Protection of Metals, Vol. 37, No. 2, 2001, pp. 101107. Translated from Zashchita Metallov, Vol. 37, No.

2, 2001, pp. 119125.

Original Russian Text Copyright 2001 by Kuznetsov.

Corrosion Inhibitors in Conversion Coatings. III

Yu. I. Kuznetsov
Institute of Physical Chemistry, Russian Academy of Sciences,
Leninskii pr. 31, Moscow, 117915 Russia
Received September 11, 2000

AbstractThe possibility to use metal corrosion inhibitors as effective components of phosphating compounds for the purpose of enhancing the corrosion resistance of the resulting conversion coatings is analyzed.
The influence of oxidants and some complexing inhibitors on the formation and properties of phosphate coatings is discussed. It is emphasized that ecologically harmful inhibitors should be replaced by new inhibitors that
meet both ecological and technological requirements.

So far there is no universal method of selecting and

employing corrosion inhibitors as additives to compounds designed to prepare conversion coatings (CCs).
However, it was exemplified with chemical oxidation
of steel and rust modification with tannin compounds
[1] that the use of inhibitors in such different processes
can not only enhance the protective properties of CC
but also improve the techniques of their preparation.
The presence of inhibitors is also useful in phosphating,
i.e., treatment of a metal surface with compounds based
on phosphoric acid or acid phosphates. Although phosphate CCs (PCCs) were always believed to be more
effective for steel protection in neutral media than magnetite ones prepared by alkaline oxidation, their corrosion resistance remained inadequate [2]. In recent
years, PCCs have widely been used for many purposes,
which makes the application of inhibitors particularly
important. They can be employed in two ways, namely,
(1) as components of a converting formulation (CF) or
(2) as special agents (mainly in aqueous solutions or
emulsions) to passivate an already prepared PCC.
The use of phosphoric acid or its salts as inhibitors
of steel corrosion has long been known, having much in
common with their function in CF. In both cases, it is
the formation of a film of iron phosphates and oxides
rather than adsorption that plays the decisive role.
A difference is that the preparation of PCCs requires
higher concentrations of phosphates and the conditions
stimulating the growth of thick salt films. For this reason, CFs are not merely acidic but contain special additives that accelerate the formation of PCCs. Accelerators of steel phosphating can be traditional oxidants
such as peroxides, nitrates, persulfates, nitrites, chlorates, and compounds of metals whose electrochemical
potential is higher than that of iron (first of all, copper,
nickel, and cobalt) [24]. Sulfides, phosphoric acid, its
salts, and zinc powder are also believed to act in such a
way, though they are not oxidants.

In the simplest case of phosphating, steel is treated

with H3PO4 , the sole inorganic acid capable of pickling
a metal with simultaneously forming a thin surface film
that temporarily protects the metal against atmospheric
corrosion and improves adhesion of paint coatings.
Such an effect is due to steel dissolution in phosphoric
acid, which successively gives primary, secondary, and
tertiary iron phosphates (Fe(H2PO4)2 , FeHPO4 , and
Fe3(PO4)2 , respectively). The two last salts precipitate
as phosphate films as soon as their solubility products
in the near-surface layer become exceeded. At this
stage, the phosphoric acid is released and reacts with a
new portion of iron to form again Fe(H2PO4)2 . The
PCC formation itself includes many steps. Initially, the
film is amorphous; the onset of crystallization and the
crystal growth are characterized by a potential jump
[5]. Then, the deposit is rearranged, with a partial dissolution of crystals and growth of others; these processes are controlled by changes in pH at the steel
solution interface.
It is interesting that solutions of alkali metal phosphates are referred to as film-nonforming [2], though
they also form thin films on steel. This name arose due
to the fact that such a solution, at high pH, rapidly
becomes supersaturated with insoluble phosphates, and
the crystal size and the film thickness decrease with an
increase in pH. It is these phosphates that have long
been used as inhibitors of steel corrosion in aqueous
solutions [6].
In acidic solutions of alkali metal phosphates
(pH < 5.0), steels are covered with very thin protective
films slightly colored owing to interference. As early as
in 1950s, it was already known that a film formed on
iron in 0.1 N Na2HPO4 includes, under natural aeration of
the solution, not only iron oxide but also FePO4 2H2O
[7]. However, the role of phosphates was believed to be
of secondary importance, because their solutions do not
passivate iron in the absence of O2 or another oxidant.
Kolotyrkin et al. [8] found that oxide passivation of

