Since
the mid-90s, physical vapor deposition (PVD) coatings have
been established as the high quality finish for sanitary and door
hardware in the U.S. Major American OEMs such as Baldwin,
Delta, Kohler, Moen, Price Pfister and Schlage Lock are marketing
these products with long-time guarantees on their appearance. Moen
received the 2000 ASM Engineering Materials Achievement Award for
its development of PVD coatings on its faucet lines.
PVD
is a vacuum deposition technique where metal is vaporized in an
atmosphere that consists of partly ionized noble or reactive gases.
In the first case, a metallic layer is grown on the substrate material.
In the second case, the metal reacts with the ionized gas, leading
to a ceramic material. PVD ceramic coatings offer an alterative
to traditional electroplating because of several characteristics:
high hardness and wear resistance, no discoloration or tarnishing,
high corrosion resistance and no attack by UV radiation
Originally,
chromium colored faucets and doorknobs were made of brass or zinc
and subsequently electroplated with a nickel/chromium finish for
leveling, high luster and corrosion resistance. Trends in recent
years show that increasingly more products are made of lower cost
materials like ABS plastic. These trends have not only led to challenges
for the electroplating companies but also for the manufacturers
of PVD equipment.
At
Hauzer, Venlo, the Netherlands, engineers have taken on this challenge
and proven that all these substrate materials can be treated in
a reproducible manner.
Limitations
of electroplated brass
In the U.S., polished brass is the most popular color in sanitary
and door hardware applications. Electroplating is the typical method
for applying brass finishes. A nickel layer is deposited followed
by a brass layer. To provide a corrosion barrier for the brass,
the product is covered with a clear coat; however, because the clear
coat is soft and attacked by UV light, the clear coat does not provide
long-lasting protection.
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Figure
1: Electroplated polished brass.
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Limitations
of PVD
PVD coatings have no leveling effect, since it is a line-of-sight
process. Also, the PVD cost is still high enough that the thickness
is a cost-determining factor. The thickness of decorative PVD coatings
is generally the range of 0.3 mm. At this thickness, a PVD coating
does not act as a corrosion barrier; therefore, usually applied
on top of electroplated products. With the PVD coating as the final
step in the finishing cycle, the previous steps play an important
role in end product quality. In this respect, a distinction has
to be made between different substrate material, such as brass,
zinc die-cast and ABS. Stainless steel as a substrate material does
not need to be electroplated and can be coated together with brass
and zinc products.
Pre-PVD
Plating
The typical electroplating layers deposited to provide corrosion
resistance and leveling consist of a nickel layer and chromium layer,
sometimes on top of a copper layer. If these layers are used as
a substrate for PVD coating, some features become more important.
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Figure
2: Top view of a decorative PVD installation.
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Zinc
die-cast. After a zinc die-casting process, the surface of the
material may be rather rough. If the copper film does not adhere
to the zinc over the entire surface, it will leave voids under the
electroplated layers. During the PVD process, the products will
be heated under vacuum, and entrapped gas will expand. The PVD coatings
will adhere to the electroplated layers, but so called blisters
will form. If the electroplating is too thin, entrapped gas may
escape and the coating stack may implode.
ABS
plastic. For PVD processes, it is preferable to have the complete
ABS surface covered by a metal film. This coverage enables more
flexibility in fixture design (electrically conductive contact between
fixture and product is necessary) and reduced outgassing of the
plastic material during the deposition process.
Cleaning
Prior to PVD Coating
A sometimes-underestimated part of the production cycle is the precleaning
of products prior to PVD coating. Part of the PVD process itself
is an etching step; however, this is mainly meant as a finishing
touch to ensure a perfect adhesion. The technology most used in
precleaning is ultrasonic alkaline cleaning.
A typical
cleaning line consists of baths with water-based alkaline cleaning
agents, rinsing baths with city water, RO water and DI water and
a vacuum or hot-air drying station. Care must be taken so that no
silicon containing buffing compounds are left in or on the products
when entering the cleaning line. The cleaning line must have sufficient
flexibility to ensure appropriate cleaning of all substrate materials.
