STUDIES ON THE ELECTRO DEPOSITION OF ZINC COMPOSITE

COATINGS AND THE ROLE OF THIOSEMICARRAZONES

IN ZINC PLATING BATHS

THESIS SUBMITTED TO ALAGAPPA UNIVERSITY IN FULFILMENT

OF THE REQUIREMENTS FOR THE AWARD OF THE DEGREE OF

DOCTOR OF PHILOSOPHY
IN
INDUSTRIAL CHEMISTRY

By
B. KAVITHA

RESEARCH SUPERVISOR
Dr. T. VASUDEVAN

-*• - ^ ' • - "^

DEPARTMENT OF INDUSTRIAL CHEMISTRY

ALAGAPPA UNIVERSITY
KARAIKUDI - 630 003, INDIA.

JUNE - 2003
 DECLARATION

I hereby declare that the thesis entitled "Studies on the

electrodeposition of zinc composite coatings and the role of
thiosemicarbazones in zinc plating baths" submitted for the award
of the degree of Doctor of Philosophy is a record of original and
independent work and that it has not formed the basis of the award of
any Degree, Diploma or any other similar title of any University or
Institution.

(B.KAVITHA)
Dr. T.Vasudevan
Prof. & Head

CERTIFICATE

This is to certify that the thesis entitled "Studies on the

electrodeposition of zinc composite coatings and the role of
thiosemicarbazones in zinc plating baths" by B.Kavitha for the
degree of DOCTOR OF PHILOSOPHY is based on the results of
studies earned out by hC"^ under my guidance in the Department of
Industrial Chemistry, Alagappa University, Karaikudi.

This thesis or any part of there of has not been submitted

elsewhere for any other Degree, Diploma. r

(T.VASUDEVAN)
PROFESSOR AND HEAD OF THE
DEPARTMENT OF INDl'STPJM. CHEkiSTRY
ALAGM^PAONIVgRSm
KARJUKUD13.
 ACKNOWLEDGEMENT

/ wtsfi to express my deepest gratitude to my guide (Dr.T.Vasudevan,

'Professor and 'Head, (Dept. of IndustnaC Cfiemistry, j4Cagappa Vntversity,
Karail{udi -wfiosefresh andstimuCating ideas made this wor^a pCeasure. 'Xothing
couCd Se more inspiring in my Cife than wor^ng under his guidance. Kis ^nd,
enthusiastic and encouraging words were a rea[ source of strength to me.

I express my than^ to the "l/ice Qf^nceHor Or.^9tflmasamy, JiCagappa

Vmversity for providing me the necessary faaCitus to carry out my research
wor^

I am than^Cto Or.^.QopaCan, ^Vr.<P.Manisanl{ar, ^Dr.<B.'Mura[ufharan,

^r.K^urumaOesh <Pra6hu, (Dr.g.(Paruthima[ %a[aignan and (Dr.S.ThamSidurai
for their encouragement in the study.

I am much gratefuf to my (Parents, KusSand and Sisters for their [ove,

care and unfading emotionaf support in all my endeavours.

I thani^Dr.MSyedJlzim andiVr.1/.<Rflj, Scientists, QECRJ, Kjirai^i

and <Dr.Ji.SuSramanui, Jisst. ^Professor, (PSQ College of Technology, CoimSatore
for their help in carrying out some of the characterization studies

I sincereCy than^!Mr.^.Santhosh for his timefy heCp in compCeting this

work^successfuUy.

I expend my than^ to Mr.9^.1(aruppiah, 9dr.94.San^rasuSramanian,

•Mr.S.Sanl{ar,'Mr.<D.(Rameshand 'MrXjSwaminathan and all the other research
scholar friends of the ^Department for their help in allpossible ways.

'FinaCly I than^Mr.S-Sal^thivel, C'ECRJfor his effort in neatly typing the

thesis.

(^.T^flvitfia)
 CONTENTS

CHAPTER-I
INTRODUCTION
1.1. Metal composites
1.1. Factors affecting electrolvtic co-deposition from a 2
heterogeneous solution
1.2. Classification of electrocomposites 5
1.3. Mechanism of co-deposition 8
. 1.4. Models for electrolytic co-deposition 10
.1.5. Industrial applicabilitv'of composite coatings 13
.6. Future development of composite coatings 15
1.2. Additives for electroplating solutions
1.2.1. Influence on properties 17
.2.2. Mechanisms 19
.2.3. The synergism of additives 23
Summary 24
References 25

CHAPTER-II

LITERATURE SURVEY AND SCOPE OF THE PRESENT

WORK

2.1. Literature survey

2.1.1. Electrocomposites 30
2.1.2. Additives for plating baths 37
2.2. Scop»e of the present work
2.2.1. Zinc composites 44
2.2.2. Additives for zinc plating baths 46
References 49
 CHAPTER - III

EXPERIMENTAL DETAILS
3.1 Electrozinc composites
3.1.1. Materials, chemicals and instrumems used 56
3.1.2. Plating procedure 57
3.1.3. Corrosion behaviour of zinc and zinc composites 59
3.1.4. Characterization of composite deposits 63
3.1.5. Structural investigations 65
3.2. Additives for zinc plating baths
3.2.1. Synthesis of ihiosemkarbazones 66
3.2.2. Materials and chemicals used 68
3.2.3. Preparation and purification of the bath 69
3.2.4 Effect of additives in zinc plating bath 69
3.2.5. Corrosion behaviour of the zinc deposits 75
3.2.6. Microhardness measurements 76
32.7 Structural investigation 76