0033-1732/01/3702-0101$25.00 2001 MAIK Nauka /Interperiodica

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KUZNETSOV

iron in these solutions is preceded by specific salt passivation, which occurs at lower current densities than
oxide one, but can be absent at a decreased phosphate
concentration or in more acidic solutions. In this potential range, the iron surface is covered with solid phase
films composed of the Fe3(PO4)2 8H2O crystals,
whereas at lower potentials deposits are amorphous.
Having assumed that iron passivation in phosphate
solutions is due to the formation of a monolayer of an
insoluble salt, the authors of [9] compared experimental and theoretical dependences of the anodic current
density on the stirring rate, the potential, and the solutions concentration. It turned out that the model based
on the adsorption of FeHPO4 alone is inadequate, and
hence the influence of a porous coating that crystallizes
from solution should also be taken into account.
Because phosphating is usually carried out in multicomponent solutions containing special additives for
accelerating the process and enhancing the PCC quality, the formation mechanism, as well as the composition, of salt films are there even more complex.
INORGANIC CORROSION INHIBITORS
Metal phosphating in a solution containing, along
with H3PO4 , zinc dihydrophosphate Zn(H2PO4)2 was
proposed in the USA in the early 1920s [4]. Currently,
this method and its modified versions are enjoying wide
use. In such solutions (pH 1.53.5), steel can be coated
with 3 to 60 m films colored from light gray to black.
Addition of zinc cations to a phosphating solution is
quite natural because they can sharply enhance the protective properties of many anionic inhibitors, including
phosphates [6, 7, 10]. Such an effect is due to the ability
of zinc to form water-insoluble hydroxide, salts, or
complex compounds, which precipitate to the steel surface, often decelerating the cathodic reaction. Zn2+ cations are especially effective during the cathodic polarization of steel in corrosive waters (e.g., sea-water),
because of their inclusion into the salt deposit. It is not
surprising that, when added to CFs in much higher concentration than that used in corrosion inhibition, the
Zn2+ cations take part in the formation of PCC. For
instance, in-zinc phosphate CFs, iron is pickled with
the hydrogen evolution (and the corresponding increase
in pH in the near-electrode layer), approximately following the equation
Fe + 34 = Fe(24)2 + 2.
(1)
As Fe2+ ions accumulate, neutral, including double,
phosphates precipitate and thus complete the approximate overall reaction
Fe + 5Zn ( H 2 PO 4 ) 2 = Zn 3 ( PO 4 ) 2
+ Zn 2 Fe ( H 2 PO 4 ) 2 + 6H 3 PO 4 + H 2 .

(2)

It was proved that zinc in phosphate films exists in

the form of hopeite, Zn3(PO4)2 4H2O (which relatively
easily loses the water on heating), and phosphophyllite,

Zn2Fe(PO4)2 . Their ratio in PCC depends on the composition of a CF and many other factors, but there is no
consensus on whether the ratio invariably determines
the coatings properties. It is only known that such
PCCs provide high adhesion of paint coatings (when
they are dried at a temperature no higher than 140C)
and effectively protect steel against subfilm corrosion.
The formation of finely crystalline thin CCs
(13 g/m2) in zinc phosphate CFs in the presence of
polyphosphates [2, 4, 11] evokes an analogy with the
inhibition of steel corrosion, which long been used in
water treatment due to a low toxicity of polyphosphates
and their ability to decelerate iron dissolution and scaling even in low concentrations. Usually, polyphosphates, e.g., hexametaphosphate, make a phosphate
film thinner and decrease the amount of slime by 20
30%. This analogy becomes especially evident when a
CF contains not only zinc salts and polyphosphates but
also nitrite as an accelerator of the process and a corrosion inhibitor. It can be seen from polarization curves of
steels in an acidic phosphate solution (figure) that
nitrite not only accelerates the cathodic reaction (which
is quite predictable because of the oxidative properties

of N O 2 ), but also substantially suppresses anodic dissolution, thus causing the electrodes passivation [5].

