.0 4.0–7.0
but because of this, throwing power i.e. distribution Iron 10 0–25 0 0.3–1.0
of plated metal is poor. Alkaline processes tend to Manganese Up to 50.0 –
have lower cathode efficiency, but in return provide
Chromium 4.0–8.0 –
very good plate distribution over the normal current
Tin – 60–80 (alkaline/
density range. The acid processes have the added neutral bath)
advantage of being able to plate over hardened
steels and cast iron.
There is still controversy regarding the comparable several zinc alloy baths are presented along with
merits of different alloying baths and the optimum the alloy contents of the electrodeposits [22–24]. A
concentrations of metals required in the bath for number of organisations, such as American Society
improvements in corrosion resistance of electrode- for Testing Materials (ASTM) and Society of Auto-
posits without incurring too high a cost penalty. The motive Engineers (SAE) have defined compositional
optimum level of protection for zinc-nickel alloys limits of various zinc alloy electrodeposits [22]. For
is reported for alloy deposits containing up to about example, ASTM B840, B841 and B842: 1994 spec-
15 wt.% nickel. Commercial electroplating solu- ify standards for zinc-cobalt, zinc-nickel and zinc-
tions marketed in the U.K, generally provide iron alloy electrodeposits respectively. Also, there
between 6 and 15 wt.% nickel in the deposits. With are companies, such as General Motors [25], Ford
regard to the zinc-cobalt alloys, the optimum cobalt [26], Chrysler [27] and Boeing [28] who publish
concentration is thought to be in the range 4 to 8 wt.%. their own specifications for zinc alloy deposits.
However, for commercial reasons, the level of cobalt Many factors, such as bath composition, ease of
generally used in the electrodeposit has been kept at operation, cost and actual performance in corrosive
a lower level around 0.3 to 1.2 wt% Cobalt. atmospheres, influence the selection of a particular
The zinc-iron alloy baths were investigated in the alloy deposit for a given application. Plating proc-
1950s, initially to develop similar corrosion resist- esses can be both acid and alkaline because each type
ance as zinc, but requiring less zinc. In Japan, earlier can have certain advantages. For example, alkaline
commercial solutions contained 10 to 25 wt% iron baths of zinc-iron and zinc-cobalt provide excellent
using acid bath. Published information in recent distribution of plating thickness i.e. good covering
 Chatterjee: Zinc Alloy Plating – General Considerations 35

Tab. 3: Typical process parametrs for various commercial zinc alloy plating baths [22-24]
Basic composition of bath  pH Temp. Plating Typical alloy
(°C) efficiency content of elec-
(%) troplate (wt.%)
Zinc Alloying metal Major chemicals    
Acid bath (g/l) (g/l) (g/l)
Zn - Ni 33 17–20.6 (Ni) 231 (NH4Cl) 5.5–5.9 32–43 90–95 6–15
Zn - Co 25–38 5.6–8.0 (Co) 112–156 NH4Cl 4.8–5.3 32–43 95–100 0.3–1.2
15.6–18.7 Boric acid
Alkaline bath              
Zn - Ni 5–10 0.6–1.5 (Ni) 100 NaOH – 21–27 30–50 4–7
4 Soda ash
Zn - Co 7.5–10 0.03–0.06 (Co) 100 NaOH   21–32 50–80 0.3–1.2
4 Soda ash
Zn - Fe 10 0.08 (Fe) 100 NaOH – 21–29 50–80 0.3–1.0
4 Soda ash

power, but are less efficient than their correspond- in the automotive and aerospace industries is pre-
ing acid baths where the reverse is true. Acid baths sented later on.
are also easier to use when the parts are made of The market shares for the individual zinc alloy vary
cast iron or heat-treated steel [22, 29]. However, greatly throughout the world. It is apparent in the
independent of which alloy bath is used, an analy- global market that the present trend in the industry
sis of cost against performance shows that although is to go for zinc-nickel system because of its better
the zinc alloy electrodeposits tend to outperform corrosion resistance performance than other zinc
zinc deposit, the materials and processing costs are alloys, in spite of greater difficulty in processing
higher. It is thus important to decide which applica- and control, and analytical procedures. It is notice-
tions need the superior finish. Also, the electrode able that despite much of the original work on zinc-
potential of alkaline zinc alloy is normally close to nickel system was carried out and patented by the
that of aluminium which makes these systems attrac- US steel companies, commercial development of the
tive for use in light body cars by minimising galvanic technology was taken up considerably by the Japa-
corrosion. The appearance of some surfaces where nese industry. In Japan where the original development
the alloy deposits had undergone post-plating con- work on industrial processes for coating automotive
version coating, such as chromate passivation, could body coil with zinc alloys was carried out, zinc-
show interference colours which may not be accept- cobalt alloy used to have about 65 % shares which
able where styling is paramount. is gradually being replaced more by zinc-nickel and
The demand for zinc alloy deposits mostly comes to some extent zinc-iron alloy deposit favoured by
from the automobile industry which was estimated the automotive manufacturers. The earliest system
[22] to account for about 75 % of the global market, introduced into Europe was zinc-cobalt deposit from
while it is around 20 % from aerospace sector – the acid baths as an alternative to conventional zinc plat-
remaining 5 % arising from miscellaneous applica- ing. This system had been closely followed by the
tions including construction [30, 31], timber [32] and ammonium chloride based zinc-nickel process [34].
tyre industries [33] and others [34] such as window The most recent addition to the range of processes
fittings, ski bindings, lock parts, central heating commercially available has been the alkaline based
tubes, electrical fittings etc. A brief discussion on zinc alloy deposits. In Sweden where the use of nickel
the applications of zinc and zinc alloy eletrodeposits is banned for health and environmental reasons,
36 Chatterjee: Zinc Alloy Plating – General Considerations