CHAPTER - IV
RESULTS AND DISCUSSION
4.1. Electrozinc composites
4.1.1. Effect of operating variables on co-deposition 79
4.1.1.1. Effect of bath loading 79
4.1.1.2. Effect of current density 83
4.1.1.3. Effect of pH 89
4.1.1.4. Effect of temperature 91
4.1.2. Validity of adsorption mechanism for 97
electrodeposited zinc composites
4.1.3. Characterization of zinc composites
4.1.3.1. Adhesion 99
4.1.3.2. Microhardness 99
4.1.3.3. Wear loss 106
 4.1.4. Corrosion resistance characteristics of zinc and
zinc composites
4.1.4.1. Weight-loss method 106
4.1.4.2. Potentiodynamic polarization method 110
4.1.5. Structural investigation of the zincelectro
composites
4.1.5.1. Optical microscopy 115
4.1.5.2. Scanning electron microscopy 121
4.1.5.3. XRD studies 124
4.2. Role of additives in zinc plating baths
(i) Hull cell studies 132
(ii) Throwing power studies 151
(iii) Current efficiency measurements 155
4.2.1 Cyclic voltammetry studies 155
4.2.2. Corrosion behaviour of the mild steel substrate in
the plating bath
4.2.2.1. Weight loss studies 177
4.2.2.2. Potentiodynamic polarization studies 181
4.2.2.3 Impedance studies 190
4.2.3. Mechanism on the role of additives as brighteners 202
4.2.4. Evaluation ofthe corrosion resistance behaviour of 205
the zinc deposits
4.2.4.1 Studies with deposits from acid plating 206
bath
4.2.4.2 Studies with deposits from alkaline 209
plating bath
4.2.5 Microhardness studies on the zinc deposits 216
4.2.6 Morphology of the deposits 216
References 225
CHAPTER-V
CONCLUSIONS 230
Scope ofthe future work 237
mpjER • I
 CHAPTER-I

INTRODUCTION

1.1. METAL COMPOSITES

Composite materials can be described as materials made by the

combination of two or more materials and are characterized by properties
that the individual components do not p>ossess. One of the oldest examples
of the development of such materials is probably the production of
duralumin, by Merica et al [1] in 1919 following the discovery of the
important phenomenon of precipitation hardening.

Electrolytic co-deposition has been put forward as a production

method in the literature since 1969. The growing interest in electrolytic and
chemically deposited composites is partly due to the flexibility of the
process and due to its interesting competitive position with respect to other
production techniques.

The excellent resistance of zinc to corrosion in varied environments

and its ability to protect steel galvanically account for its successful use
and performance in a wide variet>' of applications.

As the present work is on thedevelopment of zinc based dispersion

composite coatings and on the role of some thiosemicarbazone derivatives
as additives in acid and alkaline zinc baths, this chapter focusses on various
aspects of the above theme.

Composite material consists of two constituents - the matrix and the

distributed phase, each making a propert\' contribution to the structure [2].
 The matrix material can be a metal or plastic. The distributed phase
can be whiskers, wires, fibres, filaments or particles. The proper
combination can enhance strength and preserve ductility.

The composites in the high-performance arena today are (a)

dispersion strengthened (b) particle reinforced or (c) reinforced with
fibres, whiskers or filaments. Fine inert particles or filamentary
reinforcements with high temperature strength, combined with a soft
conventional metal matrix can produce composites [3] that perform better
than superalloys. Among these, metal matrix composites have attracted
considerable attention as a result of their ability to provide a wide range of
microstructure and properties.

Metal composites can be prepared by flame spraying, sintering,

unidirectional solidification. chemical vapour deposition and
electrodeposition. Of all the methods mentioned, electrodeposition is
superior for the following reasons.

i) A greater range of ceramic/cerment coating materials is possible,

ii) Do not require heat, thus the metallurgical properties of the
substrate are unaffected,
iii) Finefinishand accurate control are possible,
iv) Greater versatility in coating complicated geometries,
v) Small capital equipment costs,
vi) The process is highly economical and a suitable hard coating can
be applied to soft substrate metals.

1.1.1. Factors afTecting electrolytic co-deposition from a heterogeneous

solution

Electrodeposition being an electrochemical phenomenon, any factor

which can influence the electrical and hydrodynamic situation in the bath
would influence co-deposition. The most important factors are
 i) Particle pretreatment
ii) Composition of the electrolytic bath
iii) Particulate concentration
iv) Cathode current density
V) pH

vi) Additives
vii) Temperature

Particle pretreatment

Cleaning of the particles prior to addition to the electrolyte may

improve the particle occlusion in the metal matrix. Acid cleaning of white
and grey alumina powder significantly reduces particle agglomeration and
increases the amount of particles captured in nickel [4]. Boiling copper
sulphate solution was used to pre-clean alumina, silicon carbide and
barium sulphate powders [5]. A successful suspension was made by
immersing the second phase particles in a small quantity of water and
mixing it with a magnetic stirrer or blender [6] to ensure the break up of
clusters before immersing in the electrolyte.

Composition of the electrolytic bath

According to the available literature the efficiency to co-deposit

metal and ceramic is not same for all the electrolytic cells. Their
compositions play a very subtle role in influencing co-deposition. Micro
throwing power is an important bath parameter for co-deposition and the
poorer micro throwing power of copper cyanide and tluoboric baths made
particle entrapment easier [7]. Some inorganic particles that are difficuh to
co-deposit can be easily co-deposited by addition of promoters like
thallium sulphate, rubidium sulphate or caesium sulphate [8] in acid copper
sulphate baths.
Particulate concentration

The most effective method of increasing the volume fraction of

disjDersoid in the matrix is by increasing the particulate concentration in the
electrolytic bath. The volume fraction of the dispersoids in the matrix vary
either linearly or logarithmically. Linear increase in the dispersoid content
with bath loading was observed in Ni-AKOj [9]. Cu-ANOi [10]
Cr-WC (11]. Cr-AliOj [12] systems. Logarithmic increase in the dispersoid
content in the matrix with bath loading was observed in Ni-TiOi [13]
system.

Cathode current density

Effect of cathode current density on the volume fraction

incorporation of the dispersoid is very significant. However its effect
appears to be complex and is still not clearly understood. Current density
used for co depositing most of the systems consisting of Cu. Ni. Fe. Co and
their alloys was between 0.1 to 1.0 A/dm". However for chromium based
systems it ranged from 10.0 to 60.00 A/dm". Current density has no
significant effect on co-deposition in Au-polymer [14] and Kg-KhOy [15].
An increase in incorporation with current density was observed in
Fe-Al.Oj [16]. Ni-SiC [17]. Co-Cr^C. [18] and Ni-AUO.-, [19] systems.