A similar effect of N O 2 on the kinetics of electrochemical reactions is observed in a solution containing Ni2+
cations capable of enhancing the protective properties
of PCC.1
According to [13], the term accelerator is incor

rect for N O 2 and N O 3 . In zinc phosphate solutions,

they simply decelerate the formation of iron phosphates, which otherwise form on steel prior to zinc
phosphates, thus deteriorating the protective and other
properties of PCC. However, being added in excessive

amounts, N O 2 can completely passivate the steel. This

fact demarcates the formation of a PCC (during which
an inhibitor should not be too effective) and usual corrosion protection (in which, the stronger the metal passivation the better).

Among other disadvantages of N O 2 , an unexpected

and rapid decomposition of CF in the presence of a high

concentration of iron was noted [13]. N O 2 favors the

oxidation of Fe2+ into Fe3+ and, consequently, sliming

in the phosphating bath. Moreover, like chromate, N O 2

should not be used for preparing PCC, especially in hot
phosphating, from the ecological standpoint [14]

because of a high volatility of N O 2 (sodium nitrite is an

1 According to [12], in neutral media, Mn2+, Co2+, and Cd2+, as
well as Zn2+ and Ni2+, ions are characteristic cathodic-type corro-

sion inhibitors because of their ability to form insoluble hydroxides by reacting with OH generated by the cathodic reaction.
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CORROSION INHIBITORS IN CONVERSION COATINGS. III

extremely hazardous substance (I class) with a very low

maximum permissible concentration in the air of a production area (0.1 mg/m3)) [15].
Among inorganic inhibitors, ammonium and alkalimetal molybdates play the leading role in CF. Even in
the early 1970s, it was noted that the use of these
molybdates prevents etching pits from appearing and
make the surface be covered with a finely crystalline
solid PCC [16]. According to the Pourbaix diagram
[17], molybdate, in weakly acidic solutions (pH <
pKa, 2 = 6.0) at 25C, in a potential range of active iron
dissolution, can form an insoluble salt:

103

logi [mA/cm2]
0

1
2

Fe + HMoO 4 = FeMoO 4 + H + 2e,

0

(3)

1000

E = E 0.0295 pH.
In more acidic solutions, i.e., at pH < pKa, 1, the
potential of the iron reaction with molybdic acid is
more pH-sensitive (a slope of 59 mV). In a 0.1 M solution of Na2MoO4 + H3PO4 , PCCs are uniform and
firmly adhere to steel in a pH range from 1.0 to 6.0,
their thickness being maximum at pH 2.0. The formation rate of such a PCC linearly increases with an
increase in the time of the steel immersion in a solution
from 10 to 60 min. Under these conditions, the steel
potential in the Pourbaix diagram belongs to the
domain of active corrosion, but at pH 6.812.0, no CC
forms, because the steel is passive. The best corrosion
protection was provided by PCCs obtained from solutions containing H3PO4 , Na2MoO4 , NaNO2 , or
NaNO3 . In this case, the resulting films are mainly
composed of Fe3PO4 and FeMoO4 (according to Auger
electron spectroscopy, IR spectroscopy, etc.)
In neutral solutions, molybdate ceases to oxidize
steel by itself and cannot effectively protect it in the
absence of oxygen or another oxidant [18]. Moreover,
in such solutions, a dilute mixture of Zn2+ with molybdate causes the cathodic reaction to decelerate, even
without retarding the anodic one [19].
A different picture is observed in acidic deaerated
solutions. At pH 5, the passivation current density for a
low-carbon steel increases with an increase in the
molybdate concentration. Even at pH 3, passivation
phenomena appear only slightly, though the formation
of black films of MoO2 at pH < 5 indicates reduction of
the molybdate ion (or, more precisely, isopolymolybdates that exist at these pH values) [20].
Note that satisfactory PCCs can as well form in the
presence of molybdate in zinc-free solutions. For
example, good adhesion between steel and enamel was
reached when the surface activated by pickling in HCl
was treated with a solution containing Ni2+ or Co2+
(0.53.0 g/l), P2O5 (520 g/l), MoO3 (0.10.5 g/l), F

(0.22.0 g/l), N O 3 (110 g/l), and urea (0.55.0 g/l) at

4080C for 2 to 15 min [21].
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1000
2000
ESat.C.E., mV

Polarization curves for steel in a 0.3 M phosphate solution

(NaH2PO4 + H3PO4) (1) without and (2) with NaNO2
(0.025 mmol/l) [5].