Agents used for brass may not be suitable for zinc. The DI water
in the rinsing baths has to be good enough to ensure no drying stains
will form on the products. Last, the drying station has to be adjustable
to enable good drying of low- and high-temperature resistant materials.
PVD
Coating Process and Properties
As mentioned, the benefits of PVD coatings include high hardness
and wear resistance, and no discoloration or tarnishing. These qualities
depend on the parameters in the PVD process. One of the most important
factors in determining the density of the coating and, therefore,
the hardness and wear resistance of the coating, is the deposition
temperature. The density of the coating improves with higher temperatures;
however, the temperature resistance of the substrate material limits
the process temperature. For PVD processes, the energy transfer
to the film by radiant heating can partly be replaced by ion bombardment
of the growing film.
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Figure
3: Possible colors for PVD arc deposited coatings.
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With
increased ion bombardment, the density of the coating increases
(less porosity). Due to the larger compressive stress in the film,
its hardness will also be larger. This means that the coatings will
have a better wear resistance (higher hardness) and corrosion resistance
(less porosity).
In
this respect, it is necessary to make a distinction between two
PVD technologies: arc evaporation and sputtering. With sputtering
processes, the ionization level of the metal is limited to approximately
5%. In arc evaporation, the metal will pass through a very strong
electron beam, leading to ionization levels of 90% or higher. The
bombardment is even stronger because the average ionization is close
to two.
By
applying a negative potential to the substrates, these positively
charged ions are accelerated toward the products, leading to the
necessary ion bombardment of the growing film.
As
the energetic bombardment in arc evaporation processes is 35 times
higher than during sputtering, arc evaporation is the favorable
deposition technology for low-temperature materials like ABS plastics.
Decorative PVD coating chambers are mostly equipped with arc evaporation
cathodes. Figure 2 shows a schematic top view of a decorative PVD
installation.
The
system has up to six cathode positions, which can hold both arc
evaporation and magnetron sputtering cathodes. Target materials
can be chosen freely, enabling production of multi-layers and metal
compound coatings. For extended water vapor pumping speed, the system
is equipped with fast cycle cryo panels. Products are mounted on
fixtures with two- or three-fold rotation to ensure optimal coating
uniformity. With a volume of approximately three sq meters and a
locating height of two meters, the system is ideal for mass production
of consumer goods as low cost per piece.
Because
the temperature resistance of several substrate materials is limited,
coatings with identical colors and high quality have to be produced
at economically attractive prices. The standard PVD process for
electroplated brass products typically consists of the following
steps:
- Heating
and pumping. With infrared heaters, the products are heated to
their process temperature to ensure degassing has been reduced
to an acceptable level prior to the actual deposition steps. With
a combination of forevacuum1 pumps and turbo molecular pumps,
the system is pumped down to a vacuum level sufficiently low enough
to avoid negative effects on the coating quality. Special heat-up
stations have been designed to preheat the substrate table, fixtures
and products outside the vacuum chamber to reduce the cycle time.
- Target
cleaning. The arc cathode is started with closed shutters in front
of the targets to ensure a clean target surface at the beginning
of the next process steps.
- Ion
etching. The negative bias voltage accelerates metal ions from
the arc materiala critical step for excellent adhesion.
- Deposition.
By choosing among other target material, arc current, bias voltage
and gas flow of several gases, coatings of different compositions
and structures are produced.
Processes
Specific for Substrate Materials
Zinc die-cast. The combined quality of zinc die-castings
and electroplating determines the temperature resistance of the
products (between 80-180C). When the temperature limitation is known,
the process settings for preheating, pumping and heating and ion
etching steps can be tuned to prevent overheating. High quality
electroplated zinc die-cast can be coated at similar temperatures
to brass.