zinc-iron plating is preferred to zinc-nickel. The Renault because of their concern about allergy in
zinc-manganese system is receiving considerable using alloys containing nickel. A host of compa-
attention mostly at the research stage, and shows nies, namely Fiat, Peugeot, Citroen, Volkswagen
promise of even better protection. In addition, man- and BMW use conventional zinc plating because of
ganese is considered to be environmentally harm- the policy decisions based on their own investiga-
less. In the electronics industry there has been a great tions on cost and health aspects.
deal of interest in tin-zinc alloy, which is solderable
and is considered at least as a partial replacement Many automotive companies define their own spec-
of cadmium. ifications for the alloy deposits, but keep the docu-
ments for internal use only. However, there are sev-
3.1 Automotive industry eral major manufacturers in the US as mentioned
Zinc alloy electrodeposits are used more frequently earlier, namely General Motors, Ford, Chrysler and
by the automotive industry in the last decade than Boeing who publish their own specifications for zinc
ever before because of the improved corrosion pro- alloy deposits along with the expected correspond-
tection provided by the alloys on a wide range of ing corrosion resistance results on salt spray tests
steel components, such as brake callipers, fasten- following ASTM B 117 (Tab. 4) (equivalent meth-
ers, door mechanisms, fuel injection parts etc. It is ods are BS 7479: 1991 and ISO 9227: 1990). Cor-
estimated that about 80 % of the use of zinc alloy rosion protection to white corrosion is a measure of
plating in Europe are in the automotive industry. protection afforded by the passivate film, which in
Alloy plating is mostly used on sheet steel where turn will affect protection of steel substrate to red
the deposit provides a corrosion resistant base for rust. It appears that while General Motors refers to
paints. Most European automotive manufacturers white corrosion, Ford considers red rust conditions
now use pre-coated coil for some parts of the car only. Chrysler, on the other hand, refers to both
bodies, which in some cases can be up to about 70 % types of corrosion. None of the specifications, how-
of the weight of the car bodies [35, 36]. A survey ever, stipulates the tolerance of corrosion i.e. how
published in 1996 [35] provides a guideline on the much corrosion is considered to be a failure. Nev-
level of acceptance by the various automotive manu- ertheless, it is evident from Table 4 that corrosion
facturers of steel coils electroplated with zinc or zinc resistance of any zinc alloy deposit is superior to
alloys. It is apparent that there has been an increasing zinc plating, and zinc-nickel systems amongst the
use of zinc-nickel alloy deposits by Opel/Vauxhall, alloys are capable of providing exceptional resist-
Nissan and Mercedes Benz, while both zinc and ance to salt environments. However, despite high
zinc-iron deposits are being chosen by Volvo and corrosion resistance, the electrodeposition pro-

Tab. 4: Typical results on corrosion resistance of zinc and zinc alloy

deposits (8 µm thick – chromated to yellow passivation) in neutral salt
spray (5 % NaCl) tests as per ASTM B117 method [22]

Type of deposit Hours to white corrosion* Hours to red rust*

General Motors Chrysler Chrysler Ford
Zinc-cobalt 168 140–200 400–480 480
Zinc-nickel (acid) 240 300–400 1000 + 768
Zinc-nickel (alkali) 240 240–300 1000 + 768
Zinc-iron 240 – – –
Zinc-tin 96 72 400 408
Zinc 60–120 [22]   160–250 [22]  
* Zinc oxide and iron oxide are the corrosion products of white corrosion and red rust respectively
 Chatterjee: Zinc Alloy Plating – General Considerations 37

cesses for zinc-nickel alloys requires more involved the corrosion product layer on either alloy deposit
effluent treatment and also is more expensive than was different from that on zinc alone, and was tena-
zinc-cobalt or zinc-iron systems. cious and non-voluminous in nature.
It is important that the coatings should have accept-
3.2 Aerospace industry able frictional properties, particularly on compo-
Cadmium plating is widely used on aircraft for nents such as bolts and any threaded items for the
corrosion protection of steel airframe parts and aircraft [2, 7]. This is due to the fact that a large
fasteners. The toxicological problems of cadmium amount of torque applied in tightening bolts, is ex-
and the use of cyanide baths prompted the plating pended in overcoming frictional constraints. Elec-
industry to seek alternative methods of coating steel troplated cadmium is characterised by self-lubricat-
substrate. It is, however, worth mentioning that ing properties with low coefficient of friction and
except for some of the aircraft industry, cadmium is satisfactory torque-tension behaviour. In compari-
now virtually excluded everywhere. This is mainly son, assessment of lubricity of both zinc-nickel and
because a few manufacturers of aircrafts have zinc-cobalt alloys suggests conflicting results show-
threatened the legislations, arguing that if cadmium ing similar [37] or inferior quality [2, 7, 22, 38].
is not allowed to be used, they would not be liable At Rolls Royce where cadmium plating of fasteners
for any accident. Nevertheless, a range of commer- is apparently replaced by zinc-cobalt alloy plating,
cially available processes has been assessed by the and the lubricity problem is overcome by applying
aerospace industry [2, 4, 7]. An important criterion a lubricant lacquer topcoat [35].
is that the coating should provide sacrificial protec- It is worth mentioning that the Boeing Corporation
tion of the steel substrate which would be exposed has reportedly developed a zinc alloy plating system
if the coating was breached. Electrodeposits of zinc Corroban which is a zinc-nickel alloy (SAE 2417
and zinc alloys appear to offer, at the present time, E: 1993) containing an additive (BOE-NIZ LHE)
the closest alternative to both cadmium plating and that would have created an open grain structure in
use of cyanide bath. the deposit allowing hydrogen gas to diffuse out
However, use of pure zinc electrodeposit suffers easily, resulting in low hydrogen embrittling prop-
from several drawbacks as mentioned earlier, includ- erty [4]. Lesser degree of hydrogen embrittlement
ing voluminous corrosion products during sacrifi- problem of steel is also reported to be associated
cial protection if the plating is damaged, causing when electroplated with zinc-nickel alloy compared
seizure and wedging of fasteners. Furthermore, the with cadmium plating [39]. A mechanism of an
rate of galvanic corrosion of plating with respect interlayer formation of nickel with a low hydrogen
to steel can be very rapid, resulting in short-lived diffusivity beneath the zinc-nickel alloy deposit, has
protection of steel. Also, the highly electronega- been suggested to act as a barrier to hydrogen uptake,
tive nature of zinc relative to the typical aerospace and hence low hydrogen embrittlement property.
aluminium alloys, such as BS 1474: 1987: 2014 - T6,
would make zinc least galvanically compatible with 4 Mechanism of zinc alloy electrodeposition
them. In comparison, zinc alloys, such as zinc- Electroplating of binary alloys from an electrolytic
nickel and zinc-cobalt are electrochemically less bath containing two types of metal ions of different
active than zinc, and thus become more compatible electrochemical nobility would result in preferen-
with aluminium alloys (Tab. 1). In fact, zinc-nickel tial deposition of the more noble metal ion. This
alloy is expected to be by far the better of the two behaviour of normal deposition is expected from
zinc alloys and is even claimed to be more com- thermodynamic considerations, namely Nernst
patible than cadmium [2]. Both alloys, however, equation, of the ions involved. However, a reverse
exhibit superior corrosion resistance and sacrificial unexpected situation prevails when a plating bath
protection than zinc, along with improved barrier is used containing zinc and any of the more noble
properties due to the beneficial effects of alloying iron-group metals such as iron, cobalt or nickel,
elements. It has also been reported that the nature of whereby the less noble metal ion, namely zinc is
38 Chatterjee: Zinc Alloy Plating – General Considerations