For metals with electrode potentials lower than that

of steel, molybdate can be an oxidant not only in
weakly acidic, but also in neutral solutions. Thus, on
zinc, the reaction
2

O 4 + 22 + 2e = 2 + 4

(4)

is thermodynamically possible at pH 7 [22], though the

best inhibition is observed at pH 5.0. Zinc corrodes less
intensely because of the formation of a thin solid layer
of an extrinsic MoO2 oxide, a product of molybdate
reduction. Even in the mid-1840s, zinc and zinc-plated
steel were phosphated, in order to enhance their corrosion resistance and the adhesion of paint coatings [2].
However, the method of preparing PCC on some metals, including zinc, with the use of molybdate- or tungstate-containing CFs has been patented only in the last
few years [23, 24]. Among other metals, aluminum and
its alloys are of special importance. Like zinc, they
have rather low electrochemical potentials and thus are
more oxidizable. Previously, they were phosphated in
strongly acidic solutions containing, along with H3PO4 ,
2

F or Si F 6 ions (which are capable of forming Al3+

complexes) or chromic acid as a strong oxidant [2].
Replacement of chromates in these processes is
urgently needed; this problem still remains unsolved,
although some attempts to use vanadates instead of
chromates have been made [25].
While discussing the action of molybdates, tungstates, and other similar compounds in phosphate solutions, one cannot ignore their ability to form heteropoly
compounds [26]. Many of the latter are stronger oxidants than the original anions, e.g., molybdate or tungstate. Their relatively low toxicity and high adsorbability have long attracted the attention of researchers who
try to create metal corrosion inhibitors for highly corro-

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KUZNETSOV

sive media. In particular, phosphomolybdates are

known both as inhibitors of metal corrosion in hot
brines, acids, and other media [6, 27, 28] and as constituents of a solution for applying a CC to aluminum [29].
Hence, although the protective mechanism of heteropoly compounds is little understood so far, one can
suppose that their presence in a CF not only enhances
its oxidative power, but also makes the PCC more corrosion resistant.
ORGANIC CORROSION INHIBITORS
Organic compounds have long been added to CF,
though not always for the purpose of enhancing the
protective properties of PCC. Thus, although the introduction of oxalic acid diminishes sliming in the phosphating of steels, zinc, and its alloys, the resulting films
become less resistant, especially with an increase in the
acid concentration [2]. The same effect can be produced by 2-methylimidazoline [30] or urea, which was
also reported to be capable of decelerating the reduction of nitrate to nitrite [2] and preventing PCC from

growing thinner in the presence of N O 2 [31]. In general, the use of organic compounds for the application
of thick PCC in order to activate the metal surface is a
common technique in phosphating. It was even proposed to treat metal with an aqueous solution containing 5-hydroxymethylfurfural, levulinic acid, and disodium 4,5-dihydroxybenzene-1,3-disulfonate prior to
phosphating [32]. In addition to the organic compounds
mentioned above, formaldehyde, benzaldehyde, resorcinol, naphthalene, hydroxylamine, guanidine, and
some aromatic nitrogen-containing compounds
(aniline, quinoline, pyridine, and toluidine) are known
to be used as accelerators in phosphating [2]. Although
most of these additives can inhibit steel corrosion in
acidic media [6], their function in the formation of PCC
remains unclear.
Of interest is the use of urotropin, the known inhibitor of acid corrosion of steel, as an accelerator of phosphating [33]. Addition of urotropin (0.12.0 g/l) to
solutions containing 30 g/l H3PO4 and 7.0 to 7.5 g/l
ZnO makes PCC thicker (the effect is comparable to the
catalytic action of NaNO2) and increases the content of
zinc in the coating. The latter is explained by decelerating the substrate corrosion during the phosphating;
however, this does not yet indicate the enhanced corrosion resistance of the PCC in operation.
The patent literature provides examples of CFs
based on H3PO4 itself in combination with other inhibitors of acid corrosion such as various amines, quaternary ammonium salts, or thiourea, which allow paint
coatings to have better protective properties because of
their being applied to PCC rather than a nonphosphated
surface. However, the importance of these inhibitors
can be revealed solely by comparing identical systems
of paint coatings, i.e., with a reference coating applied
to a noninhibited PCC rather than to a nonphosphated