Some systems such as Au-AUO^ [20]. Co-AUOi [21]. Cu-graphite

[22] showed an initial increase in incorporation of the dispersoid followed
by a decrease as the current density was increased, maximum
incorporation being achieved at a specific current density.

Effect ofpH

Effect of pH on particulate incorporation is still not well established

and the incorporation trend seems to vary from system, to system.
 Variation in pH between 2.0 and 5.0 had little or no effect on
co-deposition in Ni-ANO.^ [23]. A maximum inclusion of TiO^ in nickel
from Watt's bath was observed at pH 1.0 [24].

Additives

Organic substances such as thiourea [25] ethylenediamine [26].

tetraethylene pentamine and amino acids such as alanine. EDTA and amino
acid sequestering agent, especially those with more than one amino group
like N.N-diethylglycine, taurine, semi-amides like asparagines etc. have
been used to give excellent results in promoting co-deposition of insoluble
inorganic particles. The amines especially polyamines and amino acids also
aid co-deposition of particles from plating bath like acidic nickel, zinc and
cadmium.

The addition of organic and inorganic additives affects the

co-deposition of the particles with metals, by either modifying the cathode
surface or the particles surface [27].

Temperature

Temperature had no significant effect on the co-deposition of AI2O3

[28] and SiC [29] with nickel when the temperature was increased from
293 to 353"C. Studies on co-deposition of inorganic particles with copper
from copper sulphate bath showed decreased particle incorporation at
higher temperatures. An increase in the incorporation of the dispersoid was
reported for Cr-graphite [30] systems with increase in temperature.

1.1.2. Classification of electro composites

The electroco-deposition [31] can be effected from a homogeneous

solution or from a heterogeneous solution. In the former method [32]
composites are produced from a homogeneous electrolyte containing two
cations of which one can be deposited from an aqueous solution, only as
the oxide hydrated oxide or other insoluble compound, and not as the
metal. Some heavy metal ions which show such properties are thorium,
uranium, neptunium etc. Composites deposited this way are chromium
refractory oxides [33]. Cr-MoOj. Ni-UO. and Ni-ThO. [34].

In the latter method insoluble particles are kept in suspension in the

plating solution by agitation. The process is known as conventional electro
co-deposition (CECD) when the cathode is kept in the vertical plane.

Electro composites could be further classified into five categories.

i) Particle - dispersed metal composites (PDMC)

ii) Fiber - reinforced metal composites (FRMC)
ili) Electroless metal composites
iv) Layered and laminated composites
v) Optical composites

Particle - dispersed metal composites (PDMC)

Particle dispersed metal composite coatings can be obtained as a

surface coating or as an electroformed material by suitable methods.

The coatings are obtained when insoluble materials in a fine powder

form are added to an electroplating bath, and electrodeposition is continued
in the conventional manner. During electrolysis the particles are
incorporated into the deposit, and a composite deposit is formed. For
preparation of electrocompwsites for practical applications the particles
should be held in suspension. Air agitation, mechanical agitation, magnetic
stirring and fluidizing with a flowing electrolyte are some of the methods
followed to create the dynamic condition.
 Composites can be plated on all substrates over which electroplating
can be done. The thickness of the coatings depends upon the size of the
particles, the nature of the particles and the nature of the metal deposited,
besides the normal bath parameters.

The particle additives include the following

i) Oxides of Al.Zr.Ti
ii) Carbides of Ti. Ta. Si. W. Cr. Zr. B. Ni
iii) Nitrides of B. Si
iv) Borides of Ti. Zr. Ni
V) Sulfides of Mo. W

vi) Graphite. Mica. Sterates. PTFE and diamond.

The conditions of electroplating are to be chosen in such a maimer

as to secure the formation of a composite with suitable volume fraction of
dispersed phase. It is possible to increase the volume fraction of the
dispersed phase in the composite by

i) Increasing the volume of the particles in the solution.

ii) Increasing the current eftlciency of the bath.
iii) Adding certain surface active agents to promote co-deposition.
iv) Adding certain monovalent cations such as TI. Rb or Cs.

Particle dispersed metal composites are used to

i) Increase the wear resistance, abrasion resistance, and creep

resistance of metals or alloys,
ii) Increase the corrosion resistance,
iii) Impart a dry self-lubricating coating,
iv) Increase the strength at elevated temperatures,
v) OtTer a heat-treatable alloy,
vi) Provide coatings useful in nuclear applications.
 The success of PDMC materials are dictated by the following factors.

i) The volume of particles in suspension determines the volume of

co-deposited particles,
ii) Critical lower limit of particle size,
iii) Uniformity of suspension,
iv) Position and geometry of the cathode,
v) Conditioning and pretreatment of the particles.

Important variables in co-dejX)sition are the metal plate, particle size

and volume, bath throwing power. pH and current density. Thus by using a
variety of suspended particles and a variety of metal-plating processes, a
wide range of composite electroplates can be obtained with special
properties. The advantages of using composite coatings are many. The
process is simple and economical and the coatings with desired properties
can be applied on any metal or alloy to alter the surface characteristics.

1.1.3. Mechanism of co-deposition

Two possible mechanisms have been postulated to explain the

electrolytic co-deposition of the insoluble particles,
i) Encapsulation or mechanical entrapment and
ii) Electrosorption

Encapsulation

Encapsulation or mechanical entrapment of the particles was first

postulated by Withers [35] in 1962. According to this theory, positively
charged particles are brought to the cathode by electrophoresis.
Electrokinetics or Zeta potential of the dispersoids play a ven. important
role in this transport. Once at the cathode, the particles are occluded in the
metal matrix.
 Martin [36] from their studies on co-deposition mechanism found
that the volume content of the particles in the composite coating is

i) Directly proportional to the volume content of the particles in the

electroplating bath,
ii) Directly proportional to the degree of agitation,
iii) Independent of pH. current density and temperature.

