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PVD coatings as an environmentally clean

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 Surface and Coatings Technology 116–119 (1999) 476–487
www.elsevier.nl/locate/surfcoat

PVD coatings as an environmentally clean alternative to

electroplating and electroless processes
B. Navinšek *, P. Panjan, I. Milošev
J. Stefan Institute, Jamova 39, 1001 Ljubljana, Slovenia

Abstract

Today the development of clean technologies in all spheres of industrial manufacturing is an essential task, not only for
material and metal finishing but also for plasma surface engineering. Among the most critical group of technologies which needs
to be replaced by alternative technologies are processes used to produce functional galvanic and decorative coatings. The
electroplating of finishes, such as hard chromium, cadmium and nickel in metal finishing is today recognized as a major source
of environmental pollution in every country. Therefore wet bath technologies have started to lose favour compared with high
performance dry coating methods such as physical vapour deposition (PVD), plasma-assisted chemical vapour deposition, chemical
vapour deposition and thermal spraying. Among these techniques, the results obtained with PVD coatings in metal cutting and
forming in the last 15 years show the most promising solution of the complicated situation in which galvanic coatings seemed to
be technologically and economically irreplaceable.
In this paper the general situation in this field is shown. Already today it is possible to replace efficiently some of the galvanic
processes in specific cases (e.g. Cr, Ni, Cd, Zn, Au). It is important to point out that PVD is considered to be a technique which
can provide not only metallic, but also alloyed and ceramic coatings with a virtually unlimited range of chemical composition and
therefore controlled protective, mechanical and wear-resistant properties. Entering into competition with galvanic coatings the
manufacturers of PVD coaters were confronted with new requirements: a huge quantity of substrates of the same size, to be
chemically and plasma cleaned and then coated at the highest possible deposition rate. For industrial mass production one can
therefore use only large PVD batch systems or in-line coaters. The alternative for today’s low price galvanic coatings is therefore
dry and clean PVD technologies, fully supported by legislation on environmental protection. The economics depend directly on
the substrate type and the quantity.
The first positive results on the replacement of electrodeposited nickel on aluminium substrates and hard chrome on soft iron
are also reported here. A soldering test was made on a sputtered nickel layer. Wear and corrosion tests were performed with iron
cores, coated with PVD CrN coating. All tests were made in the Slovenian automotive industry. Results show that for a large
number of substrates PVD clean technology is already economically competitive with galvanic coatings. © 1999 Elsevier Science
S.A. All rights reserved.

Keywords: Electroless processes; Electroplating; Pollution; PVD coatings

1. Introduction operations such as electroless and electroplating of pro-

The development of ‘clean’ technologies in all spheres
of industrial manufacturing is today an essential task
required and initiated by environmental laws and pro-
grammes of countries around the world. Among the
major sources of environmental pollution are technol-
ogies and processes used in conventional metal finishing
* Corresponding author. Tel.: +386-61-177-3278;
fax: +386-61-219-385.
E-mail address: borisnavinsek@ijs.si (B. Navinšek)
tective functional and decorative coatings.
In the last 80 years, since hard chrome became com-
mercially available, this industrial manufacturing has
developed into a huge, well-organized, sophisticated and
financially powerful multi-billion dollar business. Only
in the last decade has strong activity started aimed at
systematic replacement of some of the ‘dirty’ technol-
ogies (especially for cadmium, chrome and zinc) with
high performance dry coating ‘clean’ methods. Among
many available technologies, the highest attention has
been focused on physical vapour deposition (PVD),
chemical and plasma-assisted chemical vapour depos-

