Zinc Flake Coatings vs.

Zinc-Nickel Electroplating: New

Trends and Developments

Holger Sahrhage, COVENTYA, Guetersloh/Germany;

Michael Krumm, COVENTYA, Guetersloh/Germany;
Alain Hill, COVENTYA, Paris/France
Klaus Wojczykowski, COVENTYA, Guetersloh/Germany;

Summary
Zinc flake coatings are widely used to protect steel against corrosion. In some appli-
cations they compete against other technologies like electroplating of zinc or zinc
alloys. Both technologies are based on the sacrificial properties of zinc against steel
which leads to a cathodic corrosion protection.

With both - electroplated zinc-nickel and with zinc flake coatings - 720 or even more
hours in the neutral salt spray test according to DIN EN ISO 9227 can be achieved
without base metal corrosion. In the last years there is a big competition between
both technologies especially for fasteners in the automotive industry. In view of the
high nickel price the zinc flake coatings are generally cheaper. The topic hydrogen
embrittlement caused by hydrogen evolution during the electroplating process is of-
ten given as a strong argument to favour the zinc flake coatings against zinc-nickel to
protect high strength steel fasteners. Electroplated high strength steel parts still have
to undergo a subsequent thermal treatment to release potential hydrogen from the
steel although several studies in recent years have proved that no hydrogen embrit-
tlement occurs for fasteners plated in modern alkaline zinc-nickel electrolytes for
high-strength steel up to 1200 MPa.

On the other hand there are several reasons that favour the electroplating against
zinc flake coatings. With modern alkaline zinc-nickel processes it is generally easier
to achieve a homogenous coating thickness on complex shaped parts. The coating
thickness in the thread of fasteners has to be within a narrow defined range. A mini-
mum thickness is required to guarantee the corrosion resistance, but in the thread a
too high thickness can affect the screwing properties. With conventional zinc flake
coatings it is difficult to guarantee this dimensional accuracy since higher thicknesses
are obtained in the roots of the thread. Latest developments have overcome this
problem by modifying the rheology of the zinc flake system.

All those developments have extended the areas of application of both technologies
which is the reason why they are perceived as competitive technologies in the mar-
kets. But in the end they should be regarded as supplementary technologies which
gives the applicator a broader range of opportunities.

1 Introduction
Since the 1970s there was an on-going evolution with new developments and in-
creasing requirements above and beyond what is possible with classical zinc electro-
plating; starting with the first zinc-flake processes and low-Ni ZnNi processes (6 – 8

1
% Ni) which were realized by using ammonia containing acidic electrolytes to high
alloy ZnNi systems coming up in the 1990s.

The reported corrosion protection values as of today, are as high as 500 h to white
rust and 1200 h to red rust for the low-Ni ZnNi systems and 1000 h to white rust and
3000 h to red rust for the high-Ni ZnNi systems[1]. For zinc flakes systems which have
also barrier coating properties, the red rust values can reach several thousand hours
as well.

The corrosion performance that can consistently be achieved in industrial production

is obviously lower and what is expected from the OEMs is in the range of 96 h WR /
720 h RR for VW Ofl r672 and 240 h WR / 1000 h RR for GMW4700. For zinc flake
coatings RR numbers of 480 h to 720 h are usually expected in the Neutral Salt
Spray Test.

The plating thickness needed for electroplated ZnNi is a consistent 8 - 12 µm in order

to achieve the high values given above. For lower thicknesses the corrosion re-
sistance can decrease dramatically. In the same way the corrosion resistance of zinc
flake coatings correlates exponentially with the coating thickness. 720 h in SST can
be achieved with 7-8 µm thickness (about 25 g/m2 coating weight) whereas 2 µm of
coating thickness will give almost no protection. Corrosion performance and layer
weight for zinc flake coatings are described in ISO 10683.

2 General comparison of zinc nickel and zinc flake coating

When looking at electroplated ZnNi and zinc flake dip-spin coatings it is most evident
that they can be used for similar applications and often have to fulfil the same cata-
logue of requirements but are coming from totally different process types.

Electroplated ZnNi is a classical galvanic process with the typical pre-treatment (e.g.
soak-, electro cleaning, pickling) and as post-treatment the typical conversion coating
technology used for all zinc and zinc alloy processes (chromating or trivalent chrome
passivation & top coat). All process solutions are normally dilute aqueous electrolytes
that are used for the reaction of forming the coating but are then rinsed off.