surface. In connection with this, admitting a possible

favorable influence of acid corrosion inhibitors, we
should note that the effect of surfactants on the protective properties of PCC prepared with their use requires
a more detailed study.
The ability of surfactants to enhance the resistance
of PCC has long since been confirmed by various facts.
For instance, it was shown even in [34] that dispersing
a mixture of solid fatty acids of C12 to C20 (0.22.0 g/l)
in a solution of zinc phosphate with a nonionic surfactant results in PCCs that have good lubricating properties and outperform common zinc phosphate CCs in
corrosion resistance. Ekilik, Grigorev, et al. [35] found
that the introduction of tryptophan, i.e., 2-amino-3-(3indolyl)propionic acid, and especially 2, 4-diphenyl-6(-dimethylaminostyryl)pyrylium perchlorate into a
hot phosphating bath allows one to obtain PCCs that
protect steel in corrosive salt solutions three to five
times better than the control one. Later, it was shown
that some surfactants, in particular RN(C6H4COONa)2
[36], can be sorbed by PCC even from strongly acidic
phosphating solutions, making the coating more
resistant to atmospheric corrosion than zinc phosphate
CCs do.
Among oxidative organic accelerators of phosphating, attention should be given to nitroarenes, including
such known inhibitors of metal corrosion as nitrobenzoates, nitrophenols, nitrochromopyrazole, etc. [37
41]. However, the influence of only some of them on
the corrosion rate of a phosphated steel in a solution of
NaCl or in a humid atmosphere was studied [40, 41].
For example, the use of picric acid and 4-nitrosodimethylaniline in CFs gave PCCs with perfect uniformity
and high protective properties (table). It is interesting
that the additives themselves, in a concentration of C =
10 g/l, only stimulated steel corrosion in the chloride
solutions studied, but a PCC modified with them more
strongly decelerated the cathodic reaction. Taking the
latter into account, it is difficult to assume that picric
acid as a strong oxidant merely adsorbs on steel or penetrates into a coating. Apparently, it oxidizes the surface and makes PCC less porous.
The use of organic corrosion inhibitors, which are
capable of much stronger interactions with metal than a
mere physical adsorption, seems to be the most promising in CFs. It is reasonable that derivatives of phosphoric acid are important among them. It has long since
been known [42] that the additions of alkyl phosphates
(0.025.0 g/l) can change the structure of insoluble
compounds and decrease their amount in a phosphating
bath by 3070%, without making the bath less active.
Moreover, dialkyl phosphates can firmly adsorb on iron
and thus passivate it, the passive state being stable over
a wide potential range [43]. In a great number of the
CFs proposed [2, 44], alkyl phosphates are used to
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CORROSION INHIBITORS IN CONVERSION COATINGS. III

105

Influence of nitroarenes on the protective properties of PCCs on a low-carbon steel in 3% NaCl [41]
Corrosion rate, g/(m2 h)/Protective value, %, at pH
Converting formulation
5.0

7.0

9.0

11.0

Nontreated

0.51/

0.56/

0.46/

0.52/

50 g/l ZnO, 120 ml/l H3PO4 (BPC)

0.01/99

0.02/96

0.30/33

0.38/27

BPC + 50 g/l 4-Nitrosodimethylaniline

0.00/100

0.01/82

0.00/100

0.31/40

BPC + 50 g/l Picric acid

0.00/100

0.00/100

0.001/99.9

0.00/100

* Basic phosphating compound.

