Surface Pretreatment

130
Rev.Adv.Mater.Sci. 9 (2005) 130-177
T.S.N. Sankara Narayanan
SURFACE PRETREATMENT BY PHOSPHATE

CONVERSION COATINGS A REVIEW
National Metallurgical Laboratory, Madras Centre CSIR, Complex, Taramani, Chennai-600 113, India
Received: April 22, 2005
Abstract. Phosphating is the most widely used metal pretreatment process for the surface
treatment and finishing of ferrous and non-ferrous metals. Due to its economy, speed of operation and ability to afford excellent corrosion resistance, wear resistance, adhesion and lubricative
properties, it plays a significant role in the automobile, process and appliance industries. Though
the process was initially developed as a simple method of preventing corrosion, the changing
end uses of phosphated articles have forced the modification of the existing processes and
development of innovative methods to substitute the conventional ones. To keep pace with the
rapid changing need of the finishing systems, numerous modifications have been put forth in
their development - both in the processing sequence as well as in the phosphating formulations.
This review addresses the various aspects of phosphating in detail. In spite of the numerous
modifications put forth on the deposition technologies to achieve different types of coatings and
desirable properties such as improved corrosion resistance, wear resistance, etc., phosphate
conversion coating still plays a vital part in the automobile, process and appliance industries.
Contents
1. Introduction
2. Chemical conversion coatings
3. Phosphating
3.1. History and development of the
phosphating process
3.2. Chemistry of phosphating
3.3. Acceleration of the phosphating
process
3.3.1. Chemical acceleration
3.3.2. Mechanical acceleration
3.3.3. Electrochemical acceleration
3.4. Kinetics of the phosphating process
3.5. Process details
3.5.1. Cleaning
3.5.2. Rinsing
3.5.3. Phosphating
3.5.4. Rinsing after phosphating
3.5.5. Chromic acid sealing
3.5.6. Drying
3.6. Coating characteristics
3.6.1. Structure and composition
3.6.2. Coating thickness and coating weight
3.6.3. Coating porosity
3.6.4. Stability of the phosphate coating
3.7. Influence of various factors on coating
properties
3.7.1. Nature of the substrate
3.7.1.1. Composition of the metal
3.7.1.2. Structure of the metal surface
3.7.1.3. Surface preparation
3.7.1.4 Surface activation
Corresponding author: T.S.N. Sankara Narayanan, e-mail: tsnsn@rediffmail.com

2005 Advanced Study Center Co. Ltd.
Surface pretreatment by phosphate conversion coatings a review

3.7.1.5. Thermal treatments and machining
3.7.2. Phosphating parameters
3.8. Processing problems and remedial
measures
3.9. Defects in coatings and remedies
3.10. Characterization of phosphate
coatings
3.11. Testing the quality of phosphate
coatings
3.11.1. Evaluation of physical
characteristics
3.11.2. Evaluation of corrosion performance
3.12. Applications
3.13. Environmental impact
4. Summary
References
1. INTRODUCTION
Metals have been the backbone of civilization. Efforts have been spared to find alternatives and replacements for metals but these still play a major
role in the manufacture and construction and are
likely to do so for many more years. This is due to
the combination of several useful properties like
strength, workability, low-cost and ability to be recycled, that the metals possess. However, metals
which are extracted from their ores by chemical or
electrochemical means show a strong tendency to
revert to their oxide form at the first available opportunity, i.e., they tend to corrode [1-4] and as a result they create a tremendous economic loss besides posing a serious threat to the national resources of a country.
The methods of corrosion prevention are many
and varied. These methods may be generally classified [3] as:
Modification of the metal by alloying and/or surface modification;
Modification of the environment by the use of inhibitors; and
Change of metal/environment potential by cathodic or anodic protection.
The most commonly used method of corrosion
protection involves bulk alloying or surface modification. Surface modification is however, far more
economical than bulk alloying and is more widely
practiced. The methods generally used for surface
modification involve the formation of a physical barrier to protect the metal against its corrosive environment [5]. This can be achieved by relatively more
modern methods such as: (i) physical vapour deposition (PVD); (ii) chemical vapour deposition (CVD);
131
(iii) ion implantation; (iv) laser treatment; (v) deposition by thermal spray, plasma spray and arc methods; (vi) nitriding; (vii) carbiding; etc., or through more
conventional techniques such as: (i) painting; (ii)
anodizing; and (iii) chemical conversion coatings.
While the former methods are usually less economic
as they involve the use of sophisticated application
techniques and are meant for specialized applications, the latter methods are more cost-effective and
have a wider spectrum of end applications.
2. CHEMICAL CONVERSION
COATINGS
Chemical conversion coatings are adherent, insoluble, inorganic crystalline or amorphous surface
films, formed as an integral part of the metal surface by means of a non-electrolytic chemical reaction between the metal surface and the dipped in
solution [6]. In such coatings, a portion of the base
metal is converted into one of the components of
the resultant protective film, which is much less reactive to subsequent corrosion than the original metal
surface. This film imparts an equal potential to the
metal surface, neutralizing the potential of the local
anodic and cathodic galvanic corrosion sites [7].
They also serve as absorptive bases for improving
the adhesion to paints and other organic finishes.
Chemical conversion coatings are preferred because
of their adherent nature and high speed of coating
formation besides being economical. Further these
can be formed using simple equipment and without
the application of any external potential. Chemical
conversion coating processes are classified as phosphating, chromating and oxalating according to their
essential constituents viz., phosphates, chromates,
and oxalates respectively [8]. The present review
focuses on phosphate conversion coatings with a
special emphasize on zinc phosphate coatings on
mild steel.
3. PHOSPHATING
Phosphating process can be defined as the treatment of a metal surface so as to give a reasonably
hard, electrically non-conducting surface coating of
insoluble phosphate which is contiguous and highly
adherent to the underlying metal and is considerably more absorptive than the metal [9]. The coating is formed as a result of a topochemical reaction, which causes the surface of the base metal to
integrate itself as a part of the corrosion resistant
film.
132
Table 1. Historical development of the phosphating process.

Sl.
No.
Year/ Advancement made/process developed

Period
References
1.
2.
1906
1908
11
12
3.
1909
4.
1911
5.
6.
7.
1914
1928
1929
8.
1933
9.
10.
11.
1934
1937
1940
12.
13.
14.
1940
1941
1943
15.
1950s
16.
17.
18.
1960s
1960s
1970s
Phosphating of iron and steel using phosphoric acid and iron filings
Treatment of phosphate coatings with oxidizing agents to reduce
process time
Regeneration of the bath and formulation of zinc phosphate baths
requiring high temperature process time of one hour
Formulation of manganese phosphate bath requiring high temperature process time of 2-2.5 hours
Parkerising process with maintenance of total acid to free acid ratio
Recognition of phosphate coating as paint base
Bonderizing process with the addition of Copper accelerator-coating
time: 10 minutes to 1 hour
Use of oxidizing agents like nitrate for acceleration coating time:
5 minutes
Use of phosphate coating for cold working operations for metals
Spray phosphating phospating time: 60-90 seconds
Development of non-coating phosphate process based on sodium
or ammonium phosphates
Development of cold phosphating methods
Phosphating of aluminium surfaces using zinc phosphate and fluorides
Use of disodium phosphate containing titanium as pre-dip before
phosphating
Large scale application of manganese phosphate coatings as an oil
retaining medium for use on bearing or sliding surfaces etc.
Use of special additives to control coating weight
Spray process at operating temperature of 25-30 C
Improvement in coating quality, use of spray cleaners based on
surfactant technology
3.1. History and development of the

phosphating process
The use of phosphate coatings for protecting steel
surfaces has been known since the turn of the century and during this period the greater part of the
Worlds production of cars, refrigerators and furniture were treated this way. The first reliable record
of phosphate coatings applied to prevent rusting of
iron and steel is a British patent of 1869 granted to
Ross [10]. In the method used by him, red hot iron
articles were plunged into the phosphoric acid to
prevent them from rusting. Since then numerous
developments have taken place, of which the major
developments are listed in Table 1.
13,14
15
16,17
18,19
20
21
22
23
24
25
26
27
28
29
18,19
18,19
During the last 30 years, work has been concentrated mainly on improvements in quality, particularly to keep in pace with the recent changing
needs of the organic finishing systems. Prominent
among these are: (i) use of low temperature phosphating baths to overcome the energy crisis [3032]; (ii) use of low zinc technology [18,19]; (iii) use
of special additives in the phosphating bath [33-42];
(iv) use of more than one heavy metal ions in existing composition-particularly tri-cation phosphating
[43]; etc. New types of phosphate coatings such
as tin, nickel and lead phosphate coatings have been
introduced [44,45] besides the development of compositions for simultaneous phosphating of multiple
metal substrates [46,47]. There has been a grow-
133

Table 2. Special additives used in phosphating baths.
Sl.
No.
Additive used
Purpose
Impact
1.
-hydroxy carboxylic acids

like tartaric and citric acids,
tripolyphosphate, sodium,
potassium tartrate,
nitrobenzene sulphonate
Chelants such as EDTA, NTA,
DTPA gluconic acids and
polycarboxy o-amino acids.
Quaternary ammonium
compounds, N and P
compound containing
amido or amino group.
Calcium, Formic acid ester,
chelate of an acidic organic
phosphate
Nickel (II)
To reduce the coating

weight
Improve bath life through 49-54

lesser consumption of
chemicals
Lead compounds, tungstate

ions, gaseous nitrogen
peroxide, hydroxylamine
sulphate, hexamine
Persulphate and
permonosulphuric acid
To accelerate the
phosphating process
2.
3.
4.
5.
6.
7.
Cyclic trimetaphosphate
8.
Lauric, Palmitic, and

Stearic acids with fatty
amines and ethoxylated
amines
Carbohydrates, dialkyltriaminepentakis
methylene phosphonic
acid and its salts and
fluoborate or fluosilicate
Phosphonic acid ester,
Magnesium or zinc nitrate
Amines, Tin (IV), Arsenic
compounds, zinc salt of
an organic N-compound
Zinc carbonate
9.
10.
11.
12.
References
To increase the coating Improved corrosion

weight
protection, shorter
processing times.
Grain refinement
Better adhesion of
subsequent finishes;
better corrosion
protection.
42, 43
55-58
To improve surface
texture
Better adhesion of
subsequent finishes;
better corrosion
protection.
Reduction in
processing time
64, 65
To prevent concentration
of ferro-nitroso complex
in nitrite accelerated
zinc phosphating bath.
To reduce the operating
temperature
To increase the
tolerance to dissolved
iron
To improve lubricant
properties
Better utilization of
nitrite and reduction
in the evolution of
toxic vapours
Thinner, smoother and
improved corrosion
resistant coating
70
Improved workability
of the metal
72
To decrease scaling
Improve the service

life of heating coils
and provide uniform
heating of the bath
73-75
To prevent the build up Improved service life

of sludge on tank walls of the equipment
As inhibitors
Improves corrosion
resistance
76, 77
59-63
66-69
71
78, 79
To reduce the acidity

Consistent performance 80
of the bath and to
of the bath
maintain the equilibrium
134
Table 2. Continued.
13.
Thiourea
14
Sodium lignosulphonate
15
Methylaminoethoxysilane
16
Hexametaphosphate
Stabilizer in nonaqueous phosphating

solutions, as inhibitors
To modify the physical
form of sludge
To prevent rehydration
of phosphate dihydrate
To decrease the surface
roughness and increase
the extent of absorption
of sodium sterate
ing use of substitutes to conventional Cr(VI) postrinses [48] to suit the regulations imposed by the
pollution control authorities on the use of Cr(VI) compounds. The special additives used in phosphating
baths is complied in Table 2 and the alternatives to
Cr(VI) post-rinse treatment is given in Table 3.
3.2. Chemistry of phosphating

All conventional phosphating solutions are dilute
phosphoric acid based solutions of one or more alkali metal/heavy metal ions, which essentially contain free phosphoric acid and primary phosphates
of the metal ions contained in the bath
[18,19,24,127,128]. When a steel panel is introduced into the phosphating solution a topochemical
reaction takes place in which the iron dissolution is
initiated at the microanodes present on the substrate by the free phosphoric acid present in the
bath. Hydrogen evolution occurs at the
microcathodic sites.
Fe + 2H3PO4 Fe(H2PO4)2 + H2 .
(1)
The formation of soluble primary ferrous phosphate

leads to a concurrent local depletion of free acid
concentration in the solution resulting in a rise in
pH at the metal/solution interface. This change in
pH alters the hydrolytic equilibrium which exists
between the soluble primary phosphates and the
insoluble tertiary phosphates of the heavy metal ions
present in the phosphating solution, resulting in the
rapid conversion and deposition of insoluble heavy
metal tertiary phosphates [18,19,24,127, 128]. In a
zinc phosphating bath these equilibria may be represented as:
Improved stability of
the bath
81
Reduce the tendency

82, 83
to form a crust on heat
transfer surfaces
Improves process
efficiency
Impart hydrophobic and 84
anti-corrosion properties
Enables deep drawing
85
of tubes (~50% length)
with reduction in wall
thickness
Zn(H2PO4)2 ZnHPO4 + H3PO4 ,
(2)
3ZnHPO4 Zn3(PO4)2 + H3PO4 .
(3)
A certain amount of free phosphoric acid must

be present to repress the hydrolysis and to keep
the bath stable for effective deposition of phosphate
at the microcathodic sites. Another factor affecting
the shift in the primary to tertiary phosphate equilibria is the temperature of the bath. Higher temperatures favour easy precipitation of the tertiary phosphates in a shorter time. Hence, more amount of
phosphoric acid is needed for the baths operating
at higher temperatures. In contrast, in the case of
phosphating baths operated at room temperature,
the possibility of the increase in acidity during continuous operation is more likely [129,130] and is
normally neutralised by the addition of the carbonate of the metal which forms the coating (Zn(CO3)2
in zinc phosphating bath). Hence, depending upon
the working temperatures and the concentrations
of the constituents in the bath, the free phosphoric
acid content must be chosen to maintain the equilibrium condition. Too much of phosphoric acid not
only delays the formation of the coating, but also
leads to excessive metal loss.
3.3. Acceleration of the phosphating

process
In practice, phosphating reaction tends to be slow
owing to the polarization caused by the hydrogen
evolved in the cathodic reaction. In order to achieve
coating formation in a practicable time, some mode
of acceleration must be employed. The importance
of the acceleration of the phosphating process was
135

