TECHNICALLY

speaking
BY DONALD L. SNYDER, ATOTECH USA, INC.,
ROCK HILL, S.C.

Decorative Chromium chromium electroplating. Depending upon the process,

trivalent chromium electrolytes can either produce a
Plating Basics metallic white deposit almost identical in appearance to
the bluish white hexavalent chromium deposits, a deep-

E lectrodeposition of decorative chromium is the prin-

cipal means of imparting the physical and chemical
properties of chromium to the surface of less expensive
looking pewter or stainless steel appearing deposit or
almost black decorative deposits. In almost all chromi-
um plating applications, both hexavalent and trivalent
and easier-to-form materials such as steel and plastics. chromium deposits are interchangeable with each other;
The most desirable properties of chromium as a metal however, one or the other process might offer unique
coating are its inherent pro- advantages. For example,
tective and decorative char- the cost for hexavalent
acteristics. The deposit’s chromium solutions is typ-
high reflectivity is retained ically lower than that for
in service because of chromi- trivalent. However, the flu-
um’s excellent lubricity and oride used in many hexava-
resistance to tarnish, corro- lent chromium processes
sion, wear and scratches. will etch substrates, such as
Decorative chromium is copper and steel, resulting
almost exclusively plated in metallic contamination
over a nickel electrodeposit, of the plating bath which
which can be plated over could increase operating
substrates such as plastics, problems and rejects.
steel, aluminum, copper Trivalent chromium
alloys, and zinc die castings. processes typically do not
Nickel is preferred because it contain fluoride but will
protects the substrate from dissolve copper and iron.
corrosion, helps to give However, metallic contami-
chromium a pleasing bluish- nation is easier to remove
white decorative appearance, from a trivalent chromium
and is protected from sur- electrolyte. This makes it
face oxidation by the possible to produce nickel,
chromium. Stainless steel is free nickel/chrome looking
the only substrate that is frequently plated directly with decorative parts by plating trivalent chromium directly
chromium, but a nickel preplate before chromium is also over white copper alloys. Doing this with hexavalent
used. Multiple or single layers of nickel and copper can chromium solutions would be problematic.
precede the chromium deposit depending upon the
intended use of the part. The appearance of the chromi- HEXAVALENT CHROMIUM PROCESSES
um deposit can be significantly altered by using bright, Hexavalent chromium electrolytes require a source of
dull, satin or mechanically modified nickel deposits pre- chromium and one or more catalysts in order to plate.
ceding the chromium deposit. Decorative chromium The formulation of the traditional process (called the
deposits typically are plated in the 2-20-millionths-of-an- conventional, Sargeant or single catalyst process) con-
inch range. Thicker deposits are usually referred to as tains hexavalent chromium and sulfate as the only cata-
functional chrome and tend to be duller and contain vis- lyst. When fluoride is added as an additional catalyst to
ible cracks. the conventional hexavalent chromium plating bath for-
The traditional chromium deposit is produced from an mulation to enhance particular plating operations or the
electroplating electrolyte containing hexavalent chromi- deposit’s properties it is typically called a mixed-catalyst
um ions. About 1975, a chromium electrolyte contain- or dual catalyst bath. Proprietary organic additives can
ing the less toxic and less hazardous trivalent chromium also be used to produce dual or triple catalyst baths to
ion was introduced to replace decorative hexavalent further enhance the plating operation and deposits.