0257-8972/99/$ – see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0 2 5 7- 8 9 7 2 ( 9 9 ) 0 0 14 5 - 0
 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
ition (CVD, PACVD) and thermal spraying. The tech-
nologists and managers faced the difficult problem of
finding an appropriate alternative coating technology,
which would offer the production of cost-effective and
quality coatings following available standards for each
single case.
The research community was suddenly confronted
with a situation similar to that of 20 years ago, when
tool makers were ‘forced’ by scientists to start improving
tools and machine parts with PVD TiN hard coatings,
and later with TiCN, CrN and TiAlN coatings [1–4].
These new environmentally clean technologies slowly
improved and finally replaced highly improved bulk tool
materials, traditional surface treatments and old tool
geometries. It must be pointed out that these PVD
coatings represent a reliable and cost-effective means for
improvement of tools and machine parts. In this case
there are a small number of tools (a few to several
hundred per coating order) of the same size and rela-
tively small dimensions to be coated. Therefore in coat-
ing production PVD batch reactors are used [5]. Batch
systems are also used for large tools, e.g. in plastic
injection moulding, in metal (Al ) die casting and deep
drawing or combined tools for die forming. Such tools
and machine parts are in general expensive in compari-
son to the coating price. This means that the advantages
of PVD coatings in practice are achieved at little increase
in cost.
Electroplated and electroless coatings are commonly
used to protect surfaces from wear and corrosion, as
well as for decorative purposes [6–9]. They are in
principle low-cost and are often used for a large number
of parts or substrates of the same size. A large variety
in part-substrate shape, size and especially in material
and coating thickness additionally extends the field of
electroplating and the electroless process.
There are also many objects of large size (e.g. chrome-
plated injection moulds for plastics and metal alloy and
Al-die casting), for which alternative technology, such
as TiN or CrN coatings, not only replaces the galvanic
coating but also markedly improves the function of
the moulds.
A comprehensive review of the technical develop-
ments in this field with an emphasis on inorganic ‘met-
allic’ finishes, processes and equipment in industrial
manufacturing was given by Murphy in Metal Finishing
Journal [10]. The following topics were analysed and
relevant the references and patents cited: cleaning and
degreasing, blasting and shot peening, etching and elec-
tropolishing, pickling and descaling, stripping, polishing
and buffing, anodizing, electrodeposited metals and their
alloys (Cr, Cu, Ni, Au, Pd, Ag, Sn, Zn, others), vacuum
coatings, metallization of nonconductors and electroless
plating (Cu, Ni, others), conversion coatings and hot-
dip coatings. These topics have been also the subject of
numerous publications in the last decade, while most of
477
the new solutions and alternatives to the standard
processes which are in use in industry were initiated
by more and more strict environmental ordinances
everywhere.
New results obtained by PACVD processes show that
this deposition process offers high rates at low temper-
atures (250–350°C ) for many materials, and is a candi-
date to replace galvanic coatings in the future.
In this paper we discuss the important parameters
which must be understood and taken into account by
any R&D group which starts to consider individual
cases from industrial surface finishing where the tradi-
tional surface treatment and protective coating should
be replaced by a new ‘clean’ PVD technology. Alter-
native processes to standard galvanic coatings will be
described, while first positive results on the replacement
of electrodeposited nickel on aluminium substrates and
hard chrome with a copper undercoat on a soft iron
core will be reported as examples for successful mass
production in industry.
2. Comparison of coating conditions
When surface engineers and technologists are
required to improve or even replace a traditional surface
treatment and functional or decorative coatings with an
alternative process or coating material, numerous data
and reliable information about the available alternative
technologies especially the equipment and PVD reactors,
must be studied. The evaluation starts with a comparison
of the basic deposition conditions and parameters, with
emphasis on the reactor size and coating process, depos-
ition rates, coating properties, substrate material and
surface treatment, adhesion, wear and corrosion resis-
tance, environmental limitations and costs.
In Table 1 a selection of typical coating parameters
is shown for electroless and electroplating techniques
and for PVD processes. Only a few of the parameters
will be described in more detail.
2.1. Deposition rates and thicknesses
Modern PVD technologies (evaporation, ion plating
and sputtering) in the batch mode yield deposition rates
as high as those typical of electroplating processes. With
PVD processes a wide spectrum of thicknesses with
similar physical and chemical properties can be obtained.
Films thicker than 5 mm are deposited by the PVD
technique only for corrosion and wear protection. For
such purposes, new high rate planar magnetrons and
steering arc evaporators can be successfully used in
multi-source large batch or in-line systems. The only
limitations are the size and shape of the substrate.
When the replacement of galvanic coatings with PVD
coatings will be widely accepted by industry, in each
478 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487

Table 1
Comparison of typical coating parameters for galvanic and PVD processes

Electroless plating Electroplating PVD processes in batch mode

Coating materials
Substrate temperature (°C )
Deposition rates (mm min−1)
Process atmosphere
Coating thickness (mm)
Coating properties
Component size
Component material
Ni, Ni–P, Ni–B,
Co, Cu, Pd, Au
25–100
0.2–2.0
room temperature,
chemical reduction
2–50
to be adjusted
limited by bath or barrel
Cu, brass, iron, steel, Mg,
plastics, glass
Cr, Cu, Ni, Cd, Co, Fe, Sn, Pd,
Ag, Rh, Zn and alloys
25–150
0.2–150
room temperature, electrolysis
2–500 (up to 12 mm)
to be adjusted, optimized
limited by plating bath
easy: steel, Cu, Al, special treatment;
stainless steel, Al, Mg, plastics
difficult: Ti, Mo, W, Nb, Ta, glass
metals, alloys, nitrides, oxides,
carbides, multilayer
100 — evaporation up to 500
— ion plating, sputtering
0.2–10 — evaporation 0.02–20
— ion plating, sputtering
vacuum, plasma 10−2–10−6 mbar,
Ar, reactive gases
0.5–50
must be known in advance, optimized
to the substrate
limited by reactor size
no limits, also alloys, plastics, glass