Table 3. Alternatives to Cr(VI) post treatment.
Sl.No. Type of compounds
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13
14
15
16
17
Chromium containing
substitutes
Compound used
a. 0.001% Cr(III) as Cr- chromate complex

b.CrO3 solution reduced by HCHO
c. Cr2O72- as complex of divalent metal
d. Chromate and colloidal silicic acid
e. Aqeuous solution of Aluminium chromate polymer
f. Trivalent chromium and ferricyanide
Phosphonic acid
a. Alkane phosphonic acids
derivatives
b. Alkene phosphonic acids
c. Polyvinyl phosphonic acids
Ammonium phosphate a. Dilute solution of ammonium primary phosphate
derivatives
and/or trietha nolamine ydrogen phosphate
Carboxylic acids
a. Citric, glutaric, maleic, succinic and phthalic acids
b. Citrate in combination with nitrite
Oxidizing agents
a. Peroxides and persulphates
b. Potassium permanganate
Polymers
a. Modified hydroxystyrene
b. Melamine-formaldehyde
Tannins
a. Tannin + thiourea compound
b. Tannin + melamine formaldehyde
Tin salts
Aqueous stannous salt solution containing Mn, Pb,
Cd, Co and Ni
Zirconium and Titanium a. Ti (III) in acid solution
compounds
b. Zr or Ti with an inositol phosphate ester
c. Zr + myo-inositol phosphate and/or its salt
Molybdenum type
a. Dilute aqueous solution of MoO2 in HNO3
rinses
Hypophosphorus acid a. Hypophosphorus acid + Hydrofluorosilicic acid
and hypophosphite
b. Sodium hypophosphite + Hydrofluorosilicic acid
Mixture of organoa. Carboxyethylene phosphonic acid esters of butyl
phophates or
diglycidyl ether and bisphenol + fluorosilicic acid
phosphonates and
fluoride
Mixture of Zr, V, F
a. Hydrofluorozirconic acid + fluoroboric acid +
and phosphate ions
Phosphoric acid + amm. metavanadate
Mixture of Li, Cu and
a. Nitrate (or) carboxylate (or) acetates of Li, Cu and Ag
Ag ions
Mixture of Ti, V, Mo,
a. As nitrates, sulphates (or) chloride
Ag, Sn, Sb + cathodic b. Salt of hydroxycarboxylic acid
treatment at 0.1 to
10 A/dm2
Tetravalent Ti (or)
a. Titanyl acetylacetonate
Divalent Mn, Co, Ni
b. Divalent manganese/cobalt/nickel/copper/ethanote
or Cu
c. Divalent
Ni + Co + Sn + Pb
a. As acetates + Pb sheets + stannous chloride
Reference
86, 87
88
89
90
91, 92
93
94, 95
96, 97
98
99, 100
101
102, 103
104
105
106
107
108
109
110-113
114, 115
116
117
118
119
120
121
122, 123
124
125
126
136
felt way back in the 19th century and its development has gained a rapid momentum with the advent of the Bonderite process in 1929. Recently,
Sankara Narayanan et al. [131] have made an overview on the acceleration of the phosphating process
and justified its role on the hunting demand to reduce process time. The different means of accelerating the formation of phosphate coatings can be
broadly classified as: (i) Chemical acceleration; (ii)
Mechanical acceleration; and (iii) Electrochemical
acceleration.
3.3.1. Chemical acceleration

Oxidizing substances [132,133] and metals more
noble than iron such as, Cu, Ni, [19] etc., constitute the most important class of chemical accelerators. They accelerate the deposition process
through different mechanisms. Oxidizing agents
depolarize the cathode half-cell reaction by preventing the accumulation of hydrogen at the cathodic
sites, whereas noble metal ions promote metal dissolution by providing low over-potential cathode sites
by their deposition [134]. Since acceleration through
depolarization is preferred to mere promotion of
metal dissolution, oxidizing agents have found widespread use than metals. Moreover, they prevent the
excessive build up of iron in the bath, which can be
detrimental to good coating formation [25]. The most
commonly employed oxidizing accelerators are nitrites, chlorates, nitrates, peroxides and organic nitro
compounds either alone or in various combinations.
Common combinations are nitrite-nitrate, nitrite-chlorate-nitrate and chlorate-nitrobenzene sulphonic
acid. The characteristics of some of the commonly
used oxidizing accelerators are given in Table 4.
Some reducing agents such as alkali metal sulphites
[135], hypophosphites [136], phosphites [137], formaldehyde, benzaldehyde, hydroxylamine [138], acetaldehyde oxime [139], Pyridine N-oxime [140],
morpholine N-oxime [140], quinones [141], etc., have
also been tried as accelerators but have not been
as successful as oxidizing accelerators from the
industrial point of view.
3.3.2. Mechanical acceleration

When a phosphating solution is sprayed forcibly on
to a metal surface, coatings are formed more readily
than would be by immersion in the same solution,
since the former process eliminates the delay due
to the diffusion of the constituents in the solution to
the metal surface. The comparative kinetics of spray
and dip phosphating was determined by Laukonis

[142]. The resultant coatings are thin, fine-crystalline and perfectly suitable as a paint base. Other
means of physical acceleration are the action of
brushes and rollers [143] on the surface during processing.
3.3.3. Electrochemical acceleration

Several electrochemical methods of acceleration,
both anodic, cathodic and pulse method have been
described in literature [144-161]. Coslett recognized
acceleration of the phosphating process by cathodic
treatment as early as 1909 by Coslett [144]. Subsequent studies reveal that anodic methods are
more appropriate and advantageous than the cathodic methods, as they promote metal dissolution
as well as passivity. Zantout and Gabe [148] claim
to have achieved higher coating weights of low porosity in a shorter treatment time by the application
of a small current. Ravichandran et al., [157-159]
established the utility of galvanic coupling of steel
substrate with metals which are more noble than
steel for accelerating phosphating processes. This
methodology employs the galvanic corrosion principle for accelerating the metal dissolution reaction,
which enables a quicker consumption of free phosphoric acid and an earlier attainment of the point of
incipient precipitation, resulting in higher amount of
phosphate coating formation. The application of a
cathodic current to form phosphate coating on stainless steel using a calcium modified zinc phosphating bath was patented by Bjerrum et al. [160]. Sinha
and Feser [161] have also studied the formation of
phosphate coating on steel and stainless steel substrates by this method.
These three methods of acceleration described above are widely practiced in industries; but
each of them has its own merits and demerits.
Though chemical accelerators (Primarily those of
the oxidizing type) accelerate the phosphating process by their mere addition, their concentration in
the bath is very critical to yield the desired results.
Acceleration by mechanical means is limited to
spray processes, which are capable of providing
fresh bath solution constantly. Electrochemical
methods of acceleration though capable of yielding
higher deposition rate, the practical difficulty in adding electrics to the processing stage makes it less
popular.
137

Table 4. Different types of accelerators used in phosphating.
Type of
accelerator
Example
Effective
concentration
Advantages
Disadvantages
NO3-
1-3%
Lower sludge
Reduction of FePO4 increases

the iron content of the coating
NO2-
NaNO3
Zn(NO3)2
Ni(NO3)2
NaNO2
0.1-0.2 g/l
ClO3-
Zn(ClO3)2
0.5 - 1%
H2O2
H2O2
0.05 g/l
(liquid)
Perborate
Sodium
perborate
Nitroguanidine
Nitroguanidine
Oxime
Acetaldehyde
oxime
1-5 g/l
Affords rapid processing Corrosive fumes.

even at low temperatures Highly unstable at high bath
temperatures.
Frequent addition is required.
Stable in liquid
Corrosive nature of chlorate and
concentrates. Can be
its reduction products.
used for bath make-up High concentrations poison
and replenishment.
the bath. Removal of gelati
Overcomes the white
nous precipitate from the
staining problem.
resultant phosphate coatings is
difficult.
Low coating weight.
Bath control tends to be
No harmful products.
critical. Heavy sludge
Free from staining
formation. Limited stability.
Continuous addition is required.
No separate neutraliser Continuous addition is
is required.
required. Voluminous sludge.
Good corrosion
resistance
Neither the accelerator Slightly soluble.
nor its reduction
No control for build-up
products are corrosive. of ferrous iron in the bath.
Highly expensive.
Stable in acidic
environment
Environmentally
acceptable
Need to use highly

concentrated activating
solution before
phosphating
Spherical and/or
Decomposes in presence of Cu
columnar phosphate
or H2O2 in the bath
crystal
Does not decompose
on its own
Solubility of Quinone
High concentration causes a
wavy pattern. Lower concentra
tion not effective in acceleration
Immediate operation
Effectiveness is impaired in
of the bath
presence of Ca ions in the
Fine grained coating
bath
Improved lacquer
adhesion and corrosion
resistance. Sludge
formation is suppressed
Fine grained coating
Improved adhesion and

corrosion resistance
Organic
N-oxide
Pyridine
0.3-2 g/l
N-oxide
Morpholine
N-oxide
Hydroxylamine Hydroxylamine 0.5-5 g/l
Hydroxylamine
sulphate
Quinones
Benzoquinone
Chloranil
Amido
Benzoicacid
0.1-6 g/l
sulphonic acid sulphamide
and their
Benzenesulphoanilide
N-substituted N-cyclohexyl
derivates
sulphamic acid
Alkali metal
bromate +
Aromatic
Sodium bromate 0.8-1.1 +

+nitrocompound 0.25-0.5
m-nitro benzene- g/l
sulphonate
138
3.4. Kinetics of the phosphating

process
Kinetics of the phosphating process reveals the
steps involved in the course of phosphating and their
rates. Three different methods have been used so
far for investigating the kinetics of formation of phosphate coatings namely: (i) the gravimetric method,
by the quantitative determination of the quantity of
phosphate deposited per unit time; (ii) the electrochemical method based on the determination of free,
reactive uncoated areas through electrochemical
passivation; and (iii) the radiographic method based
on the determination of the intensity of the characteristic X-ray of the resulting compound.
All the three methods gave a similar picture of
the phosphating process that showed the coating
formation did not take place in a linear fashion, rather
it was initially very fast, after which the rate slowly
decreased with time.
Studies on the kinetics of phosphating indicate
that there are four distinct stages in coating formation (Fig. 1), namely, the induction stage (), the
commencement of film growth (), the main exponential growth stage () and the stage of linear increase in film growth (). During the induction period, the oxide film remaining on the surface even
after cleaning is removed. When film growth commences, the first nuclei are formed and the rate of
nucleation increases rapidly with time. This, however, depends considerably on the conditions of the
surface, the pretreatment procedures adopted and
the oxidizing agents present in the phosphating bath.
Growth occurs in the main exponential growth stage.
Addition of accelerators reduces the induction period and extends the stage of linear growth.
In the opinion of Gebhardt [162], the rate of phosphating depends on the rate of diffusion of Fe2+ ions
from the structural lattice to the coating/solution
interface through the coating formed. Machu [25]
has found that the rate of the phosphating reaction
is a function of microanodes on the surface.
Fig. 1. The various stages in the growth of phosphate coating (in presence of accelerator).
The overall coating growth process can be followed by potential-time curves (Fig. 2), which indicate the different stages of coating besides indicating when the effective phosphating has ceased.
Correlation of potential-time relationships with film
properties leads to the conclusion that coating formation proceeds through the following stages:
(a) electrochemical attack of steel;
(b) amorphous precipitation;
(c) dissolution of the base metal;
(d) crystallization and growth; and
(e) crystal reorganization.
But, in actual practice, it is difficult to identify the b
and c stages, and the curve mainly exhibits the
process of metal dissolution, coating formation and
coating completion. The use of potential-time measurements for monitoring the phosphating process
was first described by Machu [25]. It has also been
used by several workers to reveal the nature of the
-dFA/dt = K.FA dt
where dt change in time; FA surface area of anodes in microcells; and K reaction rate constant.
The rate of formation of the phosphate coating
depends primarily upon the metal viz., the ratio of
anode surface which was initially present, FAo, to
the anode surface at any given moment, FA. The
influence of various other factors controlling the rate
of reaction, e.g., temperature, surface condition etc.,
is reflected in the value of the rate constant K, which
is different for different processes.
Fig. 2. Potential-time curve showing the various

steps of phosphating.
139

process taking place during phosphating [145] and
the properties of the coating formed [163]. Sankara
Narayanan et al. [164,165] have discussed the usefulness of the potential-time curves in predicting the
kinetics of the phosphating process. The utility of
potential-time measurement for effective on-line
monitoring of the phosphating process is also established [166,167]. The correlation between coating weight and potential time measurements is established by Sankara Narayanan [168-170], which
enables calculation of crystallization kinetics from
potential time measurement.
Degreasing
pickling
Rinsing
3.5. Process details

In general, phosphating sequence comprises of seven
operations, as indicated in the flow chart. However,
depending upon the surface conditions of the base
metal, some of these operations may be omitted or
additional operations may be incorporated into the
system. A typical seven-stage sequence of phosphate pretreatment process is given in Fig. 3.
Phosphating
Rinsing
3.5.1. Cleaning
Perhaps, the most important requisite for proper
coating formation is a clean substrate, free from
contaminants such as oils, greases, waxes, corrosion products and other soils. Many coating failures can be attributed to the poor metal surface
preparation [171]. An ideal cleaning agent is the
one, which is capable of removing all the contaminants from the metal surface, and prevents their redeposition or the formation of other detrimental reaction products [172]. A variety of methods such
as sand blasting, solvent degreasing, vapour
degreasing, alkaline cleaning and pickling have been
used to achieve this end.
Sand blasting is an effective method of mechanical cleaning. However, it is highly expensive and its
use is justified as a field procedure where chemical
treatments cannot be used and it is necessary to
remove the loosened mill scale as well as paint [173].
Organic solvents are widely used to remove organic contaminants from the metal substrates. But
they are of toxic and flammable nature and need to
be used in large quantities, which is uneconomical.
This has led to its replacement by the vapour
degreasing technique. The unique advantage of the
latter technique over solvent degreasing is that, continuous cleaning with small quantities of solvent is
possible [174].
Alkaline cleaning provides an economical and
effective alternative to the use of organic solvents to
Chromic acid sealing
Drying
Fig. 3. Flow chart depicting the operating sequence
involved in phosphating process.
remove greases, oils and waxes. They are also used

in conjunction with surface active (wetting) agents
and emulsified hydrocarbon solvents [174]. Alkaline cleaners are particularly efficient when used hot
(approx. 79 C). While alkaline cleaning is free from
the fire and toxicity hazards associated with organic
solvent cleaning (unless emulsified solvents have
been incorporated), the corrosive effects of alkaline
materials on the skin and on ordinary clothing must
be guarded against. Caustic soda in particular can
cause serious burns to the skin and eyes and is
extremely irritating to the nasal and bronchial membranes if inhaled.
Acid cleaning or pickling using acids such as
HCl, H2SO4, and H3PO4 is a very effective method
140
for the removal of rust and mill scale [175]. Dilute
solutions (5-10% by weight) of H2SO4 and HCl are
used in presence of inhibitors to remove the inorganic contaminants by converting them into their
ferrous salts. Pickling in H2SO4 is usually performed
at high temperatures (about 60 C). H3PO4 is an
excellent time-tested cleaning agent which not only
removes organic and inorganic solids present on
the metal but also causes chemical etching of the
surface by reacting with it to produce a mechanically and chemically receptive surface for subsequent coating formation [176].
Electrolytic pickling is an alternative to chemical pickling, which provides better and rapid cleaning through an increased hydrogen evolution, resulting in greater agitation and blasting action [174].
3.5.2. Rinsing
The rinsing step followed by cleaning plays a vital
role in the phosphating sequence [172]. Rinsing
prevents the dragout of chemicals used in the earlier cleaning that may contaminate the subsequent
stages.
3.5.3. Phosphating
Suitably cleaned surfaces are next subjected to
phosphating, which causes the formation of an insoluble, corrosion resistant phosphate layer on the
substrate surface. A wide variety of phosphating
compositions are available. However, the right choice
of the components and the operating conditions of
the phosphating bath are made based on the nature of the material to be treated and its end use.
All the phosphating compositions are essentially
dilute phosphoric acid based solutions containing
alkali metal/heavy metal ions in them besides suitable accelerators [18,19,24,127,128]. Based on the
nature of the metal ion constituting the major component of the phosphating solution, these compositions are classified as zinc, manganese and iron
phosphating baths. The characteristics of the coatings obtained using these baths are presented in
Table 5.
Phosphating can be effectively performed on both
ferrous and non-ferrous metals. Among the ferrous
metals, mild steels are most frequently used although maraging steels, galvanized steels and stainless steels can also be coated [177-180]. Non-ferrous metals that can be phosphated include zinc,
aluminium, magnesium and cadmium [181-183].
Physical properties like hardness, tensile strength
and workability of the original metal are retained af-

ter phosphating [21]. The dimensional change
caused by phosphate coatings on the metal surface is of the order of 10-3 mm.
Phosphate deposition can be achieved through
the use of both spray and immersion processes and
the choice of the appropriate method depends upon
the size and shape of the substrate to be coated
and based on the end use for which the coating is
made. Spray process is preferred where shorter processing times are required. This method, however,
requires more factory floor space and special equipment for their application. Immersion process though
slower, produce uniform coatings and they require
less factory floor space as the process tanks can
be arranged in a compact manner. The benefits of
phosphating by total immersion were considered by
Wyvill [184]. But, immersion processes are more
susceptible to contamination during continuous
operation than are spray processes. Smaller parts
can be effectively and economically phosphated by
immersion process whereas spray process is more
suitable for larger work pieces. Nowadays, a combination of both spray and immersion process has
been successfully used particularly in automobile
industries [185].
Phosphating may be carried out at temperatures
ranging from 30-99 C and processing time can be
varied from a few seconds to several minutes. Suitable choice of these parameters is determined by
factors such as nature of the metal to be coated,
thickness and weight of the coating required and
bath composition. The process of phosphating involves a consistent depletion of bath constituents
and in order to obtain a satisfactory phosphate coating, the bath parameters such as: (i) the free acid
value (FA) which refers to the free H+ ions present in
the phosphating solution; (ii) total acid value (TA)
which represents the total phosphate content of the
phosphating solution; (iii) the ratio of FA to TA, expressed as the acid coefficient; (iv) accelerator content; (v) iron content; and (vi) other metallic and nonmetallic constituents present, have to be strictly
controlled within the optimum limits.
3.5.4. Rinsing after phosphating

