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Journal of Applied Chemical Research, 9, 13-23 (2009)

ISSN : 2008-3815

A Study of Coating Process of Cast Iron Blackening

N. Arab*1, M. Rahimi Nezhad Soltani 2
1
Islamic Azad University, Saveh Branch, Saveh, Iran.
2
Young Researchers Club of Islamic Azad University, Saveh Branch, Saveh, Iran.
*najarab@yahoo.com
(Received 5 Dec. 2008; Final version received 12 March 2009)
Abstract
An improved chemical composition for the production of the black oxide coatings, termed
blackening on cast Iron, and its particular relation to optimum conditions for cast Iron
blackening in the presence of chromium and silicon is studied. Black oxide coating process
at different dwell times, temperatures of chemical bath, chemical compositions of coating
bath and different preparating conditions of substrates were investigated and their effects
on coating quality were discussed. Comprehensive researches illustrate that at higher
chemical bath temperatures and immersion time of parts, the coating thickness increases
up to one micrometer, but protecting effects and adhesion of coating decreases. Chemical
bath temperature between 130C to 140C and contact times of 20 minutes was observed
as optimum. In addition, the effects of the compositions of the bath on the quality of black
colored layer are discussed. It is shown that when potassium salts were used in blackening
bath the quality of coating improved and optimum compositions of chemical blackening
bath is given. The optimum bath compositions were obtained as follows: 70 weight percent
of potassium hydroxide, 10 weight percent of potassium nitrite and 20 weight percent of
potassium nitrate. Furthermore; it is shown that acid pickling with one molar sulphuric acid
for five minutes before blackening step result in higher adhesion and coating quality.
Keywords: Chemical conversion coating, Blackening, Hot alkaline coating, Gray cast iron
coating.
Introduction
In industrial applications, parts with diverse properties are used to compliance the needs.
Among different kinds of metals coatings, conversion coatings can be called divided in two
groups: natural and chemical conversion coatings. Natural conversion coatings called oxide
coatings are naturally formed on metal substrates, while chemical conversion coatings are oxide
coatings that are artificially formed on metal substrates by means of proper chemical bathes.
From different kinds of chemical conversion coatings, oxalate, phosphate, chromate and oxide
conversion coatings, can be nemed.
Formation and deposition process of conversion coatings can be divided in chemical and

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electrochemical (anodic oxidation) processes. In chemical processes, oxide coating deposits are
formed utilizing simple immersion of parts in oxidizing solution [1, 2], but in electrochemical
processes, electrical current is the major factor in process control and anodic role [ 3, 4].
This oxidation procedure is followed by a coloring procedure using a heated (about 100-150C)
oxidizing solution containing sodium hydroxide, sodium nitrite, sodium nitrate or mixtures
thereof which reacts with cast iron substrates to form magnetite (Fe3O4) [5]. The result is the
formation of a black finish under much more favorable, milder and safer conditions. On the
other hand, this black finish is due to nucleation of magnetite phase on cast Iron substrates which
leads to enhancement of heat, oxidation and corrosion resistance. It also leads to improvement
of abrasion resistance and enhancement of cast iron substrates aapearance. Idiomatically, this
coating technique is termed Blackening [6].
Powder and liquid formulation for different metals blackening are available. Powder formulations
used in water at different concentrations depending on the metals and proprietary formula used
[7]. It is the advantages of this research that the ingredients of the present compositions are
completely compatible and that compositions may be sold in premixed form, either wet or dry,
with a relatively long useful life.
There are a great number of conventional blackening compositions useful for the surface blackening
of ferrous metals. Such conventional compositions generally comprise 50 to 90 parts by weight of
an alkali metal hydroxide, 0.1 to 50 parts by weight of an alkali metal nitrate and 0.1 to 50 parts by
weight of an alkali metal nitrite. Although such compositions are quite effective for the blackening
of most ferrous metals, but it has been very difficult to produce satisfactory black coatings on cast
Iron with conventional blackening bathes and using the optimum composition for production of
proper deep black coatings on cast Iron is very important [8].
Formation technology of blackening coating on steel substrates is very simple and it is possible
to produce satisfactory black oxide coatings with proper quality on steel substrates but because
of smut deposition on cast Iron substrates, black oxide coating has no proper quality and
frequently light and dark areas on cast Iron substrates, were formed which in addition to lower
protection, it show unsatisfactory oxide coating.
In fact, the process of conversion coating is a kind controlled corrosion process which is
artificially formed and finally forms an oxide layer on metal substrates. This oxide layer has
strong bonding with bulk and is not soluble in water or intermediary environment and is a
proper electrical insulator.
Black oxide conversion coating has special attributes that is ideal for exclusive applications.
The benefits of black oxide coating, resulted in its wide acceptance are as follow [9, 10]:

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-These finishes yield little or no dimensional change.