enhance wear and corrosion resistance of PCC and

improve adhesion of paint coatings.
Tannin is also attractive for a long time as an inhibitor of steel corrosion during phosphating, because of
its ability to form various complexes with iron. It was
found in [45] that addition of 0.51.0% tannin or a tanning extract to zinc phosphate CFs makes PCC two to
three times more resistant. Later, tannin and compositionally close glucose pyrogallate or ellagate were
included in new CFs [46], while a combination of tannin with acid phosphates was also widely used for
developing rust modifiers [1]. The mechanism of tannin
action in CFs is undoubtedly associated with the formation of insoluble iron tannates. However, it remains
unclear whether the composition of a PCC changes in
time in the same way as under the action of a rust modifier [47].
It is noteworthy that even a complexing agent that is
not a constituent of a PCC can enhance its protective
properties, merely decreasing the concentration of
Fe(II) cations, which deteriorate the quality of coatings,
in a phosphating bath. It is known that ethylenediaminetetraacetic acid in a concentration of 0.31.0 g/l
functions in such a way [2]. Presumably, a similar
mechanism is also valid for some hydroxycarboxylic
acids (according to [2], citric acid is the most effective
among them), but scarcely occurs in the case of phosphonates, which specifically interact with a metal surface [10]. Indeed, addition of aluminum and chromium
phosphonates to a cold phosphating compound significantly decreases the cathodic reaction rate on a phosphated steel in a solution of NaCl [48]. These phosphonates were recommended as additives for enhancing the
protective properties of PCCs which can be used both
to temporarily protect steel workpieces between technological operations and as primers for paint coatings.
There is no doubt that complexonate inhibitors also
affect the PCCs structure, because they can adsorb on
the surface of the crystals formed, thus changing the
kinetics of crystallization and the morphology of the
deposit itself. Based on this property, the authors of
[49] proposed to replace demineralized water by technical one, for which purpose alkanephosphonic acid
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(50200 mg/l) should be introduced into a zinc phosphate CF.

Some water-soluble polymers have much the same
mechanism of action as phosphonates in scaling inhibition. It is little wonder that some of the phosphating formulations (for instance, see [50]) include phosphonic
acids, polycarboxylates, polyethers, or amine-containing polyvinylphenols. A combination of zinc salts with
metal polyacrylates was helpful in obtaining less
porous PCCs, which are more effective and less sensitive to the cathodic exfoliation of an applied paint coating. The latter was explained by a slowed reduction of
O2 in the PCC pores [51, 52].
Complexing agents can also be added to CFs in
order to enhance the corrosion resistance of PCC in the
phosphating of nonferrous metals. For example, introduction of Chrome Azurol S (7.58.0 g/l), i.e., an acidbase polynuclear aromatic indicator capable of forming
complexes with copper cations, into a CF based on the
Mazhef salt can accelerate the zinc-phosphating of
copper and enhance the protective properties of PCC
[53].
Hence, the development of effective corrosion
inhibitors for phosphating compositions appears practically promising, but requires more detailed investigations. At this stage, one can only formulate the basic
requirements that such inhibitors should meet. Obviously, they should
be nontoxic and ecologically safe;
dissolve or be well dispersible in a CF;
be stable and nonvolatile at elevated temperature;
not passivate the base metal; otherwise, the
resulting PCCs will be very thin;
be inexpensive and industrially available; and
not deteriorate the adhesion of PCC to a metal
and keep it compatible with most of paint coatings or
concrete.
Finally, it is desirable that an inhibitor should be
capable of reacting with cations of a base metal to give
insoluble compounds that would be included in PCC.
This property can make an inhibitor more adsorbable
from aqueous solutions on phosphate crystals (so far

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KUZNETSOV

the peculiarities of this adsorption are understood even

more poorly than those for oxide adsorbents [54] and
consequently are difficult to predict). Apparently, such
an inhibitor is the best possible to change the morphology and composition of PCC.
In the case under study, a search for effective corrosion inhibitors is hindered by the multi-component
nature of CFs, the complexity of metal phosphating,
and our lack of knowledge of the adsorptivity of a
growing PCC. At the same time, it is more customary
to add inhibitors to compositions for passivation of
PCC. Unlike the method discussed above, such addition makes it possible to choose the most favorable conditions for the adsorption of an inhibitor and its interaction with the surface to be protected by, for instance,
varying the pH and temperature of a solution, a solvent,
etc. The use of corrosion inhibitors in such a way will
be discussed more specifically in the next part.
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