Decorative & Hard Chromium Plating

Dr. James H. Lindsay Jr.

Applications simple in makeup, the solution operates quite differently

There are two distinct areas of application for chromium from other acid- based baths, such as copper, nickel or zinc,
deposits: (1) decorative, because of the reflective and corro- where the soluble anode is the metal supply. The chromic
sion-resistance properties of the deposit; and (2) engineering, acid is the sole source of chromium metal. The chromium is
owing to the favorable friction, wear and heat-resistance reduced to metal from the hexavalent (Cr+6) state. The sulfu-
properties of chromium. ric acid acts as a catalyst in the complex six-electron reduc-
Decorative deposits are found on the surfaces of articles tion process. Besides being complex, the reaction is ineffi-
where a bright, highly reflective finish is desired. The char- cient. About 15 percent of the plating current goes to the
acteristic bluish haze of plated chromium offers an attractive, production of chromium metal. The bulk of the current
popular surface finish. The most familiar usage is on metal evolves hydrogen gas at the part surface. Accordingly, effi-
and plastic automotive trim. This finish is also applied on cient exhaust facilities are mandatory and the possibility of
other consumer items, including appliances, marine hardware, sparking (igniting the hydrogen) must be minimized. Propri-
furniture plumbing fixtures and bicycles, to name a few. etary agents are available to provide a foam blanket to
The production of electroplated engineering chromium is localize the gases just above the solution surface.
more commonly known as hard chromium plating. This In addition to low current efficiency, the chromium plating
finish provides resistance to wear, abrasion and heat, as well bath exhibits poor throwing power. As a result, the design and
as corrosion. Machine tool cutting surfaces, cylinder bores, anodes, with supple- mental power supplies, are used in
MacPherson strut rods, crankshafts, and hydraulic shafts are difficult cases where additional power is required to assure
examples where hard chromium deposits are used. The low coverage. Such devices are critical in the case of hard chro-
friction properties of chromium are ideal for use on the bore mium plating, which involves thick deposits.
surfaces of artillery barrels. Hard chromium is often used to Decorative chromium deposits are produced under the
restore the original dimensions of worn or undersized parts, plating conditions shown in Table 1. These conditions are
such as heavy-duty shafts for presses, turbines, etc. Here, selected so as to insure the widest current range under which
chromium is over-deposited and machined back to size with a bright deposit is obtained. This bright range sensitivity is
no loss in function or properties. another result, like throwing power, of the inherent ineffi-
ciency of deposition.
Processes In addition to sulfuric acid, proprietary catalysts have been
Chromium coatings are deposited by vacuum evaporation, developed to enhance throwing power, current efficiency,
sputtering, flame and plasma spraying, and electroplating. A bright plating current ranges, and deposit micro-cracking
clear acrylic lacquer coating over a thin (1000 angstroms) character, to be discussed later. Typical formulations include
vacuum evaporated or sputtered chromium layer has served sulfuric/fluosilicate mixed catalysts and strontium or cal-
as a decorative coating on plastic parts. Engineering coatings cium salts to control the amount of active catalyst.
of flame or plasma-sprayed chromium have found applica- Decorative chromium deposits range from 0.13 to 1.30 µm
tion where uniform thickness on irregular shapes is required (5-50µin) in thickness. These thin deposits are the final layer
and not easily obtained by hard chromium plating. The of a multilayer nickel or copper-nickel-chromium system.
primary coating method, for both decorative and engineering The thin chromium deposit replicates the surface appearance
applications, however, is electrodeposition. of the underlying plated layer. Care must be taken to assure
In general, plated chromium deposits are obtained from a that the finish of the underlying deposit is the desired one. In
solution of chromic acid (CrO3) and sulfuric acid (H2SO4), addition, attention must be paid to the activation of the nickel
using insoluble lead-antimony or lead-tin anodes. While underlayer prior to chromium plating. If there is a delay

Table 1 Table 2
Conditions for Conditions for Hard Chromium Deposits
Decorative Hard Chromium Deposits
Low Concentration High Concentration
Condition Range Optimum Condition Solution Solution
Chromic acid 200 to 400 g/L 250 g/L Chromic acid 250 g/L(33 oz/gal) 400 g/L (53 oz/gal)
(27 to 54 oz/gal) (33oz/gal) Sulfuric acid* 2.5 g/L (0.33 oz /gal) 4.0 g/L (0.53 oz/gal)
Weight ratio* 80 to 125:1 100:1 Current density 31 to 62 A/dm 2
16 to 54 A/dm2
Current density 7.5 to 17.5 A/dm2 optimum bright (300 to 600 A/ft2) (150 to 450 A/ft2)
(75 to 175 A/ft2) range Temperature 52 to 63 °C 43 to 63 °C
Temperature 32 to 50 °C 43 °C (125 to 145 °F) (110 to 145 °F)
(90 to 122 °F) (110 °F)
*Chromic acid to sulfuric acid weight ratio held at 100:1
*Chromic Acid to sulfric acid weight ratio.