-Black oxide coatings have no effects on bulk properties.
-Any demolition and / or analysis have not observed on bulk substrates.
-In blackened parts, no coating delamination was detected at all.
-This coating is inexpensive and economical [11].
-Black oxide coating leads to improvement of abrasion properties.
-This finish will not dig, upon stroke.
-Black oxide coating retains appearance properties of cast Iron parts substrates. For example if
the substrates of cast Irons had been polished, after blackening, smoothness of parts substrates
has no alteration and completely can be observed.
-Blackening coating has proper absorbability of oils.
-Because of its special color it can be used in decorative applications.
-Blackened parts without alteration of appearance color have heat-resistance up to 482C [12].
-Blackened parts in salt spray exposure test yield up to 150 hours.
-In cast Iron blackened parts no hydrogen embrittleness occur.
In this research, coated parts comprising wide range of industrial needs were coated with different
methods. A kind of oxide conversion coating deposits on cast Iron substrates with parts dipping
method in chemical bath is studied. Another method for forming a chemical conversion coating
on cast iron substrates, the chemical solution in coating process.
Blackening process in theory
From a scientific point of view, idiom of conversion coating is the name for coating that is
formed on metals substrates from reactions between atomic layers and ions in chemical bath:
mM + nAz-

MmAn + nze

(1)

M: metal that reacts with environment

A: intermediary environment ion
However, in reality the formation process of blackening coating on cast Iron substrates is more
complicated than above mentioned chemical reaction 1 and include electrochemical, chemical
and physico-chemical reactions which probably includes secondary reactions. Consequently,
complicated reactions occur and different chemical compositions are formed.
A simple mechanism of black oxide coating formation was offered by Samartsew, who proposed
that in the presence of oxidant ingredients, cast Iron will react with alkaline solution to produce
soluble sodium hypoferrite (reaction 2):
Fe + 1/2 O2 + 2 NaOH

Na2FeO2 + H2O

(2)

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The generated salt in chemical reaction (2) diffuses into blackening bath and strikes and reacts
with oxidant ingredients such as sodium nitrite or nitrate to produce soluble sodium ferrite,
Na2Fe2O2. When these ingredients react, a supersaturated solution of two and three valence
ferric oxide is produced and by means of crystallization of this solution, magnetite oxide layer
will be produced on cast Iron substrates.
Experimental
Gray Cast Iron parts with chemical composition shown in Table1were used.
Table 1. Chemical Analysis of Cast Iron Parts in Blackening Process.

elements

%CE

%C

%Si

Mn%

S%

%P

%Cr

Minimum
Maximum

4.07
4.35

3.3
3.5

2.3
2.5

0.3
0.5

0.1
0.12

0.4
0.5

< 0.2

The black oxide process was used for blackening of Cast Iron parts, applying hot alkaline
solution in its simplest form, consisting of seven steps:
1) Hot alkaline soak to remove probable greases and oils.
2) Overflowing cold water rinse.
3) Immersion the parts in acid to remove oxidation or rust.
4) Overflowing cold water rinse.
5) Coating process.
6) Overflowing cold water rinse.
7) Seal the black oxide with appropriate oil or acrylic.
Generally, in brush up steps of casting parts, surface of cast Iron parts imbrue with oils and
greases. Thus, initial degreasing by one molar caustic soda solution was done.
Cast Iron part was immersed in caustic soda solution for 15 minutes to remove oils from substrates.
Then, the part was rinsed in cold and overflowing water to remove probable residual articles
which may have been remained on parts substrates. After this step, cast Iron part was dipped in
one molar sulphuric acid for a period of 5 minutes. In the fourth step, cast Iron part was rinsed in
cold water for 2 minutes. Rinsing in cold water prevents the remaining of residual acid articles on
substrates. After these four steps, cast Iron part is immersed in blackening bath.
Evaluating the effects of coating temperatures and dwell times
In the first step of this research, effects of coating temperatures and dwell times on coating

