Blackening Processes for Zinc

Tom Rochester
Plating Systems & Technologies, Inc.
317 North Mechanic Street
Jackson MI 49201
Phone 517-783-4776
Fax 517-783-5875
e-mail tom@mechanicalplating.com
http://www.mechanicalplating.com

There has always been a need to blacken zinc surfaces, and there always will be. Some endusers
and specifiers generally prefer the cosmetic appearance of black, particularly for trim
applications. Automotive specifiers, in particular, have had an affinity for black coatings ever
since Henry Ford told the world they could have the Model T in ‘any color they wanted as long
as they wanted black.’1

Articles to be blackened can always be painted. But parts processed in bulk generally have
contact marks (“kiss marks”) and parts generally require two coats of paint. For adhesion, the
parts are usually phosphated or plated prior to painting. With just paint (i.e., no zinc) on a
ferrous substrate, red rust will appear as soon as the black coating is breached. But paints are
generally outside the scope of this talk and this article. Some of the conversion coatings I will
discuss in this article find use as paint bases as well as standalone coatings.

However, before leaving the discussion of paints, we should note that paints consist of a black
pigment (almost always carbon black, although black iron oxide (Fe3O4; magnetite) finds some
use.) Conversion coatings used to produce a black deposit consist of a black pigment that is
generated in situ and is incorporated into the conversion coating. Often this is a finely divided
metal or a metal oxide or sulfide or other compound that is black. Some of the pigments that find
use in such conversion coatings are2:

Ag finely divided silver often with some silver oxide

Cu finely divided copper Cu
CuO Copper Oxide
NiO Nickel Oxide
NiS Nickel Sulfide
Fe3O4 Iron Oxide (Iron [II, III] Oxide or magnetite)
Co3O4 Cobalt (II, III) Oxide
Mo2O3 Molybdenum Sesquioxide3
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Copper Salt-Based Processes

The earliest processes for blackening zinc consisted of dipping the zinc article in a solution of a
copper salt such as copper sulfate or copper chloride or a mixture thereof. The matte black
deposit was remarkably non-adherent, but the subsequent application of lacquer prevented ruboff
in commercial use. This process has been in use for over a hundred years. A classical treatment
would comprise blackening, drying in warm sawdust, then wiping gently with a rag soaked with
linseed oil.4

In fact, this coating is so non-adherent that its lack of adhesion forms the basis for an ASTM test.
The Preece Test5 was formerly used to determine the thickness of hot dip galvanizing long
before the advent of electronic thickness testing. The galvanized article is dipped in the copper
sulfate solution, and the black coating is wiped off with a paper towel and the process is repeated
until a copper deposit is observed on the steel substrate. Today the only authorized use of the test
is to determine the uniformity of the coating or - to put it another way - to find the thinnest area
of coating on the surface. But this test still finds occasional use as a rough measure of coating
thickness and, therefore, predicted service life, particularly when the test results are favorable
vis-a-vis competitive processes.

While the earliest descriptions of this process called for copper sulfate (blue vitriol), the process
will work with any copper salt - copper chloride, copper nitrate, and copper acetate have all been
used in this process. Even sparingly soluble copper salts such as copper tartrate give good
blacks.

There have been a large number of variations on this early process. Newer (but still quite old)
processes used sodium chloride or hydrochloric acid (muriatic acid) in conjunction with copper
sulfate. The process was still largely non-adherent, but the coating could not generally be rubbed
completely off. A typical formulation was as follows:4

Blackening Solution For Zinc Incorporating Copper Salts and Acid

Copper Nitrate Hexahydrate Cu(NO3)2 . 6H20 6.25 grams/liter

Ammonium Chloride NH4Cl 6.25 grams/liter
Copper Chloride (CuCl2 . 2H2O) 6.25 grams/liter
Hydrochloric Acid (Muriatic Acid) 20 0 or 22 0 Baumé 6.25 grams/liter

Water qs 1 liter

This, too, required lacquering after application to prevent the smut from rubbing off on the hands
and fingers of people handling the blackened object. The development of the black color is very,
very fast.
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Blackening Solution For Zinc Incorporating Copper Salts and Acid (Continued)

The deposit consists largely of finely divided copper admixed with copper oxide.

The process was arguably improved further by the addition of oxidizing agents such as
potassium chlorate or potassium permanganate6, 7 as exhibited by the following formulation:

Copper Black with Oxidizing Agent

KClO4 6 g/l
Cu(NO3)2 35 - 40 g/l
Water qs 1 liter

Processes incorporating oxidizers, though arguably better than simple copper sulfate - sodium
chloride baths, still produced smut that then required lacquering before use.