Based on the above conclusions, they proposed in 1964 a modified

particle encapsulation theory, according to which the particles are
hydrodynamically transported to the cathode by the bath agitation, where
the rapid metal deposition causes the entrapment of the partiOMAP^ IMVEIflTfi llttlKBL
unMMit
Electrosorption a^^x««k» W i ^ P ^

Brandes and Goldthorpe [37] while studying the co-deposition of

AI2O3 and SiC with copper from an acid copper sulphate and alkaline
cyanide bath, found that the influence of various bath parameters such as
pH. temp)erature. bath composition and the effect of various additives could
not be explained by the earlier theories and suggested a new theory in
1967. According to them, the inert particles adsorb ions on their surfaces
depending on the nature of the electrolyte in the bath. These charged
particles are transported to the cathode by the hydrodynamic flow of the
electrolyte by the stirring action. The electrostatic attractive forces between
the electrode and the charged particles hold them on to the cathode surface
long enough to be entrapped by the growing metal.

While the particles come into close proximity with the cathode
carried by the movement of the solution the electrical eflect may be
important in holding the particles at the cathode when the metal grows
around them. This may occur in two ways (i) the field produces an
electroldjpgtiG=ffltc5a^tion between the particles and the electroKlic solution

Al&aapp& university
CBnh^ Library

':rxP/'
in the diffusion layer surrounding the cathode, causing the particles to be
passed against the electrode as suggested by Kedward [38] or (ii) the
charged particles are held against the electrode by electrosorption. The
former mechanism depends on the field direction and zeta potential of the
particles in the solution, and the latter depends on the charges on the
electrode and the particle, the screening effect of ions in the double layer
being neglected. The study [39] on ANOj in Watt's nickel, nickel
sulphamate and copper tluoborate solution show that the onl\ way in
which electrical effect will assist co-deposition of particles is b\ holding
them at the cathode by electrostatic forces. The electrokinetic effect of
charged particles is claimed to be negligible at the cathode.

1.1.4. Models for electrolytic co-deposition

Mathematical models have been proposed to explain the

CO- deposition mechanism of the particles with the metals. The models are
useful in optimizing the various bath parameters for co deposition. A brief
account of various models proposed is given below.

Model of Saifullin and Kahlilova (1970)

This is an empirical model [40] based on the assumption that the

particle concentration in the coating is the same as that in the bulk of the
solution. An expression relating bath concentration of the particulates,
density of the metal and density of the particle has been derived.

Model ofBazzjard andBoden (1971)

The model [41] is based on the assumption that the particle size has
an influence on the co-deposition, which depends on the frequency of
collision of the particles with the cathode. Based on this approach an
empirical correlation was found between particle size, plating time and
current density used for co-deposition with weight percent incorporation of
the particles in the matrix.

Model ofGuglielmi (1972)

Guglielimi [42] has discussed the kinetics of deposition of inert

particles to explain the peculiarities shown by the co-deposition of inert
particles from electrolytic bath. He proposed a mathematical model based
on two successive adsorption steps. In the first step the inert particles are
loosely adsorbed on the cathode and they are in equilibrium with the
particles in suspension being still surrounded by adsorbed ions and solvent
molecules. The first step is postulated to be substantially physical in
character. The second adsorption step is thought to be field assisted and
therefore substantially electrochemical in character and results in strong
adsorption of the particles on to the cathode. The strongly adsorbed
particles are then progressively submerged by the growing metal.

Several investigators have demonstrated the validity of Guglielmi's

model for various systems such as Ni-Sic [43]. Cu-ANOj [44]. Cr-graphite
[45]. Au-SiC [46]. Ni-ANOj [47]. The limitation of the model is that it
does not take into account, the hydrodynamic conditions of the bath.

Model ofKariapper and Foster (1974)

This model is a modification [48] of Guglielmi's model, where an

attempt has been made to bring in the hydrodynamic factors of the bath
also into consideration. This model retains the assumptions of the
Guglielmi's model. It also assumes that, both volume fraction of the
co-deposited particles and current density are proportional to the stirring
velocity, which show a maxima and that only those particles with an
impact velocity below a certain initial value will be co-deposited.
 The model gives the measure of interaction between particles and
cathode surface as a function of certain parameters like adsorption, charge
density on the particle, potential field at the cathode, physical bond and
mechanical factors such as size, density of the particle and rate of agitation.

Model of Cells, Roos and Bulens (1987)

This model is based on adsorption mechanism, and is developed by

a comprehensive statistical treatment of the incorporation process. It is
assumed that the particles will be embedded only if a certain fraction of the
adsorbed ions on the surface of the particle is reduced and that there is no
difference between a free and adsorbed ionic species with respect to
transport and reduction process.

This model has been found to be in quantitative agreement with the

experimental results on the co-deposition of AUO^ with copper and gold
[49].

EIPET Model (1987)

The electrode-ion-particle-electron transfer model was proposed by

Valdes and Cheh. by taking into account the electrochemical nature of the
particle metal co-deposition. It is assumed that, the electrochemical
reduction of the metal ions adsorbed on the particle surface, at the cathode,
provides the essential surface, binding interaction that is responsible for
co-deposition. The activation potential r|a is the principal surface active
driving force for effecting particle incorporation.

This model has been found to be in qualitative agreement with

experimental data on the co-depwsition of alumina from an acid copper
sulphate solution [50].

12
1.1.5. Industrial applicability of composite coatings

The development of composite coatings has allowed modification of

the physical and mechanical properties of metals made by electrolysis.
There is a relatively large potential for including particles of diverse type
which might well find specialized applications. Industrial applications of
composite coatings are mainly located in the field of mechanical
engineering, in the space and automobile industries and the electrical and
nuclear sectors. The properties of composites coatings lead to classification
of the potential applications into three main categories namely.

i) Dry lubricant or wear-resistant coatings,

ii) Corrosion or oxidation resistant coatings,
iii) Dispersion - strengthened coatings.

Other interesting industrial applications developed include the

preparation of stainless steel coatings by heat treatment of an iron-nickel
electrolytic deposit in which chromium particles are embedded and
development of "satin nickel" with a dull finish obtained by co-deposition
of BaS04 or SiOi particles from a watts plating solution.

