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Chromium Plating
By Nabil Zaki
Vice President of Technology
MacDermid, Inc.
Kearny, New Jersey

Despite the simplicity of their formulations, chromium plating baths are more complicated to operate than most plating
baths, and they require rigorous controls.

CHROMIC-ACID-BASED BATHS (Hexavalent type)

In plating from hexavalent chromium baths, sulfate and fluoride ions act as catalysts. Temperature, current density and
bath composition affect the film characteristics and current efficiency. These parameters are therefore carefully controlled
in order to obtain specific deposit properties and plating rates.

Thicknesses of deposits vary from 0.25 to 0.5 micron (0.001 inch), or more for hard chromium plating.

Bath Composition

Chromic acid and sulfate are the necessary ingredients. Chromic-to-sulfate ratios range from 75:1 to 250:1. The
composition depends primarily on whether the bath is co-catalyzed, e.g. with fluorides, fluosili-cates or fluoborates, and on
the application (decorative or hard chromium).

Cr+6 is the source of chromium depos-ited from these baths. Chromic acid, Cr03, is the main
component in solution make-up. Cr+6 is reduced to Cr+3, which in turn is reduced to unstable
Cr+2 and further to Cr0.

Plumbing fixtures and fitting
shave been attractively
finished using a tribalent
chromium plating solution.
(Photo courtesy MacDermid
Inc., Kearny, NJ)
hurts bath performance.
Some Cr+3 is normally found in operating baths, and indeed in the absence of Cr+3, little or no
deposit is obtained. The introduction of small amounts of reducing agents to a new solution
helps in bath start-up.
An amount of Cr+3 exceeding two-three pct of the chromic acid content, however, reduces
cathode efficiency and causes a variety of plating problems.
The presence of other oxides of metals, e.g. iron, copper and nickel, combined with Cr+3,

While the simple chromic-sulfate baths produce about 12 pct efficiency, co-catalyzed baths may deposit at efficiencies up to
22 pct. For a given composition, there is an optimum range of current density and temperature that produces a bright
deposit. When a specific composition is found to produce the most desirable results for a given application, it should then
be tightly maintained by periodic analytical and control methods.

Table I—Single Catalyst Plating Bath Parameters:

Decorative Hard (heavy)

 Chromic Acid 225-300 plating
Chromic/Sulfate ratio g/liter 250-400
Temperature 100:1 to 75:1 to 100:1
Current density 150:1 49-65C (120-150F)
Cathode efficiency 35-46C 22-100 A/dm2
7.0-15 A/dm2 10-15 pct
Co-Catalyzed and High-Speed 6-12 pct
Baths
Hard (heavy)
Chromic Acid Decorative plating
Chromic/Sulfate ratio 210-270 200-300 g/liter
Temperature g/liter 120:1 to 230:1
Currently Density 150:1 to 43-55C
Cathode efficiency 250:1 22-90 A/dm2
35-55C 15-22 pct
7.0-15 A/dm2
10-16 pct

Typical single-catalyst and co-catalyst plating baths have the parameters shown in Table I.

In single-catalyst baths, cathode efficiency increases proportionally with chromic acid concentration, up to 250 g/ liter, and
thereafter decreases (Fig. 1). Solutions with higher concentrations of chromic acid tolerate a higher level of trivalent
chromium and iron oxide contaminants. Additions of secondary catalyst improve cathode efficiency at high concentrations
of chromic acid, up to 300 g/liter.

Analyses of chromic acid (Cr+6), sulfate, secondary co-catalyst, e.g. fluoride, as well as trivalent chromium (Cr+3) are
needed to maintain the bath composition within the required limits.

Temperature

Temperature is closely related to current density in its effect on brightness and coverage
of deposit. Generally, the higher the current density, the higher the temperature
requirement (Fig. 2). An optimum temperature range exists for a given concentration of
chromic acid. Below or above that range, dull deposits result.

In general, for decorative baths, the range is 35C (95F) to 46C (115F). For hard
chromium, the range is 49C (120F) to 65.5C (150F).