46 PLATING & SURFACE FINISHING

sufficient to allow drying (and thus passivation) of the acti- hexavalent processes. With reduced gassing, most misting
vated nickel surface, the result will be a whitish chromium and odor problems are eliminated, enhancing workplace
deposit or no deposit at all. safety. The majority of commercial experience has dealt with
The thin decorative chromium layer is brittle and, with the decorative applications. At present, the use of trivalent chro-
evolution of hydrogen a major part of the process, stresses mium deposits in hard chromium applications has been
result which are sufficient to produce deposit cracks. This successful with certain processes. Use in engineering appli-
characteristic is used in nickel-chromium multilayer deposits cations is more limited, but the promise of viable trivalent
to establish a crack pattern, which determines the amount and alternatives is in the near-term.
distribution of nickel area exposed to the environment. Dur-
ing corrosion, the exposed nickel corrodes sacrificially. If the Post-plating
crack pattern is well dispersed, the corrosion current is also Decorative chromium deposits normally require no addi-
dispersed and the ultimate penetration to the basis metal is tional finishing; the chromium layer is the final finish. Polish-
delayed, enhancing durability. Several methods have been ing and buffing are seldom used, as the micro-crack or micro-
used to establish this pattern, including dual-layer chromium, pore pattern would be destroyed. On occasion, selected areas
where a second layer induces cracks in the first, and micro- of the plated surface may be painted. Proper adhesion re-
porous chromium, where a final nickel underlayer contains quires special activation procedures prior to plating.
codeposited inert particles that induce a network of fine pores Hard chromium deposits used for salvage/build-up opera-
in the chromium overlayer. tions require machining to obtain the desired size. Grinding
Hard chromium deposits differ from decorative ones in is often used, but special precautions are required. A soft
terms of thickness. Typical thicknesses lie in the 2.5 to 500 grinding wheel, sufficient coolant, and light cutting depth are
µm (0.0001 to 0.020 in.) range. The plating solution condi- essential to avoid damaging the hard, brittle deposit.
tions are the same as those for decorative plating; the differ- Many steel parts are susceptible to hydrogen embrittlement,
ence is primarily time. Operating conditions for low- and owing to pickling and cathodic cleaning prior to plating and
high-concentration solutions are given in Table 2. to the hydrogen-evolving chromium plating process itself.
The low concentration formulation has the advantages of Further, stresses can be induced in the steel from prior
higher operating currents and lower solution dragout. The machining, grinding and heat treatment operations. Thermal
high concentration solution, on the other hand, has better treatments for hydrogen embrittlement and stress relief are
throwing power and is less sensitive to concentration changes. often required prior to and/or after electroplating.
The choice depends on the requirements and geometry of the
specific application.
Long residence times require agitation of the workpiece in
the bath to avoid solution stratification. The fume exhaust
considerations noted earlier also apply to hard chromium
plating. The low current efficiency and high engineering
chromium thicknesses lead to long plating times. A tool-steel
mold for plastics, with a chromium thickness of 5 to 13 µm
(0.0002 to 0.0005 in.) will require 30 min. High-strength steel
aircraft engine parts, requiring 75 to 180 µm (0.003 to 0.007
in.) will need 10 hr of deposition time. Plating times measured
in days are common for the salvage of crankshafts, where 255
to 3800 µm (0.010 to 0.150 in.) of chromium are required.
Racking and masking techniques are employed for proper
distribution of the chromium. In engineering chromium ap-
plications, selected area plating is more common, and mask-
ing is important. Shields, conforming anodes and auxiliary
anodes are used where complex geometries exist. Industrial
chrome plating is a lower-volume operation when compared
to decorative chromium plating and involves more complex
approaches. Thus, racking and tooling require experience and
training on the part of the operator.

Trivalent Chromium
The increasing importance of environmental concerns has
required the search for alternatives. The most promising
alternative to date is the trivalent chromium plating process.
In use for the better part of 20 years, the trivalent processes
provide decorative deposits with improved throwing and
covering power. With micro-cracked or micro-porous char-
acter, the finishes equal the appearance and durability of
hexavalent chromium deposits. A variety of commercial
processes are available from several suppliers. Solutions are
based on both sulfate and chloride chemistry. Current effi-
ciencies are significantly higher than those in conventional
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November 1998 47
 Health Impact
While metallic chromium and trivalent chromium compounds
are nontoxic, the hexavalent compounds of the metal are very
toxic and hazardous. Preparation of chromic acid-sulfuric
acid solutions mandates the use of goggles, rubber apron,
boots and respirator. Chromic acid is also a fire hazard if it
should contact organic substances, including activated car-
bon, chemicals, paper and rags. The threshold limit value
(TLV) for dusts and mists of hexavalent chromic acid is 0.1
mg/m3 for an 8-hr exposure.

Environmental Status
Wastewater limits under the EPA Metal Finishing Regula-
tions are 2.77 mg/L for any single day and 1.71 mg/L as a
monthly average.

Trends
While current trends in design have led to reduced usage of
decorative chromium finishes on automobiles, there remain
numerous other applications. Environmental concerns with
hexavalent chromium solutions have led to development of
trivalent chromium plating baths, which are environmentally
compatible and offer reduced pollution control costs. Hard
chromium deposits will continue to be used for engineering
applications. Despite the environmental problems associated
with chromic acid, industrial chromium is often the only
finish that fulfills the requirements of a given plating appli-
cation. On the other hand, heavy electroless nickel (i.e.,
nickel-phosphorus alloy) deposits possess mechanical prop-
erties that are compatible with the needs of many hard
chromium applications. In many cases, this process has been
used successfully, again with fewer environmental concerns.

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48 PLATING & SURFACE FINISHING