CHROMIUM ELECTROPLATING PROCESS AND ENVIRONMENTAL ISSUES

The electroplating on plastics is a technique that has been developed since the early 1960`s,
in the most various fields. Automotive industry, plumbing, appliances and electronics have been
seeking for combinations of low cost and outstanding performance of many types of plastic materials,
which can have it properties enhanced by the deposition of a metal layer on the substrate surface.
The main goals that is trying to achieve is corrosion and scratch resistance, besides of the required
durability and aesthetic finish.

There are two types of electrodepositing a chromium layer on a substrate: Hard chrome
plating and decorative chrome plating. The first one is also known as industrial chrome, and is focused
on enhancing the mechanical properties of the surface, such as hardness and wear resistance, by
preventing corrosion, scratch and abrasion. Experimentation made by Poeton [1] has achieved 1000
Hv in the Vickers Pyramid Number. The decorative chrome plating intend to increase the material`s
durability and makes the finish more attractive.

The hard chrome plating builds up a thicker layer than the decorative type. While decorative
chrome plating presents thickness between 0.13 to 0.25um, in the hard type it can varies from 12.5
um (the minimum thickness for acceptable enhancement of mechanical properties) to 250 um, in
applications which require high load cycles. [1]

In many circumstances it is preferable to use plastic instead of metals, since the production
and processing of most of them are relatively cheap, they usually present reduced weight and are easy
to mould and to form complex shapes. Although, several resins have poor adhesion. Chromium or
nickel (or a combination of both, according to the British Standard Specification BS4601) coating is
requested when it comes to achieve hardness or appealing finish.

Many polymers can be used as substrate for chromium electroplating, such as polypropylene,
polyarylether, polycarbonate, Teflon, among others. However, the acrylonitrile-butadiene-styrene has
proved to be the best choice in the plating industry, due to its morphological structure. This
thermoplastic presents a matrix made by acrylonitrile-styrene filled with butadiene particles (rubber)
in a uniform way. These particles can be selectively etched out of the matrix, leaving holes used as
bonding sites by the electroless plate. This enhance the adhesion required by the ensuing
electroplating process. [3]

Some methods commonly used to build a metal layer on the plastic`s surface are physical
vapor deposition (PVD), thermal spraying and the electroplating. When comparing those methods, it
is clear that the electrodeposition of chrome or nickel on the surface of the substrate is an alternative
that provides better adhesion than the other physical processes. The interaction between metal and
substrate under certain voltage allows higher levels of adhesion, once the bonding between them is
chemical instead of being purely physical. [3]

The process of chrome plating on plastics can be generally divided into four steps: Moulding
the plastic pellets into the desired shape, diverse pre-treatments, electroless plating and the
chromium electroplating process. [3]
 When it comes to moulding the plastic, the shape of the polymer must be highly polished, to
avoid defects such as pit sites. Welding parts should also be avoided and texturing can be applied to
smooth surfaces in order to hide defects like scratches. The resin must be properly dried and it is
important to ensure the proper melt temperature and avoid thermal cycle failure, as noted by John J.
Kuzmik on Polypropylene in [3], due to its high coefficient of linear thermal expansion.

There are various pre-treatments which can be applied before the actual process, such as: The
use of mild alkaline cleaners or highly wetted chromic acid solution, to remove debris before of the
etching; the use of predips, (usually solvents, such as diemthylformamide) in order to compensate any
lack of the moulding quality in highly stressed parts by swelling the surface for a uniformly etching
process; the use of etchants – strong oxidizing solutions to attack the outside layer increasing the
surface area and increasing its hydrophilicity. Etchants also leave holes that will be sites for adhesion
between the plastic and the metal, during the electroplating process. [3]