Since the chromic acid solutions used are fairly concentrated and viscous, stratification
may occur. This results in uneven temperature distribution within the solution. Agitation
is therefore required to equalize the bath temperature, to produce uniform brightness,
Chromium plated from trivalent
and in the case of hard chromium, to improve deposit hardness. solutions now has color closer to
that of chromium from hexavalent
chromium solutions. (Photo
Preheating of parts to optimum bath temperature may be needed before they are
courtesy Atotech USA, Rock Hill,
introduced to the plating tank, and in rare instances cooling of parts may be required, in SC)
order to insure uniformity of deposit. Using both heating and cooling coils in the same
tank may be necessary to maintain a precise temperature.
Current Density

At given solution composition and temperature, current density affects cathode efficiency,
brightness and hardness. Generally, the optimum current density is recommended by the
manufacturer of the plating chemicals used. At too-high current densities, burning or
roughness of deposit occur. At low current densities, lack of chromium coverage can be
expected.

Be sure to use the proper current source. Deposit hazing and/or peeling can be traced to
electrical problems, especially in conventional chromic-sulfate (single catalyst) baths.

1. Effect of chromic acid

Three-phase rectifiers with a maximum of five pct AC ripple should supply an uninterrupted concentration on current
flow of current throughout the plating cycle. Standard current densities are in the range of efficiency.
7.75-15.5 A/dm2 (0.5 to 1.0 asi) for decorative plating, and 23.25 to 100 A/dm2 (1.5 to 6.5
asi) for hard chromium plating.

Anodes

Insoluble lead or lead-antimony alloy are used. Plating of inside diameters and recessed areas may require that conforming
anodes be fixtured at close proximity (0.5-1 inch) to the surface to be plated.

In hard chromium plating, the closer the anode-to-cathode distance, the better the deposit
distribution. Lead anodes ideally should be 90 pct as long as the cathodes. Tops and
bottoms should be slightly below and above the tops and bottoms of the cathodes (parts)
respectively to prevent excessive build-up at the plated ends.

Properly operating lead anodes form a layer of dark brown lead oxide. A yellow or light
colored coating on the anodes indicates a build-up of lead chromate, which results from too
little or no current flow, such as during idle periods. This light colored layer has poor
electrical conductivity.

Cleaning and reactivating lead anodes can be performed chemically, using cleaners specially
2. At constant temperature,
formulated for that purpose. Once cleaned, the anodes should be properly rinsed and
cathode efficiency increases
with current density. at promptly returned to the tank. A satisfactory distribution of anodes consists of three anodes
constant current density, two inches in diameter or four 1.5-inch-diameter anodes per foot of anode bar.
cathode efficiency decreases
with temperature.
Self-Regulating High-Speed Baths

This type of solution incorporates fluoride complexes such as silicofluorides, in addition to sulfates. Salts of low solubility
are selected and used to release the desired anions on a controlled basis. Mixtures containing potassium or sodium
silicofluoride, and dichromate, for example, regulate the release of fluorides by common-ion effect. Mixtures of strontium
sulfate and chromate regulate the release of sulfate. Consequently, at higher temperatures, the cathode current efficiency
increases as a result of the increased solubility of catalysts in this type of bath.

Crack-Free Chromium

This is deposited from baths with low catalyst ratio and high concentration of chromic acid. Since the deposit is hard and
brittle, it cracks when subjected to strain, forming a macro-cracked layer.

Micro-Cracked Chromium

Microcracking is produced by proprietary dual-catalyst baths. The micro discontinuity of the chromium layer results in
spreading the corrosion potential that exists between chromium and an underlying nickel plate. This reduces the anodic
current flowing to any one location on the nickel, greatly retarding the rate of corrosion. Crack densities of 27-50 cracks
per millimeter are specified for optimum corrosion resistance.

Microporous Chromium

Microporous chromium also improves the corrosion resistance of nickel-chromium deposits,

in a manner similar to that just described for microcracked chromium. Regular hexavalent
chromium deposits are typically made microporous by one of two different methods.

The bright nickel layer can be topped with another thin layer of nickel plated from a bath
containing a very fine suspension of inert particles, which codeposit with the nickel.
Chromium plated over this layer deposits around these particles, creating a microporous
structure.

Another way to produce microporous chromium is to lightly spray the surface of the
chromium deposit with a hard, fine abrasive material such as 60- or 80-mesh alumina, or
3. Membrane separating anode
sand. The brittle chromium deposit breaks at the point of impact, forming micropores and
box from cathode compartment
exposing the bright nickel layer beneath the chromium. in trivalent chromium plating.