The surface that has been subjected to phosphating should be thoroughly rinsed with deionized water to remove any acid residue, soluble salts and
non-adherent particles present on it which would
otherwise promote blistering of paint films used for
finishing. Generally overflow rinsing and spray rinsing are preferred [186].
141

Table 5. Characteristics of phosphate coatings.
Characteristic
Type of coating
Iron Phosphate
Coating weight
Types
0.16-0.80 g/m2
Cleaner/coater
Standard
Organic phosphate
Common accelerators
Nitrite/nitrate
Chlorate
Molybdate
Operating temp.
Free acid (points)
Total acid (points)
Prephosphate
conditioners
Room 70 oC
-2.0 to 2.0
5-10
None
Primary use
Paint base for lowcorrosion environments

Low painted corrosion
resistance; low
unpainted corrosion
resistance
Low-carbon steel
Limitations
Materials needed
for tanks
Application method
Spray and immersion
Zinc Phosphate
Heavy Phosphate
1.4 - 4.0 g/m2

Standard
Nickel-modified
Low-zinc
Calcium-modified
Manganese-modified
Nitrite/nitrate
Chlorate
Nitrobenzene
Sulphonic acid
Room-70 C
0.5 - 3.0
10-25
Titanium phosphate
None
7.5-30 g/m2
Manganese phosphate
Zinc phosphate
Ferrous phosphate
None
Chlorate
Nitrate
Nitroguanidine
60-100 oC
3.6 - 9.0
20-40+
Manganese Phosphate
Titanium phosphate
None
Unpainted applications
Paint base for highcorrosion environments

Poor unpainted
Expensive, long processing
corrosion resistance
times
Low-carbon steel,
stainless steel or
plastic-lined steel
Spray and immersion
3.5.5. Chromic acid sealing

The phosphate coatings are usually porous in nature. The porous nature will have a detrimental influence on the corrosion resistance of the phosphate
coating unless they are sealed. A hot (70-80 C)
dilute chromic acid rinse is usually used for this
purpose. This treatment reduces the porosity by
about 50%. It improves the corrosion resistance by
the deposition of insoluble chromates on the bare
areas of the coating [25]. In addition to the benefits
derived from precipitating insoluble salts and passivating any metal that might be exposed, the dilute
chromic acid treatment is advantageous in that it
helps to dissolve protruding crystals of the phosphate coating [187]. Besides, chromic acid posttreatment leaves a residue that is slightly acidic,
which most paints can tolerate. Usually a concen-
Stainless steel or low-carbon

steel
Immersion only
tration range of 0.0125-0.050% is used. A gross

excess of chromic acid causes blistering, poor adhesion and irregular yellowing of paint [188]. A mixture of chromic acid and phosphoric acid has also
been used [188]. Acidic solutions of chromic acid
of pH 2-5 are preferred, the free acid being controlled
between 0.2 and 0.8 points and the total acid below
5 points.
The role of chromates in improving the passivity
of phosphated steel and in improving the paint film
adhesion has been the subject of many papers.
According to Cheever [189], chromium atoms are
distributed over the surface and not just between
the phosphate crystals. Wenz and Claus [190] have
shown that chromic acid final rinsing completely
removes any adsorbed calcium from tap water rinsing after phosphating, deposits some chromium and
142
alters the Zn/Fe ratio. Maeda and Yamamoto [187]
have studied the nature of chromate-treated phosphated surface using XPS. The Cr 2P3/2 spectra
suggest that the coating mainly consisted of trivalent chromium oxide with a small amount of a
hexavalent chromium compound (Fig. 4).
Deconvolution of the trivalent chromium peak results
in two more peaks which can be attributed to Cr2O3
(major part) and Cr(OH)3.1.5H2O (minor part), suggesting an intermediate compound (polymerized
state) with -ol (CrOH) and -oxo (CrO) bonds.
From the calculation based on the ratio of the two
components, the chemical composition of the chromium oxide(III) was formulated to be CrOOH.0.2H2O.
The CrOOH.0.2H2O contributes to increased paint
adhesion due to hydrogen bonding with resin components.
Though the chromic acid sealing improves the
corrosion resistance, the need for regular disposal
of Cr(VI) effluents is a matter of concern because
Cr(VI) causes serious occupational and health hazards. Several alternatives for Cr(VI) treatment were
proposed (Table 3) [191]. In spite of the development of various alternative treatments, there still
exists a strong belief that the extent of corrosion
protection provided by them is not as good as that
from Cr(VI) treatment and from the point of view of
use on an industrial scale, none of these alternative
post-treatments have been proved to be a completely
acceptable replacement to Cr(VI).
Fig. 4. Cr2p3/2 XPS spectra of phosphate coating

post-treated with chrome rinse (Parlen 60) (Reprinted from Progress in Organic Coatings, Vol. 33,
S. Maeda and M. Yamamoto, The role of chromate
treatment after phosphating in paint adhesion, pp.
83-89 (1989) with permission from Elsevier Science).
3.5.6. Drying
After chromic acid rinsing the parts must be dried
before finishing, the conventional methods used
being simple evaporation, forced drying by blowing
air or by heating [88]. Where evaporation conditions
are good, warm air circulating fans and compressed
air blow offs are the most economical methods. After drying the phosphated panels are ready for application of further finishes such as paints, oils, varnishes, etc.
3.6. Coating characteristics

3.6.1. Structure and composition
Phosphate coatings produced on steel, zinc, zinccoated steel, aluminium and other similar metals
show a crystalline structure with crystals ranging
from a few to about 100 micrometer in size. Various
workers [24,192,193] have reported a large number
of different constituents of phosphate coatings.
Machu [25] listed 30 such phosphate compounds
identified in a phosphate coating. Neuhaus and
Gebhardt [192] have tabulated the main phases in

phosphate coatings formed on metals from baths of
various phosphates (Table 6). The composition of
phosphate coatings is influenced by a number of
factors such as the method of application (spray or
dip), the degree of agitation of the bath, bath chemistry, the type and quantity of accelerator and the
presence of other metal ions. Chamberlain and Eisler
[194] have found using radioactive tracers that the
base layer was formed initially from the metal being
attacked during the first few seconds of contact with
the phosphating bath producing a very thin film. The
film contains oxides and phosphates of the metal
being treated. Ferrous phosphate is most likely to
be present in the case of steel. The growth of phosphate coating is initiated by the formation of a subcrystalline layer on which crystalline layer of phosphates build up rapidly. The number of crystals on
which growth has occurred is essentially constant
with time because nucleation and growth takes
place only at a limited constant number of areas
143

Table 6. Phase constituents of phosphate coatings on Fe, Zn and Al.
Metal in the bath
Substrate
Fe
Alkali
Fe
Fe3(PO4)2.8H2O
Fe3H2(PO4)4.4H2O
(Fe hureaulite)
FePO4.2H2O (strengite)
(Mn.Fe)5H2(PO4)4.4H2O
Mn5H2(PO4)4.4H2O
(Mn hureaulite)
Zn2Fe(PO4)2.4H2O
(phosphophyllite)
Zn3(PO4)2.4H2O
(hopeite)
Zn2Fe(PO4)2.4H2O
Zn2Ca(PO4)2.2H2O
(scholzite)
Zn3(PO4)2.4H2O
Mn
Zn
ZnCa
Zn
Al
Zn3(PO4)2.4H2O
Zn3(PO4)2.4H2O
Zn2Fe(PO4)2.4H2O
Fe5H2(PO4)4.4H2O
Zn3(PO4)2.4H2O
AlPO4
Mn5H2(PO4)4.4H2O
Zn3(PO4)2.4H2O
Zn3(PO4)2.4H2O
Zn2Ca(PO4)2.2H2O
[195]. It is believed that the formation of phosphate

coating follows an active site mechanism i.e., only
a small percentage of the surface, participates in
the nucleation of the growth sites. Machu has postulated that these active sites were the growth areas located predominantly at the grain boundaries
of the steel [196].
Light and electron microscopic studies made on
zinc phosphated steel, have shown that the formation and growth process occur in three stages.
1st stage: Depending on the zinc phosphating process, 104-106/cm2 platelet crystals are formed
on the surface. These are randomly oriented to
the steel substrate; some are parallel, some
vertical and others are inclined at an angle. Those
platelets, which are not, attached parallel to the
surface are needle-like in appearance. These first
stage crystals grow primarily laterally over the
substrate.
2nd stage: It consists of nucleation and growth of
several crystals on the upper surface of the original crystals that are attached parallel to the surface. This growth process is usually vertical to
the site and gives the appearance of additional
needle-like crystals.
3rd stage: Finally, a thin layer of zinc phosphate
spreads from the base of the original crystals.
For paint-base zinc phosphate coatings, the
Zn2Ca(PO2)2.2H2O
Zn3(PO4)2.4H2O
growth is primarily lateral. For coatings used for

oil retention and as bases for cold forming lubricants, considerable vertical growth also occurs.
The crystal habit and size depends on many factors like the bath composition, temperature, method
of surface preparation etc. Crystals may take the
form of plates, needles and grains having dimension from a few to tens of micrometers.
Many instrumental methods are available for the
examination of the constituents of phosphate coatings. These include energy dispersive spectroscopy
(EDS), electron spectroscopy for chemical analysis (ESCA) and X-ray diffraction (XRD). Neuhaus et
al. [193] have reported from XRD analysis that
phosphophyllite, Zn2Fe(PO4)2.4H2O and hopeite,
Zn3(PO4)2.4H2O are the essential constituents of
zinc phosphate coatings on ferrous substrate, substantiated by others [197, 198] also.
Phosphophyllite is formed essentially at the surface of contact with the basis metal. The quantitative ratio of these phases is variable and depends
on the total iron content of the solution. Iron
Hureaulite, Fe5H2(PO4)4.4H2O is formed when the
Fe(II) content in the solution is high. This is not
stable under atmospheric conditions and has a detrimental influence proportional to its content in the
coating.
144
Miyawaki et al. [199] have introduced the concept of P ratio to express quantitatively the proportion of these phases in phosphate coatings. It is
defined as:
Phosphophyllite
P ratio =
Phosphophyllite + Hopeite
Several authors [199,200] have correlated the P
ratio and corrosion resistance of the phosphate
coating. But according to Richardson et al. [200]
the ratio itself is not sufficient to predict the corrosion resistance.
X-ray and electron diffraction studies have shown
that hopeite and phosphophyllite are oriented perpendicular to the plane of the support besides
exhibiting that there is an excellent orientation between the substrate and the zinc phosphate coating that follows an epitaxial growth relationship.
(010) - hopeite and (100) - phosphophyllite || (100)-Fe
(100) - hopeite and (001) - phosphophyllite || Ao-Fe and
(001) - hopeite and (010) - phosphophyllite || Ao-Fe
The formation of primary valency bonds between
the coating and the polarized elements of the -iron
lattices with the production of a two dimensional
contact layer of the wustite-type accounts for the
excellent adhesion of the coating to the substrate.
3.6.2. Coating thickness and coating

weight
One of the principal factors involved in the choice of
a phosphating bath is in fact the thickness of the
deposit that it will provide. Neglecting intercrystalline
voids and surface irregularities and considering the
phosphate coating as completely homogeneous, the
thickness can be measured [201]. Phosphate coatings range in thickness from 1 to 50 microns but for
practical purposes the thickness is usually quantified in terms of weight per unit area (usually as g/m2
or mg/ft2) and commonly referred to as coating
weight. The reason for the adoption of coating weight
rather than coating thickness as the usual measure of coatings is the difficulty in measuring the
latter, compounded by the uneven nature of the substrate and of the coating.
According to Lorin [127] the ratio between coating weight (g/m2) and coating thickness (m) varies
between 1.5 and 3.5 for the majority of industrial
phosphate coatings. For light and medium weight
coatings 1 m can be regarded as equivalent to 1.52 g/m2.