14 I metalfinishing I March 2012 www.metalfinishing.com

TECHNICALLYspeaking
Mixed-catalyst baths are used when their special prop-
erties are required, but they are more expensive and slight-
ly more difficult to operate than conventional processes.
They typically plate at faster speeds, have better coverage,
have wider bright ranges, and are more tolerant to impu-
rities. They are also less sensitive to current interruptions
and can be plated over more passive surfaces.
The basic formulations of hexavalent chromium
processes are very similar. They consist of chromic triox-
ide (CrO3), which when combined with water forms
chromic acid (H2CrO4), and the sulfate ion (SO4+2)
which is added in the form of sulfuric acid or a sulfate
salt. Even though chemically incorrect, solid chromic
oxide is commonly referred to as chromic acid, its hydrat-
ed form.
A number of sometimes conflicting theories have been
proposed to explain the very complex mechanism of hexa-
valent chromium electroplating. In a simplified form,
they all contain the following multiple reactions:
Cr3+H2OjH2CrO4 CrO4j-2+2H+ (1)
-2
2H2CrO4jH2Cr2O7 +H2OjCr2O7j +2H++H2O (2)
Deposition reaction:
Cr2O7-2+14H++12(e)+CAT 2Cr0 +7H2O (3)
CAT is the required catalyst, e.g., sulfate in addition to
fluoride and/or an organic catalyst, while (e) refers to an
electron. The plating efficiency of reaction (3) is approxi-
mately 20% or less depending upon the catalyst, bath
chemistry and the current density.
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Side reactions:
2H+ + 2(e)jH2(gas) + a mist(H2SO4 +Cr+6+H2O) (4)
This side reaction consumes most of the available
power not used by reaction (3). The mist, a major HSE
concern, can be trapped within the plating tank by the
use of mist control agents or surface tension reducers.
Trivalent chromium ions are created and oxidized by:
Cr2O7-2 +14H+ +6(e) 2Cr+3+7H2O (5)
2Cr+3+3O2 -6(e) 2CrO3 (6)
Reaction (6) is catalyzed by a PbO2 film that naturally
forms on the lead anode.
Dilute conventional formulations consist of approxi-
mately 250 g/L (33 oz/gal) chromic trioxide (“chromic
acid”), and 2.5 g/L (0.33 oz/gal) sulfate. Concentrated
conventional baths contain approximately 400 g/L (53
oz/gal) chromic trioxide and 4.0 g/L (0.53 oz/gal) sulfate.
In practice, however, concentrations in between these are
widely used.
The dilute formulation offers good coverage, moderate
nickel substrate activation, and consistent current effi-
ciency. It also has a lower solution cost, plates faster, and
produces less waste to treat. The concentrated formula-
tion gives better coverage and greater resistance to impu-
rities and requires lower operating voltages; however, it is
more expensive to make up because of its higher chromi-
um concentration and more chromium is dragged out
resulting in higher waste treatment coat.
A critical point in all bath formulations is the require-
ment for close control of the CrO3/SO4 weight ratio
March 2012 I metalfinishing I 15
TECHNICALLYspeaking
needed to produce consistent plating results. Ratios of
between 80:1 and 130:1 are typical, with a ratio of around
100:1 being common for conventional processes. A low
ratio results in relatively poor throwing and covering
power and an increased limiting current density. Higher
ratios result in slower deposition rates, duller deposits,
increased covering power, and decreased limiting current
density.
The addition of a fluoride catalyst necessitates an
adjustment in the CrO3/SO4 weight ratio. Ratios of
170:1 to 210:1 are required, with 190:1 being most typical.
The chromium concentrations for both the dilute and
concentrated mixed-catalyst formulations are the same as
for conventional baths; however, the sulfate concentra-
tion is lowered due to the use of the secondary catalyst.
Unlike most plating baths in which the metal, M, is
present in solution as a cation, M+, chromium is present
as an anion complex, Cr2O7-2, which very likely under-
goes further complexing with ions such as the sulfate cat-
alyst to permit chromium deposition. Fluoride or silico-
fluoride ions are extensively used today in mixed-catalyst
formulations, especially in self-regulating baths. Self-reg-
ulating formulations are obtained by using sparingly sol-
uble salts of the fluoride catalysts. This controls the cat-
alysts’ concentration because only the required amount
of catalyst will dissolve. For this reason, less frequent cat-
alyst analysis is required. Much more routine analyses