case in mass manufacturing the PVD reactor or in-line
system will be considered individually and equipped
with an optimum configuration and number of sources,
heaters and plasma etching units. Only efficient planetary
rotation for the batch mode and a fixing system for
in-line equipment can guarantee an acceptable homogen-
eous thickness distribution and resulting coating
properties.
The advantage of electroless coatings (e.g. Ni) in
comparison with electrodeposited ones is that they are
uniform in thickness. Components can therefore be
plated to the requested size without any additional
finishing operation. Fixing systems of PVD coaters are
different for each substrate. They are in general more
expensive, more complicated and demand more
assembling.
2.2. Coating properties
The properties of electroless coatings and electro-
deposits can be easily controlled by varying the electro-
deposition parameters, by using different plating
solutions and by various additives. In accordance with
new environmental limitations, nearly all the traditional
surface coatings have been subjected to improvements
in industrial processing by scaling up of existing equip-
ment, good process control and a continuous industrially
oriented testing of the coatings produced. Numerous
innovations and patents helped the galvanic industry to
produce higher quality coatings more efficiently, and at
the same time to lower pollution of air and water. Such
galvanic coatings are mostly fine grained, nearly amor-
phous or non-crystalline. An example is electrodeposited
nickel with 10–25% phosphorus, which is used in the
electroforming of small parts [11] or moulds in artificial
teeth production [12]. Such amorphous metal and alloy
coatings, being galvanic or PVD, are of great interest
for new applications, because they possess higher den-
sity, higher corrosion resistance, better adhesion and
better mechanical properties.
For many galvanic coatings the surface morphology,
adhesion, porosity, thickness and surface hardness deter-
mine the life of the part or machine tool. Critical
parameters are surface microcracks (known from hard
chrome), changes of chemical composition and thickness
variations.
The properties of various PVD coatings (metals,
alloys, nitrides and oxides are of main interest here)
have been well documented [2] and systematically pre-
sented [13]. However, the PVD coating represents just
one aspect in a given tribo-system; consisting of sub-
strate–surface treatment–coating. Therefore, before one
chooses or designs an alternative technology for pro-
duction, the whole tribo-system must be studied in
detail. Using test substrates, a complete characterization
should be performed giving positive results in accor-
dance with the available data for the part with the
galvanic coating and including all the required surface
pre-treatment.
Functional PVD coatings (Ni, Cr, TiN, ZrN, CrN,
TiAlN, TiC, CrC, WC/C, diamond and DLC ) must in
general be thick enough (at least few mm), with good
adhesion and high wear and corrosion resistance. On
the other hand, PVD decorative coatings must sustain
abrasive wear, corrosion and ambient influences as well
as exhibiting optical characteristics (colour, reflectivity)
[14] as similar as possible to those of the competing
galvanic coating. The whole spectrum of colours can be
obtained with various PVD techniques, i.e. ZrN (the
closest to pure gold ) and Ti (N, O, C ) having a
black colour.
2.3. Adhesion
The adhesion of the analysed coating, with a thickness
optimal for the required function, must correspond to
 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
available quantitative data. In industry quantitative tests
of adhesion are made by the flyer plate, ring shear and
conical head techniques, while the common technique
in laboratory control is the scratch test with a diamond
stylus (REVETEST ) [15]. From the adhesion point of
view, ion plating processes with a previous wet ultrasonic
cleaning and then in situ plasma cleaning of the sub-
strate, are deposition techniques superior to sputtering
techniques and especially to evaporation methods. Only
rarely is an independent intermediate layer used as a
means to improve adhesion at the interface.
Therefore, PVD technologies can easily avoid all the
problems of galvanic coatings (wet substrate pre-treat-
ment steps, chemicals, etchants), even for those named
‘difficult’ in terms of adhesion in Table 1. During the
PVD process efficient low temperature pre-heating and
plasma cleaning in the deposition reactor produces
excellent adhesion to all substrates. The only limitation
is the maximum temperature typical of each PVD
process.
The adhesion of coatings thicker than 3–5 mm (for
most metals, TiN and other PVD coatings) is sometimes
a problem owing to the relatively high internal stress in
these coatings. Only coatings based on Cr (Cr, CrN,
CrC, CrON ) can be easily deposited up to 20 or even
50 mm. If thick coatings are required, mostly for corro-
sion protection, PVD and thin undercoat electroplating
can be combined [16 ]. In such a case, we partially lose
the environmental advantages.
2.4. Corrosion and porosity
When the replacement of a galvanic coating by PVD
coating is considered, the good corrosion resistance of
hard protective PVD coatings is the main aim to be
attained. Namely, the corrosion appearance is closely
related to the surface quality of the substrates, e.g.
surface morphology, defects and reactivity. This directly
influences the coating properties and especially the cor-
rosion resistance [17–20]. In the case of electroless and
electrodeposited coatings, the resistance to corrosion
can be improved by multi-step surface pre-treatments,
by control of the coating microstructure (dense and
non-porous), and by the most important parameter,
that of thickness.
Today data for the recommended minimum thickness
of various materials (Ni, Cu, Cr, Zn, Sn, Cd, Au, Ag
etc.) plated on iron, steels, brass, copper and alloys,
magnesium and alloys, plastics, glass etc. are available
through general know-how, ASTM or DIN standards
or patents. For more demanding requests, special protec-
tive coatings were developed instead of conventional Ni
or Cr coatings. These improved galvanic coatings are
known as ‘microporous’, ‘microcracked’ or combined
coatings. Today the aim of the PVD research community
479
is to develop coatings which would be close to or even
superior to these improved galvanic coatings.
When relatively thin PVD coating are used, the
surface quality directly determines the degree of corro-
sion resistance. Owing to their morphology, technologi-
cal surfaces require protective coatings, which prevent
the development of local corrosion processes, e.g. gal-
vanic, crevice or pitting corrosion, or capillary condensa-
tion. Such coatings are also declared as ‘fully dense’ and
their quality depends on the type of PVD process and
the deposition parameters.
PVD TiN coatings have been most extensively investi-
gated in terms of corrosion resistance [2,21,22]. These
studies included long-term and short-term electrochemi-
cal measurements. As substrates iron CK 45, stainless
steel AISI 304 and some alloys were used. Special
attention was given to the coating growth mechanism
(fine grained or columnar), interfacial state and interme-
diate layer and final thickness [23]. The degree of coating
porosity has been determined quantitatively by the
through-coating porosity [24]. In our department sys-
tematic studies of corrosion properties have been per-
formed with various PVD coatings ( TiN, CrN, ZrN,
TiZrN, TiCrN, TiCN, WC, TiAlN and TiN/CrN multi-
layer) [25–27]. As an example, potentiodynamic polar-
ization curves recorded for TiN coatings on various
steel substrates are shown in Fig. 1.
Usually the porosity of coatings was studied by
multicyclic voltammetry in acetate buffer solution at
pH=5.6 [25]. In this way substrates which show an
active dissolution current peak at a certain potential can
be tested, e.g. iron or steels. If the coating is porous,
Fig. 1. Potentiodynamic polarization curves, recorded in 0.5 M
H SO for (a) uncoated and (b) TiN-coated substrates, showing the
2 4
influence of the type of substrate [26 ].
480 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
the current density of the peak associated with substrate
dissolution, i , would be recorded and then increase
crit
further with the number of cycles. This behaviour indi-
cates that the electrolyte has reached the substrate
through micropores in the coating and caused its
dissolution.
Fig. 2 presents the critical current density as a func-
tion of the thickness of a CrN coating deposited onto
Ck 45 stabilized iron [25]. With increasing coating
thickness the critical current density decreases, indicating
a decreased dissolution of iron through the micropores.
If the thickness of the CrN coating exceeds 1 mm, no
iron dissolution can be detected. Hence, this thickness
can be considered as the minimum coating thickness,
which would prevent dissolution of the underlying iron.
Improvement of the corrosion resistance of PVD
deposited coatings (e.g. TiN or CrN ), can be attained
by different technical and process arrangements.
Depending on the substrate material, the TiN coating
can be as thick as possible, i.e. up to 5.0 mm, while the
Ti interlayer can be from 0.1 to 1.0 mm thick. It has
been shown that TiN coatings on martensite stainless
steel have already achieved good corrosion protection
[25]. A similar improvement has also been observed for
CrN coatings [16,28,29]. The intermediate Cr layer can
be even thicker than in the case of TiN, while for most
materials the thickness of CrN coatings can be increased
up to few tens of microns. In many cases multilayers
such as TiN/Ti/TiN, CrN/Cr/CrN, ZrN/Zr/ZrN and
TiN/CrN show better corrosion resistance than PVD
binary and ternary nitrides [30,31], even though their
total thickness is sometimes only a half of that of the
binary coating.
3. Improvements and alternatives
Among other technologies, every large metal finishing
plant also has various surface treatments, including a
galvanic shop. In such shops, surfaces of manufactured
components and parts not only obtain besides basic
protection, but also surface ‘functional’ properties such
as wear, heat and corrosion resistance, and also decora-
tive appeal if requested. Galvanic facilities use ‘wet’
processes, such as electroplating and electroless plating
of, e.g., Cr, Ni, Zn, Sn and their alloys, and together
with other deposition pre- and post-treatments generate
large quantities of heavy metal wastes, water and air
pollution.
International efforts have been under way for many
years to find improvements, alternatives and replace-
ment for most traditional functional and decorative
coatings. However, before an appropriate technology
for a single tribological case can be developed and then
successfully introduced into mass production, an opti-
mum solution has to be found. The latter has to take
Fig. 2. Critical currents measured by cyclic voltamograms for a CrN
coating deposited on Ck 45 steel and recorded using 10 mV s−1 in
acetate buffer solution, pH=5.6.
into account not only research, environmental and devel-
opment problems but also to face the cost problems. It
is especially important to study in detail existing surface
coatings and the improvements which have been recently
introduced for a chosen object.
In this section we discuss briefly some of the basic
galvanic processes which represent the major concern to
finishing shops, and their improvement and alternatives.
In Table 2 a general picture is shown.
3.1. Substitutes for cadmium
Electroplated cadmium has been used in engineering
for a long time owing to its good lubrication function
(threads) and solderability. It has also been used for
corrosion protection of iron, carbon- and low-alloy
steels, especially in saline and industrial environments.
Because Cd is an extremely toxic material, numerous
countries have already eliminated its use during the ’80s
and ’90s. However, owing to its superior combination
of high corrosion resistance and lubricity, Cd will still
be used for manufacture of aerospace fasteners and in
many military applications.
As a substitute for Cd, aluminium, zinc and zinc
alloys have been proposed and already applied in prac-
tice. Zinc was an obvious choice as a replacement for
Cd as it is known as a corrosion-resistant coating for
steels in numerous applications. Zinc–nickel (5–15%)
and tin–zinc (20–30%) alloys have also been put into
production, although on limited basis [32].
Aluminium may be deposited by an ion–vapour
deposition (IVD) process, offering excellent adhesion,
high deposition rates and controlled surface morphology
[33]. This IVD process for Al was the first PVD technol-
ogy which successfully replaced a traditional galvanic
coating. Al–Mg alloy with 10% Mg shows optimum
 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487 481