The determination of coating weight is a destructive test, which involves weighing a standard test
panel before and after stripping the coating in a
medium, which dissolves the coating and not the
substrate. Usually methods such as stripping the
coating in concentrated hydrochloric acid containing antimony trioxide (20 g/l) as an inhibitor or high
concentration of chromic acid solution (5%) or sodium hydroxide (15%) is used. A non-destructive
method based on specular reflectance infrared absorption (SRIRA) for the determination of zinc phosphate coating weight has been developed by Cheever
[202, 203]. Tony Mansour [204] has shown a good
agreement of the results obtained by this method
with X-ray fluorescence (XRF) data as well as the
gravimetric measurements. Yap et al. [205] suggest
that XRF is a nondestructive and accurate technique
for measuring the thickness of thin phosphate coatings.
The phosphating industry generally uses coating weight as a method of quality control; but it is
widely agreed that except at extreme values, coating weight does not directly relate to corrosion performance. Hence coating weight alone is of little
value in assessing the quality of coatings and must
be considered in relation to other characteristics of
the coatings, viz., thickness, structure homogeneity, etc.
3.6.3. Coating porosity

The layer of phosphate coating consists of numerous crystals of very different sizes, which have
spread from centers of nucleation to join and finally
cover the surface. A constitution of this type inherently implies the existence of fissures and channels through to the basis metal at inter-crystalline
zones. Porosity is generally fairly low, of the order
of 0.5-1.5% of the phosphated surface [25]. It is
generally believed that the porosity decreases with
increasing thickness of the phosphate coating. Porosity depends upon the type of phosphate solution, the treatment time, the iron content of the bath
and, the chemical composition of the coating [206].
In recent years, much attention has been focused
on the porosity of phosphate coatings due to the
presence of tightly bound carbonaceous residues
formed on steel during steel making [207]. Since
these cannot be removed by alkaline cleaning process, they interfere with the effective deposition of
phosphate coatings resulting in the formation of
porous coatings with inferior performance.
Several chemical and electrochemical methods
have been developed to determine the porosity of
145
terials can collect [195]. This attribute is made use

of in the protection of coated articles by impregnation of oil in the pores. Thus, a homogeneous finecrystalline coating is desirable with respect to adhesion of a paint film while a coarse-crystalline coating is preferred for protection by oils, varnishes etc.
3.6.4. Stability of the phosphate

coating
Fig. 5. FTIR absorption-reflection spectra of zinc

phosphate coating formed on steel
(a) as-prepared; (b) partially dehydrated at 150 C
for 1 hour; (c) partially dehydrated and rehydrated
at 95% RH for 70 hours. (Reprinted from Journal of
Molecular Structure, Vol. 511-512, A. Stoch, Cz.
Paluszkiewicz and E. Dlugon, An effect of
methylaminoethoxysilane on zinc phosphate rehydration, pp. 295-299 (1999) with permission from
Elsevier Science).
phosphate coatings. The time taken for the deposition of metallic copper from a copper sulphate-sodium chloride solution and the electron microprobe
determination of the amount of copper deposited in
the bare areas of the coating are the measures of
coating porosity [163]. The number of Prussian blue
spots formed per unit area of a filter paper soaked
in potassium ferricyanide-sodium chloride-gelatin
mixture placed on a phosphated sample is yet another method of determination of the porosity of
these coatings [208].
Machus [25] method of determination of porosity of coating by electrochemical means is based
on the anodic passivation of uncoated areas in sodium sulphate solution. A more recent electrochemical polarization method is based on the magnitude
of current generated by the reduction of oxygen at
the cathodically active sites on the porous coating
[209,210].
Although porosity of the coating has a detrimental effect on its corrosion performance, it has some
advantages too. The pores in the phosphate coatings act as large reservoirs into which organic ma-
The stability of the phosphate coating is an important characteristic property. Since phosphate coatings serve as an effective pretreatment for subsequent paint finishes, it is imperative that they must
be compatible with the applied paint systems. In
recent years, numerous developments were made
in the paint finishes. Among them, the cathodic
electrophoretic deposition has received a widespread acceptance. In order to be compatible with
this deposition technology, the phosphate coating
must process an excellent thermal and alkaline
stability. The importance of stability of phosphate
coating to suit the modern day finishing systems
was
discussed
by
several
authors
[18,19,24,127,211-218].
During cathodic electrophoretic deposition, the
decomposition of water produces hydroxyl ions, the
creation of which is considered to be critical as they
can cause dissolution of the phosphate coating [140,
141]. Several researchers have confirmed the dissolution of phosphate coating in high-pH environments [142-147]. It was found that approximately
30-40% of the phosphate coating gets dissolved
during cathodic electrophoretic deposition. This has
lead to a greater porosity of the phosphate coating.
Moreover, the occlusion of the dissolved ions, which
are subsequently, concentrated during paint baking affects the corrosion resistance. After cathodic
electrocoating the coated panels are usually cured
at a temperature of 180 C for 20 minutes. According to Kojima et al. [148] and Sugaya and Kondo
[149], under such curing conditions the phosphate
coating will undergo a definite weight loss associated with a structural change in the constituent crystals. It is generally advised that the loss in weight
should be restricted to less than 15%, which would
otherwise cause detoriation of the phosphate coating and a loss in corrosion resistance. The other
important factor is the ability of the dehydrated phosphate crystals to revert back to its original hydrated
form when subjected to humid service conditions.
The dehydration-rehydration phenomenon is further
confirmed by X-ray diffraction. During heating at 150
C for 1 hour the lines at 9.65 and at 19 2 dimin-
146
Fig. 6. X-ray diffraction pattern of zinc phosphate coating formed on steel (a) as-prepared; (b) partially
dehydrated at 150 C for 1 hour; (c) partially dehydrated and rehydrated at 95% RH for 70 hours. (Reprinted
from Journal of Molecular Structure, Vol. 511-512, A. Stoch, Cz. Paluszkiewicz and E. Dlugon, An effect of
methylaminoethoxysilane on zinc phosphate rehydration, pp. 295-299 (1999) with permission from Elsevier
Science).
ished or disappeared and new lines were observed

at 10.90, 11.20 and 22 2. During rehydration the
line at 11.20 2 diminished while that at 9.65 2
grew (Fig. 6). It has been observed that the rehydration of the phosphate crystals induces residual
stresses and reduce the phosphate-paint film adhesiveness [150].
Numerous research reports are available to date,
which elaborate the behavior of phosphate coatings
during chemical and thermal aggressions. The dissolution of zinc phosphate coating in high-pH environments was first reported by Wiggle et al. [142].
Later, using sodium hydroxide as a simulated medium, Roberts et al. [143] demonstrated the selective leaching of phosphorous from the coating. Van
Ooij and de Vries [144] interpreted X-ray photoelectron spectroscopic studies to show that hydroxyl
ions exchange phosphate ions in the first few layers of the phosphate coating. Servais et al. [140]
determined the chemical stability of zinc phosphate
coatings by subjecting them to immersion treatment
in 0.8 g/l sodium hydroxide solution (pH 12.3) at 40
C for 3 minutes. Similarly, the effects of high-pH
environments on zinc phosphate coatings were determined by Sommer and Leidheiser Jr. [141], using 0.01, 0.1 and 1.0 M sodium hydroxide solutions.
Kwiatkowski et al. [151] recommended a borate

buffer solution containing 0.01 M ethylenediaminetetraacetic acid (EDTA) as the medium to test the
alkaline stability of the coating and suggested its
usefulness in predicting the same at a shorter time
interval. All these studies uniformly agree that coatings richer in phosphophyllite possess greater alkaline solubility and can serve as effective bases
for cathodic electrophoretic painting.
Phosphate coatings undergo marked changes
when subjected to variation of temperature.
Thermogravimetric technique is usually used to
monitor these changes [152]. The changes occurring in zinc phosphate coating on steel upon heating was studied by Kojima et al. [148] and Sugaya
and Kondo [149]. When heated above room temperature, a gradual loss in weight occurs. This was
attributed to a nonstructural weight loss. However,
with subsequent increase in temperature dehydration of the constituent phases of the phosphate crystals, occurs. The dehydration of hopeite
[Zn 3 (PO 4 ) 2 . 4H 2 O]
and
phosphophyllite
.
[Zn2Fe(PO4)2 4H2O] commences respectively at 80
and 110 C; however, a more pronounced weight
loss occurs at approximately 150 C, where hopeite

loses two molecules of water of hydration. When
heated above 150C, both phosphophyllite and
hopeite are transformed into their dehydrated forms.
The hopeite phase is completely dehydrated at a
temperature of approximately 240 C. The weight
loss considerably increased between 250 and 600
C. Above 600 C sublimation of zinc and phosphorous occurs, which results in complete breakdown
of the coating. The change in appearance, colour
and morphology of phosphate coatings remain practically unaltered up to 200 C. However, above this
temperature, the grey crystalline phosphate coating changes to a silver grey form and appears dusty.
Above 500 C the colour changes to brown and above
600 C complete breakdown of coating occurs [148].
Bonara and his co-workers [152,153] have accounted for the observed difference in temperature
at which both the hopeite and phosphophyllite crystals lose their water of crystallization. According to
them, hopeite crystals seem to possess only one
type of crystallization water species, which may be
readily released during a progressive heating. In
contrast, the phosphophyllite have three different
crystallization water types, each with different bond
types, thus causing a differential release during progressive heating.
Based on the above facts on thermal stability of
phosphate coatings and the normal baking conditions used (180 C for 20 minutes) for curing cathodic electrocoating, it is quite obvious that both
hopeite and phosphophyllite will exist as bihydrated
crystals. The rehydration of these bihydrated hopeite
and phosphophyllite was a subject of considerable
importance as it determines the wet adhesion property. It has now been established that when placed
under a rehydration condition, like immersion in an
aqueous solution or exposure to high humid atmospheres, the hopeite bihydrated crystals undergo
rehydration to the tetrahydrated phase along with
the formation of zinc oxide. The formation of these
products induces stresses and bond relaxation at
the paint-phosphate interface and ultimately affects
the adhesiveness. In contrast to this behavior, the
phosphophyllite bihydrated crystals are found to
resist the rehydration phenomenon. Liebau [233]
has accounted for the difference in rehydration
behaviour of hopeite and phosphophyllite bihydrate
crystals. According to him, in hopeite it is the flexibility of the Zn2+ ion co-ordination state, which can
exist in either octahedral or tetrahedral coordination, thus allowing the dehydration process to occur. However, in phosphophyllite, the Fe2+ ions occupy the octahedral co-ordination sites, which are
the unsaturated co-ordination states. Hence an ir-
147
reversible structural modification has resulted during the dehydration process.

Hence it is evident that a phosphate coating richer
in phosphophyllite phase is best suited to withstand
the environments that occur during cathodic electrophoretic painting, paint curing and under service
conditions. This has necessitated modification of
the phosphating formulations to produce phosphate
coatings richer in phosphophyllite phase. The influence of the phase constituents on the stability of
phosphate coatings studied by Sankara Narayanan
[213] also confirms this generalization.
The introduction of pre-coated steels such as
zinc, zinc alloy coated steels, etc., for automotive
body panels present new challenges regarding the
stability of phosphate coatings [234]. When coated
using a zinc phosphating bath, the zinc and zinc
alloy coated steels will produce phosphate coatings, which comprise only the hopeite phase. As
stated earlier, phosphate coatings richer in hopeite
is not desirable for subsequent cathodic
electrocoating finishes. However, these pre-coated
steels show good performance with regard to formability and weldability. The extent of perforation and
cosmetic corrosion is also less with these materials and they also posses a good surface appearance. Hence to effectively make use of the zinc and
zinc alloy coated steels, the phosphating formulation has to be modified to produce coatings that are
not richer in hopeite. It is now realized that although
low hopeite content is the principle requirement for
cathodic electrocoating, it is not essential that the
coating should be richer in phosphophyllite as long
as the coating has substantial amorphous material.
The introduction of nickel and manganese modified low-zinc phosphating formulations are the most
significant modification proposed to cope up with
the cathodic electocoating, particularly in the automobile industry. The presence of Ni2+ and/or Mn2+
ions in these phosphating baths has yielded several advantages. Although there is a decrease in
coating weight, crystal formation is observed at an
early stage and the crystal size is fine for zinc phosphate crystals obtained from solutions containing
Ni2+ and Mn2+ ions. It is confirmed that these heavy
metal ions participate in forming the crystal and
brings about the crystal refinement and such an effect is found to increase with an increase in their
concentration [235,236]. It is also reported that Mn2+
ions are more effective in causing the nucleation of
the crystal when compared to the effect of Ni2+ ions
[236]. The usefulness of the addition of Mn2+ ion
has been advocated based on several other factors.
148
Mn2+ ions demonstratably improve the corrosion

resistance of coatings obtained from a low zinc phosphating process. The presence of Mn2+ ions in low
zinc phosphating bath increases the rate of formation of phosphate coatings. Hence, it is possible to
decrease the bath temperature, which in turn allows a considerable amount of savings in the heating costs. Moreover, the addition of Mn2+ ions in the
phosphating bath helps to increase the working width
of the phosphating bath. Also, the presence of manganese in the zinc phosphate coating resists the
formation of white spots on galvanized steel. However, it is also cautioned that if the manganese content exceeds a certain level, a decrease in corrosion resistance may occur. Advanced analytical
techniques have shown that the manganese tends
to be distributed throughout the coating whereas
nickel is concentrated at the interface and the presence of both contributes to maximum performance.
Based on the results of the electron spin resonance
(ESR) technique, Sato et al. [237] confirmed that
both nickel and manganese are present in the zinc
phosphate films respectively, as Ni(II) and Mn(II).
According to them, the nickel and manganese doped
hopeite are formed by the following mechanisms:
Zn(H2PO4) ZnHPO4 + H3PO4 ,
(4)
3Zn(H2PO4) Zn3-xMex(PO4)2.4H2O + H3PO4 . (5)

The chemical structure of the modified hopeite
crystal in general was considered as
Zn 3-x Me x(PO 4) 2 . 4H 2 O, where Me = Ni or Mn.
Accordingly, the chemical structure of the doped
hopeite when nickel and manganese coexist is
suggested as Zn 3-x-z(Ni xMn Z)(PO 4)2. 4H 2 O. The
possibility of existence of such a structure was
confirmed by various analytical techniques such as
electron spin resonance (ESR), extended X-ray
absorption fine structure (EXAFS), laser Raman
spectroscopy, etc. [237-243].
Besides the modification of the phosphating bath
by Ni2+ and/or Mn2+ ions, developments were also
made in modifying the surface of the steel sheets.
The formation of a Fe-P coating of about 2 g/m2
containing a phosphorous content of 0.5% or below, on Zn-Ni or Zn-Fe steel sheets is another notable development [234, 244]. These materials are
commonly known as double-layered Fe-P/Zn-Ni and
Fe-P/Zn-Fe alloy plated steel sheets. The
phosphatability of these steel sheets are highly
comparable to that of cold-rolled steel sheets. It is
the presence of micro quantity of phosphorous, uniformly dispersed in the iron coatings, which activates the surface and enhances the reaction with
the phosphating bath, resulting in the production of
closely packed phosphophyllite rich coating, having a crystal size of 3-5 mm. The formation of such
a coating improves the wet adhesion property. Hence
the modifications made in the phosphating formulations to produce coatings richer in phosphophyllite,
to serve as an effective base for electrocoat finishing systems [225], are rightly justified.
3.7. Influence of various factors on

coating properties
3.7.1. Nature of the substrate
3.7.1.1. Composition of the metal. The presence
of alloying elements and their chemical nature cause
distinct difference in the extent of phosphatability of
the substrate. It is generally believed that steels
with small amounts of more noble metals such as
chromium, nickel, molybdenum and vanadium can
be phosphated without much difficulty. However, if
the concentration of these elements exceeds certain limit then the steel will encounter with a decrease in the intensity of acid attack resulting in a
poor coating formation and among the noble metals
in causing such an effect, chromium is considered
to be the most detrimental one [245]. The
phosphatability of cold rolled steel containing varying amounts of chromium, nickel and copper is given
in Table 7. It is evident from Table 7 that the
phosphatability is not affected when the total concentration of chromium, nickel and copper is in the
range of 200-300 ppm and gets drastically affected
when the total concentration of these metals exceeds 800 ppm. The amount of carbon, phosphorus, sulphur, manganese and silicon can also influence the phosphatability of the steel to a great extent. Low carbon steels undergo phosphating easily and produce superior quality coatings. With increasing carbon content, the rate of phosphating
becomes slower and the resultant crystals are
larger. In fact, when dealing with the carbon concentration in steel, it is the distribution and the form
in which it is present is rather an important criterion
in predicting its probable effect on sensitization,
nucleation and crystallization. The presence of ferrite crystals improve metal attack while on the other
hand increasing concentrations of pearlite leads to
coarsening of the phosphate crystals as the crystal
nuclei develop only to a small extent on the islands
of pearlite [127,246]. The deleterious effect of surface carbon content has been the subject of many
investigations and based on the amount of surface
carbon, steels have been classified as bad or good
with reference to their suitability to phosphating
149
Table 7. Phosphatability of cold rolled steel containing varying amounts of chromium, nickel and copper
(after Kim [245]).
Substrate
designation
Cu + Ni + Cr
(ppm)
Surface roughness
(Ra) (mm)
Phosphatability*
Coating weight (g/m2)