and chemical control of the catalysts are needed in non-
self-regulated formulations since the catalyst must be
added to the bath as they are depleted. However, this
offers a much wider range of operating conditions.
Chromic acid concentrations may be maintained by
making frequent specific gravity determinations of the
operating solution using a hydrometer. Occasionally,
more accurate chromium analyses should be conducted
by an analytical method specific for chromium.
Chromium is consumed and dragged out of the bath.
Since lead anodes are used, the chromium must be replen-
ished by additions of chromic acid (chromic trioxide).
Sulfate concentrations should be determined frequent-
ly by using a centrifuge to measure the volume of the sul-
fate precipitated by the addition of barium. Occasionally,
gravimetric analyses should be conducted to confirm this
quick, less accurate method. Sulfate concentrations may
be raised by adding sulfuric acid. To add 0.05 g/L sulfate
(SO4), add 0.0295 ml/L concentrated (66° Bè) H2SO4.
Sulfate can be dragged into as well as dragged out of the
tank. To lower the concentration of sulfate by 0.05 g/L of
H2SO4, add 0.01 g/L barium carbonate to precipitate the
sulfate. Sulfate is an impurity in other chemicals such as
chromic acid. For this reason, sulfate should be con-
trolled carefully and any sulfate present as impurities
should be accounted for.
Plating tanks are typically lined with polyvinyl chloride,
(PVC, Koroseal). The historical use of lead lined tanks is
no longer recommended. Auxiliary equipment should be
16 I metalfinishing I March 2012
constructed of PTFE (fluorocarbon resin) or tantalum.
Titanium can be used except when a fluoride catalyzed
chromium process is used. A ripple filter on the rectifier
is used to reduce plating current problems. A non- PFOS
surfactant must be used in regions that it is restricted by
regulations. Table II contains additional information.
TRIVALENT CHROMIUM PROCESSES
Decorative trivalent chromium, a safer and more efficient
system, was commercialized in the mid 1970s as an alter-
native to hexavalent chromium processes with its many
HES issues. In addition, trivalent chromium eliminated
most of the operational problems associated with hexava-
lent chromium chemistry: high toxicity, low current effi-
ciency, poor metal distribution, lack of coverage around
holes, burns in high-current-density areas, and “white-
wash.” Depending on the design of the part being plated,
productivity might be improved because these advantages
might permit a higher rack density and lower reject rate
compared to hexavalent chromium processes.
The literature contains far less information on the
chemistry of trivalent chromium processes than for hexa-
valent. This is the result of the relative newness of the
commercially successful processes, the proprietorships of
the processes, and the wider differences in the chemistries
used. Basically, the significant reactions in all the trivalent
chromium processes are very simple.
Deposition reaction:
Cr+3+3(e)jCr0(metallic chromium) (7)
Side reaction:
Cr+3jCr+6+3(e) (8)
Reaction (7) requires only 3 electrons compared to the
six required by hexavalent chromium processes, thus dou-
bling the electron efficiency of the process. The unwant-
ed reaction (8) can take place at the anode under some
conditions.
The electrolytes for the different trivalent chromium
plating processes differ in chemistry, but they all contain
a source of trivalent chromium, that is typically added as
a sulfate and/or chloride salt. They also contain a stabi-
lizing material (called a catalyst in hexchrome processes)
that combines with the chromium to permit it to plate in
the desired form. Salts are also added to increase conduc-
tivity in the solution. Wetting agents are used to help in
the deposition reaction and to reduce the surface tension
of the solution. This essentially eliminates the formation
of a mist at the anode and cathode. It also helps lower the
solution viscosity resulting in more solution draining
from the part when compared to hexavalent chromium
processes.
Historically, the two general formulations of trivalent
chromium processes obtain their generic names by the
method they used to eliminate the side reaction (8) – sin-
gle and double cell processes. The original single-cell
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TECHNICALLYspeaking
Trivalent Chromium Hexavalent
Mixed Sulfate Chromium