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quality were investigated. After preparation steps, cast Iron parts were immersed in undermentioned coating bath and were blackened at temperatures of 130, 135 and 145C and dwell
times, of 10, 20 and 30 minutes. After blackening, cast Iron parts were rinsed in cold water and
sealed with an appropriate rust-preventive topcoat.
This hot black oxidizing solution is blends of 70 weight percent of sodium hydroxide (caustic
soda), 10 weight percent of sodium nitrite and 20 weight percent of sodium nitrate. The present
blackening compositions are water-soluble solids which are stable in dry form for extended
periods of time. In order to convert them to usable form, the composition was dissolved in water
in above-mentioned amounts.
Evaluating the effects of chemical compositions
In the second step of this research, effects of chemical Composition of blackening bathes on
coating quality were investigated. After the preparation steps, cast Iron parts were blackened
in two different coating bathes, for period of 20 minutes at boiling temperature of 135C. The
first bath had above-mentioned chemical composition and second bath was blend of 70 weight
percent of potassium hydroxide, 10 weight percent of potassium nitrite and 20 weight percent of
potassium Nitrate. Blackening the parts in two different bath followed by rinsing in cold water,
until no residual articles from blackening bathes were observed. After these steps, blackened
parts were sealed with appropriate water-displacing oil.
Evaluating the effects of pre-preparing conditions
In the last step of this research, effects of preprepation conditions of coating surface and their
effects on coating quality were investigated. Some of cast Iron parts were pickled in one molar
sulphuric acid solution for 5 minutes and after rinsing with cold water, parts were blackened.
Another step cast Iron parts without pickling in sulphuric acid were blackened in similar bath.
It need to be mentioned that in the both step of this research, cleaned parts without any rust or
oxidation were used. After blackening step, all parts with similar conditions, were rinsed with
overflowing and cold water for 2 minutes and black oxide coating was sealed with appropriate
oil. Blackened parts were compared and analyzed.
Results
Effects of dwell time and temperature on coating quality
Figure 1 illustrates the effects of dwell time and temperature of blackening bath on coating quality:

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145C

10

135C

130C

10

20

0.5

Coang Thickness (m)

Weight of Coang (mg)

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30

Time (min)
Figure 1. Effect of Swell Time and Temperature of Blackening Process on Thickness and Weight of Coating.

All three graphs were resulted from blackening of cast Iron parts in different temperatures and
times. For measurement of coating thickness, metallographic techniques in specified Angle
were used. The results shows that increasing the coating temperature and swell time, increases
the coating thickness from 0.4 to 1.2 micrometer. However, increasing of coating thickness,
the adhesion and bonding of coating layer to cast Iron substrates and protecting efficiency of
coating decreases.
Effects of chemical composition of blackening bath on coating quality
Results of comprehensive studies show higher quality of black oxide coating was formed in
blackening bath which contains potassium salts as compared to black oxide coating which was
formed in blackening bath containing sodium salts. In addition to better appearance properties
such as, uniformity, adhesion and corrosion resistance are greatly enhanced using of potassium
oxidizing salts in blackening bath. Salt spray tests by potassium oxidizing salts on the cast Iron
blackened parts have shown the superiority of corrosion resistance when compared with blackened
parts that were oxidized in sodium salts. In salt spray tests, lifetime of cast Iron parts which were
blackened in solution containing potassium salts, were 150 hours and lifetime of cast Iron parts
that were blackened in solution containing sodium oxidizing salts, were 120 hours.
Effects of acid pickling step on coating quality
The exhibit improvement of coating quality in cast Iron parts that were pickled in one molar
sulphuric acid for 5 minutes prior to blackening step. Cast Iron parts that were blackened without
acid pickling, had coating layer with lower adhesion but blackened parts that had acid pickling

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step by one molar sulphuric acid had coating layer with higher adhesion. Even in preparation steps
for metallographic studies, this coating layer had very high adhesion.
Discussion
Results of this studies revealed the effects of different parameters on black oxide coating quality.
The operating temperature of the coating bath has an important effect on the primary and
secondary reactions rate and higher temperatures tend to increase the reaction rate. Experimental
evidence indicates that, although many iron alloys can be successfully processed at ambient
temperature, certain less reactive alloys such as gray cast Iron benefit from application of
coating at higher temperatures to overcome any low initial reactivity of metal surface. So it is
better to have optimum temperature.
It can clearly be seen that the coatings deposited onto cast Iron parts substrates at temperatures
above 145C is thicker but its protecting effects decrease due to its high porosity and very
low adhesion to cast Iron substrates [1]. Weber [1] expressed that probably increasing the
coating temperature leads to acceleration of some secondary reactions that prevent deposition
of magnetite phase onto cast Iron substrates and this leads to lower adhesion. Therefore, it may
be reasoned that in the formation of conversion coating process, increasing coating thickness
within chemical oxidation of cast Iron parts, as in electrochemical process (Figure 2 - graph A),
is not liny and increasing of coating thickness is self-inhibitor (Figure 2 - graph B). So higher
temperature leads to self-inhibitory at higher coating thickness and coating thickness increase
but because of acceleration of some secondary reactions that prevent deposition of magnetite

Coang thickness

phase, adhesion of coating layer decrease.