In the centre
In the edge
CRS-A
CRS-B
CRS-C
CRS-D
300
200
800
1000
<0.8
>1.2
<0.8
>1.2
1
1
5
4
4.32
4.04
2.86
3.54
3.87
5.39
3.09
3.59
* Based on visual appearance. Rating: 1 Good; 5 Poor.
[247,248]. Grossman [248] has found up to 30 times

as much carbon on bad steels as on the good
steel samples. A direct correlation between surface
carbon content and the porosity of the phosphate
coatings on the one hand and their salt spray resistance when painted on the other hand was found by
Hospadaruk et al. [207,249]. Wojkowiak and Bender
[250] using a multiple regression analysis have confirmed the existence of a positive correlation between
the extent of underfilm attack and the surface carbon content of the steel.
Takao et al. [251,252] have investigated the effect of phosphorus on the phosphatability of ultra
low-carbon steel sheets. According to them, the
addition of phosphorus was beneficial in refining the
grain size and increasing the surface coverage.
Moreover, they have proved that the phosphorus
addition helps to improve the perforation corrosion
resistance after painting. In contrast, Kargol and
Jordan [253] have claimed that phosphorus alloy
addition inhibits the hydrogen recombination during
the initial stages of phosphating resulting in increased
porosity and inferior corrosion performance. The rate
of attack of the metal in phosphating solution is also
affected by the concentration of sulphur. The
phosphatability of the dual-phase (Si-Mn) steel is
primarily controlled by the balance of silicon and
manganese [254].
Although it is clearly evident that every common
constituent element of steel has its own influence
in determining its phosphatability either to a greater
or smaller extent, the most unfavorable from the
phosphating point of view are those which are alloyed with carbide forming elements such as chromium and tungsten, and the surface carbon content. As a result, attempts have been made to eliminate such troublesome factors. Accordingly, the
surface carbon content of the steel chosen for phos-
phating has to be within the specified limits. Fujino

et al. [255] have concluded that a contamination of
greater than 8 mg/m2 deteriorates the phosphate
coating and resistance to corrosion after painting.
Blumel et al. [256] and Balboni [257] have predicted
an upper limit of 7 mg/m2. But Coduti [258] has concluded that this amount has to be a maximum of
4.3 g/m2 for good performance since only an average performance has resulted when the concentration lies between 4.3 and 6.4 mg/m2.
3.7.1.2. Structure of the metal surface. The structure of the metal surface has also its own influence
and considered to be equally as important as that
of the composition. Ghali [259] has made a thorough study of the surface structure in relation to
phosphate treatment. It is generally believed that
greater the surface roughness, the higher the weight
of the coating deposited per unit of the apparent
surface area and the shorter the time of treatment
required. Moreover, increasing surface roughness
gives a corresponding increase in the fineness of
the coating structure whereas polished surfaces
respond poorly to phosphating. Beauvais and Bary
[260] have reported that if the metal surface possesses a greater number of surface concavities and
fissures, there will be an increased acid attack during phosphating resulting in good anchorage of the
coating. According to Kim [245], phosphatability can
be improved by increasing the surface roughness.
Balboni [257] has considered that a surface roughness of 0.76-1.77 m is acceptable for most of the
cases.
The growth of the phosphate coating is considered to be an epitaxial growth phenomena and literature reports have convincingly established the
following epitaxial relationships in the case of a zinc
phosphate coating on mild steel constituting the
phosphophyllite (FeZn2(PO4)2.4H2O) and the hopeite
150
(Zn3(PO4)2.4H2O), by means of X-ray diffraction. According to Ursini [261, 262] the orientation relationship (412) phosphophyllite /(111) Fe role is very
important for epitaxial growth on cold rolled steel
and for an increasing adhesive bond. Laukonis [142]
has studied the role of the oxide films on phosphating of steel and concluded that it is easier to deposit zinc phosphate coatings on ferric oxides than
on ferrous oxides. Hence it is evident that it is not
only the surface roughness but also the orientation
and the presence of the oxide film will influence the
phosphating process to a considerable extent.
3.7.1.3. Surface preparation. The cleaning methods adopted can also influence the phosphating of
steel sheets. It is essential to remove any greasy
contaminants and corrosion products from the surface to obtain a good phosphate finish. Degreasing
in organic solvents usually promotes the formation
of fine-grained coatings while strong alkaline solutions and pickling in mineral acids yield coarse coatings. Though, the prevention of the excessive metal
attack during pickling is effected by potent inhibitors, it is generally observed that surfaces that have
been pickled with an effective pickling inhibitor are
difficult to phosphate unless a strong alkaline cleaning operation is employed to remove the inhibitor
residues. Moreover, it is believed that the smut
formed during pickling operation can also influence
the amount and crystal size of the phosphate coating [188]. However, there are reports available, which
are successfully employing potent inhibitors in the
pickling bath, which eliminates the usual detrimental effects on phosphating. It is claimed that the
inhibitors adsorbed onto the metal surface reduces
the amount of hydrogen in the surface layer of the
phosphated metal and the phosphate coating produced in such a way are satisfactory for lowering
friction, facilitating cold working and as undercoats
for paint [263].
3.7.1.4. Surface activation. The activating effect
of colloidal titanium phosphate was discovered by
Jernstedt [264] and latter explored by several others [265]. The mechanism of the activation has been
established by Tegehall [266]. The colloids in the
aqueous dispersion are disc shaped particles which
have the composition of Na4TiO(PO4)2.0-7H2O. These
particles are physically adsorbed on the metal surface during the application of colloidal dispersion.
When the activated substrate comes in contact to
a zinc phosphating bath, an ion exchange between
the sodium ions on the surface of the titanium phosphate particles and the zinc ions of the phosphating solution takes place [267]. The ion-exchanged

particles act as nucleation agents for the zinc phosphate crystals because they have nearly the same
stoichiometry and offer a crystallographic plane for
an epitaxial growth.
The rate of nucleation of the phosphate coating
may be markedly increased by imposing an additional activation of the cleaned metal surface. A process for activating steel surface prior to phosphating was patented by Yamamato et al. [268] and
Donofrio [269]. Hamilton [270] has proposed a combination of acid cleaning and a phosphating compound for surface activation, while Hamilton and
Schneider [271] and Morrison and Deilter [272] have
proposed a highly alkaline titanated cleaner prior to
phosphating. Use of 1-2% disodium phosphate solution containing 0.01% of titanium compounds have
been extensively used in industries [273]. Other
compounds like dilute solutions of cupric or nickel
sulphates, oxalic acid and polyphosphonates help
in increasing the number of initial nuclei formed during phosphating and their subsequent growth, to
yield thin and compact coatings of fine-grained nature.
3.7.1.5. Thermal treatments and machining.
Thermal or thermo-chemical treatments cause the
formation of heterogeneous phases, which usually
alter the grain size. Since the initial metal attack
during phosphating occurs mainly at the grain boundaries, the size of the grains becomes an important
factor in influencing phosphating and dictates the
effect of thermal or thermo-chemical treatments.
Moreover, upon thermal treatment, the distribution
of the constituent elements of heterogeneous alloys may vary and depending upon which the cathodic and anodic sites on the surface will result
and decides the phosphatability. When studying the
effects of annealing of a 0.3Mn-0.2Ti modified steel
at 280 C in H2-N2 atmosphere, Usuki et al. [274]
has concluded that such a treatment leads to the
formation of manganese oxide and titanium oxide.
Since the surface concentration of manganese is
3-4 times as large as that of titanium, the treatment
enhances the phosphatability of the modified steel
by promoting the formation of a predominant proportion of manganese oxide on the surface. Like
wise, Hada et al. [275] have studied the effect of
thermal treatment on the phosphatability of the uncoated side of one-side painted steel. When heated
for 2 min. at 280 C, the crystal size and the coating weight were increased and the P ratio was declined causing an inferior paint adhesion. On the
other hand when heated for a longer period there
results the diffusion of manganese from the bulk to
the surface thus improving the phosphatability.

The influence of cold-rolling and the conditions
of annealing on the formation of phosphate coatings were studied by several authors [276-278] According to Shimada and Maeda [278], increased deformation during cold-rolling and a high-treatment
temperature favour the phosphate coating formation
with a good surface coverage whereas a rapid rise
in temperature in the heat treatment yields an
unfavourable condition. Cavanagh and Ruble [279]
have showed that tempering treatments following
surface hardening processes has a significant effect on the response of steel to phosphating. Machined surfaces accept phosphate coating very easily and often experience a very high rate of deposition.
3.7.2. Phosphating parameters

The composition of the phosphating solution and
the concentration of its constituents determine the
nature of the coatings formed. Higher concentrations of heavy metal ions in accelerated phosphating solutions yield coatings of better protective value
[280]. Concerning the acidity of the bath, the free
acid value (FA), total acid value (TA) and their ratio
(FA:TA) should be maintained at the required optimum level to obtain coatings of improved quality.
Increase in total acid pointage generally produce
coatings of higher coating weight and the free acid
value is considered to be critical since the initial
etching attack of the free phosphoric acid present
in the bath forms the basis of phosphate coating
formation. As the conversion of soluble primary phosphate into insoluble heavy metal tertiary phosphate
takes place with the regeneration of phosphoric acid,
it is believed that a certain amount of free phosphoric acid must be present to repress the hydrolysis
and to keep the bath stable for effective deposition
of phosphate coating. Higher temperatures favour
easy precipitation of tertiary phosphates in a shorter
time. Hence, more amount of phosphoric acid is
needed for the baths operating at higher temperatures. In contrast, in the case of phosphating baths
operated at room temperature, the possibility of the
increase in acidity during continuous operation is
more likely [129,130] and is normally neutralized
by the addition of the carbonate of the metal, which
forms the coating (Zinc carbonate in zinc phosphating bath). Hence, depending upon the working temperatures and the concentration of the constituents
in the bath, the free phosphoric acid content must
be chosen to maintain the equilibrium conditions.
Too much of phosphoric acid not only delays the
151
formation of the coating, but also leads to excessive metal loss.

Literature reports have revealed the effects of
insufficient metal dissolution as well as the high
acidity of the phosphating bath [281,282]. According to Kanamaru et al. [281] when the dissolution of
iron from the steel during phosphating is insufficient,
the hopeite epitaxial growth plane conforms to the
phosphophyllite epitaxial growth plane (100) and
mixed crystals with a high Zn/P ratio grow along
the steel surface whereas when the dissolution is
sufficient, the iron concentration in the solution increases, the intrinsically free precipitation of
phosphophyllite without the restraint of epitaxy becomes predominant and phosphate crystals with a
lower Zn/P ratio grow. However, when the acid concentration is very high, the phosphated material was
found to be susceptible to hydrogen embrittlement.
The effect is compounded if the exposure time is
also increased and it is generally believed that even
the relief treatments that are normally practiced are
not effective when the acid concentration is abnormally high [282]. Hence, it is clearly evident that
the acid coefficient must be maintained properly to
produce good quality coatings. Usually, baths of
higher acid coefficients form more fine-grained coatings. The conversion ratio, defined as the ratio of
amount of iron dissolved during phosphating and the
corresponding coating weight [31] is considered to
be important as they can predict the efficiency of
the phosphating process. However, the inability to
generalize its definition for many phosphating baths
limits its acceptance as a control parameter in phosphating operations [283].
El-Mallah et al. [284] have considered the pH of
the bath as initial pH and the pH at which the consumption of all the free phosphoric acid completes
as the final pH and correlates the difference between
them with the extent of phosphatability. According
to them, reducing the difference between the initial
and final pH leads to the acceleration of the phosphating process and in causing such an effect the
heavy metals and reducing agents such as hydrazine, potassium borohydride were evaluated. Several additives have been attempted to maintain the
pH of the phosphating baths. In this respect, organic acids and their salts proved their ability to
buffer the pH of an iron phosphating bath made up
with hard water [285]. Similarly, the decrease of the
total and free acidity by means of some buffer additives to prevent any significant dissolution of zinc
coating during the phosphatization of zinc coated
steels.
152
The concentration of the accelerators is also very
important. Though increase in accelerator concentration favours better coating formation, too high concentration may cause passivation of metal surface
and inhibit the growth. When phosphating bath is
modified by the addition of surface active agents,
the concentration of accelerator should be optimized
in accordance with the influence of these additives
[286]. The iron content of the bath is also very critical. Although, a small quantity of iron salts favour
phosphate precipitation (Break-in of the bath), the
corrosion performance is largely affected as the fraction of the ferrous salts in the coating is increased
[287]. The unfavourable effect of Fe(II) is usually
decreased by the addition of complexing agents like
Trilon B [288]. A method for controlling the iron content of zinc phosphating bath was proposed by Hill
[289]. In the case of an iron phosphating bath, the
ratio of ferrous to ferric iron in solution has been
related to the tendency for flash rusting. The frequency and intensity of flash rust increases as the
ratio of ferrous to ferric iron in solution decreased
[290].
Addition of specific compounds to the phosphating baths has also their own influence on phosphating. The incorporation of calcium ions in a zinc phosphating bath has resulted in a considerable change
in the crystal structure, grain-size and corrosion
resistance of the phosphate coatings. In fact, the
structure of the zinc phosphate coating changes
from the phosphophyllite-hopeite to schlozite-hopeite
[291]. The reduction in grain-size (25 m to 4 m)
and the improvement in the compactness of the
coating and corrosion resistance, makes this kind
of modification of zinc phosphating baths as an important type of phosphating and it has been classified as calcium-modified zinc phosphating [172].
Similarly, the inclusion of manganese and nickel
ions in the zinc phosphating bath proves to be useful in refining the crystal size and improving the corrosion resistance of the resultant phosphate coatings. It has been established that manganese and
nickel modified zinc phosphate deposits on steel
have an ordered structure and possess a high corrosion resistance [292]. The immense use of manganese and nickel ions in modifying the hopeite
deposits obtained on galvanized steel in such a way
that the modified hopeite deposit becomes equivalent to phosphophyllite to withstand the thermal and
chemical aggressions, was very well established
[293] and as a result of such a pronounced influence of the nickel and manganese ions, they have
also been classified as nickel and manganese modi-

fied zinc phosphating [172]. Moreover, such modifications have lead to the development of tri-cation
phosphating baths consisting of zinc, manganese
and nickel ions which explored its potential utility
to phosphate aluminum, steel and galvanized steel
using the same formulation [294-296]. Besides
these major types of modifications, phosphating
baths have experienced a variety of additives incorporated in the bath intended for a specific purpose.
Each additive has its own influence on the
phosphatability of steel depending upon the operating conditions [297-301]. Sankara Narayanan et al.
[41] have classified the type of special additives used
in phosphating and the purpose of their use. The
favourable condition and the precautions in using
these additives were recommended in the respective documents.
Every phosphating bath reported in literature has
a specific operating temperature and the baths were
formulated in such a way that an equilibrium condition of the conversion of soluble primary phosphate
to insoluble tertiary phosphate exists at that temperature. Insufficient reach of temperature does not
favour the precipitation of tertiary phosphate resulted
from the conversion. However, when the baths were
overheated above the recommended operating temperature, it causes an early conversion of the primary phosphate to tertiary phosphate before the
metal has been treated and as a result increases
the free acidity of the bath, which consequently
delays the precipitation of the phosphate coating.
Hence, in an operating line, which has operating
time, this effect leads to the production of phosphate coatings with a poor coating weight and inferior corrosion performance. Sankara Narayanan and
Subbaiyan [302] have discussed the decisive role
of overheating the phosphating baths and outlines
the possible way of eliminating the difficulties encountered due to this problem.
Likewise, every formulation has been assigned
a fixed operating time based on the kinetics of the
phosphating process using the particular bath followed by coating weight measurements or potential measurements with respect to the treatment
time. It has been established by many workers that
increasing the treatment time beyond the saturation point do not have any influence on the performance of the coating. But it has been warned that
any attempt of reducing the treatment time to decrease the amount of phosphate deposition will be
disasters.
The method of deposition of phosphate coating
or the phosphating methodology can influence the