Table 2
Galvanic coatings, various improvements already applied and PVD technologies as alternatives

Coating type Improvements PVD alternatives

cadmium (5–20 mm) Zn, Zn–Ni (5–15%), Sn–Zn (20–30%), Al ion vapour deposition sputtered alloys
Zn–Co, Zn–Fe, Al–ceramic coat
zinc (2–30 mm) Zn–Ni, Zn–Sn, Ni–SiC Al ion vapour deposition sputtered TiAlN and alloys
hard chromium (5–30 mm — functional, HVOF – alloys, thermal spray, Cr-sputtered, arc CrN, CrC, Cr/CrN, Cr/TiAlN,
0.5–3 mm — decorative) plasma spray, Ni–W–Si carbide ENiP+Cr sputtered, plasma nitriding + CrN
electroless nickel — ENiP,B (3–50 mm) alloy Ni–W–B, HVOF alloys, white Cr/Cr N, Ti N, Zr N
2 2 2
plasma spray
nickel (1–50 mm, also 12 mm) Ni-sputtered
brass-decor (2–15 mm) Cr+MS — sputtered, ZrN/brass colour
gold-decorative (0.5–10 mm) thickness decrease, combined coatings TiN, ZrN, Cr/TiN, Ti/TiN, TiN thin Au
silver (1–10 mm) contacts: Au–Ni, Pd–Ni, Sn Ti/TiN, CrN, Nb/NbN

corrosion behaviour regarding pitting corrosion, even
though the films are only 0.2 mm thick [34]. These Al–
Mg alloys have also been sputtered by an unbalanced
planar magnetron [35]. The authors have also extended
their research to other alloys, such as Zn–Mg and Al–
Mg–Zn, which together with Al–Zn sputtered alloy [36 ],
are all candidates for replacement of Cd, as well as
of zinc.
3.2. Substitutes for zinc
protection (corrosion, wear, temperature) of the object,
which has a given material and geometry. The process
must provide an optimum deposition rate, stoichiome-
try, microstructure and morphology and good adhesion
to the substrate [35]. Only if the properties obtained are
better or close to those obtained by galvanic coatings,
will PVD technology be considered for introduction on
the production line. Besides that, ecology and economy
(capital investment) will also help to make the decision
easier.