For best corrosion resistance, the pore density in both cases must exceed 10,000 pores per square centimeter.

Cleaning and Surface Preparation

Inadequate cleaning of the basis metal will lead to poor plating results. In decorative plating, hazy, pitted or non-adherent
nickel deposits will be obtained as a result of inadequate surface preparation. The thin chromium deposit will magnify and
reflect these defects.

Table II—Comparison of Working Parameters of Trivalent Sulfate Type Versus

Hexavalent Baths

Trivalent Hexavalent
Concentration of chromium 5-6 100-250
g/liter 3.5-3.9 0
pH 40-50 40-50
Temperature (C) 4-9 10-15
Current density A/dm2 Lead (alloy) Lead (alloy)
Anode: Shielded Anode Composite metal oxides
Anode: Insoluable Anode Good Poor
Throwing power Tolerant Causes "white wash"
Reaction to current interruption Low level of Cr3 High level of Cr3
Effluent Mild effect, similar to nickel Strong acid burn and ulceration
Skin contact Microporous Induces microdiscontinuities
Deposit structure 0.1 micron/min at 7 A/dm2 0.1 micron/min at 10 A/dm2
Plating rate

Allowing a nickel plated surface to dry during transfer will passivate the nickel and produce milky, hazy or no deposit when
chromium plated. In hard chromium plating, surfaces of the basis metal should be free of oil, grease or rust.

Etching of steel and stainless steel insures proper adhesion. The extent of etch needed depends on the composition of the
steel. Carbon steel should be etched for 15-30 sec and up to 45 sec if the steel has been heat treated. Etching is best
performed in non-catalyzed solutions of 210-225 g/liter (28-30 oz/gal) chromic acid to prevent overetching by sulfate, and
particularly by fluoride catalysts.
Reverse etching in the same plating bath usually introduces an excessive amount of iron into the bath and should be
avoided.

TRIVALENT CHROMIUM PLATING

Toxicity of Cr+6, low current efficiency, poor metal distribution, burns in high-current-
density areas, "white-wash" and lack of coverage around holes are some of the problems
associated with Cr+6 plating baths. These factors led to the eventual development of a safer
and more efficient system, based on trivalent chromium.

Trivalent chromium plating baths for decorative applications enjoyed a steady, although
initially slow, acceptance as a substitute for hexavalent chromium plating. Their main
attraction lies in the fact that they eliminate many of the shortcomings of hexavalent
chromium solutions.
4. Trivalent chromium can be
plated from cell with shielded
Bath Chemistry anode (left) or from single cell.

