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NO. 210

orative introduction
Today, both hexavalent chromium [chrome(VI)] and trivalent chromium

latin [chrome(III)] electroplating processes are commercially available for


decorative chrome plating operations. Because electroplating with
chrome(V1) has historically been easier than chrome(III), chrome(V1) was

with essentially the only decorative chromium process used for almost 70 years.
Electroplating with chrome(VI), however, is more toxic than chrome(I1r)
and presents a real threat to both you and your-workers. What is more,
chrome(V1) operations cost you more in waste management and disposal
costs. This factsheet contains information which can help you avoid the
problems associated with chrome(V1) plating processes.

Chrome(V1) is dangerous to plating shop personnel. It is a highly toxic


material, known to cause skin ulcers and dissolve mucous membranes upon
prolonged exposure. In decorative chrome plating, problems with
chrome(V1) are further compounded as plating times are shorter and more
parts are removed from the tank per hour of plating compared to functional
chromium plating. In a system where parts are manually removed, workers
are exposed to the bath chemicals more often.
Rinsing concentrated chrome(V1) plating solution from the plated part can
be difficult because of its high viscosity. Inevitably, a large quantity of
chrome(V1) gets dragged out of the tank along with the parts. The dragged
out chrome(V1) contaminates rinsewaters, stains parts, and exposes shop
personnel to additional health hazards.
As a result ofthe chemistry of chrome(V1)’s electrolyte, large quantities of
hydrogen and oxygen gas are generated during plating. The gases bubble to
the tank surface and carry liquid particles of chromic acid solution into the
air. This mist-can be inhaled. Good ventilation, use of mist suppressants,
and good housekeeping can minimize the transfer of chrome(V1) from the
tank, but does not totally eliminate it. Air scrubbers, which are expensive to
purchase and operate, are typically required to reduce airborne chromium
leaving the plating shop to very low levels. Protective gear may also be
necessary to keep airborne chromium from workers.