For many years zinc electroplated coatings combined
with chromating techniques have provided soft, ductile,
decorative, corrosion-resistant and solderable surface
finishing in the automotive, machine and construction
industries. Zinc protects the substrate (steels, copper,
aluminium) by sacrificing itself and thus corrodes before
the base material is attacked. In recent years increasing
requirements in the automotive industry, where designs
and materials are changing quickly, caused attention to
be focused on the development of environmentally more
acceptable coatings, e.g. Zn alloys (Co, Ni, Fe, Al, Mg,
Mn), multilayers and multifunctional coatings. Among
these alloy materials Zn–Ni with 8–14% nickel is of
particular interest owing to its good corrosion resistance
(if necessary, to avoid white corrosion Zn–Ni is chro-
mated), even at elevated temperatures [37]. Tin–zinc
alloy with 20–30% zinc combines the best properties of
both materials for the protection of steel. Zinc–cobalt
and zinc–iron are also frequently used in practice.
PVD technologies will be used to substitute zinc alloy
galvanic coatings only if we can develop an optimized
deposition process for the above-mentioned zinc alloys,
i.e. Zn–Ni, Zn–Co, Zn–Al, Zn–Mg, Zn–Fe and Zn–Sn.
It is well known that problems with the development of
deposition process for such alloys are more complex
than with currently available nitride hard coatings, e.g.
TiN, CrN or ZrN [2,33]. For a selected alloy one of the
available processes (ion plating, unbalanced magnetron
sputtering deposition or ion-beam-assisted deposition)
should be optimized, according to the required surface
3.3. Substitutes for hard chromium
Electrodeposited hard chromium is used as a protec-
tive layer against wear and corrosion and as decorative
trim on millions of different products throughout the
world. This coating is produced from a wet chemical
bath containing hexavalent chromium ions (Cr+6). In
all environmental regulations, Cr+6 is classified as a
confirmed human carcinogen. Hard chromium plating
produces large volumes of chromium-containing toxic
waste, air pollution and water contamination [38]. For
these reasons, alternative processes, substitute materials
and new designs have been under study for many
years [39].
Among alternative plating processes are trivalent
chromium and electroless Ni–P and Ni–W coatings,
while alloys such as Ni–W–B or Ni–SiC composites can
substitute chromium where functional applications, such
as wear resistance, are needed. Plasma spray techniques
have been successfully applied to steel, aluminium and
magnesium components. Coatings that are used to pro-
vide a wear-resistant surface include WC–18Co, Co–
28Mo–8Cr–3Si and Co–25Cr–10Ni–8W alloys, and are
known to perform better in cases where scuffing occurs.
High velocity oxygen fuel ( HVOF ) spray processes have
also shown great promise as a substitute for hard chrome
[40]. HVOF coating characteristics are similar to those
of other thermally sprayed coatings, but their advantage
is the extreme coating density, higher adhesive and
cohesive strength, and nearly six times lower sprayed
482 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
surface finish than in plasma spray coatings. As coating
materials WC–Co, Cr C –NiCr(80/20), Cr C /Mo–
3 2 3 2
NiCr and Triballoy 400 have showed highly wear-
resistant surfaces (a few 100 mm thick), especially for
machine components and tools. All these techniques are
also used for rebuilding worn components.
Vacuum applied coatings (PVD) have been investi-
gated intensively as a replacement for galvanic coatings
in certain applications. Today processes of vacuum
evaporation, ion-beam-assisted deposition, ion plating,
unbalanced magnetron sputtering and cathode arc
deposition can produce a wide spectrum of hard, protec-
tive, corrosion- and oxidation-resistant coatings. But
only a few can be considered as direct substitutes for
hard chromium in large scale production. Among these
are sputtered and cathode arc deposited chromium (Cr),
chromium nitride (CrN ) and carbide (CrC ), titanium–
aluminium nitride ( TiAlN ), diamond-like carbon
(DLC ), silicon carbide (SiC ) and various multilayers.
For PVD coatings to replace 0.5–30 mm thick hard
chromium the thickness has a decisive role. It is easy to
deposit thin CrN and CrC layers for decorative applica-
tions, even on substrates of different geometry and
material. The combination of PVD coatings on Ni–P
galvanic coatings has been found to be very successful
in meeting extreme demands in corrosion protection of
decorative layer components [7]. Such duplex coatings
have also shown good tribological properties when
deposited on relatively soft materials. These coatings
have proven to be successful even in replacement of
much thicker coatings, i.e. 10–30 mm. Namely, most
machine components have Rockwell hardness values of
32–54 HRC, which is much softer than the values of
HSS tool steel (60 HRC ) or tungsten carbide (92 HRC ),
to which hard PVD coatings are commonly applied.
Such soft substrates can be improved first with an
intermediate coating of 10–20 mm thick electroless
nickel–phosphorus ( ENiP) and in accordance with the
requested surface final finish and properties (high micro-
hardness from 2000 to 3500 HV , low coefficient of
0.025
friction, corrosion wear resistance), a subsequent opti-
mum thickness of PVD CrN or other coating. Thick
CrN coatings can also be produced using unbalanced
magnetron sputtering by deposition of an inner layer of
soft substoichiometric CrN followed by an upper layer
of CrN of standard quality. Such thick coatings have
proved to offer good adhesion and high wear resistance
for various types of soft materials.
One can also increase the substrate hardness by
plasma nitriding (100–200 mm diffusion zone) in a sepa-
rate apparatus, or by duplex coating performed in situ
[41]. Such duplex coatings, using a CrN and TiAlN top
coating, have already replaced hard chrome in alumin-
ium die casting and hot forging, in abrasive plastics
extrusion and recently in hot forging of steel parts.
Replacing hard chrome electroplated coatings will be
a long process and will be limited in the near future to
certain applications and to those locations where alter-
native technologies are available.
3.4. Substitutes for nickel
Electroless nickel and electroplated nickel are two of
the few surface finishing processes that can satisfy
requirements for functional (wear, corrosion) and deco-
rative applications [6,42]. There are many positive prop-
erties of nickel coatings and therefore the range of their
application is broad: watch bands, costume jewellery,