Several advances in technology have taken place, making the process more readily acceptable to platers.
There are currently at least three basic types of trivalent chromium
baths available. A single electrolyte bath, chloride or sulfate based,
using graphite or composite anodes, and special additives to prevent
oxidation of trivalent chrome at the anodes (see accompanying
"Single-Cell Trivalent Chrome" sidebar).
Another type, a sulfate-based system, uses shielded anodes.
Conventional lead anodes are surrounded by boxes sealed on one side chromium plating processes.
by a selective ion membrane (Fig. 3, 4) and filled with dilute sulfuric
acid.
The membrane used is a perfluorinated sulfonic acid, reinforced with
an inert Teflon® fabric. The membrane prevents the migrating
trivalent chromium ions in the solution from reaching the anode, thus
preventing their oxidation to the hexavalent state.
The mechanism provides for excellent pH stability during plating. The the anode, and if hexavalent chromium were
bath is capable of producing light-colored deposits very close to the
appearance of deposits from hexavalent baths.
Table II summarizes the differences between Cr+6 and Cr+3 plating-
bath parameters.
The sulfate type trivalent chromium solution is maintained as one
would maintain a conventional bright nickel bath. It utilizes a primary
additive containing the trivalent chromium ion and a secondary
additive that contains grain refiners and brighteners. These materials
are added on an ampere-hour basis, using chemcial-feed pumps
actuated by an ampere-hour meter.
Metallic impurities affect results as shown in Table III. These
impurities can be plated out on dummies as can be done with nickel
baths, or through an external purification cell on a continuous basis.
Ion exchange columns can also be used, as well as precipitating
agents followed by filtration.
A new insoluble catalytic anode has been developed for use in direct
contact with the electrolyte of the above sulfate-based system. The
new anode is designed to maintain an electrode potential level that
will prevent oxidation of trivalent chrome at its surface. No selective
oxidation additives are used in the electrolyte. Consequently, the
same high tolerance to metallic impurities, light colored deposits and
pH stability of this sulfate-based process are maintained. The users
have a choice in selecting the shielded anode or the insoluble direct
contact type anodes with the same bath. This new development will
make it possible to use conforming and auxiliary anodes for plating of
complex shaped configurations.
Deposit Characteristics
Trivalent chromium baths produce deposits that are inherently
microdiscontinuous. Under about 0.65 micron (25 millionths of an
inch), trivalent chromium deposits are microporous. Typical density of
the pores in a microdiscontinuous deposit is 20,000 to 60,000
Single-Cell Trivalent Chromium
A major distinction between trivalent chromium
processes is the chemistry used to prevent the
formation of hexavalent chromium at the anode
during plating. This must be done, since
hexavalent chromium is a poison to all trivalent
Fig. 4 shows the anode configurations of the
shielded anode type and single-cell trivalent
chromium plating.
The single-cell process has built into its chemistry
mechanisms to prevent the presence of
hexavalent chromium. No hexavalent can form at
added, the chemistry of the single-cell bath would
immediately convert the hex to
tri. This ability to convert hex to tri instantly
permits continued deposition of chromium from
the single-cell bath.
The working parameters of the two available
versions of the single-cell process are shown in
Table A. The room-tempera-ture process produces
deposits similar in color to that of stainless steel or
pewter. The elevated-temperature produces
blue-white chromium almost identical in color to
that from hexavalent baths. These solutions are
more sensitive to metallic impurities than
hexavalent baths. The trivalent baths are easily
purified.
Metallic impurities can be removed from single-cell
baths by three methods. They can be plated out
on dummies. They can be removed quickly by
adding a chemical purifier that precipitates large
quantities of metallic impurities at one time. Or
they can be removed by ion exchange of a
continuous basis. The elevated-temperature
single-cell process can produce deposits over 0.25
mil thick and maintain the physical properties of
hexavalent chromium deposits of similar
thickness.
—Dr. Donald L. Snyder
World Wide Technical
Marketing Manager
Atotech USA
Cleveland, Ohio
pores/sq cm. At higher thicknesses deposits are microcracked.

The effect of microdiscontinuous chromium plating is to dissipate electrochemical corrosion current over a wide surface
area, thus improving corrosion resistance.

Room-temperature and sulfate-type, trivalent chromium processes plate at rates similar to those of hexavalent chromium
baths—about 0.1 micron or four millionths of an inch per minute.

The elevated-temperature chloride process plates at about 0.25 microns or 10 millionths of an inch per minute.

The hardness of the deposit is similar to that of traditional hexavalent chromium—about 700 to 1,000 Vickers.

Another advantage of the trivalent chromium bath is its ability to tolerate current interruptions without passivating or
production of white "clouds" and hazes in the deposit. Stripping and replating over nickel can be carried out easily, with no
adverse effects.

Comparison of Effluent Treatment for Cr+6 and Cr+3

As trivalent chromium plating baths contain no hexavalent chromium, effluent treatment of the subsequent rinse waters is
both simpler and cheaper. Most hexavalent chromium baths contain about 250 g/liter of chromic acid, equivalent to 130
g/liter of chromium metal. Even if a dragout rinse is used, the running-water rinses usually contain a high concentration of
Cr+6.

Effluent treatment consists of acidification of the rinse waters to obtain

Table III—Metallic Impurities and Their
the required pH of 2.5, followed by reduction of the Cr+6 to Cr+3, using
Effects on Trivalent Baths
sulfur dioxide or sodium bisulfite, according to the following equation:
Maximum Effect
CrO3 + 2 NaHSO3 + 2H2SO4 Metallic Tolerance, Produced
Cr2(SO4)3 + Na2SO4 + 3H2O Impurity mg/liter If Exceeded
Ni 500 Darkening of deposit
Cr (VI) 30 Defects at low cd
Finally the solution is neutralized and this causes precipitation of
Cu 30 White blooms at high cd
chromium hydroxide.
Zn 70 Darkness at low cd

The theoretical requirement is three kilograms of sodium bisulfite (60-62 pct SO2) plus two-three kilograms of sulfuric acid
to reduce one kg of hexavalent chromium. A trivalent chromium electrolyte may contain only five g/liter of chromium and
require only neutralization to achieve precipitation. On precipitation, the volume of sludge generated by a hexavalent
chromium electrolyte is approximately 30 times greater than that from a trivalent bath.