preferentially deposited at a suitable range of deposition of noble metals occurs. However, a rise
cathodic current densities. Such a phenomenon is in pH at the cathode surface is normally expected to
described as anomalous codeposition. There have follow hydrogen evolution during plating [39, 49,
been diverse opinions and models suggested in the 55–60] due to the reduction of hydrogen ions and
literature to explain anomalous deposition. A brief dissolved oxygen, and the migration of hydroxyl
critical review of the various mechanisms including ions in the solution. Around pH 5 or over [10, 39,
an up to date survey of the literature is presented 55–57], basic compounds of zinc including hydrox-
next for general applications. ide precipitate on the cathode masking the surface
Historically, the phenomenon of anomalous co- from the electrolyte, and thereby retarding elec-
deposition of alloys was first noted by Foerster [40] trochemical reduction of the expected more noble
in 1897, which was again observed by Schoch and metal ions. The net result is that although zinc is
Hirsch [41] at the turn of the century. In 1920s, more active i.e. more electronegative than the iron-
Glasstone et.al. [42–44] in their work on the elec- group metals, it is deposited preferentially by a
trodeposition of zinc-nickel alloys suggested that subsequent solid state chemical reduction of zinc
nickel would deposit via a less noble metastable compounds such as hydroxide.
intermediate form. The metastable phase would Raub [61] suggested that the reduction of zinc
normally convert instantaneously to nickel, except hydroxide was thermodynamically more plausible
in the presence of zinc cation which was believed than direct discharge of cation; although later on,
to have suppressed such conversion. However, no Fukushima et. al. [60] established that the equi-
experimental evidence of metastable phase for nickel librium potentials for direct cation discharge and
had been put forward. zinc hydroxide reduction were thermodynamically
With interest still continued on zinc-nickel system, identical at the critical pH for zinc precipitation. It
Lustman [45] in the 1940s proposed that the anom- was concluded that no additional overpotential was
alous deposition was related to the stabilities of required for zinc hydroxide reduction. Thus the
various solid solution phases of zinc-nickel alloy, precipitation of zinc hydroxide not only suppresses
namely an α-phase at low and γ-phase at high cur- deposition of noble metals, such as nickel, but may
rent densities respectively. It was expected that nickel also act as an intermediate stage for the electrodepo-
deposition was unlikely to dominate in a narrow sition of zinc. In 1963, Brenner [14] summarised
transient range between low and high current densi- the most plausible hypotheses advanced through the
ties. However, there was no experimental verifica- early 1960s, and proposed a mechanism in a simi-
tion to support this theory of suppression of nickel lar vein as HSM by suggesting that the deposition
deposition in the intermediate range of current den- of the iron-group metal was adversely affected by
sities, nor to account for the effect of plating param- an addition agent (probably the zinc hydroxide pre-
eters such as pH and temperature on the composi- cipitate) formed by reaction at the cathode which
tion of the electrodeposited alloy. Furthermore, no inhibited deposition of the more noble metal. How-
information was available to confirm the existence ever, there was no experimental evidence to confirm
of α and γ solid solutions of zinc-nickel alloy. the chemical composition or physical state of the
A theory based on hydroxide suppression mechanism addition agent.
(HSM) proposed and advanced by several workers Despite considerable support of HSM theory, it has
[8, 15, 46–54], appears to be the most plausible been refuted by several studies where no evidence
explanation of anomalous codeposition of zinc alloys. of zinc hydroxide precipitation in the deposit can
According to HSM, formation and adsorption of a be found [62–67, 67A]. The deposition reactions of
hydroxide compound of the less noble (zinc) metal the zinc alloy are expected to be a diffusion control
on the cathode surface in the presence of oxygen process related to concentration polarization and
dissolved in the electrolyte, would suppress reduc- hence limiting current densities of the ionic spe-
tion of the more noble (iron-group) metals. At the cies. For simultaneous electrodeposition of zinc and
initial stages of electroplating, the expected normal nickel for example, it was observed that the limit-
 Chatterjee: Zinc Alloy Plating – General Considerations 39

ing current density of zinc is lower than that of the polarisation scan shows an increase in concentra-
nickel [68]. Based on schematic illustrations, zinc tion of zinc ions in the diffusion layer with evolu-
is shown as expected to deposit to a greater extent, tion of hydrogen which is indicative of a decrease
and hence resulting in anomalous deposition at in concentration polarisation and hence an increase
intermediary current densities [65] as reported else- in the deposition rate of zinc. It is worth mentioning
where [10, 15]. The deposition reactions of iron- here that the phenomenon of underpotential depo-
group metals compared with zinc, are expected to sition of zinc [64] (i.e. deposition of zinc ions at
progress with difficulty because of greater concen- potentials less negative than the standard reduction
tration polarization than zinc. potential of zinc) can be explained to be related to
Most of the recent models are primarily based upon nothing but a thermodynamically predicted process
the Butler-Volmer equation which combines both based on the Nernst equation.
the thermodynamic parameters such as equilibrium
potentials, and the kinetic factors such as exchange 5 Corrosion behaviour
current densities and transfer coefficients. It is con-
5.1 Corrosion resistance
sidered [66, 69–71] that zinc deposition is mass
transport controlled, and the evolution of hydrogen Field/outdoor tests for corrosion of zinc (or any)
enhances the diffusion of the zinc ions [69,70] in plated steel panels normally involve observation of
contrast to the ions of the iron group metals, such as slow corrosion of the deposits, such as white powder
cobalt ions for which the reduction for deposition is of zinc oxide followed by red rust of iron oxide
activation controlled and more polarized than zinc developing over months of exposure Such tests are
deposition [71]. The growth of the deposit is then obviously extremely time consuming. The problem
limited by diffusion of ions only. is overcome by introducing accelerated test meth-
ods, which are short term tests for rapid assess-
The anomalous deposition is explained [66] by taking
ment of coating performance. The methodology is
into account of the convection process induced in
proving to be useful for quality control of deposits,
an electrolyte by hydrogen evolution during plat-
assuming that the results thus obtained would be
ing. It is well known that mass transfer by convec-
equivalent to those expected from normal use in
tion greatly enhances a diffusion-controlled process
service based on historical data from field exposure
(relating to minimising concentration polarization),
of similar deposits [76]. An assessment of corrosion
but has little effect on charge-transfer process (i.e.
resistance of zinc and its alloy deposits is normally
activation polarization). This concept would imply
carried out by applying one or a combination of the
that the convection process in an electrolyte would
following methods:
favour a system with intrinsically faster kinetics,
namely higher exchange current density and higher – neutral salt spray/fog test (ASTM B 117 or BS
transfer coefficient such as associated with zinc 5466 Part 1) using 5 % NaCl,
compared with the iron group metals [64, 72–74]. – sulphur dioxide/Kesternich test (ASTM B 605 or
Such a model could explain faster growth of zinc DIN 50018),
in preference to iron group metals [64]. For the – electrochemical techniques, such as linear polar-
zinc alloy deposits, the phenomenon of anomalous isation and potentiodynamic polarisation scans
deposition can thus be attributed to faster reduction (ASTM G59 and G102), and
kinetics of zinc ions relative to the iron-group metal – conventional weight loss measurement.
ions, primarily due to the effect of hydrogen evolu- The most frequently applied test is the first of the
tion accompanying the deposition during anoma- methods, where samples are exposed to neutral salt
lous deposition [66]. spray. Although valuable as a comparative test, its
An indirect support to the above concept is reflected limitations have long been recognized. For exam-
in the work on the effect of additive on zinc plating ple, it may predict behaviour in a marine atmosphere,
[75]. It is stated that for an equilibrium reaction: but unlikely to do the same for engineering compo-
[Zn(OH)4]2– = Zn 2+ + 4OH– nents of a motor vehicle. For this reason, a number
40 Chatterjee: Zinc Alloy Plating – General Considerations