Molybdate Blacks

Molybdate blacks have been used for over a century. The earliest molybdate blacks were quite
simple, generally consisting of ammonium molybadate made slightly alkaline with aqua
ammonia. A typical example is from Porter.8

Simple Molybdate Black

Ammonium Molybdate 12.5 - 25.0 grams per liter

Aqua Ammonia as required to produce a pH of 9.5 - 10.5

Temperature ambient to slightly warm

Immersion Time 1 - 10 minutes

Another slightly different formula is given by Schwartz.9 The black color imparted to zinc
substrates is attributed to molybdenum sesquioxide (Mo2O3).3
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Second Generation Molybdate Blacks

The next generation of so-called “molybdate blacks”were invented by Mirza Baig and Bruno
Leonelli.10 They incorporated nickel in the formula and were generally more reliable and gave
better (i.e., glossier and more consistently black), albeit at a higher operating temperature. A
typical formulation is as follows:

Molybdate Black With Nickel

Nickel (+2 )generally from Nickel Chloride 0 - 2 parts

Chloride ions 0.5 - 35 parts
Molybdenum ions (+5 and +6) 0.5 - 20 parts
Acetate ions from sodium acetate and sodium diacetate 0.01 - 20 parts
Fluoride generally from sodium bifluoride 0 to 4 parts

Usage 0.5 opg to 3 opg

Temperature 135 0 F. to 180 0 F
pH 4.0 to 6.0

Black Nickel Plating11

It is well-known to deposit black nickel electrochemically. An early bath was developed by

Waclaw Wesley for INCO .12 Substantially the same chemistry may be used to form a black
immersion coating on zinc. The deposit, consisting essentially of nickel sulfide, is glossy, black,
and tends to be iridescent. A typical formulation is:

Nickel - Thiocyanate Black for Zinc

Nickel Sulfate (NiSO4. 6H2O) 20 grams/liter

Ammonium Thiocyanate (NH4SCN or NH4CNS) 20 grams/liter

Activated parts are dipped in this solution at room temperature for 1 to 2 minutes (until an
acceptable black is formed), rinsed and dried. The deposit is glossy, iridescent, and provides no
corrosion protection. Topcoats of various forms may be used to enhance the corrosion
protection.
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Nickel-Containing Blackening Processes (Continued)

Blackening processes utilizing nickel (and there are other minor processes not described in this
paper) may be near the end of their history, as the European Union develops regulations limiting
or eliminating the use of nickel salts.

Silver Chromate Blacks

The “Golden Age of Black Conversion Coatings” started on April 14, 1945 with the filing of
Jesse Stareck’s Patent Application for what we generally know as “Silver Chromate Blacks.”
The patent issued on October 4, 1949.13

The “Golden Age of Black Conversion Coatings” ended on September 18, 2000.14

Here is a narrative of the discovery, in the inventor’s own words (and under oath):

“The fortuitous use, in a chromate solution in which surface conversion coatings

were being produced on zinc plated articles, of a thermal coil which had been
used in a silver plating solution had led to an unusual and important discovery.
Olive drab coatings were being obtained in an chromate solution, when
unexpectedly and unexplainably black coatings of a deep tone, good luster and
unusual adherence properties were obtained. There was in before me the ideal of
workers in this art, but the result could not then be explained. On the recurrence
of the phenomenon, I set to work to discover the cause and after considerable
study and work found that the result was caused by the presence of a silver salt in
the chromate solution which had leached out of the thermal coil which had
previously been used in the silver plating solution.”

The invention process is described differently by Herb Geduld in Zinc Plating15, who described
the story he relates (in which the silver source is silver solder used in repair) as ‘perhaps
apocryphal.’
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Silver Chromate Baths (Continued)

Stareck’s preferred bath composition was as follows:

Silver Chromate Bath for Zinc

Cr+6 (from Chromic Acid) 65 grams per liter

Sulfate (SO4-2) (from Sulfuric Acid and/or Sodium Sulfate 68 grams per liter
Acetate (from Acetic Acid, Sodium Acetate, or Sodium Diacetate) 43 grams per liter
Ag+ (generally from Silver Acetate) approximately 0.2 - 0.3 g/l

A disadvantage of processes utilizing silver salts well-known to platers is that the bath is very
easily contaminated by chlorides. The preferred method of avoiding the problems associated
with chloride contamination is to prepare the bath with distilled or (usually) deionized water, and
to provide a similar sour rinse before the black chromate. Chloride contamination produces
deposits that are greyer and give less corrosion protection. Suppliers, though, were quite happy
to provide silver nitrate solutions to platers who refrained from using the less-expensive
alternative of utilizing distilled or DI water. It was a rough ‘rule of thumb’ among plating
suppliers that if a plater was using a silver chromate black, his purchases of proprietary
chemicals would double when compared to those using clear or yellow chromates.