A dilution of about 100 times with rinse waters might produce an effluent from the plating process of about 50 ppm
(mg/liter), of Cr+3 before any further dilution occurs from other sources in the factory.

Hexavalent Chromium Plating Troubleshooting Guide

Common Plating Problems. Identifying the origin of a plating deficiency is the necessary first step in solving the
problem. The basic causes of poor plating usually fall into three categories:

• Faulty bath chemistry.

• Improper temperature and/or current density.
• Poorly finished and/or inadequately cleaned basis-metal surface.

Skill and experience will often permit a fairly precise identification of the source of any specific fault, or at least suggest the
likely category in which it will be found. However, chemical analysis, Hull Cell tests, and reliable service recommendations
give the best foundation for successful troubleshooting. The most common defects are listed here, together with their
probable causes and some remedial steps.

Table A—Working Parameters of Single-Cell Trivalent Baths

Room Elevated
Temperature Temperature
Concentration of chromium, g/liter 15-25 15-25
pH 2.8-3.5 2.3-2.9
Temperature, C 20-22 27-44
Current density. A/dm2 8-13 8-13
Maximum thickness millionths 50 1500+
Anodes Graphite Graphite
Line of anodes Indefinite Indefinite
Throwing power and Covering Better than hexavalent Better than hexavalent
power Tolerant Tolerant
Reaction to current interruption Low levels of Cr3 Low levels of Cr3
Effluent None None
Misting Mild effect, similar to Mild effect, similar to
Skin contact nickel nickel

Deposit structure Microporous Microporous

less than 25 millionth Microcracked Microcracked
greater than 25 4 millionth per minute 10 millionth per minute
Plating rate Only to remove solids Only to remove solids
Filtration