of other tests are developed, namely the rest of the against specifications. Of course, it would be most
methods. Kesternich test is devised to simulate a useful for the relevant industry if a graph could
highly industrialized atmosphere. For electrochemi- be provided showing a relationship between plat-
cal techniques and weight loss measurement, aerated ing thickness and corrosion resistance of an alloy
aqueous solution containing 3.5 % NaCl is gener- deposit. But for economic and practical reasons, the
ally used as the electrolyte. A Cyclic corrosion test thickness of zinc alloy plating in the finishing indus-
is also another test method sometimes adopted, try is kept to a minimum that would fit for its pur-
especially by the automotive industry [77, 78] to pose. As a result, corrosion tests are mostly reported
compensate deficiencies of neutral salt spray and [4, 6, 22, 34, 81] for thickness’ in the range between
Kesternich tests. It involves exposure to a sequence 7 and 12 µm showing a broad agreement between
of humidity, salt spray and dry heat over a period various results (Tab. 5a, b) and thus any graphical
of twenty-four hours. The test would be repeated as representation, although attractive, is avoided in the
many cycles as required. present text. The results illustrate that corrosion
Ideally, a laboratory testing method should simulate resistance of zinc alloy deposits is better than zinc,
service conditions in such a way as to be able to and compares favourably with that of cadmium [2,
produce similar ranking order of materials for cor- 4]. Examination of photomicrographs in the litera-
rosion protection as would be obtained in the field. It ture indicates that porosity of a reasonably thick
is worth pointing out that based on such ranking one (~ 10 μm) electrodeposit from an acid or alkaline
would not necessarily be able to address the some- bath would hardly be different because of the physi-
what vexed question of how much corrosion shown cal mechanism of growth morphology of a thick
in the laboratory tests constitutes failure in service. electrodeposit.
An important factor in the overall performance of Based on corrosion results of chromated zinc alloy
zinc and its alloy coatings is the essential applica- deposits exposed on the underside of trucks over a
tion of a chemical conversion coating to maximise period of four years on, it is apparent that zinc-
corrosion protection in all but acidic environments. cobalt coating with an average corrosion rate of
It is evident [79, 80] that there is a considerable 1.14 µm/y performed better than the zinc nickel
synergistic effect between the improvements found coating (1.31 µm/y) or electroplated zinc only coat-
by the addition of alloying elements to zinc and that ing (1.48 µm/y) [5]. There are also several automo-
achieved by using compatible conversion coating tive manufacturers who stipulate their own accept-
treatment which involves uses of chemically haz- ance standards for corrosion resistance of various
ardous hexavalent chromium. It would produce a zinc alloy deposits. Typical results [22] are shown
finish with a display of colours ranging from yellow, in Table 4 where the deposits were chromated to
bronze, olive to black with increasing resistance to yellow passivation before being exposed to neutral
corrosion. There is, however, some doubt about the salt spray test. Results from both Tables 4 and 5a, b
compatibility of the passivating conversion coating show similar trend. More specifically, better corro-
solution used for pure zinc plating to be similarly sion resistance of zinc-nickel deposits over zinc is
effective on zinc alloy plating [80]. Some investiga- well known [15, 35, 36]. Although there are some
tion is going on to develop an alternative non-chro- variations between various results, the optimum
mium type solution which would be more environ- nickel content appears to be broadly in the range
mentally acceptable. of 10 to 15 %. Thicker coatings (> 4 µm) provide
There have been great variations in the claims for enhanced corrosion protection [36].
corrosion performance of coatings. This is because Other conditions being equal, such as corrosion
results are influenced by many factors including plat- conditions and type of coating, corrosion protection
ing conditions, plating thickness, type of colour con- (red or white rust) is likely to be a linear function of
version coatings and type of test method used. Suf- the coating thickness. However, the optimum alloy
ficient consistency is nevertheless achievable from content differs from system to system. For example,
the majority test methods to judge performance in the case of zinc-nickel alloy deposit, as the nickel
 Chatterjee: Zinc Alloy Plating – General Considerations 41

concentration in the deposit increases, the protective manganese system appears to offer considerable
nature of the coating changes with the alloy becom- advantages over other zinc alloys in terms of times
ing electrochemically more noble and hence less to red rusting of steel substrate [87–89]. The cor-
sacrificial to the substrate steel [82]. A mechanism rosion product apparently being densely formed,
of surface dezincification is involved which will be would suppress the cathodic oxygen reduction reac-
discussed later on. The superiority of zinc-cobalt tion, and thereby reduce the overall corrosion rate
coatings has been well reported [5, 83–85] except [90]. However, the plating process itself suffers from
at high cobalt content [86]. For example, little dif- several drawbacks in being difficult to control with
ference in corrosion resistance was noted between poor efficiency. The zinc-tin electrodeposits with high
pure zinc and chromated Zn-4.8 % Co. However, tin contents show good corrosion resistance in the
significant resistance was observed at much lower both salt spray and Kesternich tests, but the results
cobalt concentrations (< 0.6 %). from relative humidity tests suggest the resistance
For zinc-iron system, information is not widely avail- to be nearly the same as zinc plating [9, 91, 92].
able, although its corrosion rate has been reported Since initiation of corrosion is essentially a surface
to be half of that of pure zinc [87]. It is, however, phenomenon, susceptibility of an electrodeposit to
clear that the sacrificial property of the coating will corrosion is related to the active centres, namely the
be sustained over a wide range of iron contents (10– density of porosities on the plated surface. Integrity
30 %) because of the corrosion potential remaining of a deposit in terms of uniformity and compact-
more electronegative than steel (Tab. 1). The zinc- ness, can be assessed by measuring microhardness

Tab. 5a: Corrosion resistance of Zinc Alloy Deposits [4, 6, 22, 34]

Typical corrosion protection to neutral salt spray (5 %) ASTM 117B [4] 