A
B

Time
Figure 2. Variation of Thickness in: A- Electrochemical Process, B- Chemical Process.

Applying the optimum coating temperature prevents self-inhibitory in lower coating thickness and
results in higher coating thickness as well as uniform, proper and bonded coating. Figure 2 illustrates
the variation of coating thickness and shows self-inhibitory in chemical blackening process.
Figure 3 illustrates SEM micrographs of blackened samples that were blackened at different

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temperatures of130, 135 and 145C. It is clearly seen that coating at temperature of 145C
(Figure 3- C), the coating layer is porous and leads to lower adhesion and protecting effect.
However, it can clearly be seen that at coating temperature of 135C (Figure 3- B), the coating
layer is proper and uniform, but lower coating temperature, shows lower coating thickness.
Thus, optimum temperature between 135 to 145C leads to proper, uniform, smooth and deep
black finish and higher coating thickness.
In respect to the effects of chemical composition of blackening bath on coating quality, it can be argued
that increasing of coating quality in potassium content chemical bath, results from more reactions
of potassium salts and proper secondary reactions in comparison with sodium salts. Thus, using of
potassium salts in blackening bath leads to better adhesion of coating layer onto cast Iron substrates.
SEM micrograph of coating caused by potassium containing coating bath is shown in figure 4, and
SEM micrograph of coating due to sodium containing coating bath is shown in Figure 5. It is clearly
seen that coating layer due to potassium containing coating bath (Figure4) is more uniform and proper
in comparison with coating layer due to sodium containing coating bath (Figure 5). Also, the coating
layer due to potassium containing coating bath (Figure 4), according XRD analysis, shows higher
magnetite (Fe3O4) in comparison with coating layer due to sodium containing coating bath (Figure 5).
This difference is due to more reactions with cast Iron substrates and proper secondary reactions.

Figure 3 . SEM micrographs, Effect of Temperature on Coating Process A) Coating Temperature: 130C,

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(B) Coating Temperature: 135C, (C) Coating Temperature: 145C.

Figure 4. SEM micrograph of Coating due to Potassium Content Coating Bath, According XRD analysis.

Figure 5. SEM micrograph of Coating due to Sodium Content Coating Bath, According XRD analysis.

Regarding the acid pickling mechanism on coating quality, the results show that cast Irons have
a natural resistance to corrosion. It appears that acid pickling slightly oxidizes elements merals
such as chromium and silicium at the cast Iron surface to form a very thin protective oxide film.
This pickling step destroys the corrosion-resistance of the cast Iron, so that the cast Iron is then
will be in a condition very susceptible to blackening. Image of grill with blackening coating
with previous acid pickling step is shown in Figure 6.
It can clearly be seen that the grill shows a brilliant, lustrous, uniform and deep black coating,
which is very satisfactory and susceptible.

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N. Arab et al., J. Appl. Chem. Res., 9, 13-23 (2009)

(a) Grill with Satisfactory Black Oxide Coating (b) Cast Iron parts: 1-before blackening, 2- after blackening
Figure 6. Cast Iron Parts with satisfactory blackening coating.

Conclusion
- Due the important effects of blackening bath boiling point on coating quality, the precious
control of coating temperature is very important. It was found that temperature between 135C
to 140C is required to achieve smooth, deep and jet black finish.
- Generally, conventional blackening bathes offer the use of sodium salts but this research
showed that using of blackening bath containing potassium salts will lead to higher quality and
uniform coating. The application of blackening bath containing potassium salts, in addition
to preventing negative effects of some elements on the cast Iron blackening, it also prevents
decreasing the efficiency and lifetime of the bath.
- In order to blacken cast Iron surface it is necessary to pickle the metal surface with an etching solution
such as one containing hydrochloric acid. After this step, cast Iron is in a condition very susceptible
to blackening. Results of this research showed that acid pickling before coating step have important
effects on improvement of blackening process. Some of researches confirm this result.
- Coating quality of blackened parts in potassium containing coating bath, is higher than blackened
parts in sodium containing coating bath. In some cases, corrosion resistance of this parts as
determined by salt spray exposure test has remarkable increase and yield up to 150 hours.
Acknowledgments
Authors are grateful to Oreie, manager of Atmosphere Casting Co., for research supports.
References
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[3] HE Xin-Kuai, Chen Bai-Zhen, LI Xiao-Dong, J. Cent. South Univ. Technol., 13, 135
(2006)

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[4] A. Sharma, R. Uma Rani, S.M. Mayanna, J. Thermochimica Acta, 376, 67 (2001).
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