coating formation to a great extent. The most commonly used methods of deposition namely the dip
and spray process, although have received considerable attention, it is believed that the dip process
is most likely to produce an equiaxed structure
which is consider to be beneficial from the corrosion protection point of view. The influence of permanent magnetic field during phosphating is studied by Bikulcius et al. [303]. According to them,
when exposed to perpendicular magnetic field, the
zinc phosphate coating results in larger crystallites
with lower corrosion resistance whereas the effect
of parallel magnetic field is insignificant. However,
the application of a magnetic field either in perpendicular or parallel mode results in a fine-grained,
uniform and more compact zinc calcium phosphate
coating.
Electrochemical method of phosphating always
yields a heavy coating weight [148,304]. In recent
years, studies have been attempted in electrochemical phosphating to produce phosphate coatings
richer in a particular phase by selecting an appropriate applied potential [147]. The success of this
kind of phosphating methodology has been restricted by the difficulties encounter in adding
electrics to the existing process plants. Mechanical vibration of steel during phosphating is considered as a method for obtaining a fine grained phosphate coating. However, the amount of coating
formed is found to be inversely proportional to the
frequency of vibration [305]. Ultrasonically induced
cavitation produces a great number of active centres, which results in a high rate of nucleation. This
leads to a uniform fine-grained phosphate coating
with low porosity [307,308].
3.8. Processing problems and

remedial measures
Maintenance of the bath parameters and operating
conditions at an optimum level is a major and complicated process, especially in continuous and largescale phosphating. In actual practice, the finishers
have come across several situations that the bath
is not working properly. These problems viz., overheating of the bath, creation of an excess acidity at
the metal/solution interface especially in the case
of cold phosphating, change in acidity of the bath
due to carryover of the alkaline solution used for
degreasing, the local increase in acidity due to the
scaling of the heating coils and so on, were discussed elsewhere [129, 302]. Moreover, baths that
have been used for a long time are rendered ineffective due to the formation of sludge of ferric phos-
153
phate. Sludging occurs to a greater extent in

unaccelerated and highly acidic baths and has to
be removed periodically to assure proper bath operation [18,19]. In order to maintain bath parameters
and to enhance bath life, make-up solutions and
solids are usually required. These additives are so
formulated that they can be handled easily and are
inexpensive.
3.9. Defects in coatings and remedies

The most commonly encountered defects in phosphated parts are low corrosion resistance, stained
coating with variable corrosion resistance and coatings covered with a loose white powdery deposit.
The possible cause for these defects are insufficient
care in degreasing and cleaning, incorrect acid coefficient, incorrect solution composition, use of incorrect operating conditions, incorrect maintenance
of chemicals, excessive sludge formation and faults
in after-treatment. These causes, either singly or in
combination, lead to these defects.
Low corrosion resistance of coatings may be a
result of incorrect acid coefficient, incorrect bath
parameters and operating conditions, presence of
certain metallic impurities like aluminium, antimony,
tin and lead compounds and the presence of chloride ions in the bath. Improper sealing and abnormally thin coatings may also lead to inferior corrosion resistance. Stained coatings may be formed
due to improper cleaning and degreasing. Incorrect
distribution of articles in the phosphating bath and
wrong ratio of work surface to solution volume may
be other causes. Over heating of the phosphating
bath, make-up during processing, heavy sludging
and sludge suspended in the bath leads to the formation of coatings with a loose powdery deposit.
Proper cleaning and degreasing, correct maintenance of work surface to solution volume ratio,
control of bath parameters and operating conditions
within the strict limits, avoidance of overheating and
excessive sludge formation will yield coatings of consistent good quality and corrosion resistance.
3.10. Characterization of phosphate

coatings
A variety of instrumental methods, which include,
scanning electron microscopy (SEM), electron probe
microanalysis (EPMA), X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electron spin resonance
(ESR), X-ray fluorescence (XRF), extended X-ray
absorption fine structure (EXFAS), Fourier transform
154
infra red spectroscopy (FTIR), Raman spectroscopy,
differential thermal analysis (DTA), differential scanning calorimetry (DSC), secondary ion mass spectrometry (SIMS), atomic force microscopy (AFM),
glow discharge optical emission spectrometry
(GDOES), quartz crystal impedance system (QCIS),
conversion electron Mossbauer spectrometry
(CEMS), acoustic emission (AE) testing, etc. were
used to characterize phosphate coatings [308-340].
SEM is the most commonly and widely used
technique for characterizing phosphate coatings. It
is used to determine the morphology and crystal
size of phosphate coatings. SEM serves as an effective tool to study the nucleation and growth of
the phosphate coatings and makes evident of the
fact that the initial growth of the phosphate coating
is kinetically controlled and at a latter stage it tends
towards mass transport control [322]. SEM also
substantiates the fact that preconditioning the substrate before phosphating enables the formation of
a fine-grained and adherent phosphate coating.
EPMA is used in the determination of the porosity of phosphate coatings in which the number of
copper spots deposited in the pores following immersion in copper sulphate solution (pH 5.0) [323].
XRD is primarily used to detect the phase constituents present in phosphate coatings the
phosphophyllite and hopeite phases in zinc phosphate coating. Though the manganese and nickel
modification of zinc phosphate coating reveals only
the presence of hopeite phase, there observed to
be significant variations in the orientations of the
hopeite crystals as evidenced by the relative intensities of the H(311), H(241) and H(220), H (040)
peaks. XRD is also used to characterize phosphate
coatings in terms their P ratio.
Van Ooij et al. [324] applied high resolution Auger electron spectroscopy (AES) in combination with
energy dispersive X-ray spectrometry (EDX) to study
the nature of chromium post passivation treatment.
According to them, Cr(III) was not detected at the
metal/phosphate boundry but on the surface of phosphate crystals and that the Fe/Zn ratio was increased
in the surface and subsurface layers.
XPS is used to detect the nature of various species in phosphate coating. The presence of fatty
acid-like contaminants on the metal substrates can
be identified from the C 1s spectra. Similarly, the
Zn 2p3/2 and P 2p spectra enable identification of
Zn3(PO4)2. Besides, the formation of ZnO or Zn(OH)2
and NaHPO4 could be identified from the Zn 2p 3/2
and P 2p spectra, respectively. The Fe 2p3/2 will give
an idea about the presence of Fe2O3 and FePO4 in

the coating [187]. Cu 2p spectra obtained from the
sample phosphated using a solution containing 1
ppm of Cu2+ ions show two components at binding
energies 933.6 eV and 932.2 eV [325]. The former
signifies Cu2+, although the latter could arise from
either Cu+ or Cu metal. All evidence supports the
Cu deposition occurring during the phosphating process.
ESR is used to confirm the modified structure of
hopeite films formed on the surface of pre-treated
steel sheets. The zinc phosphate film formed from
the bath that does not contain manganese or nickel
ions exhibits no ESR signal. This is because ESR
could only detect paramagnetic transition metal ions
with an unpaired electron whereas in zinc phosphate
coating the ten electron spins of zinc (II) metal ions
(3d10) in the d orbitals are paired with one another.
However, ESR detects the manganese and nickel
components in the modified zinc phosphate coating and proves that manganese and nickel exist as
Mn(II) and Ni(II) in these coatings [316].
XRF is used to determine the nature of nickel in
nickel modified zinc phosphate coating. The XRF
spectrum obtained for metallic nickel is compared
with that of the modified zinc phosphate coating.
The Ni L peak of metallic nickel occurs at 34.18
whereas the Ni L peak of the nickel component of
modified phosphate coatings occurs at 34.06, indicating that the nickel component in the films is
not in the metallic state [316].
EXFAS was used to assess the crystal structure of manganese modified zinc phosphate coating [318]. The radial distributions of the first
neighbouring atoms appeared at a distance of 0.146
nm for unmodified hopeite and at 0.144 nm for manganese modified hopeite. This decrease is due to
the disorderness of modified zinc phosphate coating following the introduction of manganese. EXFAS
study also confirms that the manganese component is substituted for zinc component in the octahedral structure.
SIMS was used to detect the presence of titanium, which are adsorbed on to the metal surface
and act as sites for crystal nucleation [313].
The crystal structure of hopeite and phosphophyllite are hydrated. So once heated, dehydration
reactions are expected to occur. Differential thermal analysis (DTA) performed on phosphate coatings shows that there is a clear disparity in the dehydration process of these two phases as evidenced
by a 50 C difference in temperature in the endothermic peaks corresponding to hopeite and
phosphophyllite phases. In the case of nickel and
Fig. 7. Thermal behaviour of zinc phosphate crystals as hopeite and phosphophyllite studied by differential thermal analyzer: Curve A: Unmodifed
hopeite; Curve B: Hopeite with 1.8 wt.% Ni + Mn;
Curve C: Hopeite with 5.6 wt.% Ni + Mn; Curve D:
Phosphophyllite) (Reprinted from Surface & Coatings Technology, Vol. 30, N. Sato, Effects of heavy
metal additions and crystal modification on the zinc
phosphating of electrogalvanized steel sheet, pp.
171-181 (1987) with permission from Elsevier Science).
manganese modified zinc phosphate coatings the

temperature of the endothermic peaks shifts to higher
temperatures and becomes equivalent to the endothermic peak of phosphophyllite (Fig. 7) [326].
DSC is used to assess the thermal behavior of
phosphate coatings. Manganese and nickel modified zinc phosphate coatings formed on steel and
electrozinc coated steel, in the as deposited condition, show strong endothermic peaks at temperatures below 175 C associated with the loss of water molecules from the phosphate. On the other hand
the DSC traces obtained for these phosphate coatings after stripping the cured paint film exhibit no
strong endothermic peak over the temperature range
up to 200 C, confirming that under paint stoving
conditions the more labile water molecules have
been stripped from the phosphate coating (Fig. 8)
[313].
155
Fig. 8. DSC curves of nickel and manganese modified zinc phosphate coating formed on (a) steel and
(b) electrozinc coated steel. Solid line represents
before stoving and broken line represents after
stoving and removal of paint. (Source: R.A.
Choudhery and C.J. Vance in Advances in Corrosion Protection by Organic Coatings, D. Scantelbury
and M. Kendig (Eds.), The Electrochemical Society, NJ, 1989, p.64. Reproduced by permission of
The Electrochemical Society, Inc.).
DSC also proves the ability of nickel and manganese modified zinc phosphate coating in resisting the rehydration compared to unmodified zinc
phosphate coating. Unmodified zinc phosphate coatings obtained on zinc coated steel exhibit two endothermic peaks at 103 and 135 C with a total heat
flow of 100 J/g. After exposure to 100% RH for 63
hours, these endothermic peaks appear again, with
a slight shift in peak temperature towards higher
temperatures, indicating that the unmodified zinc
phosphate coating is completely rehydrated (Fig.
9). In contrast, manganese and nickel modified zinc
phosphate coating exhibit a much stronger resistance to the redhydration process when subjected
156
Fig. 10. DSC curves for nickel and manganese

modified zinc phosphate coating. Solid line represents before stoving and broken line represents after stoving and subsequent rehydration. (Source:
R.A. Choudhery and C.J. Vance in Advances in
Corrosion Protection by Organic Coatings, D.
Scantelbury and M. Kendig (Eds.), The Electrochemical Society, NJ, 1989, p.64. Reproduced by
permission of The Electrochemical Society, Inc.).
Fig. 9. DSC curves of unmodified zinc phosphate

coating (a) before stoving; and (b) after stoving and
rehydrated at 100%RH for 63 hours. (Source: R.A.
Choudhery and C.J. Vance in Advances in Corrosion Protection by Organic Coatings, D. Scantelbury
and M. Kendig (Eds.), The Electrochemical Society, NJ, 1989, p.64. Reproduced by permission of
The Electrochemical Society, Inc.).
to similar conditions (Fig. 10) [313]. The main limitation of DSC is that the phosphate coating has to
be physically removed from the substrate.
Handke has demonstrated the use of FTIR to
study the mechanism of phosphate coating formation [327]. FTIR is sufficiently sensitive to distinguish between different types of coatings in terms
of composition and crystallinity [313]. FTIR is also
sensitive to the degree of hydration of phosphate
coatings. The FTIR spectra of nickel and manganese modified zinc phosphate coating on cold rolled
steel (CRS) and zinc coated steel (ZCS) under conditions namely, before heating, after stoving at 180
C for 20 minutes and after exposure to 100% RH
for 14 days was analyzed (Figs. 11 and 12). The
assignments of the FTIR spectra for CRS and ZCS
are given in Tables 8 and 9, respectively. The FTIR

spectra of phosphate coatings on CRS and ZCS
are similar before heating. On heating there are significant changes in the FTIR spectra of ZCS while
the changes for steel are less noticeable. On exposing to 100% RH it is evident that phosphate coatings formed on ZCS shows greater tendency to rehydrate, indicated by the increase in intensity of all
peaks associated with water vibrations. On the other
hand phosphate coating formed on CRS exhibit very
little tendency to rehydrate; the spectrum essentially remains constant.
The infrared and Raman spectra of -hopeite and
phosphophyllite are shown in Figs. 13-15 [341]. They
resemble the room temperature spectra reported by
Hill and Jones [342] and Hill [343]. The infrared and
Raman spectra of both compounds display a large
number of bands. In addition, the infrared and Raman
spectra of these compounds resemble each other
very strongly. Hence distinction of the respective
peaks in phosphate coatings is not easy. However,
there are some peaks, which are different for these
compounds, are useful in identifying these compounds. For example the Raman bands at 1150,
1055 and 310 cm-1 are typical for -hopeite whereas
the Raman bands at 1135, 1070 and 118 cm-1 are
useful for identifying phosphophyllite in phosphate
coating.
157
Table 8. The assignments of the FTIR spectra of nickel and manganese modified zinc phosphate coating
on cold rolled steel (after Choudhery and Vance [313]).
Wavenumber
(cm-1)
Shape/Intensity
Assignment
Before heating
for 20 minutes
3536
3214
1643
1145
Sharp/Strong
V. broad/Strong
Sharp/Medium-St
W. Sharp/Strong
Free O-H
OH/H2O stretching
H2O bending
P-O stretching
1121
Sharp/Strong
P-O stretching
1080
Sh./Strong
P-O stretching
1020
Sharp/Strong
P-O stretching
997
933
643
Sharp/Strong
Sharp/Strong
Sharp/Medium
H2O rocking
P-O stretching
O-P-O bending/
H2O waging
The influence of metal components in hopeite

films was investigated using Infrared and Raman
spectra [243]. The IR spectra of hopeite films exhibit peaks at 3500 to 3000, 1640, 1200 to 900 and
640 cm-1. The peaks at 3500 to 3000 cm-1 correspond to the stretching vibration of O-H in H2O, the
peak at 1640 cm-1 to the deformation of H-O-H in
H2O and the three peaks at 1200 to 900 and that at
640 cm-1 to PO43- in the hopeite films. There are four
basic vibrations for PO43-, namely, 1, 2, 3 and 4 in
which 1 and 2 are inactive in IR absorption whereas
3 and 4 are active. Hence the three peaks at 1200
to 900 cm-1 correspond to the 3 mode and that at
640 cm-1 to the 4 mode. A comparison of the IR
spectra of nickel and manganese modified hopeite
with unmodified hopeite indicate that the incorporation of nickel and manganese into the hopeite films
After stoving
at 180 C
Lost
Broadens
Shifts to 1629
Shoulder 1170
appears
and shoulder at
1082 now a peak
Shoulder 1170
appears and
shoulder at 1082
now a peak
Shoulder 1170
appears and
shoulder at 1082
now a peak
Shoulder 1170
appears and
shoulder at 1082
now a peak
Lost
Broadens
After exposure
to 100%
RH for 14 days
All peaks
similar to stoved
sample with
only a slight
increase in peak
height
affects the coordination state of PO43- and cause