ABS
plastic. In addition to temperature limitations, another problem
of ABS plastic is its porosity and tendency to adsorb high amounts
of water vapor. Degassing cannot be forced by heating the products
to high temperatures; therefore, it has to be controlled in the
vacuum chamber itself. With the normal vacuum pumps having low pumping
speeds for water vapor, it takes a long time to pump down an installation
to its necessary vacuum level. With the introduction of fast cycle
cryo panels, the amount of time needed to pump down to a base pressure
of 3E-mbar is reduced to approximately 15 minutes.
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Figure
4: Influence of nitrogen flow on the color of ZrCN coatings.
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Stainless
steel panels with tubing soldered to the back are mounted within
the vacuum chamber. Water vapor in the chamber is adsorbed and trapped
by a cooling medium with temperatures down to 150 Kelvin. In this
way, the pumping speed for water vapor is increased immensely, and
cycle times can be reduced to similar levels as for metal substrates.
An extra benefit from the cryo panels is additional cooling for
the products, opening a larger process window for heating and quality
improvement by ion bombardment.
PVD
Colors
PVD coatings can be produced in a wide color range. Several target
materials can be chosen as long as they are conductive for arc evaporation
technology. Metals used as target material in decorative PVD processes
are zirconium, titanium, chromium, titanium-aluminum alloys and
niobium. With the multi-target system, it is also possible to make
compound coatings from more than one metal.
Ceramic
coatings are made to increase the hardness and color window of the
deposits. Introducing reactive gases during the deposition produces
these hard coatings. The most used reactive gases are nitrogen and
methane or acetylene to produce metal-nitride, metal-carbide and
metal-carbonitride films. Sometimes oxygen is also used to produce
oxides, oxinitrides, etc. These metals can be produced in a certain
color range, depending on the metal-to-gas ratio in the film (also
called stoichiometry) and the structure of the coating.
To
change the stoichiometry and structure of the coating and its color,
arc evaporation current, bias voltage, gas flow and temperature
can be used: arc evaporation current, bias voltage, gas flow, temperature.
The
process temperature affects the density and structure of the coating
and, therefore, its color. This means that even with identical currents,
bias voltages and gas flows, color difference will exist between
products coated at different temperatures. With the goal to coat
different substrate materials with identical colors in mind, other
process parameters have to be found to counterbalance the effect
of temperature. The effects of arc evaporation current, bias voltage,
argon, nitrogen and acetylene flow have been examined in detail.
Figure 3 shows the influence of the nitrogen flow on the color of
zirconium-carbonitride coatings for a certain combination of evaporation
current, argon and acetylene flow. Colors are measured in CIE-L*a*b*
values.2
Zirconium
is the most used target material for decorative applications in
sanitary and door hardware because of its relatively wide color
range.
Process
Control
The process parameters for each collating (color) are stored in
recipes with different process steps. During the process, all relevant
process parameters are continuously monitored and controlled by
an automatic control system. By storing the relevant parameters
in recipes and controlling and monitoring them during the processes,
it is possible to have an excellent reproducibility of the coating
quality. PVD yields up to 98% have been achieved on a long-term
basis.
The
combination of these, specially designed installations with high
flexibility and reliability and automatically controlled processes
enable excellent reproducibility of a magnitude of colors on different
substrate materials in multiple machines worldwide at any moment
in time. Faucets assembled of brass, zinc and ABS products will
show no color deviation, even if the substrate materials are purchased,
electroplated and PVD coated in different locations.
1 A
PVD chamber is usually operated in the E-3 or E-2 mbar range (1Torr+1.333
mbar) and has a base pressure in the E-7 mbar range. Pressures such
as this can be obtained using oil diffusion or turbomolecular pumps.
To obtain a vacuum on the high-pressure side of the turbo pumps
and to pump down the system from atmospheric pressure a rotary vane
and root pumps (forevacuum) are used.
2 Commission
Internationale dEclairage is the most commonly used color
space and is based on human perception of color.