Dry lubricant or wear-resistant coatings

For the application, the second phase are chosen which have a
lubricating ability e.g. graphite, molybdenum disulphide and synthetic
materials such as PTFE which result in an improved wear resistance as
with silicon carbide, diamond, and titania. The loss of material due to wear
diminishes with increasing amounts of the particles embedded. The
industrial applications include Cu-SiC coatings for electrical contacts.
Cu-WC coating with good erosion - resistance and anti-arc properties.
Ni-SiC and Co-CriC^ coating for bearings in automobile and aircraft
industries. Electrolytic Ni-SiC coating with 5% SiC is used as scaling

13
components in the Wankel-motor [51]. They have ver>' high permissible
maximum load. Nickel-PTFE composites with non-stick characteristics on
moulds was developed [52]

Corrosion and oxidation resistant coatings

A well-known application of co-deposition to improve the corrosion

resistance of coatings is the production of microporous chromium layers by
co-deposition of non-conducting particles in the underlying nickel layer.
Corrosion of the nickel will thus occur over an increased surface resulting
in a smaller depth of attack. Cr-ZrC coatings offer good resistance to
sulphur corrosion. In an oxygen enriched atmosphere Ni-ANO-, composite
coatings have a better oxidation resistance than plain nickel [53] and good
results are also reported for electrodeposited nickel-silicon carbide
composites by Stoff and Ashby [54]. A report on the oxidation behaviour
of cobalt-chromium carbide electrodeposits [55] shows significant decrease
in the oxidation rate.

Dispersion strengthened coatings

Due to the dispersion small insoluble particles in the metallic matrix

a strengthening effect can be expected in composite coatings. In systems
like nickel-alumina [56]. nickel-titania [57] an increase of the hardness at
increasing weight percent embedded particles is generall\ observed. In
nickel-graphite deposits a marked decrease in hardness with increasing
graphite content was determined [58]. The co-deposition of oxides and
carbides with copper or nickel increases not onl\ the hardness but also
room tempjerature yield strength, ultimate tensile strength and electrical
resistivitv.

14
1.1.6. Future development of composite coatings

The lack of much enthusiasm in the industrial applications of

electrolytic composite coatings is due to the following accounts.

i) Limited knowledge of the mechanism of co-deposition of inert

particles makes the choice of the electrolysis conditions largely
empirical.

ii) Information on mechanical and physical properties of composite

coatings is very limited, as is the effect of different electrolysis
conditions on these properties.

From the technical and scientific knowledge acquired in recent year

it is possible to indicate some of the limitations in the technology. They are

i) As most industrial proprietarv' plating baths contain addition

agents as brighteners and stress relievers their suitability for
composite plating can be taken for granted.

ii) In some baths, the bath ingredients and the pH ma\ promote the
agglomeration of particles either in the plating bath or in the
deposit, resulting in the production of deposits with inferior
properties.

iii) These continues a need for the development of know-how.

related to more flexible operation.

iv) Second phase particles have to be kept in suspension, with good

wettability and this posses a problem in some cases. Surfactants
are used to solve these problems. Utmost care should be taken to
obtain the optimum combination of ionic and non-ionic

15
 surfactants in order to prevent flocculation and sagging of the
particles.

v) Physical and mechanical properties of composite coatings will

be determined by the behaviour of particles in the metal matrix.
Further research to improve the adhesion of the particles to the
matrix is necessary.

vi) Special care should be taken to obtain uniform co-deposition

over the parts to be coated.

With the above limitations the developments of composite plating in

the future will largely depend on the discoverv of unique applications
based with tailor made properties of composite coatings. For this free
exchange of information between users, designers, producers and
researchers is quite necessary.

1.2. ADDITIVES FOR ELECTROPLATING SOLUTIONS

The use of additives in aqueous electroplating solutions is extremely

important owing mainly to the interesting and important etTects produced
on the growth and structure of deposits [59]. Addition agents [60]. are
substances not necessarily ingredients, which are intentially added to metal
depositing solutions in small quantities to produce a beneficial change in
the character of the deposit. Generally their effects seem to be out of
proportion to their concentration [61]. The potential benefits of additives
include brightening the deposit, reducing grain size, reducing the tendency
to free, increasing the current density range, promote leveling, changing
mechanical and physical properties, reducing stress and pitting.

16
1.2.1. Influence on properties
While the additives may affect more than one property and there is a
clear evidence that when several additives are present in the bath their
effect is synergistic and are often considered in the following aspects.
Influence on brightening

Deposits obtained from electrolytes free from additives are normally

matt. Their surface is uneven on a microscale. so that a high proportion of
light reflected from them is scattered. In order to ensure maximum specular
reflection of light, the micro roughness of a surface must be less than the
shortest wavelength of light. Bright deposits can be obtained directly from
the plating bath by incorporating additives in solutions. These are called
brighteners. Brighteners are divided into two types. They are primary and
secondary brighteners.

The primary brighteners are brightness preserving additives whose

main effect is to reduce the brittleness and internal stress of deposits [62].
They contain one or preferably more organic groups of the type =C-S02 in
the molecule. Sulfonic acids, sulphonates. sulphonamides. sulphonimides.
sulphuric acids are some belonging to this type. They are commonly used
in relatively high concentrations and may result in the substantial inclusion
of the organic matter in the deposit.

Brighteners of the second class ie.. the compounds which are

generally termed secondarv brighteners are additives which bring about
very bright finish. They consist either of salts of metals with high hydrogen
over voltage like zinc, cadmium etc or certain unsaturated organic
compounds with strong adsorption tendencies. Ver> small amount of these
materials have a marked effect on the properties of the deposit. Another
characteristics is that as the concentration of the addition agent is increased
the cathode potential continues to increase.

17
Influence on leveling

Leveling is the ability of the bath to produce deposits relatively

thicker in small recesses and relatively thinner on small protrusions with an
ultimate decrease in the depth or height of the small surface irregularities.
The additives which bring about leveling are called levelers. Levelers in
general increase the cathodic polarization. These produce a level deposit
on a more macroscopic scale and act by adsorption at points where
otherwise there would be a rapid deposition of metal. Typical examples of
levelers which are employed in nickel baths are saccharin, coumarin and
thiourea.