Type of deposit (Deposit Hours to Hours to  
thickness 8–12 µm) white rust red rust
Zinc   300 approx.  
Cadmium   900 approx.  
Electoless nickel   1000 approx.  
(high phosphorus)
Zinc-iron 400–800 1000 approx.  
Acid zinc- cobalt 150–500 1000–2000  
Alkali zinc-cobalt 250–500 1000–2000  
Alkali zinc-nickel 350–800 2000–2500  
Acid zinc-nickel 300–1000 2500–3000  
Deposit Properties of Zinc Alloys [6] 
  Chloride Alkaline   Chloride Alkaline
  Zinc-Cobalt Zinc-Cobalt Zinc-Iron Zinc-Nickel Zinc-Nickel
Alloy content 0.3–0.9 % cobalt 0.3–0.9 % cobalt 0.3–0.9 % iron 10–13% nickel 5–8 % nickel
Corrosion resistance > 400 hours > 400 hours > 300 hours > 1000 hours > 600 hours
on salt spray
ASTM B 117)*
Kestermich test results* 6–8 6–8 4–6 2–3 2–3
(cycles)
Hardness (Vickers) 180–20 180–200 100–140 160–200 200–250
100-g load
Formability Excellent Good Fair Good Fair
* Typical results for 0.3 ml (8 µm) deposits (yellow chromated) to 5 % red rust 
 42
Tab. 5b: Corrosion resistance of Zinc Alloy Deposits [4, 6, 22, 34]
Neutral Salt Spray Corrosion Resistance (7.5 µm Thickness), hours [22] 
Type of Zinc Alkaline Zinc-Cobalt Alkaline Zinc-Iron Zinc-Nickel    
chromate passivation
  FWC FRR FWC FRR FWC FRR FWC FRR    
Blue bright* 24 48–72 24–30 72–120 24–30 72–120        
Yellow 60–120 160–250 220–480 500–700 220–480 500–700 300–400 700–900    
Olive drab 96–150 350–450         800–1000 1200–1500    
Black (silver) 48–72 160–300 48–120 160–350 48–120 160–350        
Black (nonsilver)     240–500 600–800 240–500 600–800        
FWR: Forming white corrosion, FRR: Forming red rust 
* Blue bright chromate are only available for zinc-cobalt and zinc-iron alloys below 0.2 % cobalt or iron 
  Neutral Salt Spray (NSS) Test – White Corrosion [34]   Neutral Salt Spray (NSS) Test – Red Corrosion 34
Type of finish Zn Zn-Co Zn-Ni Zn-Fe Zn/Fe/Co Zn/Fe/Co Zn Zn-Co Zn-Ni Zn-Fe Zn/Fe/Co Zn/Fe/Co
120 °C/1h 120 °C/1h
Clear 20 20–50   70+ 90+ 70+ 20 320–350        
Yellow 75–150 150–250 500+ 200–300 300+ 200+ 175–250 400–700 2000 400–500 1000+ 1000+
Bronze 125–200 250+ 500+ 300 400+ 200+ 299–400 600–900 2000 600+ 1200+ 1200+
Olive 150–200     250–400   2000      
Black 24–48+ 250+   300+ 400+ 200+ 124–148 600+   600+ 1200+ 1200+
7 µm deposit minimum                        
Chatterjee: Zinc Alloy Plating – General Considerations

Note: Olive drab on Zn/Co can only be produced on an alloy containing 0.2–0.25 % Co maximum 
All figures indicated are approximate 
Results may vary from one cabinet to another 
 Chatterjee: Zinc Alloy Plating – General Considerations 43

of the deposit which improves noticeably from pure metals more noble than zinc, is supported by some
zinc to zinc alloy deposits [4, 6, 22, 81, 93–96]. This experimental work [97]. An assessment of the phys-
is indicative of better quality of deposit, hence cor- ical integrity of pure nickel coating (15 µm thick)
rosion protection of zinc alloys compared with pure on steel in 3 % sodium chloride (NaCl) solution
zinc. Any comparison must be, however, made on showed development of rust spots after 30 and 80 h
deposits produced under similar conditions, because with pure nickel and zinc coatings respectively. On
the hardness values are easily affected by plating the other hand, the protective value of zinc-nickel
conditions, such as treatment time and applied cur- coating against corrosion under similar condition
rent density as reported for zinc plating [93, 94]. showed noticeable improvement to over 120 h, indi-
cating that the alloy deposit could not only provide
5.2 Corrosion mechanism the necessary barrier against corrosion of the steel
substrate, but also being more electronegative than
5.2.1 Electrochemical studies
steel, would protect the substrate in case the coating
The primary function of pure zinc or zinc alloy was breached.
coatings is to provide protection to the steel sub-
strate against corrosion by
The primary function of the alloying elements, namely
– acting as a barrier between the substrate and cor- iron, cobalt and nickel in the zinc alloy deposit is
roding environment, and to modify the corrosion potential of the deposit.
– being able to sacrificially protect the coated steel The alloy becomes slightly more noble than zinc,
if it is exposed to the corrodant, because of pre- and thereby slowing down the corrosion rate of the
existing flaws or damage in the coatings. deposit. At the same time, the deposit is still sac-
Effort is made to discuss about the vexed question rificial with respect to the steel substrate. Conse-
of which of the above two factors becomes more quently, for the same plating thickness, an alloy
important under what conditions. Whenever break- deposit compared with conventional zinc is capable
down of the coating occurs, electrochemical cells of providing with longer protection of underlying
are established between the steel substrate and coat- steel [22]. Both the barrier and sacrificial anodic
ing. Galvanic current will flow from the coating to protection properties of zinc alloy deposits have
the exposed substrate if the coating is sacrificial been studied in aerated 3 to 5 % NaCl solutions
(anodic) to steel. The steel substrate will corrode to by electrochemical techniques and neutral salt fog
expose the familiar iron oxide (red rust) corrosion tests [2, 98, 99]. Information obtained from elec-
products only when both the above properties are trochemical methods, namely open-circuit potential
lost. The overall corrosion resistance property of (OCP) measurements and polarisation techniques
the deposit can be improved, however, by applying as well as weight loss measurements, would enable
post-plating chemical treatment producing chromate one to consistently resolve corrosion of coated steel
conversion coatings [2, 79, 80]. by identifying a balance between the barrier and
From plating point of view, exclusive metallic coat- sacrificial properties of the coatings. The salt spray
ings of pure transition elements like cobalt, nickel, corrosion tests, on the other hand, can be expected
chromium or manganese could provide satisfactory to provide a good indication of the sacrificial cor-
barrier hence corrosion protection to steel substrate rosion protection capabilities of the coatings. The
by virtue of their relatively noble (passive) nature trends of the results from such tests are not always
compared with pure zinc. Since such deposits are straightforward to compare with the short term
more electropositive than steel, they are therefore electrochemical tests which provide an indication
not capable of providing sacrificial protection to of corrosion of coatings without exposing the sub-
steel. As a result, once the coating is damaged with strate. However, both sets of data are useful since they
the steel substrate exposed to the corrodant, the sub- can be considered complementary to each other for
strate will immediately start to corrode. This view the overall interpretation and prediction of the cor-
of unreliable protective property of plating with rosion behaviour of coatings.
44 Chatterjee: Zinc Alloy Plating – General Considerations