Chromium, g/L 15 - 25 10 - 20 100 - 200

pH 2–3 3.2 – 3.8 <1

Temperature, oF 70 – 120 120 - 140 90 - 120

Cathode Current Density, A/ft2 70 - 150 70 - 150 175 - 300

Anode-Cathode Ratio 2:1 2:1 1:1 – 3:1

Anode material Carbon Precious metal coated titanium Lead-Tin (7%)

Rectifier voltage Up to 12 Up to 12 4 - 12

Agitation Mild air Mild air Optional

Maximum deposit thickness, μm >1 ≈ 0.3 >5

Deposition rate, μm/min 0.15 – 0.25 0.02 – 0.03 0.1 – 0.18

Table I. Chromium Plating - Typical Operating Conditions

process uses graphite anodes immersed directly into the
plating solution. An interaction between the anodes and
the chemistry of the process eliminated the formation of
hexavalent chromium. A secondary chemical mechanism
converts hexavalent to trivalent if any does appear in the
solution. The anodes, which are destroyed only by
mechanical means, are placed below solution level to
eliminate misting. Since this process utilizes both sulfate
and chloride (and boric acid), as in nickel baths, it is now
commonly referred to as a mixed salt trivalent process.
Just as with nickel electrolytes, the mixed chloride-sulfate
formulation enhances the operation of the process. This
is most noticeable in plating rate and deposit thickness
(Table I). The chloride helps to make it easier for the
mixed process to meet the automotive company’s specifi-
cation for 0.25 to 0.5 microns of chromium. Other fac-
tors are listed in Table II.
The double-cell process originally reduced the side reac-
tion (8) by isolating the chromium containing solution
from the anode through a membrane box. Because of
maintenance problems and the amount of space that the
anode boxes took from the plating area inside the tank,
they have been almost completely replaced by insoluble
metallic catalytic composite anodes with a projected life
of 3 to 5 years. With the elimination of the need for an
isolated anode, today this process is commonly referred
to as a sulfate process. The electrolyte contains no chlo-
ride ions.
Once through the learning curve, control of trivalent
chromium plating processes is typically easier than for
hexavalent chromium processes. The literature says that
an operator should “think nickel plating not chromium
plating” when controlling a trivalent chromium process.
The troubleshooting guides for trivalent chromium
processes are a few lines long as compared to several pages
for hexavalent chromium.
The additives are added based upon amp-hours, specif-
ic gravity, and pH. In addition, chemical analysis on a
monthly basis appears to be sufficient for control. All
trivalent chromium processes are far more sensitive to
metallic contamination than hexavalent processes.
Metallic impurities darken the deposit and alter the
throwing and covering powers. However, most trivalent
processes utilize a regenerateable resin to remove all com-
mon metallic contaminates directly from the working
solution. Less desirable, but a quick chemical purification
method or a slow dummying method can also be utilized.
These methods eliminate the problems attributed to
metallic contamination.
Today, most industries using decorative chromium
deposits, such as the automotive/truck industry, approve
the use of trivalent chromium for both interior and exte-
rior parts. The almost complete elimination of the color
difference between hexavalent and trivalent chromium
deposits and the demonstrated corrosion resistance is
greatly responsible for this wide acceptance. Some triva-
lent chromium deposits have also been found to be much
more resistant to calcium chloride corrosion (Russian
Mud) than hexavalent chromium deposits.
OPERATIONS
The typical operating conditions for trivalent compared
to hexavalent chromium electroplating processes are
shown in Table I.

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TECHNICALLYspeaking
Trivalent Chromium Hexavalent
Mixed Sulfate Chromium
Throwing power Good Good Poor

Covering power Good Good Poor

Current interruptions Completely tolerant Completely tolerant Intolerant

Rectifier ripple Completely tolerant Completely tolerant Intolerant

Deposit structure Amorphous Amorphous Crystalline

Micro-discontinuous Yes as plated Some Need particle nickel

High current density No burning Some misplate Burning

Ease or rinsing Easy Easy Moderate (viscous)

Filtering Occasional Daily with carbon Never

Conditioning/dummying Very seldom Routinely on start up Routinely on start up

Passivity of unplated surfaces Needs Needs Natural “chromating” gives

post-treatment post-treatment mild protection
Waste treatment Easy ≈ 1/10 the sludge, no Easy ≈ 1/10 the sludge, no Moderate
PFOS PFOS
Relative safety Similar to nickel Similar to nickel Similar to cyanide

Misting Almost eliminated Almost eliminated Heavy, need to be controlled

Odor Almost eliminated Almost eliminated Strong and dangerous

Removal of impurities Easy Easy Hard

Chromium contamination Hexavalent chromium Occasional treatment for Treatment for trivalent
destroyed hexavalent chromium chromium
Table II. Trivalent and Hexavalent Chromium Comparison

