Shop Talk

Selection & Applications of Inorganic Finishes:

Chromate Coatings
Written by Fred Pearlstein
Updated by Dr. James H. Lindsay, AESF Fellow

In general, chromate films are applied by immersing

parts in an acidic solution containing dichromate or Table 1
chromic acid and an activator (usually, nitrate, sul-
fate, chloride, formate or fluoride). An oxidation- Salt-spray corrosion resistance of zinc plate
reduction reaction occurs on the metal surface with
formation of substrate metal ions and trivalent chro- Chromate Hrs to White Corrosion Product
mium ions. Single-dip bright 8 to 24
An accompanying increase in the pH of the solu- Leach-type clear 24 to 48
tion immediately adjacent to the metal surface results Iridescent yellow 96
in the precipitation of a gelatinous film comprised Bronze 96 to 144
largely of chromic hydroxide (and substrate metal Olive drab 120 to 172
compounds) and in which soluble chromates (hexava-
lent chromium) are incorporated. This freshly formed Rarely is it desirable to leave a zinc- or cadmium-plated
coating, after rinsing and drying, is rather soft and vulner- surface bare, especially considering that the cost of apply-
able to damage but soon hardens. If practical, it is some- ing a chromate film is a small fraction of that for applying
times advisable to permit aging up to 24 hr before han- the metal deposit. Chromate coatings are required on zinc
dling. and cadmium for most military applications and are applied
The water-soluble chromates are effective corrosion by immersing racked parts, by slowly rotating the parts in
inhibitors for most metals. Corrosion inhibition is a very barrels, or by swirling the parts in perforated baskets.
important factor in the ability for chromate coatings to A single-dip clear chromate coating accompanied by
prevent corrosion of the underlying metal when exposed chemical polishing can be applied on smooth deposits of
to many natural environments. However, the coating itself zinc and cadmium to provide an attractive, bright finish
also contributes some protection by presenting a barrier with a blue-white tint not unlike that of decorative chro-
between the metal and the environment. mium. A clear bright chromate can be formed in a two-step
Chromate coatings exhibit a phenomenon called “self operation that involves the application of a yellow film fol-
healing” - the ability to protect metal at areas where some lowed by leaching in mild alkaline (e.g., 20 g/L Na2CO3 at
of the coating has been removed as the result of a scratch or 50°C; 122°F) or acid (e.g., 1 mL/L H3PO4 at 25°C; 77°F)
an abrasion. The inhibitive soluble chromates are leached solution.
from the chromate film to protect adjacent bare metal The yellow-green iridescent-type chromate coatings are
areas when a moisture film is present during environmen- extensively used for improved corrosion resistance. The
tal exposure. Cronak process1 was the first to produce this type of chro-
mate coating and found widespread use for many years.
Zinc and Cadmium Typical formulations (200 Na2Cr2O7.2H2O + 6 mL/L H2SO4
or 50 g/L CrO3 + 3 mL/L H2SO4) may be employed by
Chromate conversion coatings on zinc- or cadmium-plated
a 10-second immersion at 25°C (77°F). However, more
steel, zinc die castings or galvanized steel are often used as
effective proprietary solutions are available. Solutions for
a final finish to retard the formation of white or gray prod-
chromating galvanized steel coil usually contain fluoride
ucts from corrosion of the zinc or cadmium during envi-
activator.
ronmental exposure. The chromate coating effectively pre-
A typical iridescent chromate coating is 0.5 µm (0.02
vents surface discoloration from fingerprint-perspiration
mil) thick, contains 4 to 12 µg/cm 2 of leachable hexavalent
as the result of handling. From this consideration alone,
chromium, and prevents the appearance of white salts from
application of a chromate coating is usually advisable.
corrosion of the underlying metal for more than 96 hr of
salt-spray exposure.
By modifying the solution formulation, chromate coat-
Based on an original article from the “AES Update” series ings of bronze or olive-drab color are readily applied by
[Plating, 66, 30 (January 1979)] a single-dip operation. The darker colors, often favored