For cathodic reactions involving oxygen reduction of immersion time (504 h) [2, 101] and was more
during electrodeposition, the barrier properties electronegative (around –1030 mV) compared to
have been assessed by measuring corrosion cur- those of the zinc alloy deposits, and would thus pro-
rent density (Icorr) which in simple terms is related vide higher levels of sacrificial protection to steel.
to the corresponding corrosion rate. Thus the lower However, problem arises in the practical use of pure
the value of Icorr, the better the barrier protection zinc, which, as mentioned before, undergoes very
properties of the coating for corrosion protection high rates of galvanic corrosion, resulting in unde-
of steel. For example, Icorr (μA/cm2) for pure zinc sirably voluminous corrosion products. In contrast,
plating decreased from 10.0 in unchromated to 4.6 OCP values of the zinc alloy coatings although less
in chromated deposit [80]. In a similar test with electronegative hence less active than zinc, they are
zinc-nickel alloy plating, Icorr decreased from 4.5 sufficiently electronegative, namely –850 to –960 mV
in unchromated deposit to about 0.3 in chromated (SCE) for Zn-14Ni plating compared to –610 mV
sample. In general, the experimental results showed (SCE) for steel to provide some degrees of sacrificial
that Icorr of zinc alloy plating after 1 h immersion in protection to the steel substrate [3].
3.5 % NaCl was much lower than that of pure zinc It was, however, apparent from the electrochemi-
plating. On prolonging the immersion time (504 h), cal results that OCP of zinc alloy deposits became
Icorr of the alloy deposit not only decreased further, more electropositive as the immersion time was
but the drop was appreciable enough to go below prolonged which is indicative of increasing degree
the Icorr of cadmium coating, and thereby providing of electrochemical nobility of the deposit with
a formidable barrier. This behaviour of Icorr decreas- time. Such ennoblement effect can be attributed to
ing with increasing immersion time for the alloy the dezincification process producing an increase in
deposits, has been explained mainly to be due to a surface concentration of the more noble iron group
dealloying effect which is more specifically related metals. Any chromate conversion treatments would
to a dezincification process [79, 99–104]. apparently suppress the dezincification process and
Surface analysis of zinc alloy deposits, e.g. zinc- thereby enhancing corrosion protection by improv-
nickel showed the concentration of nickel in the ing the barrier property. Finally, it is of academic
deposit after immersion in NaCl solutions to increase, interest to note that Icorr is inversely related to OCP
indicating the onset of dezincification whereby the for the zinc alloy deposits which would imply the
surface becomes enriched in the more noble metal corrosion process of the alloy deposit to be pre-
of the alloy deposit, namely the iron group metals. dominantly under anodic [79] rather than cathodic
Consequently, the barrier property of the coating is control [105].
improved which would enhance corrosion resist- Electrochemical studies on corrosion resistance of
ance along with a lowering of Icorr. It would thus a range of zinc alloy coated steels in alkaline solu-
appear that the process of dezincification allows tions showed the resistance to be dependent on the
formation of an effective barrier or passive layer, alkalinity of the solutions and their chloride con-
which would reduce the rate of anodic dissolution. tents [106]. Corrosion behaviour of these coatings
However, if the concentration of the noble alloying changed from passive state to active dissolution
elements is too high, this protective barrier breaks with increasing pH (< 12.6) and in the presence of
down [79]. chloride ions. The zinc-nickel coatings had poor
For coatings to be sacrificial, they need to be anodic corrosion resistance that was attributed to micro-
to steel as mentioned above with the galvanic cur- cracking of the coatings in these environments. In
rent flowing from the coating to the steel substrate contrast, it was found that pure zinc and zinc-cobalt
and thereby affording cathodic protection to the alloy coatings with chromate conversion treatments
substrate. The sacrificial properties of coatings have provide the best resistance to corrosion in these
been investigated by measuring OCP in 3.5 % NaCl environments.
solution [2]. The results showed the OCP value for There have been considerable investigations reported
pure zinc deposit to remain stable for long period in the literature on neutral salt fog tests conducted
 Chatterjee: Zinc Alloy Plating – General Considerations 45

on coated steel in accordance with ASTM B117. coatings. The latter is formed as the primary cor-
It is established that in the neutral salt environ- rosion product on pure zinc coating and is a semi-
ment, barrier properties of coatings assessed from conductor which has high electron conductivity and
electrochemical measurements, tend to dominate aids the cathodic oxygen reduction reaction at the
over sacrificial properties. For example, cadmium electroplated surface without thus being able to
electrodeposit known to possess better barrier inhibit corrosion [107].
properties than zinc deposit, also performs better In contrast, Zn(OH)2 is the main corrosion pro-
in the neutral salt fog tests. Zinc coatings despite duct on zinc alloy deposits, which is more com-
its excellent sacrificial properties, are noticed to be pact than ZnO, has low electron conductivity and
rapidly consumed in salt fog. This is partly due to retards oxygen reduction with a consequent lower-
the presence of high concentrations of dissolved ing of the corrosion rate than that of pure zinc coa-
oxygen and chloride ions, and the rapid formation ting. There is, however, another school of thought
of an essentially non-protective zinc oxide corro- [95, 108–110] where the passive corrosion layers on
sion products (white rust) on the plated surface. the electrodeposits of both pure zinc and its alloys
However, addition of iron group metals to form are expected to be mainly ZnO. The corrosion inhi-
zinc deposits, enhances corrosion performance of bition action of the alloy deposit is suggested to be
the alloy deposit in the salt fog tests possibly by related more to a dopant-vacancy interaction rather
improving their barrier properties via dezincifica- than an electronic effect, because the corrosion
tion phenomenon. The nature of corrosion product layers on the alloy deposits are considered to exist
of the alloy deposit was tenacious and non-volumi- as degenerated semiconductors. Photoelectrochem-
nous, and was thus completely different from that ical and impedance measurements as well as X-ray
of zinc alone. photoelectron spectroscopy were carried out to
In the marine atmosphere, the sacrificial properties characterize the passive layers in terms of structural
of metal coatings appear to assume dominance over and electronic properties, which would determine
barrier properties, provided the corrosion rate of the the corrosion behaviour of the deposits.
coating remains relatively low [2]. This is opposite An assessment of the contribution of the iron group
to the situation found in the neutral fog environment alloying metals (d-metals) to the improvement on
and accounts for the reversal in behaviour for pure the corrosion behaviour of the coating, showed a
zinc. Electrodeposited zinc-cobalt alloy contain- distribution of the d-metal doping in the passive oxide
ing only small amount of cobalt (0.8 wt.%) seems layers when it is above a certain level (~ 1 atom%)
to improve corrosion protection to steel in marine causing an increase in the valence electron charge
atmosphere. In contrast, the corrosion performance density of the zinc atoms [95]. Based on electro-
of zinc-nickel alloy in the marine exposure trials chemical data, an interaction between the dopant
was poor despite better protection in the neutral salt (d-metal) and mobile negatively charged zinc cation
fog test The poor performance of the zinc-nickel vacancies has been suggested. Accordingly, the
alloy has been attributed to the relatively high con- dopant captured at a zinc vacancy, can scavenge a
centrations of nickel in the alloy which significantly mobile zinc cation vacancy, which normally sup-
reduce the ability of the coating to sacrificially pro- ports the overall corrosion current. An immobile
tect steel. ion pair is thus formed with the loss of a mobile
vacancy, and making the alloying metal immobile
5.2.2 Electronic and structural properties
at the same time in the passive layers. The more
The mechanism of enhanced corrosion resistance electropositive the dopant is with respect to zinc,
afforded by zinc alloy deposits, has also been dis- the more zinc vacancies would be trapped by the
cussed in the literature in terms of electronic prop- dopants captured at zinc vacancies. A high corro-
erties. It is reported [9, 87] that transition metals sion resistance can thus be expected with the loss of
like nickel or cobalt retards the dehydration of pas- negatively charges mobile cation vacancy, resulting
sive layers of Zn(OH)2 to ZnO during corrosion of in a decrease in corrosion current due to the forma-
46 Chatterjee: Zinc Alloy Plating – General Considerations