EQUIPMENT tive plating characteristics. The plating amps for trivalent

Trivalent chromium tanks and equipment are very similar
to the design of nickel tanks. Tank linings must be made
from suitable synthetic material such as PVC, plastisol or
polypropylene. Air agitation design can be identical. The
sulfate/chloride mixed trivalent process uses graphite
insoluble anodes that only need to be replaced when
mechanically damaged. The sulfate process uses insoluble
anodes with a recoatable catalytic coating. Titanium or
Teflon spaghetti coils are used for heating and cooling in
both trivalent processes. When converting from a hexava-
lent to a trivalent chromium process it is almost always
better to reline or replace the tank and remove the old ven-
tilation equipment. Even a small amount of residual lead
can cause plating problems. An operational hexavalent
chromium rectifier usually can be used.
The current carrying capacity of the plating racks must
be designed for the amperage they will carry. They should
also be designed so that the parts on the racks will utilize
the bath’s plating benefits and minimize the bath’s nega-
chromium processes are at least one half those used for
hexavalent processes so the racks can be designed for the
lower current. In general, racks designed for hexavalent
chromium processes can be used in trivalent processes,
but the reverse is not true.
Since trivalent chromium processes will not “burn” and
they have greater covering and throwing powers than
hexavalent processes (see Table II), parts many times can
be placed closer together on the racks and high current
density areas can face the anodes. The racks can be
designed for optimum nickel plating. Racks used with
hexavalent chromium are designed to accommodate the
deficiencies of the chromium process. This increases pro-
ductivity and makes shielding and robbing of the part’s
high current density areas, as is required for hexavalent
chromium processes, unnecessary. Auxiliary anodes are
sometimes necessary with hexavalent processes to obtain
coverage in the recesses but might not be used with triva-
lent processes.

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TECHNICALLYspeaking out material as possible back to the tank. Any plating
solution that cannot be recovered must be waste treated.
Bath A Bath B Bath C Even though this reduces plating solution waste, reduced
drag-out keeps contaminants in the plating solution,
Chromic acid, g/L 250 340 250 thus complicating the requirement to maintain a pure
enough plating solution to obtain the required deposit
Fluosilicic acid, g/L - 0.34 0.25 properties.
Acetic acid, g/L 216 - - Due to hexavalent chromium’s poor draining charac-
teristics and its misting, a large amount of solution is
Barium acetate, g/L 7.6 11 - unavoidably removed from a decorative chromium plat-
ing tank. Vacuum evaporators and ion exchange are
Temperature, oF 100 70 90 examples of methods used to return dragged-out hexava-
lent chromium back to the plating tank in order to save
Current density, A/ft2 40 – 90 200 150 - 450 chemical and waste treatment expenses; however, due to
Table III. Decorative Black Chromium Formulations the difficulty of removing metallic impurities from hexa-
valent chromium plating solutions, it is common to send
a solution containing an excess of metallic impurities out
Bath A Bath B for recovery.
Chromic acid, g/L 525 340 Trivalent chromium is much more sensitive to metallic
impurities than hexavalent chromium; however, the
Sulfate, g/L 1 0.98 chemistry of most trivalent chromium processes makes it
easy to remove metallic impurities. This eliminates the
Fluorsilicate, g/L 7 6 need to ever discard the solution due to normal metallic
contamination. Atmospheric evaporators can be used to
Temperature, oF 90 – 105 Room - 95 reduce solution volume so all the trivalent chromium
Voltage 6 – 18 6 - 18 that can be captured is returned to its plating tank. In
most trivalent chromium processes, metallic impurities
Time of plating 8 10 can be removed quickly by chemical precipitation or slow-
(minutes to produce ly by dummying. The most effective way is to use a resin
10 millionths) treatment directly on the plating solution to remove all
Table IV. Hexavalent Chromium Barrel Formulations common metallic impurities. This eliminates the build
up of metallic impurities and excludes any change in
Trivalent chromium processes do not require scrubbers deposit color or properties associated with metallic impu-
and, if the room is adequately ventilated, tank ventilation rities. If a trivalent chromium plating solution has to be
might not be required. In many regions, the same prac- waste treated its cost is approximately one-tenth that of
tices used for nickel baths apply to trivalent chromium. treating an equal volume hexavalent chromium.
This is due to the almost complete
elimination of misting and odor.
Trivalent chromium processes have a
non-PFOS mist suppressor, a low
chromium concentration, and a
greatly reduced toxicity and oxidiz-
ing properties as compared to hexa-
valent chromium. Trivalent chromi-
um solution drains and rinses easily,
thus greatly reducing the amount of
chromium drag-out. If any solution
does dry on the part, it is less haz-
ardous since the chromium is in the
trivalent state. It also does not stain
the part.