Milky Deposit
Possible Cause: Corrective Step:
High chromic acid/sulfuric ratio Increase sulfate additions
Chloride contamination Remove chloride with silver carbonate
Iron contamination Dilute bath
Excess trivalent chromium Clean anodes and reoxidize trivalent
chromium
Poor nickel surface Carbon treat nickel to remove organic
contamination, improve rinsing of nickel and
use a nickel activator
High Temperature Reduce to normal, check control
Hazy Deposit
Possible Cause: Corrective Step:
High chromic acid/sulfate ratio Increase sulfate concentration
High chloride contamination Remove chloride with silver carbonate
Iron contamination Dilute bath
Excess trivalent chromium Clean anodes and reoxidize trivalent
chromium
Low temperature Increase temperature to normal
Current density too high Adjust anode-to-cathode ratio
Intermittent current flow Check electrical contacts
Poor nickel surface Improve rinsing, use nickel activator
Gray and Dull But Smooth Deposits
Possible Cause: Corrective Step:
High chromic acid/sulfate ratio Increase sulfate concentration
 Current surge when contact is made Reduce current
High temperature Check temperature controllers
Dull Spots in High-Current-Density Areas
Possible Cause: Corrective Step:
High chromic acid/sulfate ratio Increase sulfate concentration
Passive nickel Improving rinsing, use nickel activator
Bipolar condition Use live entry to chromium bath
Blue Deposits
Possible Cause: Corrective Step:
High temperature Reduce temperature to normal
Rough Deposits
Possible Cause: Corrective Step:
Low sulfate Low temperature Add sulfuric acid to increase
Surface preparation Adjust temperature to normal
Surface preparation Improve cleaning and rinsing
Suspended particles in bath Filter bath and eliminate source
Burned Deposits
Possible Cause: Corrective Step:
High chromic acid/sulfate ratio Increase sulfate concentration
Low chromic acid Add chromium salts
Excess trivalent chromium Clean anodes and reoxidize trivalent
chromium
Too-high current density Reduce current density or increase
temperature
Low temperature Increase temperature to normal; preheat
large, cold parts
Brown Spots or Rainbows
Possible Cause: Corrective Step:
Low sulfate or catalyst Increase sulfate concentration; submit
sample for analysis
Inefficient contacts Check racking, build-up on hooks and rack
tips, contact on bus bars.
Poor Adhesion
Possible Cause: Corrective Step:
Insufficient etch Increase etch time; check etch bath
Surface contamination Improve rinsing and/or cleaning cycle
Intermittent contact Clean and check contacts; work should
enter chromium bath live
Poor nickel deposit Check surface preparation before nickel
plating and condition of nickel bath
Poor Coverage
Possible Cause: Corrective Step:
Low chromic acid content Add chromium salts
Low chromic acid/sulfate ratio Precipitate excess sulfate with barium
carbonate (See Table V)
Plating current too low Raise current density
 Oxidized contacts Clean contacts
Scaled anodes Clean anodes
High temperature Reduce temperature to normal
Passive nickel Activate nickle surface in nickel activator
Slow Deposition Rates
Possible Cause: Corrective Step:
High chromic acid/sulfate ratio acid Add the proper amount of sulfuric acid
Too-low current density Increase voltage; check parts distribution;
check for current leakage
Scaled anodes Clean anodes
Oxidized contacts Clean contacts
Insufficient power supply Increase rectifier size
Iron contamination Dilute bath
Excess trivalent chromium Follow procedure for the reoxidation of
trivalent chromium
Too high temperature Reduce to normal temperature
Partial Deposition Rates
Possible Cause: Corrective Step:
Too-low current density Increase voltage, clean rack contacts, clean
anodes
Uneven current density Improve arrangement of parts on rack
Passive nickel Activate cathodically or immerse in
hydrochloric acid 50 pct
Gas pockets Suspend parts so gas escapes freely
No Deposit
Possible Cause: Corrective Step:
Reverse polarity Make proper connections
Defective contacts Clean contacts
Excess sulfate Check ratio and correct
Chloride contamination Remove chloride with silver carbonate
Pitted Deposits
Possible Cause: Corrective Step:
Pitted nickel deposit Filter nickel bath
Pitting in basis metal Improve basis metal preparation
Solution contamination from Improve grinding and cleaning procedure
magnetic particles on ground surfaces
Gas pitting Reposition work on racks to avoid gas
formation

Table IV—Conversion of Excess Sulfate to Barium Carbonate

Required

Excess Bath Volume (gal)

sulfate
100 200 300 400 500 600 700 800 900 1000
to be
removed Barium Carbonate Required (oz)
(oz/gal)

0.01 2.2 4.4 6.6 8.8 11.0 13.2 15.4 17.6 19.8 22.0
0.02 4.4 8.8 13.2 17.6 22.0 26.0 30.8 35.2 39.6 44.0
 0.03 6.6 13.2 19.8 26.4 33.0 39.6 46.2 52.8 59.4 66.0
0.04 8.8 17.6 26.4 35.2 44.0 52.8 61.6 70.4 79.2 88.0
0.05 11.0 22.0 33.0 44.0 55.0 66.0 77.0 88.0 99.0 110.0
0.06 13.2 26.4 39.6 52.8 66.0 79.2 92.4 105.6 118.8 132.0
0.07 15.4 30.8 46.2 61.6 77.0 92.4 107.8 123.2 138.6 154.0
0.08 17.6 35.2 52.8 70.4 88.0 105.6 123.2 140.8 158.4 176.0
0.09 19.8 39.6 59.4 79.2 99.0 118.8 138.6 158.4 178.2 198.0
0.10 22.0 44.0 66.0 88.0 110.0 132.0 154.0 176.0 198.0 220.0

Note: 1 oz/gal = 7.5 g/liter

Table V—Conversion of Excess Sulfate to Barium Carbonate Required

Excess Bath Volume (gal)

sulfate
100 200 300 400 500 600 700 800 900 1000
to be
removed 66° Bé Sulfuric Acid Required (fl oz)
(oz/gal)