These black chromates generally provided 96 hours to white corrosion, but lab samples could be
carefully processed to give almost 200 hours to white corrosion.

Stareck later patented a similar process for blackening cadmium.16

Ken Bellinger of Conversion Chemical saw a commercial opportunity to provide a more

concentrated powdered version of Stareck’s process17.
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Powdered Silver Black Processes

A typical formulation given by Bellinger was:

Dry Powder Formulation for Blackening Zinc

Chromic Acid 46.60% by weight

Sodium Bisulfate 42.10% by weight
Monosodium Phosphate 6.80% by weight
Silver Nitrate 1.09% by weight
Sodium Nitrate 3.41% by weight

Temperature 80 0 F. - 90 0 F.
Immersion Time 20 to 40 second dip

In commercial manifestations of this patent, hexavalent chromium salts usually were used in
place of chromic acid, which is a very strong oxidizer and is hygroscopic as well. Chemists
familiar with formulating chromates will note the use of the phosphate ion in Bellinger’s
formulation. Phosphates have been used to produce a green or olive drab chromate, particularly
in so-called “one part” olive drab chromates. These generally give better corrosion protection
than chromates with no phosphate; phosphates are known to act as corrosion inhibitors.
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Chromate plus Dye Processes

Due to the high cost of the silver chromate baths many platers opted to use a less expensive
process which entailed chromating followed by dyeing. The process did not give as good a color,
nor did it give as good a gloss.18

A typical chromate conversion coating was as follows, although some platers used conventional
yellow chromates. 15

Single Dip Olive Drab Chromate

Sodium Chromate 2.5 kg

Chromic Acid 1.0 kg
Nitric Acid 420 Bé 650 ml
Formic Acid 90% 6 liters
Water qs 100 liters
Temperature 25 0 - 32 0 C.
Immersion Time 5 - 30 seconds

After drying and rinsing, the parts are immersed in:

Black Dye 0.25%

Acetic Acid To adjust pH to just under 4.0 (Measured electrometrically)
Temperature Ambient to approximately 1000 F.
Immersion Time From 30 seconds up to approximately 2 minutes

After rinsing, the parts may be lacquered. The single dip olive drab chromate above gives
excellent results; however the bath life is limited due to the oxidation of the formic acid by the
chromic acid.
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Non-Silver Blacks

Copper’s place in the Periodic Table - just above Silver - suggests that it may be possible to
replace the silver in a silver chromate with copper. A development of the Lithuanian Academy
of Sciences reported just such a formula 19, but Geduld 15 reported that it had no commercial
success because of difficulty of control and poor corrosion resistance. Pavco briefly attempted to
improve this ‘NSB’ process with little lasting success. 20 Copper-based conversion coatings to
produce black on zinc may yet find commercial success.

Trivalent Black Passivates

There are a number of blackening processes for zinc utilizing trivalent chromium salts. Most of
these are barely out of the laboratory and field experience is highly variable. These blackening
processes deposit a finely divided metal or insoluble metallic compound that is deposited and
incorporated in the film of the trivalent passivate.

The most common formulating strategy for trivalent black passivates has a history much like that
of hexavalent black chromates. Platers had long noticed that in acid zinc chloride baths, the
combination of high iron in the bath and chromates gave a dark deposit. This was particularly
true for ‘green chromates,’ in which the activating anion was phosphate. And when zinc-iron
plating baths became available a few years ago, black non-silver chromating was achieved with
the combination of iron, phosphate, and hexavalent chromium. Formulators have now achieved
a similar black with iron, phosphate, and trivalent chromium.

This formula can be deconstructed to give a non-chrome blackening process followed by (if
desired) trivalent passivating. The black pigment that is generated in situ has not been
determined, but it is likely that it is an iron phosphate of mixed (i.e. +2 and +3) valence or
perhaps even magnetic iron oxide (Fe3O4), which is well known as the pigment that is deposited
in blackening of iron in the so-called “black oxide” process, which entails alkaline oxidation of
iron at an elevated temperature.
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Trivalent Black Passivates (Continued)

A very approximate formulation for black trivalent passivates is as follows:

Component Concentration

Cr+3 approximately 4.5 g/l

NO3- 0.1 - 0.6 g/l
PO4-3 up to approximately 15 g/l
SO4-2 up to approximately 15 g/l
Cl- up to approximately 15 g/l
Complexing agent up to approximately 15 g/l
Co+2 up to approximately 15 g/l
Fe+2 (generally as ferrous sulfate) As required to get depth of color

Even the so-called “third generation” black trivalent passivates still offer only 48 hours of
corrosion protection to white rust. 21 It is remarkable that we are working in an industry in which
product performance is getting worse instead of better and, in many cases, costs are going up
instead of down.