writing utensils, scissors, chairs, spectacle frames and
on many technical articles. However, because of the fact
that nickel is classified as a serious allergen, it should in
general be used only in technical applications where
nickel is necessary because of its excellent corrosion
resistance. The decorative sector is the first where nickel
should not only be avoided but replaced by an another
metal or alloy coatings.
Nickel is successfully used as an intermediate layer,
as a partner for alloy deposition, and as a diffusion
layer. In electroforming nickel is typically used for its
levelling and brightening ability in order to improve
substrate quality and to fulfil many technical require-
ments [7,17]. Some of them are good solderability,
further platability, and in alloy form, improved hardness
and wear resistance.
The reduction and substitution of nickel coating will
be complicated and slow. In electroplating processes
nickel has already been replaced in many cases with e.g.
bronze, iron, palladium and cobalt [43].
Alternative PVD processes for high rate Ni deposition
are electron beam evaporation, low temperature arc
vapour deposition, ion plating and magnetron sputtering
[44]. Nickel is a magnetic material, and therefore a
special type of magnet is needed for magnetrons to
increase the magnetic field penetration through the Ni
target, better use of target material and to obtain high
enough deposition rates [45].
Besides pure nickel coating, it is easy with a cathode
arc process to sputter or evaporate nickel alloys such as
Ni–Cr, stainless steel or nickel-rich alloys. One of the
alternatives is NiCrTi low temperature sputtered coat-
ings, with high microhardness (950–1100 HV ) and
0,025
oxidation resistance [45]. Some results show that high
rate chromium, white Ti N and Zr N, and Cr/CrN are
2 2
also candidates for nickel replacement.
As in the production of other materials, in the case
of nickel applications pollution prevention and strict
process quality control of the applied electrochemi-
cal technologies have become of universal concern.
Therefore PVD processes are expected to replace tradi-
tional nickel coatings, although initially only in certain
specific cases.
 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
3.5. Substitution of decorative coatings
Hard gold, gold alloys, silver and combinations with
copper, nickel, palladium and shiny hard chromium are
only a few of the traditional colours used generally for
decorative applications. Vacuum processes have been
used for a long time to produce decorative, hard and
corrosion-resistant decorative coatings [14]. If one uses
only vacuum evaporation technology, different colours
can be obtained with titanium, zirconium, chromium,
hafnium and silicon compounds. Sputtering methods
provide additional hard metals and alloys, which in a
reactive mode yield a colour spectrum from white-
metallic to black [46 ]. Gold–yellow hard coatings have
been replaced by TiN, Ti/TiN, TiN+Au (thin film) and
Cr/TiN, depending on the substrate material [47].
During the ion plating of titanium, various colours other
than gold–yellow can be deposited (white-metallic, gold
brown, violet, blue, black) with only a slight modifica-
tion of the chemical composition. Besides TiN, TiCN
can be obtained in gold to red–brown colours, while
ZrN can give from white metallic, to various brass
colours. Brass coatings can be also substituted by
Cr+sputtered brass coatings. Grey colours are typical
of carbides of Ti and Cr, and with various compositions
of TiAlN brown–grey, violet–grey and blue–grey colours
can be deposited.
A wide spectrum of colours has been obtained with
reactive sputtering of Cr, Ta, Ti, W, Mo and Zr in the
gases N , O , CH , SiH and B H . Good adhesion has
2 2 4 4 2 6
been observed to a wide spectrum of base materials
(stainless steel, titanium, special alloys, hard metals,
copper and aluminium alloys, zinc and polymers), with
very different electrochemical, mechanical and physical
properties, which besides decorative appeal, also provide
protection against wear and corrosion.
The combination of galvanic coatings with PVD
coatings has also been successfully used for decorative
applications [7,29,48]. This technique helped manufac-
turers to avoid high quality surface finishing methods,
many of them producing serious sources of pollution.
On the other hand, a basic coating quality can be
preserved, even if fashions change annually and new
colours or colour tones are requested from the coating
centre.
Today the use of various PVD coating technologies
for decorative applications is increasing much faster
than for technical or functional applications. The
reasons for that are the following: the broad range of
colours available, corrosion and wear resistance better
than that of the galvanic coating to be substituted, the
use of less expensive substrates and the ability to
compete economically with traditional galvanic
technologies.
483
4. New demands for deposition equipment
The profitability of PVD processes in comparison
with modern galvanic processes is still under discussion
between coating experts and managers of both sides.
The statement ‘‘ PVD coatings are more expensive than
electroplating’’ is no longer valid, if we take into account
environmental limits, substrate material, size quantity
and the quality of the surface improvement. Large
quantities of low-cost substrates can be successfully
coated in an optimum reactor arrangement, in which
high deposition rates and the highest possible through-
put of substrates can be achieved. Some recent data
show that high speeds are more important than high
deposition rates [32,39]. Additionally, an efficient
plasma etching and heating system, if needed, must be
provided in every deposition equipment of this type.
During the last decade, several groups have studied
high rate processes. As a basis the main plasma-assisted
PVD processes can be used. These have been developed
and are still in use to produce various hard coatings
[49]. Plasma-activated high rate evaporation using a
low voltage and a high power electron beam and spotless
coating arc systems are known to permit deposition
rates of 0.2–1.0 mm s−1 [50]. Particular attention was
devoted to high rate magnetron sputtering [51]. Recently
an overview of magnetron sputtering on large scale
substrates was presented [52]. The deposition rates
obtained with magnetron sputter cathodes are typically
one order of magnitude lower (max. 0.1 mm s−1 for
sputtering of Al ) than those of thermal evaporation
(1 mm s−1 for Al ). For magnetron target materials with
high sputtering yield (e.g. Cu, Al, Ag, brass, Al bronze)