0.01 0.05 1.0 1.6 2.1 2.6 3.1 3.7 4.2 4.7 5.2
0.02 1.0 2.1 3.1 4.2 5.2 6.3 7.3 8.4 9.4 10.4
0.03 1.6 3.1 4.7 6.3 7.8 9.6 10.9 12.5 14.1 15.7
0.04 2.1 4.2 6.3 8.4 10.4 12.5 14.6 16.7 18.8 20.9
0.05 2.6 5.2 7.8 10.4 13.0 15.6 18.2 20.9 23.5 26.1
0.06 3.1 6.3 9.6 12.5 15.6 18.8 21.9 25.0 28.2 31.3
0.07 3.7 7.3 10.9 14.6 18.2 21.9 25.6 29.2 32.9 36.5
0.08 4.2 8.4 12.5 16.7 20.9 25.0 29.2 33.4 37.6 41.8
0.09 4.7 9.4 14.1 18.8 23.5 28.2 32.9 37.6 42.3 47.0
0.10 5.2 10.4 15.7 20.9 26.1 31.3 36.5 41.8 47.0 52.2

Note: Fluid ounces × 29.5737 = cubic centimeters

Trivalent Chromium Oxidation. If anode deficiencies and bath contaminants (iron, copper, or other metal ions, unstable
mist suppressants, or stray parts corroding on the floor of the tank) allow the trivalent chromium concentration (Cr+3) in
the bath to exceed the recommended maximum of around two pct, reoxidation is necessary.

Reoxidation of the Cr+3 requires that the bath be electrolyzed with clean (active) anodes, using an anode/cathode area ratio
of 30:1 and the highest bath temperature permissible. Occasionally the electroplater can process loads of work using a high
ratio of anode-to-cathode area to salvage his bath. More often he will adopt one the three alternatives:

1. Periodic reoxidation of bath by electrolysis.

2. Continuous reoxidation of bath by means of a reoxidation cell within the plating tank.
3. Continuous reoxidation of the bath in a separate reoxidation tank.

Regardless of the method used, the reoxidation requires an anode current density of approximately 20 asf. The cathode
current density will then be about 600 asf, if the proper anode:cathode area ratio has been maintained. Specific pointers on
each of the three alternative procedures follow.
Periodic Reoxidation of Bath. Raise the plating-bath temperature to at 5. Cathode selector for use in reoxidation of
least 145F, or to the highest temperature permis-sible for the tank-lining trivalent chromium.
material, and space the tank anodes evenly along the anode bar. Position
a small-diameter cathode rod (copper) between each pair of anodes. The
diameter/length relationship of the cathode rods should relate to the
effective anode area as indicated in Fig. 5. In the event the cathode is not
of the same length as the anodes, the indicated length to be plated
should be centrally positioned. If necessary, mask or tape the top section
to permit proper positioning.

Electrolyze the chromium plating bath until the Cr+3 concentration is down
to about one pct of the chromic acid concentration. The duration of the
bath electrolysis will depend on the initial Cr+3 concentration, the total
anode area available for the particular bath volume, and the temperature
of the bath. The efficiency of oxidation will decline as the Cr+3
concentration drops. For example, less electrolysis will be needed to lower When using tank anodes for the intermittent
the trivalent chromium level from five pct to four pct than to reduce it procedure, determine effective anode area for a
from two pct to one pct. pair of anodes. For example, two anodes with 1.5
inches OD have an immersed length of 30 inches.
The surface area is 2 x 1.5 x 3.14 x 30 or 282.6 in.
It may be necessary to electrolyze the bath for several overnight periods To find the cathode length to use between the two
or over a weekend to lower the Cr+3 concentration to the desired level tanks anodes, draw a line across from 282.6 in2 to
the line showing the diameter of rod to be used. A
(one pct of the chromic acid present). If the current/volume ratio is five
24-inch length of 1/8 inch OD rod should be used.
A/gal of solution, the anode current density 20 asf, and the cathode
current density 600 asf, it will take about two hours of electrolysis (on the average) to reduce the Cr+3 concentration 0.1
oz/gal. PFD

REFERENCES

Dennis, J.K. and Such, T.E., Nickel and Chromium Plating, Butterworth Publishers, 1986.

Canning, Handbook on Electroplating, 22nd edition, 1978. Salauze, J., Traite'De Galvanoplastic, 2nd edition, 1950.

Zaki, N., "Advances in Trivalent Chrome Plating," AESF Chromium Colloquium, 1987.

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