SOLUTION MAINTENANCE
The best waste treatment method is
to minimize the amount of solution
dragged out of the plating tank.
Secondly, return as much dragged-

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TECHNICALLYspeaking
Hexavalent chromium processes are essentially insensi-
tive to organic contamination since the hexavalent
chromium ion destroys most organics, resulting in the
formation of trivalent chromium ions. Being a contami-
nant, an excess of trivalent chromium must be reconvert-
ed back to hexavalent chromium. The common way is to
dummy at a high cathode current density (e.g., anode cur-
rent density of 12 A/ft2, cathode current density of 600
A/ft2). Trivalent chromium processes are also relatively
insensitive to organic impurities but sometimes organics
must be removed. Occasional carbon filtering is sufficient
for some processes while routine carbon/peroxide treat-
ments are needed for others.
CORROSION PROTECTION
Decorative chromium deposits play an important role in
the base metal protection provided by nickel/chromium
systems. They offer hardness, appealing color, tarnish
resistance, wear resistance, and corrosion resistance. Even
though decorative trivalent and hexavalent chromium
deposits are used interchangeably, there are some impor-
tant differences. For example, hexavalent chromium ions
impart short-term corrosion protection on non-chromi-
um plated surfaces by “chromating” the part. Trivalent
ions do not and so post-plating treatments are necessary
to obtain the equivalent protection
When corrosion resistance is important, most specifica-
tions encourage or require micro-discontinuous chromi-
um deposits. With a controlled pattern of microscopic
pores or cracks, the corrosion potential between the
chromium and underlying nickel deposits is spread out
over thousands of corrosion sites. This reduces the anod-
ic current on the nickel at any one site thus greatly reduc-
ing the individual corrosion rate. This results in a fine
pattern of corrosion sites (Active Sites) uniformly spaced
over the surface. A typical standard will specify a mini-
mum of 10,000 micropores per square centimetre or over
30 microcracks per millimetre. Without micro-disconti-
nuity all the corrosion potential is concentrated in a few
sites resulting in unsightly, irregularly spaced, large cor-
rosion sites.
Hexavalent chromium deposits must undergo special
treatments to produce micro-discontinuity. Plating
chromium over very fine inert particles that are code-
posited in a nickel strike (particle nickel) over the bright
nickel deposit is the typical way of producing microp-
orous chromium. Lightly spraying the hard, brittle
chromium deposit with hard 60 to 80 mesh particles pro-
duces microporous chromium at the contact points.
Some trivalent chromium deposits are micro-discontinu-
ous as plated. Deposits under about 20 millionths are
microporous. Deposits over about 25 millionths are
microcracked. Under some conditions these trivalent
chromium deposits might not need particle nickel to
obtain the desired number of Active Sites.
If micro-discontinuity is not induced, hexavalent
20 I metalfinishing I March 2012
chromium will typically macrocrack (visible to unaided
eye) in service if plated over 20 millionth in thickness.
Most chromium specifications requiring corrosion pro-
tection specify between 0.25 to 0.5 microns of chromium
(10 to 20 millionths). Hexavalent chromium processes
labelled as “Crack-free” deposits will typically macrocrack
in service since, like all chromium deposits, they are hard
and brittle. Because the appearance of the part after cor-
rosion is very important, in North America most specifi-
cations have eliminated microcracked deposits from use
because they tend to lose their reflective appearance much
faster than microporous deposits.
DECORATIVE BLACK CHROMIUM
Thin black chromium deposits are used for functional
and decorative applications. Important functional appli-
cations include solar energy collectors for heat production
and anti-glare surfaces. Decorative functions include fur-
niture, plumbing fixtures, optical equipment, boat equip-
ment, and automotive and builders’ hardware. The deco-
rative jet black finish enhances users’ appeal for the prod-
uct and so its popularity depends upon the customers’
changing desire for black finishes.
As plated, black hexavalent chromium deposits have a
decrease in wear and corrosion resistance. However, black