10 Plating & Surface Finishing • Decem be r 2002

 resisting separation of the organic coating from undercut corrosion.
However, not all chromate films are a suitable base for paint.
Although chromate coatings are applied predominantly by chem-
ical reaction of metal surfaces and solution, proprietary anodic pro-
cesses are available that produce coatings claimed superior in wear
resistance of the freshly formed films and in corrosion resistance.
Steel cartridge cases, rack plated with zinc, are chromated using an
anodic process to provide optimum properties for military applica-
tion.
The effectiveness of chromate coatings is usually determined
by either the salt-spray test, the diphenyl carbazide test (for con-
centration of leachable hexavalent chromium) or the lead acetate
spot test. The last simply involves application of a drop of 50 g/L
Pb(C2H3O2)2.3H2O (made with distilled water) at a pH of 6.2±0.6
on the surface after the chromate film has aged 24 to 72 hr. The
Figure 1—Corrosion of chromated zinc-plated steel after 96 hr of salt-spray delay of a black or dark discoloration (> 1 min for zinc substrate; >
exposure: (A) no chromate; (B) chromated, unheated; (C) chromated, heated 2 6 sec for cadmium substrate) is indicative of a good-quality chro-
hr at 500°C (932°F); (D) chromated, heated 2 hr at 750°C (1382°F); (E) heated
mate coating.
2 hr at 1000°C (1832°F); (F) chromated, heated 2 hr at 1500°C (2732°F); (G)
chromated, heated 2 hr at 2000°C (3632°F)..
Aluminum
by the military for camouflage purposes, are usually indicative of Chromate coatings are usually applied to aluminum from a solution
greater concentration of hexavalent chromium and, thus, improved containing chromic acid, a fluoride-containing ion and an accelera-
corrosion resistance. Proprietary solutions that form lustrous, black tor (e.g., ferricyanide).3 Parts are usually treated by immersion but
chromate coatings in a single-dip operation are available. Typical many are sprayed or brushed. A number of suppliers have proven
salt-spray corrosion resistance of chromated zinc plate is shown in that their proprietary formulations can produce coatings to pass
Table I. military requirements (QPL-81706).
A variety of colors may be applied by immersing the freshly The chromate coatings may be iridescent, yellow, brown or
formed chromate in organic dye solutions. Pastel colors are attained green, with appearance affected by the surface finish of the alu-
using the clear or light-colored chromate films. Darker colors can minum. Clear coatings are applied by a brief treatment in special
be obtained with the darker chromate coatings. The dyed films solutions or by the removal of most of the soluble chromate com-
have decorative applications but are most often used for identifi- pounds from the yellow chromate coatings by leaching in hot water
cation purposes. For example, fasteners or assembly components or immersing in dilute sodium carbonate solution. A wide variety
may be color-coded to avoid errors in selection where differences of colors can be produced by immersing the aluminum with freshly
in configuration are not readily discernible. formed or leached chromate film into an appropriate dye bath (usu-
Some studies indicate that chromate films add little to the overall ally about 2 g/L dye, at pH 4.0 with acetic acid, 600°C; 1400°F)