May 1993
Table 1. Trivalent and Hexavalent Chromium Comparison'
Trivalent Chromium Hexavalent
~~~~~ ~~
Single Cell Double Cell Chromium
Throwing power Good Good Poor
Covering power Good Good Poor
Current interruptions Tolerant Tolerant Intolerant
Rectifier ripple Tolerant Tolerant Intolerant
Deposit structure
Micro-discontinuous Microporous Microporous Special Processes
Resistance to burning Excellent Excellent -LOW
Ease of rinsing Easy Easy Moderate
Color buffing requirement , Seldom Seldom Occasional
Filtering requirement Only after purification Daily with carbon Never
Conditioning/dummying Never Start up 8:routinely Start up each day
Passivity of nonplated surfaces Needs post dip Needs post dip Chromated surfaces
Color of deposit
Ambient temperature Pewter or stainless steel NIA Blue-white
, Elevated temperature ~ Metallic whte Metallic white
Waste treatment Easy Easy Moderate
Relative safety Similar to nickel Similar to nickel - Similar to cyanide
Misting Almost eliminated Almost eliminated Heavy
Odor Almost eliminated Almost eliminated Strong 8: dangerous

In January 1986, the California Air Resources Board In most plating applications, chrome(V1) and
(CARB) identified chrome(V1) as a toxic air chrome(II1) processes are interchangeable. However, in
contaminant and a possible human carcinogen. A the conventional treatment of chrome(V1) wastewater,
chrome(V1) control plan was approved by CARB in chrome(V1) must be reduced to chrome(II1) before it
February 1988 along with the adoption of the first can be precipitated. Approximately three pounds of
control measure to reduce emissions from chrome sodium metabisulfite are needed in the reduction step to
plating and chromic acid anodizing operations. For treat each pound of chromic acid. In the chrome(II1)
decorative plating shops, the control measure requires system no reduction step is needed. The quantities of
that uncontrolled emissions be reduced by at least 95% chemicals used, the need for auxiliary equipment, and
or a rate of less than 0.15 mg/amp-hour. the costs of labor are significantly reduced. Chemical
costs for treating chrome(II1) rinsewater are
CayOSHA standard GISO 5 154 sets minimum air
approximately one-tenth that of the costs for treating
control velocities for local exhaust ventilation systems
chrome(V1) rinsewater. The amount of sludge generated
for chrome plating tanks. Failure to comply with GISO
from treatment is reduced by as much as 80%.
5 154 may constitute failure to comply with the Safe
Drinlung Water and Toxic Enforcement Act of 1986, Performance differences of the two plating operations
popularly known as Proposition 65. Proposition 65 are shown in Table 1. The typical operating conditions
prohibits employers from exposing workers to certain for chrome(II1) and chrome(V1) electroplating processes
chemicals (including chrome(V1)) above specified are compared in Table 2 .
levels without first warning them.

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There are two significant reactions in the chrome(II1) involves the plating of metallic impurities on to a
processes. Both are very simple: dummy cathode. The problem with dummying,
Deposition Reaction: however, is that it takes a long time to complete,
typically 8 hours for metallic impurities at a
Cr'" + 3e'+ CI" concentration of 100 ppm. Dummying slows down
production. For the single cell process, there are two
Side Reaction:
other methods apart from dummying that can be used.
Cr"' + Crv'+ 3e- First, there is chemical precipitation wherein you can
choose from a variety of commercially available
The side reaction takes place at the anode under some purifying chemicals that remove the metallic impurities
conditions. To prevent the side reaction from occurring, in about an hour. Second, a selective ion exchange unit
either a single cell process or a double cell process can can be installed to continuously treat the plating
be used. The single cell process has the anode in the solution. The installation of an ion exchange unit is
same chrome(II1) ion containing solution as the cathode often the preferred method of treatment for the single
or part, hence the term "single cell". An insoluble inert cell process (see case study).
graphite anode is used for this process. The bath
chemistry in combination with the anode prevents the As dummying is the only way to remove metallic
formation of chrome(V1) ions. impurities from the double cell process, it must be done
at the beginning or end of each plating shift. Otherwise,
The double cell process requires the isolation of a lead an off line tank can be installed to allow for the
anode from the chrome(II1) ion containing solution that simultaneous dummying of an alternate bath of plating
surrounds the cathode or part. The anode is in an anode solution during the plating shift.
box that physically separates it from the electrolyte by
an ion-selective membrane. For this reason, the process The double cell process must also be treated to remove
is referred to as a "double cell" process. organic impurities which are either dragged in from the
preceding nickel plating tank or generated during

Table 2. Typical Operating Conditions for Chromium Plating


Trivalent Chromium Hexavalent
Single Cell Double Cell Chromium
2.3-3.5 3.j13.9
70- 120 70-130 - 100-115
- 40-125 ~ 40-150 175-300 . -
ild Air *+ Mild Air Optional
,
Rectifier voltage, volts 4-15 4-15 4-12
Anode material Carbon Lead-7% tin Lead-7% tin
Chromium concentration, g/L 4-20 5-10 150-300
-
. Maximum ~dick/;l=, &I ~ -
Room Temperature
. High Temperature " 1 or more - about 0.01

Plating rate, mil per min


Room Temperature 0.005-0.007 N/A 0.005-0.007
High Temperature 0.007-0.010 0.004 or less N/A

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plating by the breakdown of organic additives. Since no Both of the chrome(II1) processes, single or double cell,
breakdown products occur in the single cell process, can use the same bath tanks, equipment and rectifiers as
only occasional treatment for excess organics is those used for chrome(V1) plating. For process control,
necessary. Activated carbon treatment removes the chemical analysis of the baths are typically conducted
organics for both processes. more often with chrome(II1) than with chrome(V1) as
the baths are more sensitive and take more care. Platers
generally rely upon a pH meter for pH control, a
hydrometer for chromium concentration. and an amp/
hour meter for timing bath additions. The concentration
Some platers and their customers are reluctant to of metallic impurities in the bath is determined by a test
convert from chrome(V1) to chrome(II1) because they paper similar to pH paper.
remember the problems with the older chrome(II1)
processes. Historically, the operational problems of Since chrome(II1) deposits resist buming, a higher
chrome(II1) included: poor metal distribution, amperage rectifier can be used to increase the process’
requirements for extremely high limiting current throwing power. Throwing power is the property of the
densities, and +buming,d the formation of dark-colored plating bath to distribute metal uniformly over parts.
deposits during plating. Today, however, all of these The rectifier does not have to be AC-filtered to remove
problems can be managed. ripple, as is required for chrome(V1).