the highest deposition rates were obtained in the self-
sputtering mode [51]. This process combines the advan-
tages of sputter deposition (good adhesion and structure
and the ability to coat large surface with uniform
thickness), with high rate e-gun evaporators. Such a
deposition source system built in a sophisticated equip-
ment design will be probably used in the future for a
chosen type of substrate.
Alternative PVD coatings can be deposited in avail-
able large batch systems or in continuous (in-line) PVD
coating systems, which have been designed and equipped
with optimized sources for a given quality of the sub-
strate. The size of batch coaters is limited to approx.
1.5 m in height and 2 m in diameter. When all the
technical problems have been solved, substrate geometry
and systems of fixturing determine the throughput of
substrates and its economy. Generally, in-line systems
represent large investment costs and up to now were the
main reason why the PVD process was declared to be
so much more expensive than galvanic technology.
However, it has been shown recently that above a critical
production volume continuous production systems are
484 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
more profitable than available batch systems when low-
cost components for mass production need to be
coated [53,54].
Because of very different demands for the develop-
ment of deposition equipment, new designs and devel-
oped technologies have mostly been patented [10]. It
has been reported that various PVD processes can be
technically and economically applied in complex equip-
ment, which in one case was used for surface modifica-
tion of stainless steel in the form of coils. With efficient
heating and plasma cleaning, ion plating ( TiN, TiC ),
high rate sputtering (Cr, Al O ) and plasma CVD
x y
(SiO ) protective corrosion-resistant, decorative and
x
electrical insulation has been obtained on steel bands
by an in-line dry coating system [55]. In such a coating
system the substrates may be foils or bands of metal,
alloy or plastics.
Automatic high volume and combined PVD pro-
duction systems are expected to be used in future for
replacement of galvanic processes. Low temperature
deposition processes with high deposition rates, good
adhesion and appropriate coating structure will addi-
tionally help to expand the use of PVD technologies in
this field.
One could expect that a single ‘centre for alternative
surface coatings’, which would include various coating
processes and a high throughput of substrates, would
satisfy the needs for an industrial area, for a local
community or just for one alternative coating (e.g.
nickel ) on one substrate (in large volume of a few ten
millions) for a larger European area.
5. Positive results from mass production industry
2 years ago we found that in the ISKRA
(Autoelektrika automotive industry in Slovenia), where
TiN and CrN coatings have been used to improve tools
and machine parts for more than 15 years, PVD technol-
ogy could be used to replace some traditionally used
galvanic coatings. For example, heat sinks made of
aluminium are electroplated with Cu+Ni coatings in
order to prepare the surface for soldering the button
power diode. The rotating core of switches in starters is
made of magnetic soft iron and electroplated with hard
chromium in order to achieve good wear and corrosion
protection. In both cases results were positive and
alternative PVD technologies are ready to be introduced
into mass production.
5.1. Sputtered nickel as a replacement for electroplated
nickel on aluminium
A negative type of aluminium heat sink and a com-
plete rectifier set are shown schematically in Fig. 3. The
heat sink is a cold drawn Al profile. The technical
standards for the alternator include as critical parame-
ters the electrical conductance and mechanical strength
of the contact between the power diode, soldered with
a Pb–In–Ag solder, and the Al heat sink. The critical
pull-off (shear) forces on the diode should be higher
than 700 N. Traditionally, the Al surface was first chemi-
cally activated and then coated with approx. 2 mm
Cu+5 mm Ni. With such a galvanic treatment, the
critical shear force was typically measured to be between
1000 and 1200 N.
As a substitute, nickel was sputtered for test measure-
ments in a Balzers SPUTRON DC ion beam sputtering
apparatus and in Balzers LLS 502 sputtering equipment,
using a special magnetron source for nickel sputtering.
In both pieces of equipment plasma cleaning was avail-
able. The goal of this systematic study was to obtain
optimum nickel properties with the lowest nickel thick-
ness. It is important to mention that the hardness of the
aluminium substrate was 82–86 HV , while the
0.025
microhardness of the 2.5 mm thick nickel coating was
250–280 HV . Such a nickel coating did not increase
0.025
the initial aluminium surface roughness R , which was
a
0.35–0.45 mm (typical for cold drawn surfaces).
The mechanical strength test was made on the indu-
strial production line at the ISKRA-Avtoelektrika plant.
The soldering of the power diodes to the nickel-coated
aluminium heat sinks was also performed there on the
automatic line. This operation is needed to assemble the
rectifier sets for alternators. The shear force, as a mea-
sure of the adhesion of the diode to the heat sink coated
with a nickel layer, was measured for each diode (three
on each heat sink). The results were surprisingly good.
With nickel PVD coatings, 0.5, 0.8 and 1.3 mm thick,
sputtered directly on plasma cleaned aluminium surface,
average critical shear forces were between 1180 and
1370 N (see Table 3). Results were obtained for two sets
of heat sinks. Some single contacts even sustained up to
1700 N shear force on the edge of the 5 mm thick power
diode (only 5 mm in diameter), soldered on the 0.8 mm
thick sputtered nickel layer. Such results seem to be
technically difficult to achieve and show that an
extremely efficient PVD process was applied to the
aluminium.
Corrosion tests of the heat sinks and rectifier sets
were performed in an ASCOT salt spray test cabinet for
144 h, with 5% sodium chloride fog at a temperature of
35°C. After 144 h the aluminium surface was slightly
corroded, while mechanical and electrical tests showed
no difference from the initial values.
The following conclusions are relevant for future
applications of this PVD technology:
1. original cold drawn aluminium profiles can be used;
2. cleaning (ultrasonic and plasma etching) is more
efficient;
3. plasma cleaning of aluminium is the critical process
 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487 485