protection of the metal deposit to steel basis metal during outdoor for decorative or color-coding applications. The chromate film is
atmospheric exposure while others indicate substantial improve- applied with only a negligible change in the dimensions of the
ment. Results are apparently dependent on the type of environment metal.
involved.
It is usually not advisable to use a chromate coating as a sub-
stitute for adequate thickness of a metal deposit. However, it has
Corrosion Resistance
been shown from salt-spray studies that very thin (1.0 µm; 0.04 Chromate coatings provide a high degree of corrosion resistance to
mil) metal deposits, which may form at highly recessed areas, are aluminum at a low cost. A normal coating of perhaps 0.5 µm (0.02
greatly improved in protective value by a chromate film from a mil) thickness will protect 2024-T3 alloy for more than 168 hr of
solution formulated to keep metal loss to a minimum. In this con- salt-spray exposure. The corrosion resistance varies with the alloy
text, it is best to eliminate or minimize the dilute nitric acid dip that and heat treatment, but most wrought materials are less corrodible
usually precedes chromating, as greater metal loss may result from than 2024-T3. Some castings with a high content of silicon may be
this treatment than from the chromating process. more difficult to protect.
Chromate is an excellent corrosion-preventive coating for alumi-
The Heat Factor num, provided a high degree of both wear and abrasion resistance
is not also required. Interestingly, chromated aluminum resists cor-
It is well known that heating of chromated zinc adversely affects rosion even better in natural environments than is indicated by salt-
corrosion resistance. Heating in dry air at about 75°C (167°F) spray results. For example, iridescent chromate-coated 2024-T3
or above results in a decrease of the available (leachable) inhibi- panels were unaffected in appearance after two years of tropical
tive hexavalent chromium by an irreversible dehydration phenom- marine exposure, whereas comparable bare panels were catastroph-
enon and cracks appear in the surface film.2 The adverse effects ically deteriorated by exfoliation corrosion (Fig. 2).4 It is therefore
are worsened as temperature increases and, after heating at above not surprising that innumerable commercial and military items are
100°C (212°F), the protective nature of the chromate film may be chromated as a final finish. Like chromated zinc, the corrosion
nullified (Fig. 1). Since zinc- or cadmium-plated high-strength steel resistance of chromated aluminum is adversely affected by heat.
(Rockwell C-40 or above) requires heating(191±14°C; 375±25°F) Another important application of iridescent to yellow chromate
to relieve hydrogen embrittlement, the chromating operation is coatings on aluminum is as a base for paint and lacquers to enhance
deferred until after baking. adhesion and prevent the spread of undercoat corrosion from
Chromate coatings on zinc or cadmium are sometimes used regions where bare metal becomes exposed as the result of impact
as a base for paint, lacquer or varnish and function similarly damage. The combination of an epoxy primer (MIL-P-23377) and
to phosphate coatings in enhancing the protective properties and