After those treatments, the material is rinsed with water and subjected to a neutralizer
(sodium bisulfite, for example) to remove the excess of etchants by chemical reduction. Preactivators
can be applied in some polymers, such as polypropylene, in order to enhance the activator absorption.
The activators (usually containing precious metals such as palladium), act as a catalyst of the reaction.
Accelerators may be used to remove the excess tin and allow palladium to work properly as a catalyst.
However, contaminants as hexavalent chromium, iron and others can make the accelerator removes
palladium causing skip plate (plating void). [3]

The electroless plating is a preplate cycle, and the workpiece is immersed in a bath containing
a semi-stable solution in order to grow a thin and adherent metallic film on the surface (usually Cu or
Ni), to render it conductive. [3]

The electroplating process can be described as the growth of a hard layer on the polymer
surface. The piece to be plated works as the cathode of the circuit, and the anode materials can vary
from pure or alloyed lead (usually with silver, tin or antimony due to its corrosion- resistive behaviour)
to iron, steel, stainless steel, nickel and titanium. Chrome cannot be selected to be the anode, since it
would not be deposited in the cathode as quick as would be dissolved in the anode, due to the low
cathode current efficiency. [5]

Both components are immersed in an electrolyte bath, composed of chromium oxide (CrO3)
and sulfuric acid (sulphate), in the case of the hexavalent chromium plating. A power supply provides
direct current to the anode, and the oxidation occurs in order to oxide the metal and dissolve ions in
the solution. Chromium is passive in the electrolyte until Cr+3 is reached by dissolution of the CrO3
in the bath under a minimum potential. Those cations are reduced in the cathode (workpiece) and the
chromium oxide layer and plated on the surface. Variables such as the temperature and the voltage
can be controlled to achieve specific thickness and brightness. For decorative coatings, for instance,
the temperature normally varies from 35 to 45 Celsius, while for hard coating the range is between 50
and 65 Celsius. Clearly, high voltages lead to higher temperatures. [5] The experimental apparatus is
described on the figure below:
[6] Figure 2 - (A) Plating Tank; (B) Plating Solution; (C) Anodes; (D) Cathode (workpiece); (E) Rectifer

Overall, the chromium electroplating is a reliable and inexpensive process which can be
processed in large batches, what increases the productivity of the manufacturers. The chromium oxide
layer on plastics enhance the surface`s mechanical properties and provides higher durability to the
material, aside from the attractive silver coloured coating which is aesthetically acceptable.

Although the chrome plated material does not cause any harm, health and environmental
issues must be taken into account when performing the chromium electroplating process. A proper
waste disposal of the electrolyte bath and rinse water is extremely important, due to it very toxic
behaviour. The use of hexavalent chrome electrolyte can contaminate the air and the groundwater
through the emission of toxic off gases. There are environmental protection organizations which
regulate the amount of chromium released, and some procedures can be applied to the process in
order to minimize the environment contamination such as the use of stable wetting agents.
Perfluorinated sulfonate agents have shown an effectiveness around of 95% on the emission
reductions. [5] [1]

In addition to that, the chromium plating process exposes the operator to various health
hazards. The acid irritates and corrodes membranes of the nose and throat and the skin can be
affected with ulcers and dermatitis. Studies have pointers that hexavalent chrome can be
carcinogenic, what has been causing problems with the legislation (Restriction of Hazordous
Substances Directive – RoHS) [2] [1]
REFERENCES

[1] Poeton surface treatments, http://www.poeton.co.uk/chromium.htm

[2] Ivan Kolev, Coating on Plastics – Technology Designed for a Wide Range of Solutions

[3] John J Kuzmik, Plating on Plastics, Chapter 14

[4] Joseph Edwards, Electroplating – A guide for designers and engineers

[5] NENAD V. MANDICH AND DONALD L. SNYDER, ELECTRODEPOSITION OF CHROMIUM

[6] Plating Resources, INC, http://plating.com/general.htm

[7] THE ELECTRODEPOSITION OF CHROMIUM AND THE INFLUENCE OF THE CATHODE METAL; By J.

W. CUTHBERTSON. 2