splitting or shifting of peaks. The three peaks at
1200 to 900 cm-1 corresponding to the 3 mode of
hopeite film shows splitting and the peak at higher
wavenumber is shifted by 10 cm-1 towards the lower
wavenumber. The 4 peak of nickel and manganese
modified hopeite generates a new peak at 580
cm-1.
Laser Raman spectra of hopeite films exhibit four
peaks in the region between 1150 and 930 cm-1,
with the main peak appearing at 996 cm-1. These
four peaks are due to PO43-, which has four basic
vibration modes 1, 2, 3 and 4, all of them are
Raman active. If the PO43- in the hopeite film exists
as a perfect regular tetrahedron, then only peaks of
1 and 3 should appear. But in practice, there are
four peaks. PO43- in hopeite films affects the sym-
158
Table 9. The assignments of the FTIR spectra of nickel and manganese modified zinc phosphate coating
on zinc coated steel (after choudhery and vance [313]).
Wavenumber
(cm-1)
Shape/Intensity
Assignment
Before heating
for 20 minutes
3545
3290
1635
1135
Sharp/Strong
V. broad/Strong
Sharp/Strong
Sh./Strong
Free O-H
OH/H2O stretching
H2O bending
P-O stretching
1098
Sharp/Strong
P-O stretching
1069
Sharp/Strong
P-O stretching
1026
Sh./Strong
P-O stretching
1003
925
638
Sharp/Strong
Sharp/Strong
Sharp/Medium
H2O rocking
P-O stretching
O-P-O bending/
H2O waging
metry of the regular tetrahedron structure by interaction with the surrounding crystalline structure so
that the symmetry will become distorted. As a result, the degeneracy of the vibration modes will be
united and split and hence results in four peaks.
Three peaks, except for the main peak, correspond to the stretching vibration mode of 3, which
split into three peaks; the main peak around 900
cm-1 corresponds to the symmetrical stretching vibration of 1. The level of interaction of PO 43- with its
surroundings affects the number of basic vibrations,
the Raman band or the intensity of the Raman spectrum. With the incorporation of manganese or nickel
in the hopeite films, the Raman band of the main
peak as well as the three peaks of 3 are shifted to
a lower wavelength. Increasing the metal content in
hopeite films has an increasing effect on the data of
After stoving
at 180 C
Lost
Broadens
Shifts to 1649
Shoulder 1184
appears and
shoulder at 1026
now a peak
Shoulder 1184
appears and
shoulder at 1026
now a peak
Shoulder 1184
appears and
shoulder at 1026
now a peak
Shoulder 1184
appears and
shoulder at 1026
now a peak
Lost
Broadens
After exposure
to 100%
RH for 14 days
Water stretching
peaks intensify.
Spectrum begins
to resemble the
one obtained for
sample before
heating
Raman band. Raman spectra showed a sensitivity

to the degree of modification of hopeite films by metal
components to a greater extent than did IR spectra.
AFM is used to study the effect of surface preconditioning on phosphatability of zinc coated steel.
AFM is useful in getting a better understanding of
the activation process [328].
Quartz crystal impedance system (QCIS) was
used to study the formation of phosphate coating
from a manganese modified low-zinc phosphating
bath [329]. It involves rapid and simultaneous measurement of admittance spectra of the zinc coated
piezoelectric quartz crystal resonator (PQC). By
measuring the equivalent circuit parameters and frequency shift of the zinc coated PQC resonator, the
growth kinetics of the phosphating process can be
159
Fig. 11. FTIR Spectra of nickel and manganese modified zinc phosphate coating formed on steel. (a) Full
range; and (b) Selected range. The top, middle and bottom spectra represent before stoving, after stoving
and after stoving with subsequent rehydration, respectively. (Source: R.A. Choudhery and C.J. Vance in
Advances in Corrosion Protection by Organic Coatings, D. Scantelbury and M. Kendig (Eds.), The Electrochemical Society, NJ, 1989, p.64. Reproduced by permission of The Electrochemical Society, Inc.).
Fig. 12. FTIR Spectra of nickel and manganese modified zinc phosphate coating formed on zinc. (a) Full
range; and (b) Selected range. The top, middle and bottom spectra represent before stoving, after stoving
and after stoving with subsequent rehydration, respectively. (Source: R.A. Choudhery and C.J. Vance in
Advances in Corrosion Protection by Organic Coatings, D. Scantelbury and M. Kendig (Eds.), The Electrochemical Society, NJ, 1989, p.64. Reproduced by permission of The Electrochemical Society, Inc.).
160
Fig. 13. Infrared spectra of -hopeite and phosphophyllite in the region 40001400 cm-1 (Reprinted
from Spectrochimica Acta Part A, Vol. 57, O.
Pawlig, V. Schellenschlager, H.D. Lutz and R.
Trettin, Vibrational analysis of iron and zinc phosphate conversion coating constituents, pp. 581-590
(2001) with permission from Elsevier Science).
Fig. 14. Infrared spectra of -hopeite and phosphophyllite in the region 1200100 cm -1 (Reprinted
from Spectrochimica Acta Part A, Vol. 57, O.
Pawlig, V. Schellenschlager, H.D. Lutz and R.
Trettin, Vibrational analysis of iron and zinc phosphate conversion coating constituents, pp. 581-590
(2001) with permission from Elsevier Science).
monitored. QCIS is also used to measure the change

in viscoelasticity of zinc phosphate coatings, which
decreases with increase in phosphating time and
the concentration of sodium nitrite [330].
The utility of GDOES in the analysis of phosphate coatings has been attempted by several authors [331-334] and phosphate coatings deposited
on cold-rolled, hot-dipped galvanized, galvanneled,
electrogalvanized and Zn-Ni or Zn-Fe electroalloycoated sheets were characterized. It has been reported [331] that the profiles of the elemental distribution throughout the film thickness can be obtained
with high sensitivity. GDOES provides more detailed
information on the constituent elements, depth, di-
rection and the crystal growth process than conventional chemical and X-ray methods. Quantification of the results has also been attempted in the
case of GDOES based on the integrated intensity
of the constituent elements. Maeda et al. [331] have
suggested the possibility of utilizing this method for
quantitative determination, after establishing a linear relationship between integrated intensity and
coating thickness of phosphorus and nickel.
GDOES is considered to be the most appropriate
method for depth profiling thick phosphate coatings
[335]. GDOES due to its higher detection sensitivity compared to XPS, confirms the adsorption of
titanium phosphate on zinc coated steel [328].
161
ure between the phosphophyllite and hopeite. Hence

it is evident that with the help of AE testing it is
possible to detect the onset of a process such as
cracking of the coating and/or adhesion failure and
the extent to which these failures shall occur.
3.11. Testing the quality of phosphate

coatings
Methods to evaluate the quality of phosphate coatings involve the determination of its physical characteristics as well as the performance in corrosive
environments. Kwiatkowski et al. [344] have reviewed
the testing methods of phosphate coatings.
Fig. 15. Raman spectra of -hopeite and phosphophyllite in the region 1300100 cm-1 (Reprinted
from Spectrochimica Acta Part A, Vo. 57, O. Pawlig,
V. Schellenschlager, H.D. Lutz and R. Trettin, Vibrational analysis of iron and zinc phosphate conversion coating constituents, pp. 581-590 (2001) with
permission from Elsevier Science).
AE is also used as a tool to characterize phosphate coatings [336-340]. Phosphate coating exhibit only a single peak during AE in a ring-down
count-rate against strain curves. The amplitude distribution verses events curve recorded for steel/phosphate systems at a strain rate of 10 percent showed
emissions with amplitudes only below 40 dB. Rooum
and Rawlings [338, 339] have shown that it is possible to assign the source of failure mechanism to
the peaks of amplitude distribution. Each failure
mechanism was characterized by events centred
on specific amplitudes. In their study they attribute
the peak at 22 dB to the cracking of the hopeite
needles and the peak at 26 dB to the adhesion fail-
3.11.1. Evaluation of physical characteristics

(a) Examination of physical appearance. Phosphate
films on steel may range in colour from light gray
to dark gray, depending on the type of bath and
the grade of steel substrate used. After sufficiently strong scratching of phosphate coating
with a fingernail, a white scratch should appear
on the surface without causing an injury to the
coating visible to the naked eye.
(b) Determination of coating thickness and coating
weight. The local thickness of phosphate coatings on steel is usually determined by magnetic,
electromagnetic and microscopic methods
[18,19,127,128]. The average thickness is usually expressed in g/m2 or mg/ft2. Destructive
methods of determination of coating weight are
widely adopted. These methods involve the determination of change in weight of a coated specimen after dissolution of the coating in a suitable
medium. Concentrated hydrochloric acid containing 20 g/l of antimony trioxide is usually used at
room temperature for this purpose. Other solutions commonly used are 5% solution of chromic acid at room temperature and 20% sodium
hydroxide at 90 C. The difference in weight after coating removal is divided by the surface area
of the work in m2 to obtain unit coating weight in
g/m2.
(c) Determination of acid resistance. It is calculated
as the difference in weight per unit area of the
panel before phosphating and after stripping off
the coating; and is expressed in g/m2.
(d) Testing of physical properties. The absorption
value and hygroscopicity are the important parameters relating to the physical properties of
the phosphate coating. Evaluation of the absorption value of the phosphate coating involves the
measure of the gain in weight per unit area when
subjected to immersion in diacetone alcohol for
162
two minutes and allowed to drain the excess for
three minutes [345]. The gain in weight of the
phosphated panels, when subjected to a humid
atmosphere in a closed container at room temperature for six hours, gave the hygroscopicity
of the coating [345].
(e) Estimation of porosity. Estimation of the porosity of the phosphate coating involves both chemical and electrochemical methods. The chemical (Ferroxyl indicator) method was based on
formation of blue spots (Prussian blue) on a filter paper dipped in potassium ferricyanide - sodium chloride - gelatin mixture when applied over
the phosphated surface for one minute. The number of blue spots per sq. cm gives a measure of
the porosity of the coating. The electrochemical
method of determination was based on the measurement of the oxygen reduction current density when immersed in air-saturated sodium hydroxide solution (pH 12). The current density
values measured at -550 mV, where oxygen reduction is the dominant reaction at the uncoated
areas reveals the porosity of the coating
[209,210]. Although, both the Ferroxyl test and
the electrochemical test are used in an industrial scale to assess the porosity of phosphated
steel, the former method is found to be qualitative and not very effective in distinguishing the
porosities of panels phosphated using different
baths. In contrast, the electrochemical method
is far reliable besides its simplicity in operation
and quicker measurements of the porosity. The
advantage of the electrochemical method has
been discussed elsewhere [209, 346].
(f) Determination of thermal and chemical stabilities. The thermal stability of the coating was usually determined by calculating the percentage
loss in weight when the phosphated panels were
subjected to drying at 120 and 180 C.
The chemical stability of the coating, in particular, the alkaline stability is very important as it
determines the effectiveness of the phosphate
coating as a base for cathodic electrophoretic
finishes. This is determined by calculating the
percentage residual coating when immersed in
alkaline media. Immersion in sodium hydroxide
solution is recommended to test the alkaline
stability. Recently, Kwiatkowski et al. [347] have
recommended a borate buffer solution containing 0.01M EDTA as the medium to test the alkaline stability of the coating and proved its usefulness in predicting the same. A similar calculation of the percentage residual coating when

subjected to immersion treatments in buffered
solutions of varying pH from 2-14 can give an
insight about ability of the phosphate coatings
to withstand different chemical aggressions and
to prove their effectiveness in preventing the cosmetic corrosion [219].
(g) Evaluation of surface morphology. The surface
morphology of the phosphate coating is usually
assessed by scanning electron microscope
(SEM). This technique reveals the distinct features of the crystal structure, grain size of the
crystallites, the coating coverage and uniformity;
the parameters that determine the performance
of the coating.
(h) Determination of P ratio. The P ratio is usually
determined by measuring the intensity of the
characteristic planes of the constituent crystallites of the phosphate coating. In a zinc phosphate coating, which consists essentially of
hopeite (Zn3(PO4)2.4H2O) and phosphophyllite
(Zn2Fe(PO4)2.4H2O), the P ratio is defined as
[199]:
P ratio =
P
P+H
Where P Intensity of the characteristic planes

of phosphophyllite and H
Intensity of the
characteristic planes of hopeite.
(i) Adhesion measurements. The standard laboratory method of estimation of adhesion is the peel
off test, which involves the determination of the
extent of adhesion at scribed areas using a pressure sensitive adhesive tape. Usually adhesion
in the dry state will be good since it mainly depends on the cohesive failure of the paint film.
Wet adhesion is of prime importance and is usually determined after subjecting the painted panels to immersion treatment in de-ionized water
at 45 C for 240 hours. Depending upon the extent of peeling, rating will be made between 0
and 5B as per ASTM D 3359-87 [348].
3.11.2. Evaluation of corrosion performance
(a) Rapid preliminary quality control tests. Preliminary investigation of coating quality for on-line
monitoring mainly involves two empirical tests
of which one involves inspection for rust spots
after immersion in 3% sodium chloride solution
for 5-30 minutes and the other is concerned with
the time taken for metallic copper deposition from
a copper sulphate-sodium chloride-hydrochloric
acid mixture.
(b) Laboratory corrosion resistance tests. The most
frequently used laboratory tests for evaluating

the corrosion resistance of phosphate coatings
include (i) immersion test, (ii) salt spray (fog)
test, (iii) humidity test and (iv) A.R.E. salt droplet test.
(i) Immersion test. This test consists of determining the time required for the first appearance of
corrosion on the basis metal when immersed in
3% sodium chloride solution. The change in
weight expressed as g/m2 for every 24-hour period of immersion is also determined and correlated to the corrosion resistance of the coating.
(ii) Salt spray test. Evaluation of corrosion resistance of the phosphated and finished panels is
performed by subjecting them to a salt mist of
5% sodium chloride solution in a salt spray
chamber for a specified length of time. The extent of spread of corrosion from a scribe made
on the panel, rated after ASTM B 117-85 specifications, is a measure of the corrosion resistance of the phosphate coating [349].
(iii) Humidity test. This test is used for the evaluation of phosphated panels with and without further finishes. By subjecting the phosphated panels to highly humid conditions (90-95% relative
humidity) at slightly elevated temperatures (4248 oC), assessment of corrosion likely to be induced due to the porosity of the coating can be
made. The extent of blistering of paints due to
the presence of soluble salts on phosphated and
finished panels when subjected for 1000 hours
in the humidity chamber is also related to its
corrosion performance.
163
(iv) A.R.E. salt droplet test. This test consists of

the evaluation of the corrosion resistance of the
phosphated panels by determining the loss in
weight after five days of exposure in humid condition inside a closed cabinet at room temperature with a single spray of synthetic seawater
on each day [350].
(c) Electrochemical methods of testing. The electrochemical methods of testing the phosphate
coating mainly involves the anodic polarization
studies in 0.6M ammonium nitrate [346,351] and
AC impedance measurements in 3% sodium
chloride solution [352-363].
Zurilla and Hospadaruk [209] proposed a method
to assess the porosity of phosphated steel based
on oxygen reduction current density in air saturated
0.1 N sodium hydroxide solution. Since cathodic
reduction of oxygen occurs at the uncoated areas,
the measure of current density values at a fixed
potential (550 mV vs. SCE) reveal the porosity of
the coating. Kiss and Coll-Palagos [355] utilized
cyclic voltammetry to evaluate the porosity of phosphate coatings. Fig. 16 shows the typical cyclic
voltammogram obtained for zinc phosphate coated
steel in 5% sodium chloride solution (pH 6.5; 25
C). The voltammogram can be classified into three
major regions based on the potential values. The
anodic peak observed between 550 mV and 950
mV is believed to be due to the oxidation of Fe, Fe2+
and/or the formation of a complex compound in the
pores of the phosphated steel and its intensity is
Fig. 16. Cyclic voltammogram obtained from zinc phosphate coated steel in 5 wt.% sodium chloride solution (pH 6.5; 25 C) (After Kiss and Coll-Palagos [355]).
164
Fig. 17. Anodic polarization curve obtained for zinc phosphate coated steel in 0.6 M ammonium nitrate.
related to the porosity of the phosphate coating.