Since the advent of RoHS and ELV, there has been a marked decline in the corrosion resistance
and the appearance of zinc-plated and blackened parts. As a result, there has been a significant
shift in the market from plating to painting.
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References

1. Ford, Henry. My Life and Work (1922).

2. Jansen, Rolf and Preikschat, Patricia. “Trivalent Black Layers with Cathodic Protection.”
Presentation at Interfinish 2000. Available at www.surtec.com

3. Lide, David, Ed. The Handbook of Chemistry and Physics, 75th Edition, 1995 questions the
existence of this compound. CRC Press, Boca Raton, Florida.

4. The Canning Handbook on Electro-Plating, Polishing, Bronzing, Lacquering and

Enamelling, 16th Edition, 1949, W. Canning & Co. Ltd., Birmingham England, pp 488 - 489. I
have heard from Terry Clarke of MacDermid PLC in England that MacDermid has plans to
revise the Canning Handbook. If this is done, it would be a most welcome addition to the
technical literature of our industry.

5. (ASTM A239-95 [2004], “Standard Practice for Locating the Thinnest Spot in a Zinc
[Galvanized) Coating on Iron or Steel Articles”). ASTM International, 100 Barr Harbor Drive,
West Conshohocken PA 19428-2959.

6. Nechamkin, Howard, U.S. Patent 2,415,651 “Process for Black Finishing Metals, Patented
February 11, 1947.

7. Metal Colouring, by David Fishlock. Robert Draper Ltd, Teddington, England 1962. Pp. 258
- 263. Another very good book (though obviously quite dated) is Metal-Colouring and
Bronzing, Second Edition, by Robert H. Hiorns, MacMillan and Company, Ltd., London 1907.
This book is available online as part of the Google Books project. It is amazing and wonderful
to have instant access to books such as these (and there are many of them) that are past statutory
copyright protection. Also available on Google Books is Langbein, Dr. George. A Complete
Treatise on the Electro-Deposition of Metals. Henry Carey Baird & Co., Philadelphia 1913
(see especially pp 532 - 533).

8. Porter, Frank, Zinc Handbook, Marcel Dekker, Inc. New York, 1991 See Chapter 25.
Blackening Processes for Zinc
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9. Schwartz, Walter. Blackening of Metals, Plating and Surface Finishing, June 1982, pp 26 -
29. (note that Schwarz is German for Black).

10. U. S. Patent No. 3,217,279, March 31, 1964 “Aqueous Black Coating Composition
Containing Molybdenum Ions and Process of Blackening a Metal Surface Therewith” Mirza L.
Baig and Bruno Leonelli. Filed September 27, 1960.

11. AESF Proceedings, 1952 pp 101 - 107 An Explanation of Black Nickel Plating Earl J.
Serfass, et. al.

12. Wesley, Waclaw. U.S. Patent 2,844,530 “Black Nickel Plating (to INCO). Patented July 22,
1958.

13. Stareck, Jesse Edwin. U.S. Patent 2,483,510 “Composition for Dip Coating Solution and Dip
Process for Coloring Zinc.” Patented October 4, 1949.

14. Directive 2000/53/EC of the European Parliament and of the Council of 18 September 2000
on end-of life vehicles. See also subsequent related regulations available most readily at
http://www.gmw3059.com.

15. Zinc Plating, Herb Geduld, ASM International and Finishing Publications Ltd., 1988. A
wonderful book. If you want to really learn about zinc plating, this is the place to start.

16. Stareck,. Jesse Edwin. U.S. Patent 2,524,577 “Dip Process for Coloring Cadmium.”
Patented October 3, 1050.

17. Bellinger, Ken and Chapdelaine, Gene. U.S. Patent 3,219,489 “Composition and Method for
Blackening the Surfaces of Cadmium and Zinc” to Conversion Chemical. Patented November
23, 1965.

18. As Mark Twain’s Huckleberry Finn said (unoriginally): “You pays your money and you
takes your choice.”

19. Rozovosky, V. G. And Sarmaetis, R. R. “Corrosion resistance of black chromate films on

zinc,” Plating and Surface Finishing, Oct. 1981, pp 54 - 56.
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20. Rick Painter and Fred Farkas of Pavco, personal communications.

21. Dingwerth, Björn, et. al.,“The Black Barrier: Characteristics of High-Performance Black
Passivates for Zinc Substrates.”, Metal Finishing, October 2008, pp 37 - 44, especially page 40.