Influence on wetting

Wetting agents are added to the electroplating baths to prevent

hydrogen bubbles sticking to the surface and growing to a size which
would locally prevent deposition and cause formation of a pit. In their
absence, the hydrogen which is evolved in a parallel reaction to metal
deposition can become occluded in the deposit causing hydrogen
embrittlement. Oxidizing agents [63] such as hydrogen peroxide, per
borates and permanganates are generally used for the prevention of pitting
during electro deposition of metals.

The type of organic compounds employed in bright nickel plating

baths are alkyl aryl sulphonates [64] with 12-14 carbon atoms in the alkyl
chain, alkyl phenol polyglycol ethers, sulphonated alcohols, etc. These
wetting agents decrease the surface tension of the bath. The most common
wetting agent is sodium lauryl sulphate.

Influence on stress relieving

Internal stress in electrodeposition is a subject that has plagued the

plating industry for a long time. Practically all electrodeposits contract or

18
expand during or after plating process. This produces residual stress in the
electrodeposits which is either tensile or compressive depending upon the
metal being deposited and the conditions of deposition. High internal
stresses may markedly reduce the corrosion resistance of the deposit and in
extreme cases may even cause it to crack and flake otT. Such stresses will
also reduce the fatigue life of a plated component. Numerous methods
have been developed for measuring internal stress in electrodeposits. The
additives which reduce the internal stress in the deposits are called stress
relievers or stress reducers. Typical examples used in plating industry are
saccharin, p-sulphonamide. 1.3.6 naphthalene trisulphonic acid. The origin
of stress and the way in which these additives bring about stress reduction
are explained by several theories [65]. These additives also change the
structure of the deposit and even change the preferred orientation or the
type of lattice.

1.2.2. Mechanisms

Additives act as grain refiners and levelers because of their effects

on (i) electrode kinetics (ii) the structure of the electrical double layer at the
plating surface.

Since additives are typically present in extremely small

concentrations, their transport towards the electrode is nearh' always under
diflusion control and therefore quite sensitive to flow variations. The
effects of additives are often manifested by changes in the polarization
characteristics of the cathode. Many are thought to function by adsorption
on the substrate or by forming complexes with the metal. This results in
development of cathodic over potential which is maintained at a level
which allows the production of smooth, non-dentritic plates having the
desired grain structure [66]. Numerous mechanisms have been suggested to
explain the behaviour of additives. Additives act by a) blocking the surface

19
b) changes in Helmholtz potential c) complex formation including induced
adsorption and ion bridging d) ion pairing e) changes in interfacial tension
and filming of the electrode f) hydrogen evolution effects g) hydrogen
adsorption h) anamolous co-deposition and i) the effect of intermediates.

Bright deposits with the required properties can be obtained directly

by incorporating additives in the bath. The mechanism of their action is not
fully understood. Among the various mechanisms proposed, two are
significant, one is based on adsorption and the other on complex formation.

Adsorption theory or dirt mechanism

The most commonly proposed mechanism has been dirt mechanism

[67]. The additive is viewed as merely a piece of dirt interfering with some
process. The addition agents are generally substances that have a high
surface activity, that is to say they tend to adhere to or rather to be
adsorbed on the surface. Increase in cathodic polarization is usually
observed but decrease has been found for carbon disulfide in silver
cyanide baths and for thiourea in the copper solution. The increase in
cathodic polarization occurs as result of either sharp reduction in size of the
active cathode surface and hence local increase in current density or as an
increase in activation energy for the p>enetration of cations to the cathode
surface across the adsorbed layer. Addition agents are effective in
increasing the cathodic potential and has the ability to decrease the crystal
size of the deposit or to alter the type and degree of preferred orientation.
If the colloid or other substances [68] attaches itself to the surface and the
growth of the crystal nucleus will be prevented. When ions are discharged,
thes thus start a fresh nuclei and the result is that, the deposit is fine
grained. Sometimes the deposits have in fact been found to contain a
certain proportion of course grained cr\'stals as might be expected from the
fact that thev tend to coat the crvstal nuclei. It is eas\ to understand how an

20
excess of additive can cause the deposit to become brittle. Since the
crystals are covered with a relatively thick layer of the added substance, the
deposit will tend to break apart at the surfaces separating the crystal.

The metal surface charge has an important bearing on the adsorption

of both ions and neutral molecules. If the surface charge is negative, the
electrostatic repulsion will oppose adsorption of anions while favouring
adsorption of cations. However a positive charge on a metal surface will
promote adsorption of anions. The potential at which there is no charge on
a metal surface is called the potential of zero charge. Whether or not
adsorption will occur on a metal surface at a given potential, depends not
only on the position of the potential relative to the zero charge potential,
but also on the chemisorption forces opjerating between the particle and the
metal surface. Adsorption of neutral organic molecules usually occurs only
within a specific potential range on each side of the zero charge potential of
the cathodic surface. Beyond that range they are displaced by ionic
adsorption.

The way in which electrocrystallisation proceeds is also influenced

by colloidal suspensions of metal hydroxides which form the catholytes
during electrolysis [69]. Nickel generally forms smooth deposits in
sulphate and chloride solutions in the absence of any additive. The
deposition of nickel is always accompanied by the simultaneous discharge
of hydrogen ions and the pH increases near the cathode thus leading to the
formation of hydroxide or basic salts. These acts just like addition agents
adsorbed on the surface and cause the deposit to become smooth.

The activity of the compound to make the cathode potential more

negative at a fixed current density depends on

21
 i) The acidic or basic character of the compound,
ii) Size of the molecules and
iii) The number of available pairs of electrons in the
molecules

Cathodic polarization was appreciably increased by low

concentration of basic compounds with the large number of available pairs
of electrons and or with a large molecular size. The comparative
effectiveness of chemical groups in increasing polarization, decreased in
the following order in the electrodeposition of nickel.

Nitrogen in conjugated bicyclic ring > nitrogen in conjugated

monocyclic ring> nitrile > aldehydes > amino > nitro > t-amine sulphone >
sulphonylamide > sulphonate > carbonyl ketone > phenolic. In leveling,
adsorption of additives can take place preferentially on active or growth
areas such that repeatable step crystal growth is inhibited at these areas
which results in preferential deposition in depressions and inactive points.