Lower Viscosity Chrome(II1) solutions drain and rinse from parts more easily since they are less concentrated
and Reduced (22 g/L versus 150 g/L for hexavalent solutions) and less viscous than chrome(V1). A
Drag-out significant reduction in drag-out volume and material costs for makeup chemicals is the result.
Fewer Rqjects The throwing power and covering power of chrome(II1) is very good. Parts are almost
and Higher impossible to bum and there are no whitewashing problems as compared to chrome(V1).
Production As a result, there are fewer rejects. Also, parts can be placed 30 to 40% closer together
Yields on the racks. This increases production yield.
Lowered Waste With a chrome(II1) system, it is unnecessary to add sodium bisulfite or other reducing agents
Treatment Costs to the wastewater to convert chrome(V1) to chrome(II1) before precipitation. Lower material
concentrations reduce the amount of sludge generated by as much as 80%.
Less Auxiliary Chrome(II1) processes do not require air scrubbers or tank ventilation if the shop is
Equipment adequately ventilated. Also, auxiliary anodes that are sometimes necessary with chrome(V1)
processes to obtain coverage in recesses are seldom necessary in chrome(II1) processes.
Less Operational control of chrome(II1) plating processes is typically easier than for chrome(V1)
Maintenance processes. Chemical additions are based upon amp-hours, specific gravity, and pH only.
Fewer Health Health hazards associated with misting and odor are almost completely eliminated with
Hazards chrome(II1) processes because of the low chromium concentrations and the greatly reduced
toxicity and corrosion properties of chrome(II1) as compared to chrome(V1). There are also
fewer waste handling problems.
Regulatory Chrome(II1) is not a suspected human carcinogen nor classified as a toxic air contaminant as
Advantages is chrome(V1) by the California Air Resources Board. Chrome(II1) processes more easily meet
the strinpmt industrial wastewater discharge requirements set by the Regional Water Quality
Control Boards and local sewage authorities.

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Capital costs for making the switch are generally to choose between low current density dummying and
limited to the costs of the new bath chemicals and the chemical precipitation for removing impurities from the
costs of disposing of the old. The lead anode must be plating solution. Low current density dummying was -
replaced if switching over to a single cell process. The rejected because of the long hours of down time
old process tanks must be given a thorough cleaning to required. They chose weekly chemical precipitation

remove all lead and chrome(V1) residues to avoid eve:: though the ::hemicaisto purify the system were
poisoning the new bath chemicals. A selective ion expensive. However, color variations in parts still
exchange unit may also be procured to maintain quality remained a problem, especially towards the end of the
control of bath metallic impurities to prevent coloring of week. They subsequently installed a selective ion
parts. exchange system for $27,000 to remove metal
impurities. This eliminated approximately $1,0oO per
month for purification chemicals. Monthly costs for
replacinghegenerating the ion exchange system were
$200.
Foss Plating found that filter maintenance and sludge
Foss Plating, in Santa Fe Springs, California, is a handling were reduced significantly as a result of
family-run chrome plating shop that has been in installing the selective ioii exchange sysrern. 35th the
business for over 40 years. Today, about thirty people chemical purification process, filters had to be cleaned
are employed in the shop. Their current plating line is a as much as four times because the residue was an
fully automated single cell chrome(II1) system which extremely messy, gelatinous substance. A post dip was
they converted from chrome(V1) in 1989. The cost of also needed in the chrome rinse line to remove
conversion was about $30,000. precipitates from the plated part. The post dip was a
Foss Plating realized a return on their investment within chelate that needed to be isolated from the waste
the first year of operating the chrome(II1) system. They treatment system.
saw an increase in productivity, greater system Foss Plating is still using a hexavalent chromate dip for
efficiency, fewer rejects, and less treatment costs. The pacification of nonplated areas. While this occasionally
better throwing power and covering power of requires treatment of chrome(V1) waste, the amount is
chrome(II1) allowed them to increase the surface area of much smaller than with chrome(V1) plating.
parts on the racks about 7096, from 35 square feet to 60 .
square feet, without burning, shading. or whitewashing
of the parts. At the same time, they realized a more than
90% decrease in the number of rejected parts and
eliminated almost all need for color buffing. 1. Snyder, D. L., “Decorative Chromium Plating,”
Automotive specifications were easily met too, since the Metals Finishing Guidebook and Directory Issue ‘91
chrome(II1) process produced low stress microporous (pg 179-187)
deposits. 2. Snyder, D. L., “A Comparison of the Corrosion
Foss Plating found that chrome(II1) plated more Characteristics of Trivalent and Hexavalent
efficiently from an energy standpoint. With chrome(V1) Chromium Electrodeposits,” Plating & Surface
plating, only 10 to 15% of the amperage went to Finishing (June 1974)
applying the plate. With chrome(III), up to 95% of the 3. Snyder, D. L., “Trivalent: The Second Decade,”
amperage went to applying the plate. This allowed Foss Products Finishing (March 1988)
to use the same rectifier, while significantly reducing
energy costs. 4. Dumey, L. J., ed., Electroplating Engineering
Handbook, Fourth Edition (1984)
The two biggest disadvantages i - 0 3 ~ TIPting experienced
with chrome(II1) were discoloration from i m p u r k s II
5. H.T.M. Project, Board of Public Works, City of Los
the bath and the need to pacify the nonplated areas of Angeles, Fact Sheet - Plating with Trivalent Chrome
pals. %-henm & h g !hc switch to chrome(III), they had (NoveInduLw9qa

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For more information on chrome(H1) plating processes, For more information on pollution prevention, contact:
contact: Department of Toxic Substances Control
Metal Finishing Association of Southern Califomia Office of Pollution Prevention and
5000 Van Nuys Blvd., Suite 300 Technology Development
Sherman Oaks, CA 91403-1717 P. 0. Box 806
(818) 995-7338 Sacramento, CA 958 12-0806
(9 16) 322-3670
Low interest loans for small businesses for procurement
Northern Califomia Association of Metal Finishers
of new equipment for waste minimization activities are
P.O. Box 190566
available from:
San Francisco, CA 941 19
(4 15) 399-9702 Department of Commerce
Office of Small Business
801 K Street, Suite 1700
National Association of Metal Finishers Sacramento, CA 95814
401 North Michigan Ave. (916) 322-1395-
Chicago, IL 606 11-4267
(312) 644-6610

STATE OF CALIFORNIA

DEPARTMENT OF TOXIC SUBSTANCES CONTROL


Office of Pollution Prevention and Technology Development
P. 0. Box 806
Sacramento, CA 95812-0806

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