Kiss and Coll-Palagos [355] termed this peak as
porosity peak. The peak height at 800 mV or the
integrated area under this anodic peak was used to
predict the porosity.
Anodic polarization study in 0.6 M ammonium
nitrate solution is one of the recommended methods of electrochemical evaluation of corrosion resistance of phosphate coatings (Fig. 17) [346]. During anodic polarization in 0.6 M ammonium nitrate
solution, at potentials more negative than 0.33 V,
phosphated steel undergoes active dissolution.
Above 0.33 V, the first passivation region occurs
due to the adsorption of hydroxide ions at the electrode surface. The occurrence of the second active
region is due to the replacement of hydroxide ions
by phosphate ions available at the electrode/solution interface. Replacement of the adsorbed phosphate ions by nitrate causes the occurrence of the
second passive region. Hence it is clear that these
active and passive regions are the result of the competitive and potential dependent adsorption of anions at the electrode surface. It should be noted
here that the appearance of this second current
density maximum is specific to phosphated steel
and it is not observed for uncoated steel when tested
under similar conditions. Hence the value of the
second current density maximum can be used to

evaluate the corrosion resistance of different phosphate coatings [346].
The other important method of evaluation of the
corrosion resistance of phosphate coatings is the
electrochemical impedance spectroscopy (EIS). It
provides a rapid, nondestructive means of evaluating corrosion rate and mechanism of corrosion of
phosphate coatings. Literature reports on the evaluation phosphate coatings [357-363] suggest that the
corrosion behaviour of phosphate coatings in contact with the corrosive medium (3.5% NaCl) can be
explained on the basis of a porous film model since
the electrolyte/coating-metal interface approximates
such a model. Accordingly, the phosphated substrates are considered as partially blocked electrodes when comes in contact with 3.5% NaCl solution. This implies that the metal substrate is corroding in the same way when unprotected in a much
smaller area where coverage is lacking. Since the
capacitive and resistive contributions vary directly
and indirectly, respectively, with respect to the area,
based on these measured parameters, predictions
on the corrosion rate of different phosphate coatings can be easily made. Fig. 18 shows the Nyquist
plot obtained for zinc phosphate coated steel in 3.5%
NaCl solution exhibiting a semicircle in the high fre-
165
Fig. 18. Nyquist plot obtained for zinc phosphate coated steel in 3.5 wt.% sodium chloride solution.
quency region followed by a linear portion in the low

frequency region. An equivalent electrical circuit
model, which involves charge transfer resistance
(Rct), the double layer capacitance (Cdl) and the
Warburg impedance (Zw) can be proposed to simulate the behaviour of phosphate coating in 3.5% NaCl
solution. The change in the values of these parameters with time gives an account of how the coating
degradation has occurred and helps to establish a
mechanistic pathway. High values of charge transfer resistance and low values of double layer capacitance signify a coating of better performance.
The appearance of Warburg impedance suggests
that corrosion of phosphated steel is a diffusion
controlled. [352-354,362-365].
3.12. Applications
Phosphate coatings have been put to a wide variety
of applications; salient among them is the corrosion protection, as bases for paint, to provide wear
resistance and an aid in cold forming of steel
[18,19,24,127,128,366,367].
Phosphate coatings provide an effective physical barrier to protect corrosion-prone metals against
their environment. Due to their insulating nature, the
phosphate coatings prevent the onset and spreading of corrosion. These coatings provide effective
corrosion protection to ferrous and non-ferrous met-
als alike. The extent to which these coatings provide corrosion resistance is dependent on the thickness and weight of the coating used. However, better corrosion protection can be achieved by finishing these coatings with paints, oils, etc. Phosphate
coatings provide an effective base for the application of paints and this constitutes their most widespread application [368]. They can be used as an
excellent base for more recent methods of paint
applications such as electrophoretic painting and
powder coating [369,370] and shown to improve the
corrosion resistance of steel coated subsequently
with cadmium, zinc, nickel, etc., both in industrial
as well as marine atmospheres [371]. The application of phosphate coating also improves the adhesive bonding of plain carbon steels [372].
The mechanism of pyrite oxidation in acidic media
involves preferential release of iron into the medium.
The phosphate treatment results in the formation of
iron phosphate coating and significantly reduces the
chemical oxidation of pyrite [373]. The formation of
a phosphate layer on the surface of iron powders
induces a significant improvement of the oxidation
resistance in the temperature range of 300-700C
[374]. The oxidation resistance of ultrafine copper
powder is increases by phosphating [375]. Rebeyrat
et al. [376] based on thermogravimetric experiments
suggest that phosphating of bulk -iron significantly
decreases the gain in weight due to oxidation.
166
The NdFeB type magnets are highly susceptible to attack from both climatic and corrosive environments, which result in corrosion of the alloy and
deterioration in both its physical and magnetic properties. The poor corrosion resistance of NdFeB
type magnets in many aggressive environments is
associated with the presence of ~ 35 wt.% of neodymium in their composition. Neodymium, along with
other rare earth (RE) elements belongs among the
most electrochemically active metals. The application of a zinc phosphate coating proved to be a most
useful method to improve the corrosion resistance
of NdFeB magnet [377,378]. The improvement in
corrosion resistance of NdFeB magnet following the
application of a zinc phosphate coating is shown in
Fig. 19.
Phosphating is a widely used method of reducing wear on machine elements and moving parts
[379,380]. Phosphate coatings function as lubricants, in addition their ability to retain oils and soaps
further enhances this action. Heavy manganese
phosphate coatings, supplemented with proper lubricants are most commonly used for wear resistance applications [381]. The manganese phosphates widely used in automotive industry are the
best to improve the ease of sliding and the reduction of associated wear of two steel surfaces sliding
one against the other. The phosphate coatings pos-

sess no intrinsic lubricating properties but can absorb or hold a considerable quantity of lubricant by
virtue of their porosity [382,383]. This combination
favours an easier running-in at higher surface pressures by forming a non-metallic barrier that separates the two metal surfaces and reduces the danger of seizure and associated pitting. There is also
less noise produced at such surfaces and they have
an in-built capacity, in emergencies, to run dry for a
limited period [384]. Phosphating increases the sliding distance to scuffing as well as the scuffing load,
whilst marginally reducing the coefficient of friction.
No advantage was found in phosphating dry sliding
surfaces. Phosphating reduces the likelihood of
adhesive wear in marginal or poorly lubricated sliding couples. The choice of phosphate coating is
primarily dependent on the surface finish of the sliding counterface; thin coatings are suitable for smooth
surfaces whereas against rougher surfaces thicker
coatings are preferred [385].
The power used in deep drawing operations, sets
up a great amount of friction between the steel surface and the die. This will decrease the speed of
drawing operation and the service life of tools and
dies [386,387]. Application of light to medium weight
non-metallic zinc phosphate coating to steel surfaces, which permit the distribution and retention of
a uniform film of lubricant over the entire surface,
Fig. 19. Potentiodynamic polarization curves of NdFeB magnet in 3.5% sodium chloride solution (a) Uncoated NdFeB magnet; and (b) Zinc phosphate coated NdFeB magnet.

prevents metal to metal contact and makes possible the cold forming and extrusion of more difficult
shapes, than is possible without the coating
[85,388-390]. A combination of zinc phosphate and
lubricant film prevents welding and scratching of steel
in drawing operations and greatly decreases the
rejections. Bustamante et al. [391] suggest the
usefulness of pre-phosphate coating of zinc and zinc
alloy coated steel sheet in preventing the damage
during the forming process.
Phosphate coating is used as an absorbent coating in laser surface hardening of steel [392-394].
Although, all the three major type of phosphate coatings, namely, the manganese, zinc and iron phosphate coatings were used as absorbent coatings,
the former was found to be frequently employed in
majority of the cases. Besides these, phosphate
coatings have also been found to be useful as thermal control coatings in satellite components [395].
3.13. Environmental impact

The environmental impact of metal finishing operations is a matter of serious concern and phosphate
pretreatment operation is no exception to this. The
wastes generated from phosphate pretreatment line
can be broadly classified into liquid wastes arising
from acid pickling, alkaline cleaning, rinsing stages
and chromic acid sealing stage, etc. and solid
wastes arising from the sludges formed during phosphating. It is estimated that the total outlet of wastewater is about 20,800 g/m2 and the solid residue
generated in the whole phosphating process is
about 49.0 g/m2. The phosphating process discharges 400 g/m2 CO2- equivalent mass to the environment, which demonstrates that conventional
phosphating, has some green house effect. Fortunately, the influence on human health is not so heavy
since the average local toxic level (LTL) is estimated
to be 1.6 ppm/ppm [396]. Unlike the wastewater
discharge, the environment cannot absorb the solid
residue. The phosphating sludges are generally considered as hazardous waste materials and are,
therefore, subject to strict regulations as to disposal.
It is estimated that fifty million pounds of sludge
results from phosphating operations each year.
Hence it is not only desirable but also mandatory to
identify a means for recovering various sludge components.
Phosphating sludge, in general, has 20 wt.% iron,
10 wt.% zinc, 1-3 wt.% manganese, <1 wt.% nickel
and 50-55 wt.% phosphate (composition on dry
basis). Hence efforts are focused on the recovery of
zinc, iron and phosphate for preparing phosphating
167
solution and/or make-up feed. Among the various

methods proposed for reclaiming phosphating
sludge, pyrometallurgical processing - reduction
sintering processes, for recovering the metals zinc,
iron and nickel in addition to sodium phosphate;
wet chemical processing by leaching constituents
with acids and bases and reusing them in the preparation of phosphating solutions; and digestion with
mineral acids, removal of constituents and their reuse are prevalent.
United States Patent 5,350,517 [397] describes
a process in which the phosphating sludge is digested with nitric acid, the iron is selectively extracted with liquid/liquid extraction and the extract
thus obtained is reused in the preparation of zinc
phosphating solution. The extractant used is monoester of 2-ethylhexyl alcohol with phosphoric acid
in kerosene. The use of mineral acids for extracting
zinc and phosphate ions from the phosphating sludge
and subsequent use of the extract as a phosphating solution is also suggested in the British Patent
1545515 [398]. Besides, this patent also suggests
the possibility of leaching phosphate from the undissolved residue containing iron and phosphate ions
with alkali so that, ultimately, an iron-containing residue remains behind. The phosphate in the alkaline
liquor is precipitated as zinc phosphate and may
also be used for the preparation of phosphating solution.
United States Patent 5,376,342 [399] describes
a process which involves the following stages: (i)
dissolution of the sludge in phosphoric acid; (ii) filtration of undissolved solids; (iii) precipitation and
recovery of iron phosphate; and (iv) addition of requisite metals to the zinc and phosphate containing
aqueous phase and recycling the resultant zinc
phosphate solution to the zinc phosphating operation as a make-up feed. The iron phosphate, which
precipitates in the process, may be used as an
animal feed additive.
Mixing the phosphating sludge with an alkaline
solution, drying the mixture and sintering it at 5001300 C in the presence of a reductant converts
phosphate in the sludge to a water soluble phosphate salt, reduces the zinc and iron to their metallic state and volatizes the zinc from the reaction
zone. Leaching the sintered cake with water recovers the soluble phosphate and the iron [400].
United States Patent 5273667 [401] describes
a process which involves collecting the phosphate
sludge, dewatering using a filtering process, drying
the dewatered sludge at an elevated temperature to
a moisture content of less than 10 wt.% and reduc-
168
ing the particle size of the dried sludge to less than
about 20 mesh. The dried and ground phosphate
sludge has been found to be an excellent lubricant
additive, which is suitable for use in lubricant formulations designed for the metal treatment, metal forming and industrial lubrication.
United States Patent 4986977 [402] suggests a
method for treating the phosphating sludge with an
aqueous base to achieve a pH greater than 10 that
results in precipitation of iron hydroxide. The iron
hydroxide is recovered and the aqueous phase is
acidified to a pH of 7-10 to cause precipitation of
zinc hydroxide.
Baldy [403] suggests that the phosphating
sludge generated from automotive pretreatment process may contain up to 25 wt.% of oil and removal
of oil is essential for the full recovery of all useful
components. The removal of oil is accomplished by
the addition of H2O2 to an acidic dispersion of the
sludge that displaces the oil from the remaining
mixture. According to him, the recovery of zinc phosphate sludge involves the following four stages:
Phase I is the separation of oil from the sludge.
Phase II is the extraction of zinc, manganese and
nickel from the sludge following digestion with phosphoric acid. Phase III is the conversion of the iron
phosphate residue from phase II to pigment grade
iron oxide and sodium phosphate that may be acidified to an iron phosphate concentrate.
The use of phosphating sludge in the process of
clinker production is suggested as one of the possible mode of reclamation of such waste by Caponero
and Tenorio [404]. Their study proves that an addition of up to 7.0% of phosphating sludge to the raw
cement meal of Portland cement did not cause any
damage to the clinkerization process. X-ray diffraction analysis shows that there is no significant modification in the yielded clinker proportional to the
sludge additions, neither is there atypical phases
formed with additions up to 5.0% of phosphating
sludge. Differential thermal analysis of the mixture
with up to 7.0% dry sludge additions does not show
any significant difference from the analysis of the
cement clinker raw meal. Additions of the phosphating sludge up to 5.0% significantly modify only the
zinc content of the clinker that was produced. The
major element of the sludge, zinc, shows an average of incorporation of 75%.
4. SUMMARY
This review outlines the various aspects of phosphating. Although, numerous modifications were
proposed recently, on the deposition technologies

to achieve different types of coatings and desirable
properties such as improved corrosion resistance,
wear resistance, etc., phosphate conversion coating still plays a vital part in the automobile, process
and appliance industries, as it has unique advantages in the cost-wise placement among all the
emerging deposition technologies and pays off the
finisher with a handful of profit.
ACKNOWLEDGEMENT
Financial support given by the Council of Scientific
and Industrial Research, New Delhi, India, is gratefully acknowledged. The author expresses his sincere thanks to Dr.S. Srikanth, Scientist-in-charge,
NML Madras Centre and Prof. S.P. Mehrotra, Director, National Metallurgical Laboratory,
Jamshedpur, for their constant support and encouragement.
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130

Rev.Adv.Mater.Sci. 9 (2005) 130-177

T.S.N. Sankara Narayanan