In leveling and brightening there are differences in opinion about

whether additive adsorption is on active sites, geometrical protrusions or
specific crystallographic faces and whether the influence is on diffusion or
deposition. But there is general agreement that the additive is essentially
acting only as dirt and is able to attach itself to the surface.

Complex formation theory

The use of complexing agents [70] is very common in electroplating

baths. In a solution containing metal ion and comple.xing agents one
expects to have a variety of complex ions containing various numbers of
ligands and solvent molecules. The relative concentrations of each complex
ion in the solution can be calculated from a series of stabilitv constants.

TT
 Complexing ligands such as CN". NH3". CI'. Br'. V. SCN'. succinate
and tartrates at very low concentration are readily adsorbed on metal
surfaces and form complexes with metal ion. increasing the amount of
metal ion adsorbed on the electrode and thus increasing the rate of
reduction [71]. This kind of mechanism is referred to as anions or ion
induced adsorption.

Another explanation of catalysis caused by complexing is ion

bridging, i.e.. the ability of a complexed ion to accelerate the rate of flow
of electrons through the additive from the electrode to the metal ion [72].

1.2.3. The synergism of additives

The literature contains much information about the conjoint use of

additives producing high quality cathodic deposits. When used alone,
certain additives do not produce sutTiciently good deposits, but their
leveling or brightening effect is remarkable in synergetic combinations
with other additives.

Dextrin is generally used with thiourea and enhances brightening in

the electrodep>osition of copper from a sulphate solution [73]. Calcium or
sodium ligninsulphonates. used as additives in lead electro refining baths,
produce a relative smooth plate, but with heavy edges. However, conjoint
use of the lignin sulphonates and aloes [74]. ligninsulphonate and
tlavanonic combinations [75] or lignin sulphonate and a water soluble
block copolymer of propylene oxide and ethylene oxide [76] has the effect
of smoothening the edges and in general of producing a much more
uniform plate, essentially free of nodules and trees.

In nickel electrodeposition from Watts type bath it is recognized to

produce full brightness and a synergistic effect takes place [77]. In the case
of using a combination of sodium allyl sulphonate and N-allyl

23
quinaldinium bromide, it was suggested that the charged groups of both
these additives would be arranged alternatively on the surface. This
arrangement of alternate negative and positive ions might be attractive
forces, which may contribute to a greater blockage of the surface, thus
promoting leveling.

SUMMARY

In this introductory chapter all basic aspects related to metal composites

including some of the limitation in the fields and scop)e for future
development are briefed. The quality of electrodeposits are mostly
governed by the additives in the bath. A general discussion on the role of
additives highlighting their different functions is briefed.

24
REFERENCES

1. P.D.Merica. R.C.Wallenberg. H.Scott. Bull. AIME. 150. 913-949

(1919).

2. Indira Rajagopal. Product Finishing. January..63-69 (1984).

3. V.P.Greco. Plat. Surf. Finish.. 76. 62 (1989).

4. R.S.Saifullin. J. Appl. Chem.. (USSR). 39. 764 (1966).

5. R.S.Saifullin, R.E.Fomina nad A.R.Saifullin, Zaschcita Metal. 22

611 (1986).

6. F.K.Saulter. J. Electrochem. Soc. 11. 557 (1963).

7. E.A.Brandes and D.Goldthorpe. Metallurgia. 96. 195 (1967).

8. T.W.Tomaszewski. LC.Tomaszewski and H.Brown. Plating. 56..

1234.

9. M.Pushpavanam and B.A.Shenoi. Metal. Finish.. 77. 38( 1977).

10. E.S.Chen. G.R.Lakshmi Narayanan and F.K.Scutter . Metal Trans.

937(1971).

11. Raj Narayanan and Sujit Singh. Metal Finish.. 81(3). 45( 1983).

12. Raj Narayanan. Surf. Finish.. 84, Proc. 71" AES Annual Tech.
Conf, July 16-20. New York (1984).

13. G.N.K.Ramesh Babu. V.S.Muralidharan and K.2.Vasu, Plating.

Surf. Finish.. 78(5). 126(1991).

14. G.B.Munier. Plating. 56-10. 1151 (1969).

15. J.Hoashi. J. Metal Finish. Soc. Japan. 15. 7. 258(1964).

16. T.P.Konzina. R.S.Saifullin and M.F.Skalozub. Blestyaschehie.

Komb. Metal Pokryfiya. 2. 88 (1967).

2S
17. M.Viswanathan. Metal Finish. 71-11. 38 (1973).

18. E.C.Kedward. C.A.Addison, and AAB.Tennett. Trans. Inst. Met.

Finish., 54. 8(1976).

19. M.N.Joshi and M.K.Totlanki. Proc. P' National Conf. Electroplating

and Metal Finishing. Dec. (1978). New Delhi. Published by
National Productivity Council. Delhi. Oct p. 185 (1981).

20. J.R.Roos. J.P.Celis, C.Buelens and D.Gooris. Application of

Polarization Measurements in the Control of Metal Deposition
(Process Metallurgy (Ed..) 1 H Warren. Elsevier Science Publishers.
Netherlands.. 197(1984).

21. E.S Chen and F.K.Sautter. Plat. Surf. Finish.. 63-9 28 (1976).

22. Md Ghouse. M.Viswanathan. and E.G.Ramachandran. Metal Finish.

55.(1980).

23. P.K.Sinha. N.Dhananjayan and H.K.Chakrabarti. Plating. 60. 55

(1973).

24. M.Pushpavanam. G.Varadarayan. S.Krishnamoorthy. Metal Finish..

72(10).46(1974).

25. J.E.Hoffmann and C.L.Mantell. Trans. TMS - AIME. 236. 1015

(1964).

26. R.S.Vai'be. Kult Izdeliya. 30 (1967).

27. J.Foster and A.M.J.Kariapper. Trans. Inst. Metal Finish.. 51. 27

(1973).

28. F.K.Sautter. Electrodeposition of Dispersion Hardened Nickel-

Aluminium Alloys. Report No AD275956. Office of Technical
Services. US Dept. of Commerce. Washington. DC 25 Feb (1962).

-JA
29. J.Sadowska Mazur. M.E.Warwick and R.Walker. Trans. Inst. Metal
Finish.. 64 - 4. 142(1986).