Pl a t i n g & S u r f ace Fin ish in g • Decem b er 2 0 0 2 11

polyurethane topcoats (MIL-C-81773) is representative of a system
applied to chromated aluminum for protection of aircraft and other
weapon systems. However, the zinc chromate primer (TT-P-1757)
and alkyd enamel topcoats (TT-E-529) are used more often.
After painting, chromated aluminum can be subjected to ele-
vated temperature (which would adversely affect the unpainted sur-
face) without apparent effect on the protective value of the painted
metal. An alternative to the chromate film as a base for paint is the
wash primer.

Other Applications
Colorless chromate coatings are applied to aluminum when the
characteristic appearance of the metal is desired. A clear organic
coating can be used to provide increased protection. The very thin
chromate coatings (clear or light iridescent per MIL-C-5541, Class
3) are also used for electrical or electronics applications where low
electrical surface resistivity is required. Though the resistivity of
chromated metal is somewhat greater than that of freshly cleaned
aluminum, the chromate film prevents formation of oxides and cor-
rosion products that would otherwise greatly increase surface resis-
tivity. Similarly, the thinner chromate films are applied on alumi-
num parts that require welding since the coating does not apprecia-
bly interfere with the process and because it prevents formation of
oxides that might interfere.
Mention should be made of the phosphate-fluoride-dichromate Fig. 2—Corro-
treatment5 of aluminum that results in formation of an amorphous sion of 2024-T3
coating of attractive green or blue-green color but which contains aluminum after
no hexavalent chromium and does not pass the corrosion-resistance two years of
requirements of military specifications. However, these coatings tropical marine
have good resistance to weathering and humidity and have found exposure: (A)
important final-finish applications for such items as screening and bare, (B) chro-
cyclone fencing; they also serve as an excellent base for paint or mated.
lacquer.
There are efforts to develop conversion films for aluminum (as
well as other metals) that will provide the effectiveness of chro- Chromate coating on magnesium provides significant corrosion
mate coatings without the use of the toxic chromates in the treat- resistance and is used as a final finish to provide temporary
ment solutions. One such treatment6 is already showing commer- protection during shipment and storage or when relatively
cial interest and further developments in this area are anticipated. mild environmental exposures are expected. Magnesium die
castings, used extensively for exterior automotive components (e.g.,
Magnesium fuel pumps, engine crankcases, transmission cases, blower
fans), have served successfully when protected simply with
Magnesium alloys, particularly castings, have found many impor-
a chromate coating and film of oil. However, for military applica-
tant applications (e.g., space vehicles, military equipment contain-
tions, the chromate is seldom used as a final finish but serves as an
ers, automotive parts, materials-handling equipment, etc.) primar-
effective base for protective organic coatings. One or more coats
ily because of their high strength-to-weight ratio. It is the lightest
of alkali-resistant primers (vinyls or epoxies) containing inhibitive
and most active (chemically) of the common structure metals and
chromate pigment and one or more finish coats are recommended. A
the oceans contain an almost inexhaustible supply.
minimum of four coats is recommended for severe exposures.
Magnesium reacts with water or neutral salt solutions to pro-
The following types of chromate coatings find most common
duce hydrogen gas and magnesium hydroxide; a drop of water on
use:
a bare magnesium surface will rapidly become distinctly alkaline.
Fortunately, the alkalinity produced tends to stifle the initial rapid
• Type I—“Chromium Pickle Treatment:”* An iridescent film is
rate of attack and thus magnesium corrosion occurs at a slower
applied by immersion (e.g., 1.0 min in 180 g/L Na2Cr2O7.2H20
rate than most steels and less catastrophically than some alumi-
+ 185 mL/L HNO3 at 22°C; 72°F) for application to wrought
num alloys in natural outdoor environments. However, when mag-
and many cast alloys. A modified solution** is more suitable for
nesium is in contact with most heavy metals, a high potential dif-
certain cast alloys such as AZ91b.
ference is established and rapid and intense galvanic corrosion of
• Type III— “Dichromate Treatment:”*** This is a more involved
the magnesium will result. It is therefore most important to pre-
treatment than Type I entailing an acid-fluoride pickling
vent galvanic corrosion by using protective coatings, tapes, seal-
step (e.g., 5 min in 230 mL/L HF, 49 per cent, at 25°C;
ants and gaskets to effectively insulate the dissimilar metals, or to
77°F)), followed by immersion in dichromate solution (150
coat any dissimilar metals with aluminum, cadmium, tin or zinc
for improved compatibility. It is also advisable to avoid sump areas
of possible moisture accumulation and to apply organic protective
coatings when feasible. *Dow No. 1, The Dow Chemical Co., Midland, MI.
**Dow No. 20, The Dow Chemical Co., Midland, MI.
***Dow No. 7, The Dow Chemical Co., Midland, MI.