tion of immobile ion pairs with the elimination of Similar mechanism is, however, not applicable to
mobile charge carriers. zinc-cobalt deposit where the corresponding texture
is similar to those of zinc and zinc-iron deposits. The
5.2.3 Crystallographic texture difference in corrosion behaviour was considered
A variation in corrosion rates of single crystals of to be related to localised distortions in the crystal
zinc has been related to the differences in the pack- structure. The ratio of c- and a-axial parameters of
ing density of crystallographic planes [111]. It was h.c.p. structure reflects packing density of atoms
suggested that an increase in packing density was and the electronic effects of the phase [119] and is
associated with an increase in activation energy for normally expected to be 1.633 which if exceeded
dissolution/corrosion, resulting in lowering of cor- would mean extension of ‘c’ spacing i.e. more dis-
rosion rates. Investigations on aqueous corrosion tortion of the crystal lattice. The axial ratio was
and anodic polarization of low-index single crystal 1.806 for zinc-cobalt deposit compared with 1.825
faces of zinc showed active and passive behaviour of and 1.854 for zinc-iron and pure zinc deposits
various planes [112, 113]. For example, the (110) respectively [117]. A lower c/a ratio for zinc-cobalt
surface plane exhibited the highest reactivity in terms deposit would mean a relatively denser, less dis-
of corrosion rate, followed by (100) and (002) planes. torted crystal lattice formation which would imply
Extending the concept to electrodeposit, it has been a less active structure for anodic dissolution of the
reported that a crystallographic texture is predomi- deposited phase and also less cathodic reduction of
nantly developed when zinc is electrodeposited oxygen. The relatively lower c/a ratio of zinc-cobalt
from aqueous solutions [114]. The corrosion rate alloy deposit was thus suggested to be the major
was apparently, as for single crystals of zinc, higher likely contributory factor for improved corrosion
for planes with lower density, namely (1120 > 1010 resistance of the electrodeposit. However, a higher
> 0001) [115], which was later on contradicted by c/a ratio for zinc-cobalt deposit equalling that of
others [116]. Nevertheless, the indication of the pure zinc has been reported elsewhere [71] which
presence of a relation between crystallographic ori- would, of course, invalidate the above mechanism
entation and corrosion rate of pure zinc coatings, of high corrosion resistance of zinc-cobalt deposit.
encouraged investigators to extend the idea to zinc
5.2.4 Surface morphology
alloy deposit [117]. Alloy additions can have dif-
ferent effect from that of pure zinc on the crystal- The corrosion behaviour of an electrodeposit can
lographic orientation of the electrodeposited layers be directly related to the change in surface texture.
[118] which were detected to characterise hexagonal An assessment of corrosion resistance of zinc alloy
close-packed structure (h.c.p.) [71, 117, 119–121]. electrodeposits seems to be easier to achieve with a
Based on results from neutral salt spray tests and study of the surface morphology than the compo-
electrochemical polarization measurements in aer- sition of the coatings [93, 122]. For example, it is
ated 0.9 M NaCl solution on zinc and zinc alloy recognised that an increase in current density would
deposits, it was concluded that the presence of lead to the formation of rough deposits shown by
nickel (12 %) or cobalt (0.6 %) in the zinc matrix scanning electron microscopy (SEM) [10, 93],
increased corrosion resistance of the coating, while which would result in developing local corrosion
iron addition (0.4 %) did not show any apparent cells with ultimate increase in corrosion rates. The
improvement over pure zinc [117]. The crystal- poor corrosion resistance of pure zinc with amor-
lographic texture and lattice cell parameters of all phous structure improves considerably with changes
these electrodeposits produced from alkaline baths in surface morphology to fine, compact crystalline
were subsequently determined. The low corrosion structures of zinc alloy deposits [21, 79, 81].
rate of zinc-nickel alloy deposit was explained to It has been reported that an alloy deposit with nodular
be due to the predominant presence of basal plane grains of measurable size would provide better cor-
texture in the coating that has the highest packing rosion protection than structures with non-meas-
density in the crystal lattice. urable elongated grains [122]. For the same elec-
 Chatterjee: Zinc Alloy Plating – General Considerations 47

trodeposit, the grain structure becomes finer and alloys, and does not appear to be detrimental to the
more compact as the alloy content of the deposit overall corrosion resistance of the alloy deposit.
increases. This is confirmed by SEM work which The networks of micro-cracks in the alloy coatings
showed that optimum refined micrographs at 12.4 % would facilitate escape of hydrogen and thereby
nickel and 10.7 % cobalt for zinc-nickel and zinc- lessening the degree of possible damage from hydro-
cobalt alloys respectively [79]. In reality there is gen embrittlement. Also, such network would con-
little to be gained in terms of cost-effectiveness for tribute to the excellent corrosion resistance of the
deposits such as zinc-cobalt alloy if the cobalt con- coatings in the following way. Based on a similar
tent is well in excess of 1 %. It has been reported mechanism as for micro-cracked chromium plating,
that the deposit structure changes from dendritic type it is possible that the amount of corrosive attack at
to nodular form with a decrease in grain size as the any one site is minimised by spreading the potential
cobalt content is raised from 3.3 to 12.4 % [71]. points of attack over the metal surface via a network
The surface topography of deposits is related to the of micro-crack.
presence of additives as well as the plating condi-
6 Hydrogen embrittlement
tions. SEM photographs of deposits obtained from
electrolyte without additives showed an irregular Hydrogen embrittlement (HE) is a serious, in some
structure with grains of different shapes and sizes cases unavoidable problem in electroplating indus-
[123]. A change to a compact, uniform structure with try. It is associated with any electroplating process
a fine-grained texture (indication of an increase in using an aqueous solution. Thus a zinc alloy elec-
nucleation density) was obtained (presumably with trodeposit with satisfactory corrosion resistance,
improved corrosion resistance) by using a bath con- can undergo premature failure in service due to
taining organic additives which are used for wetting hydrogen embrittlement. In this context, it would be
the substrate, and also to stress relieve and brighten appropriate to briefly discuss the basic mechanism
the electrodeposit. With regard to the effect of plat- of the deleterious effect of hydrogen on steel [126].
ing condition, the effects of current density, temper- Electrodeposition from an aqueous electrolyte is
ature etc. on the microstructure via SEM work has always associated with generation of nascent/atomic
been reported [10, 33, 93]. For example, in the case hydrogen at the steel cathode via electrochemical
zinc-cobalt deposit at ambient temperature, growth reduction reaction. Hydrogen atoms capable of dif-
of a series of crystals or grains consisting of a stack fusing into the crystal lattice of the steel substrate,
of hexagonal platelets was obtained which changed accumulate and can get trapped at high stress points,
to a nodular form with a number of surface cracks such as microvoids and grain boundaries. If the life-
at a higher bath temperature of 55 °C [33]. time of atomic hydrogen (H*) is too short to survive
An important part is played by SEM in studying the under a particular processing conditions, molecular
corrosion mechanism of zinc-nickel electrodeposit. hydrogen (H2) will result which being incapable of
SEM photomicrographs of zinc-nickel deposits with diffusion through the lattice, will leave the metal
8 to 20 % nickel reveal crystalline structure with surface as gas bubbles:
well defined lamellar micro-cracked texture normal 2H+ +2 e- → 2H* → H2↑
to the substrate which closely follows the surface The internal pressure exerted by hydrogen atoms
topography [124, 125]. The most corrosion resistant at the trapped sites can lower the tolerance limit of
electrodeposit containing 12 to 14 % nickel often components below the applied external stress/load,
comprised two layers of different micro-cracking resulting in catastrophic failure. HE can be initi-
with the outer layer having more micro-cracks in most ated by a small amount of hydrogen. For example,
cases. The incidence of micro-cracks on the surface of a simple calculation assuming microvoids trapping
some zinc-nickel alloys can be associated [9] with all the absorbed atomic hydrogen, showed that the
an internal stress around 190 to 340 MN/m2.The internal pressure arising from as low as 8 ppm
occurrence of this cracking phenomenon can be hydrogen entrapped in 0.01 % microvoids could
related to the internal stress on some zinc-nickel be as high as 717 Mpa [126]. The pressure would
48 Chatterjee: Zinc Alloy Plating – General Considerations