chromium deposits have a greater degree of microporosi-
ty, which helps absorb oil, waxes, and paint. Along with
other post-treatments, this property might be used to
improve its corrosion resistance, wearability, and appear-
ance. Dark trivalent chromium deposits have properties
similar to standard chromium deposits. If extended cor-
rosion protection is required, some post-treatments might
be required. These deposits have become very desirable to
designers for interior and exterior automotive parts.
Most black chromium processes are proprietary because
of the difficulty of obtaining consistent plating character-
istics and deposit properties. In many applications, plat-
ing black hexavalent chromium over regular chromium is
recommended. For all decorative and most functional
black chromium deposits, the typical thickness is [approx-
imate] 0.25 microns. Three general formulations for black
hexavalent chromium processes are given in Table III. Low
carbon steel anodes can be used with plating times of up
to 10 min. Most formulations will only produce a maxi-
mum deposit thickness and then stop plating due to the
nonconductive nature of the deposit. To produce black
deposits, barium salts are typically added to remove any
traces of sulfate. Dark trivalent chromium process are all
proprietary due to their complex chemistry.
BULK CHROMIUM PLATING
Plating racks are typically used to hold parts, transfer
parts to and from the plating solution, and to carry the
direct current to the part. Very small parts such as eyelets,
screws, nuts, and bolts have high labor costs when placed
individually on racks so they are sometimes bulk plated in
barrels or trays; however, even under the best of plating
conditions, the chromium reject rate can be very high.
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TECHNICALLYspeaking
This is due to incomplete coverage and black/gray
deposits mostly resulting from poor cathode contact and
current interruption.
Under special conditions, both hexavalent and trivalent
chromium processes have been used for bulk plating of
parts. Table IV contains simple barrel hexavalent chromi-
um formulations. Hexavalent chromium has been used
primarily and special proprietary formulations have been
developed that can produce near 100% coverage if precise
control is used. Since current interruptions are not avoid-
able in barrels and trays, highly complexed-fluoride-con-
taining solutions are normally used. It is extremely
important that the bright nickel used prior to chromium
not be passive. This is typically accomplished by plating a
minimum of 0.1 mil of nickel in a barrel and, with a few
rinses in between, transferring the parts directly into the
chromium tank. Since the parts are not held by a rack,
poor or no contact with cathode leads is common.
Contact must depend upon gravity, while being damp-
ened by the solution, to hold the part against the cathode
contact points.
To increase the likelihood of good contact and satisfac-
tory plating, platers use low current density, low temper-
atures, and specially designed barrels and trays. Cathode
contact points in barrels are constructed from wire mesh,
solid steel liners, button contact points less than an inch
apart, or steel bars that tumble the parts as they move.
Large barrels with small loads also help to increase the
frequency of contact and reduce temperature build up
inside the confined space of the barrel. In general, the
highest practical current density possible, without burn-
ing, should be used.
Screw and spiral design plating equipment are also
used. The parts are put into the barrel at one end and
transferred through the barrel for plating inside the
threads of the screw. This permits a continuous flow of
plated parts. Vibratory agitation and centrifugal force
barrels are also available. In all cases, the barrels must be
constructed so that the hydrogen gas generated during
plating can escape from the barrel rather than being
trapped and possibly exploding. Tray plating requires
that parts be layered onto a metallic screen and vibrated
or tumbled during plating.
Trivalent chromium solutions have recently been tried
for barrel and tray plating of chromium. Since current
interruptions do not hurt the deposit in trivalent chromi-
um processes, and burning is not a problem, this tech-
nology will probably become more popular in the future.

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