The zinc flake coatings on the other hand are coming from classical paint technology
using high concentrations of lamellar shaped zinc flakes in order to form, after curing,
a coating that mimics the electroplated zinc coating i.e. a dense sacrificial layer with
a continuous zinc phase in contact with the base material. The applied liquid (for the
base coat) is a thick suspension that usually contains a certain amount of organic
solvent. After a chemical degreasing typically a mechanical shot-blasting or a phos-
phating step is used as pre-treatment, in order to create a surface that allows adhe-
sion of the paint like coating. In case of electroplating there are dedicated chemical
steps needed to create an activated metal surfaces to form the strong intermetallic
bond of base material and coating. After electroplating a conversion treatment with
trivalent passivates is mandatory to protect the ZnNi from corrosion. Such a conver-
sion treatment is unnecessary for zinc flake coatings since the zinc flakes are already
protected against early corrosion by a chemical treatment during the manufacturing
of the zinc flakes coating formulation.

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In both cases (for ZnNi and zinc flakes) additional corrosion protection and specific
mechanical and optical properties can be achieved or improved (coefficient of friction,
glossy black aspect) by a post-treatment with organic or organic-inorganic top-coats

Although there are water borne systems on the market top-coats for zinc flake coat-
ings usually contain solvents and need higher temperatures for curing. Those pro-
cesses are accepted in plants that already handle the base-coat and thus are
equipped with the necessary equipment. Also, with those systems a very high corro-
sion performance can be achieved which is often needed in the typical applications of
zinc flake coatings (e.g. automotive exterior, under body). A top-coat on zinc-flake
base coats also plays a crucial role to improve tribology, chemical resistance and
galvanic corrosion.

Because both systems have their strengths and weaknesses in certain areas, it is
important to give guidance, which system is to be selected. Doing that one has to
keep in mind that the processes are fundamentally different as described above and
a comparison is not as straightforward as e.g. between electroplated Zn and ZnNi.
The engineer can easily make the mistake of concentrating too much on a single as-
pect where one alternative might be superior. It is important to see all aspects from
application to intrinsic properties of the coatings to the expected and real behaviour
in the service life of the part. The table below lists some of the advantages and dis-
advantages commonly mentioned by applicators and OEMs.

Table 1: Comparison of properties of zinc-nickel electroplating vs. zinc flake coatings

Property ZnNi Zinc Flakes
Corrosion protection very good ++ + good
Ductility/bendability ok + - poor
Adhesion very good + - ok
Friction properties very stable + + very stable
Hydrogen embrittlement critical - + no problem
for high strength steel (if H+-free preparation is
over 1200 MPa (435 HV) used)
Layer distribution ok + - not uniform e.g. in the
thread of screws
Preparation chemical cleaning +/- + easy (e.g. by shot blasting)
Spectrum of parts can vary from very small + - limited size,
to very large screws not < M6
Shelf life not critical, usually sever- + - limited shelf life (like paints)
al years
Environmental consid- electroplater has to han- -/+ + zinc flake formulations con-
erations dle toxic nickel salts, tain solvents
waste water
Costs lower energy costs - + lower chemical costs
(if no hydrogen deembrit-
tlement is necessary)
higher chemical costs

There will always be applications where one of both alternatives is clearly in favour,
but there is also an overlap with a direct competition.

New generations of ZnNi as well as zinc flake coatings which solved some of the is-
sues specific to the respective systems improved performance in the classical appli-

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cations of each alternative but also let the overlap area grow (see fig. 1). Some of
those new developments and improvements will be described in the following.

Figure 1: Choice of the right process for cathodic corrosion protection

2 Recent Improvements in ZnNi Plating

The major disadvantages of ZnNi compared to zinc flake coatings are coming from
the fact that it is an electrolytic process which is bound to fundamental electrochemi-
cal rules. The metal distribution is primarily a function of the electric field distribution
which makes it hard to homogeneously plate parts with a more complicated geome-
try. For ZnNi as an alloy deposited from two different metal species in the electrolyte
this correlation also applies to the alloy composition. The alloy composition on the
other hand is critical for the high corrosion protection which has an optimum window
for the ZnNi γ-phase (12 – 15 % Ni)[2].