12 Plating & Surface Finishing • Decembe r 2002

 g/L Na2Cr2O7.2H2O
+ 2.5 g/L CaF2) at
or near the boiling Table 2—Applications of Chromate Coatings
point. The treatment
imparts an attractive, Chromate coating type Substrate Typical applications
uniform brown color Clear Zn, Cd, Al Electronic chassis, fasteners, wire goods, tools
to most alloys. The Iridescent Zn, Cd, Al, Mg Bicycle parts, auto carburetors, fuel pumps, paint base
resultant chromate Bronze/Olive Drab/Black Zn, Cd, Al, Mg Optical equipment, weapons components, springs, hardware
coating is superior in Dyed Zn, Cd, Al Simulated brass, color coding, fasteners
corrosion resistance
and as a paint base
to the Type I coat-
ing.
• Type VI—“Chromic Acid Brush-on Treatment:”† The coating Tin
applied by brushing is primarily used as a touch-up treatment Chromate and chromate-phosphate treatments for tin-plated steel
and produces coating characteristics similar to that of Type I. have been developed to enhance the protective properties of the
The solution is quite dilute (10 g/L CrO3 + 7.5 g/L CaSO4.2H2O) tin while preventing discoloration, particularly from sulfur com-
and the final water rinse may be omitted when rinsing is not fea- pounds. The coatings are generally invisible or nearly so; examples
sible or if it is desired to eliminate the need for rinsewater waste are 5-sec immersion in 10 g/L NaOH + 3 g/L Na2CrO4 at 90°C
treatment. A nonchromate brush-on coating based on phosphate (194°F), or 30 sec in 19 g/L NaOH + 9 g/L Na3PO4.12H2O + 8
solution, is also available;†† studies are currently in progress to g/L Na2Cr2O7.2H2O at 65°C (149°F). Cathodic dichromate treat-
develop the treatment for production immersion applications. ment (e.g., 30 g/L Na2Cr2O7.2H2O, pH 5.0, 60°C; 140°F, 6 A/dm2;
• Type VIII—“Chromate Treatment:” This is a proprietary treat- 60 A/ft2) applied to tin-plated steel provides excellent protection
ment that produces coatings approaching the quality of the Type against discoloration during storage and is an effective base for lac-
III finish, but with a much simpler procedure involved. quer. An alternative is cathodic treatment in 20 g/L Na2CO3, pH
9.5, 50°C (122°F), 10 A/dm2 (100 A/ft2).
Beryllium
The remarkable heat-sink capabilities, exceptional dimensional sta- Silver
bility, low density and unique nuclear properties of beryllium have Proprietary solutions produce clear chromate films on polished
led to applications in inertial guidance equipment, high-energy silver that are quite effective in retarding tarnishing in contact with
braking systems and nuclear reactors. Beryllium is subject to cor- hydrogen sulfide gas or sodium sulfide solution. The chromate film
rosion in salt environments and the corrosion products can present does not adversely affect, to a significant extent, the low contact
a safety hazard as they are highly toxic when inhaled. Chromate resistance and solderability of the surface. However, there is some
conversion coatings can be applied from most solutions developed question of the ability of the chromate film to provide long-term
for application to aluminum or by use of the solution: 200 g/L tarnish resistance in mild household environments.
Na2Cr2O7.2H2O +1.8 g/L HF (48 per cent) at 25°C (77°F). The
coatings are effective for providing corrosion resistance during
environmental exposure.
References
Beryllium is subject to catastrophic oxidation in air at high tem- 1. E. J. Wilhelm, US patent 2,035,380 (1936).
peratures, e.g., >700°C (1292°F), particularly when some water 2. A. Gallaccio, F. Pearlstein and R. DʼAmbrosio, Metal Finishing,
vapor is present; the beryllium apparently reacts much more read- 64, 50 (August 1966).
ily with the oxygen of water molecules than it does with gaseous 3. C. W. Ostrander and N. R. Congiundi, US patent 2,796,370
oxygen. Remarkably, a chromate film protects most beryllium (1955).
alloys against oxidation for considerable time in moist air at up to 4. F. Pearlstein and L. Teitell, Materials Performance, 13, 22,
900°C (1652°F). (March 1974).
5. F. P. Spruance Jr., US patent 2,494,910 (1950).
Copper & Brass 6. N. Das, US patent 3,964,936 (1976).

Chromate coatings can be applied to brass and copper while pro- Editorʼs note : The preceding article is based on material contrib-
viding chemical brightening to produce a lustrous decorative finish uted by Fred Pearlstein for the “AES Update” series that ran in this
with improved resistance to corrosion. Bronze to chocolate-brown- journal. Since this article was written much has changed. Indeed,
colored chromate coatings of superior protective properties also the outlook for hexavalent chromate has drastically changed.
can be applied and are readily capable of being dyed. Chromate Nevertheless, these processes remain revelant to a large portion of
coatings have been applied to brass components of military fuze- the finishing community. The reader may benefit both from that
timing mechanisms for improved corrosion resistance, but the information and the historical perspective of the technology. The
increase in friction coefficient resulting from the chromate intro- Update series, was begun and coordinated by the late Dr. Donald
duced functional difficulties. Chromated copper or brass resists Swalheim, and brought practical information to the metal finisher.
formation of blue-green corrosion products during salt-spray expo- In some cases here, words were altered for context. P&SF
sure of 48 hr or more, whereas bare copper alloys exhibit corrosion
products after several hours of exposure.

†
Dow No. 19, The Dow Chemical Co., Midland, MI.
††
Dow No. 18, The Dow Chemical Co., Midland, MI.

Pl a t i n g & S u r f ace Fin ish in g • Decem b er 2 0 0 2 13