(a) (b)

Fig. 3. Diagram of a negative type of heat sink ( left), and a photograph of a complete rectifier set (right).

Table 3 6. such thin nickel layers forming the contact to the

Critical shear force on three diodes (D1, D2 and D3) on positive (P) power button diode are also corrosion resistant;
and negative (M ) types of heat sink coated with 0.8 mm thick nickel
coating sputtered in LLS 502 equipment, obtained during a mechanical 7. above the critical production volume, which in this
strength test case is over one million per year, the PVD technology
described becomes less expensive than the traditional
Run 2 Force (N ) 0.8 mm Ni nickel electroplating;
No D1 D2 D3 Ar 3×10−3 8. compared with the situation 10–15 years ago, when
TiN hard coating was introduced into industrial
P4 1250 1200 1450 manufacturing, more research work, technological
P5 1250 1400 1300
development and industrial tests are needed.
M4 1400 1700 1350
M5 1300 1250 1400
average 1300 1388 1375 1354
5.2. Ion-plated chromium nitride as a replacement for
hard chrome plus nickel undercoat on soft iron
in the production of an efficient nickel coating on
aluminium; The lifetime of the switch in an starter must be longer
4. no intermediate layer is needed to obtain excellent than the starter itself, or it must be able sustain more
adhesion of a thin (0.8 or 1.3 mm) nickel layer to than 30 000 operations. Therefore, the rotating core,
aluminium; which is a built-in brass tube and made of magnetic soft
5. much lower thickness of nickel, compared to Cu+Ni iron, must be protected with a protective coating to be
galvanic coatings, is sufficient to fulfil all the stan- wear and corrosion resistant. Traditionally, such cores
dard tests; with ground surface (R =0.5–0.8 mm) are electroplated
a

(a) (b)

Fig. 4. Diagram of a switch with rotating core made of magnetic soft iron ( left), and a photograph of such components (right).
486 B. Navinšek et al. / Surface and Coatings Technology 116–119 (1999) 476–487
with 8 mm nickel plus 2 mm hard chrome. The microhard-
ness of such a coating combination is 680 HV . Fig. 4
0.025
shows the diagram of such a switch and a photograph
of such a component. After 30 000 test operations, many
deep longitudiual grooves and remarkable abrasive wear
can be observed on the core surface.
We decided to use a chromium nitride coating depos-
ited by ion plating as a replacement. We deposited 3.0–
5.0 mm thick CrN with a 0.5 mm thick Cr intermediate
layer. Depositions were performed at 400°C in Balzers
BAI 730 M equipment, using a low voltage thermionic
arc [5,56 ]. Typical deposition rates were 4.0 mm h−1.
Such switches with cores of ion-plated chromium
nitride of various thickness were built into test starters
in the ISKRA Avtoelektrika plant. After 48 000 opera-
tions no damage and no ambient influence was observed
on the core surface. Corrosion tests in a 5% sodium
chloride fog at 35°C for 144 h showed that:
1. if the CrN layer is only 3.0 mm thick, the surface
roughness R of the core must be lower than 0.3 mm;
a
2. for the standard surface treatment the chromium
nitride coating must be 4.5–5.0 mm thick;
3. a thicker chromium intermediate layer (0.5 mm
instead of standard 0.2 mm) helps to improve the
corrosion resistance of soft iron core.
The replacement of electroplating of the soft iron
core by ion plating is economically acceptable (even
though the coating costs are today 50–80% higher) if
approx. 400 000–500 000 cores per year are deposited.
6. Conclusions
The introduction of PVD processes as a substitute
for galvanic technologies in the mass production indus-
try represents the development of environmentally clean
technologies in new industrial surroundings.
A comparison of various galvanic and PVD process
which can produce metallic, alloyed or ceramic coatings
was presented. The coating thickness, adherence to the
substrate and corrosion resistance of PVD coatings on
low-cost substrate materials play a decisive role in the
successful substitution of the well organized and com-
mercially successful galvanic coatings.
Alternative PVD technologies were presented for
cadmium, zinc, hard chrome, nickel, noble metals and
decorative coatings. High rate ion plating, magnetron
sputtering and cathode-arc processes offer the basis for
future research work and development in this field.
Taking into account the large numbers of substrates (in
hundreds of thousands or millions), the high throughput
and process speed, new design of the equipment will be
needed. Large batch systems and continuous or in-line
equipment should include various types of high rate
deposition sources, all of them with heating and efficient
plasma cleaning.
Two positive results from the mass production indus-
try in Slovenia were described. Electroplated nickel was
replaced by sputtered nickel on the aluminium heat sink
of an alternator rectifier, while nickel+hard chrome was
replaced by chromium nitride hard coating plus a chro-
mium intermediate layer on the soft iron rotating core
and built-in switch of an starter. All the tests were
positive and show that both new technologies can be
introduced into mass production industry.
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