For all galvanic processes it is also crucial to have a grain structure that results in a
compact metal layer as a function of transport processes at the cathode, meaning to
avoid “burning” in the high current density areas on a part.

Very often ZnNi deposits fail in corrosion protection or appearance due to

 Too low plating thicknesses in low current density areas
 Too high or too low Nickel content in some areas of the parts.
 Burned deposit in the high current density area.

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In alkaline ZnNi processes the right choice of specific nickel complexing agents and
brightener molecules (mostly aromatic compounds)[3] already caused a huge leap in
plating performance since the early 1990s.
Recently COVENTYA introduced the newest generation of alkaline ZnNi electrolytes
(PERFORMA 288) that allow to deposit very ductile, homogeneous and burn-free
ZnNi deposits.

In all galvanic processes hydrogen is produced at the cathode while plating whenev-
er the current efficiency is lower than 100 %. This would be another intrinsic disad-
vantage of ZnNi vs. zinc-flake coatings. In an extensive study[4] we could show that in
the case of ZnNi the specific layer structure allows effusion of hydrogen, so that no
hydrogen embrittlement of the coated steel occurs. It was shown that fasteners up to
a hardness of 1200 MPa do not need a hydrogen relief bake after ZnNi plating.

For acidic ZnNi electrolytes the above mentioned properties of plating homogeneity
are even harder to achieve. Very often burn-free deposits can only be achieved with
complicated bath agitation equipment.

3 Recent Improvements in Zinc Flake Coating

Just like the weaknesses of electroplated ZnNi are the weaknesses of electroplating
in general, it can be said that the weaknesses of zinc-flake coatings are general
weaknesses of paints and paint application.

Failures and issues with zinc-flake coated parts are often due to one of the following
factors:
 Thread fill or internal drive fill in fasteners
 Too low thickness and early corrosion on exposed areas (edges, corners)

root

Screw (thread)

crest

Figure 2: SEM picture of cross section of a new generation zinc-flake coating on the
thread of a fastener.

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Consequently improvements of zinc flake coatings are mainly improvements of the
layer thickness distribution on the part. The layer thickness distribution is determined
by the application technique and the flow behaviour (rheology) of the process solu-
tion. A big difference can be made by adapting the application process and improve-
ments with centrifuge baskets following a sequence of specific movements in differ-
ent directions while spinning off excess paint or multiple subsequent layer application
are market standard now.
The rheology of the zinc-flake process solution can be adjusted with different addi-
tives, polymers or particles of different shapes and forms which change the viscosity
of the solution at different shear rates and leave a little bit more or less material in the
different areas of the part during the spin off process.

COVENTYA recently developed a zinc flake base coat that shows an excellent layer
thickness distribution which is mainly seen in the root and crest of the thread of fas-
teners. Fig. 2 shows a scanning electron microscopy picture of a cross section of the
newly developed flake coating indicating a high homogeneity of the plating thickness.

The high coating thickness homogeneity leads to superior corrosion resistance com-
pared to other zinc flake products that were available until now. Fig. 3 shows fasten-
ers after salt spray test comparing a common and a rheology modified zinc flake pro-
cess.

Rheology modified M arket Standard Flake Coating

Figure 3: Apple to apple comparison of fasteners after Neutral SST (ISO 9227).

4 Conclusion
When choosing the right coating for high-performance corrosion protection the appli-
cator might for some application have the choice between ZnNi and zinc flake coat-
ings. When selecting one process over the other it should be respected that both
coatings, even though serving the same purpose, are fundamentally different and a
desired or undesired property should not be overseen. Most importantly the applica-
tor should be informed about the latest developments in both fields that might have
large influence on the choice.

5 References
[1] T. Murai, „Performance Characteristics of Zinc–Nickel Alloys and Dip-Spin Coatings”,
Metal Finishing, 2009

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[2] Rainer Paulsen, “Vergleich von Abscheidung der Zn-Ni-Legierungschichten“, ZVO
meeting Würzburg 2008

[3] US6468411B1

[4] Ali El Hajjami, „Characterization of thin Zn-Ni layer coatings deposited on low carbon
steel“,Applied Surface Science, 254, 2007, 480-489