increase with decreasing percentage of microvoids. [10] K. R. Baldwin, C. J. E. Smith and M. J. Robinson; Trans IMF 72 (2)
79, 1994
Thus electroplated components of high-tensile steel [11] G. D. Wilcox and B. Peterson; Trans IMF 74 (4) 115, 1996
containing a much smaller percentage of micro- [12] S. S. Abd El Rehim et. al.; Trans IMF 77 (1) 31, 1999
voids as well as greater number of grain bounda- [13] H. Geduld: Zinc Plating; Finishing Publ. Stevenage, Herts., 1988
[14] A. Brenner: Electrodeposition of Alloys; Vol. 1 and 2, Academic
ries and dislocation defect sites, is likely to develop Press, New York, 1963
hydrogen pressure high enough to cause hairline [15] D. E. Hall; Plating and Surf. Finish. 70 (11) 59, 1983
cracks with ultimate failure in service than a low [16] G. Black; Met. Fin. May, 209, 1946
[17] D. H. Schantz; U.S.-Pat. 2,419,231, April, 1947 – ref. 5 of Geduld’s
tensile steel. In fact, it is recommended (BS 1706: Book (Ref. [13])
1990 or ASTM F 519) that electrodepostion on all [18] E. J. Roehl; U.S.-Pat. 3,420,754, January, 1969 – ref. 6 of Geduld’s
high strength or surface hardened steels with tensile Book (Ref. [13])
[19] E. J. Roehl; U.S.-Pat. 3,558,442, January, 1971 – ref. 7 of Geduld’s
strength more than 1050 MPa (corresponding hard- Book (Ref. [13])
ness around Rockwell C 34) may result in failure by [20] W. A. Wesley; U.S.-Pat. 2,844,530, July, 1958 – ref. 27 of Geduld’s
hydrogen embrittlement. Book (Ref. [13])
[21] T. Adaniya et. al.; Plating and Surf. Finish. 72 (8) 52, 1985
Theoretically, the risk of hydrogen embrittlement is [22] D. Crotty; Met. Fin. 94 (9) 54, 1996
likely to be more acute with an acid electrolyte with [23] D. Crotty and R. Griffin; Plating and Surf. Fin. 84 (4) 57, 1997
[24] N. Zaki; Prod. Fin. (3) 52, 1999
more evolution of hydrogene than an alkaline bath.
[25] General Motors; Zinc Alloys: GM 6280M – ref. 1 of D. Crotty
However, the risk of embrittlement is likely to be (Ref. [22])
greater with an electroplating process with poor [26] Ford Motor Co.; Zinc Alloys: WSA-M1P87-A1, WSH-M1P86-A
and WSE-M1P93-A – ref. 2 of D. Crotty (Ref. [22])
cathode efficiency. For example, zinc-nickel deposits [27] Chrysler Motor Co.; Zinc Alloys: PC 8955 – ref. 3 of D. Crotty
which appear to offer suitable corrosion protection, (Ref. [22])
is likely to suffer from the problem of embrittle- [28] Boeing; Zinc-Nickel Alloy: BAC 5637 – ref. 6 of D. Crotty (Ref. [22])
[29] C. Johnston; Met. Fin. 97 (8) 40, 1999
ment if produced from an alkali than an acid bath.
[30] N. R. K. Short and J. K. Dennis; Trans IMF 75 (2) 47, 1997
This is because of the much lower current efficiency [31] B. A. Wilson; Trans. Metal Finishers’ Assoc. India 6, 143, 1997 –
of the alkaline process (60 %) [39] compared with ref. 6 of M. Pushpavanam; Bull. Electrochem. 16 (12) 559, 2000
[32] J. K. Dennis, C. Zou and N. R. Short; Trans IMF 73 (3) 96, 1995
the acid process (90 %) [6, 22]. More hydrogen is
[33] H. Yan et. al.; Trans. IMF 77 (2) 71, 1999
expected to be produced by the former process, [34] M. Roper and J. O’Grady; Trans IMF (Bull.) 74 (4) July 3, 1996
resulting in greater absorption of hydrogen into the [35] S. A. Watson; The Present Status of Zinc-Nickel Alloy Coatings;
basis steel with ultimate adverse effect more pro- Interfinish ‘96; Birmingham, UK, September, IMF, 1996
[36] S. A. Watson; Trans IMF (Bull.) 70 (1) 28, 1992
nounced on the deposit quality. A de-embrittlement [37] G. F. Hsu; Plating and Surf. Finish. 71 (5) 52, 1984
method would rectify the problem, which involves [38] C. H. Ko et. al.; Plating and Surf. Finish. 78 (10) 46, 1991
baking the plated parts for an appropriate time and [39] M. J. Carr and M. J. Robinson; Trans IMF 73 (2) 58, 1995
[40] F. Foerster; Z. Elektrochem. 4, 160, 1897
temperature prior to chromate passivation. The au-
[41] E. P. Schoch and A. Hirsch; J. Am. Chem. Soc. 29, 314, 1907
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issue, especially for fasteners, and have special in- [43] S. Glasstone; J. Chem. Soc. 129, 2887, 1926
spection to ensure pre-chromating de-embrittlement [44] S. Glasstone and T. E. Symes; Trans. Faraday Soc. 23, 213, 1927
[45] B. Lustman; Trans. Electrochem. Soc. 84, 363, 1943
heat treatment.
[46] I. Levin; Chemist-Analyst 41, 89, 1952
[47] J. Matulis and R. Slizis; Electrochim. Acta 9, 177, 1964
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