30. Raj Narayan and B.H.Narayana. J. Electrochem. Soc. 128. 704

(1981).

31. E.P.Rajiv and S.K.Sheshadri. Bulleting of Electrochemistry 8(8).

August. 376-383 (1992).

32. N.Trockij. German Pat.. 742. 972. Dec. (1943).

33. J.C.Withers. J. Electrochem. Soc. 107. 185C (1960).

34. G.S.Petit et al.. Plating Surf. Finish. 64. 10. 46 (1977).

35. J.C.Withers. Prod. Finish. 26. 11. 62 (1962).

36. P.W.Martin. Metal Finish.. 11-31. 447 (1965).

37. E.A.Brandes and D.Goldthorpe. Metallurgia. 96. 195 (19677).

38. EC Kedward. Metallurgia. 79. 225 (1969).

39. JM.Sykes and DJ. Alner. Trans. Inst. Metal. Finish. 52. 28 (1974).

40. R.S.Saifulin and R.G.Khahlilova. J. Appl. Chem.. (USSR). 43-6.

1266(1970).

41. R.Bazzard and P.J.Boden. Trans. Inst. Metal Finish.. 50-2 (1972).

42. N.Gugleilmi. J. Electrochem. Soc. 119. 1009 (1972).

43. J.Sadowska Mazur et al.. Trans Inst. Metal Finish.. 64-4. 142
(1986).

44. JP Cells and JR. Roos. J. Electrochem. Soc. 124-10. 1508 (1977).

45. Raj Narayanan and B.H.Narayana. Rev. Coatings and Corrosion.

4-2. 113(1981).

46. H.Guo and Z.Wang. J.Tkianjin. Univ.. 1. 13 (1985).

27
47. N.Masuko and K.Mushake. J. Metal Finish Soc. Japan. 28-10. 534
(1977).

48. AMJ. Kariapper and J.Foster. Trans. Inst. Metal Finish.. 52. 87
(1974)..

49. J.P.Celis. JR.Roos and C.Buelens. J. Eelctrochem. Soc. 1346. 1402

(1987)..

50. C.White and J.Foster. Trans. Inst. Metal Finish. 59. 8 (1981)..

51. W.Metzger. R.Ott. Galvanotechnik. 12 (1970).

52. K.Naitoh. S.Matsumura. K.Araki. 10* Int. Cong.. Metal Finishing.

Proceedings. 224-227 (1980).

53. V.O.Nwoko. L.L.Shreir. Corrosion. 31(7). 252-254 (1975).

54. F.H.Stott. D.J.Ashby. Corrosion Science. 18. 183-198 (1978).

55. B.P.Cameron. J.A.Carew. J.Foster. lO"^ Int. Cong.. Metal Finishing.

Proceedings. 219-223 (1980).

56. N.Furukawa. T.Hayashi. J. Met. Finish. Soc. Japan. 28 (10).

527-533(1977)

57. G.P.Greco. W.Baldauf. Plating. (3). 250-257. (1968).

58. M.Viswanathan. M.Ghose. Metal Finishing. 77 (10). 67-69 (1979).

59. Electrodeposition. The Materials Science of Coatings and

Substrates. J.W.Dini. Noyes Publications. New Jersey. USA. P. 195.

60. S.Field and A.D.Weil. "Electroplating" Sir Isaac Pitman & Sons
Ltd.. Landon. 136(1951).

61. C.A.Hampel. The Encyclopaedia of Electrochemistrv. Reinhold

Publishing Corporation. New York 14. (1964).

62. E.B.Saubestre. Plating. 45. 912). 1219 (1958).

28
63. E.Raub and M.Stalzer. Metalloberfache. 17. 134 (1963).

64. I.P.Komkov. A.F.Divinskii. O.A.Petrova and M.A.Belenkii.

Chemical Abstracts. 59. 2392 (1963).

65. T.P.Hoar and D.J.Arrowsmith. Trans Inst. Metal Finish. 36(1). 1

(1958).

66. D.M.Hembree. Jr.. "Linear Sweep Voltammetry to Determine

Lignin Sulfonate in Lead Plating Baths". Plating & Surface
Finishing. 73. 54 (Nov. 1986).

67. C.C.Roth and H.Leidheiser. J. Electrochem. See. 100. 553 (1953).

68. M.A.Loshkaroyov and Y.M.Loshkaroyov. Sur. Technol.. 6. 397

(1978).

69. S.Glasstone, "The Fundamentals of Electrochemistry and

Electrodeposition" Amer Electroplaters" Soc. 78 (1943).

70. A.Brenner and H.S.SenderofT. Proc. Amer. Eelctroplaters Soc. 85.

35(1948).

71. C.Ogen and D.Tench. J Electrochem. Soc. 128. 539 (1981)

72. V.F.Vargalyk. V.S.lvanfo and Yu.M.Loshkarerl. EelctroKhimiya.

14.780(1978).

73. D.R.Tumer and G.R.Johson. J. Electrochem. Soc. 109. 798 (1962).

74. R.C.Kerby and H.E.Jackson. Can. Metal. 17. 125 (1978).

75. Th.C.Franklin. V.Tetten and A.Altan. J. Electrochem. Soc. 135 (7).

1538(1988)

76. G.RQuimby. US Pat. 3554884 (1968).

77. S.Beaum and B.Rilev. J. Electrochem. Soc. 106. 309 (1959).

29
 mpjER • II

LiJEmm smmm
SCOPE Of m PRESEHJ M/ORK
 CHAPTER-II

LITERATURE SURVEY

2.1.1. Electrocomposites

Nickel based composites

Nickel based electro composites have been extensively studied by

several investigators [1-8].Various particles like AI2O3. TiOi. SiC. WC.
Cr^Ci. Tie. diamond. MoSj. graphite etc. were co-deposited to achieve
superior performance than the singular Ni matrix.

Pushpavanam et al. [6] and Sinha et al. [5] studied the co-deposition
behaviour of AI2O3 with Ni at different pH's.

Various investigators [1.2.5] have reported the effect of current

density on the co-deposition behaviour of ANO^ with Nickel.

Effect of various additives on the co-deposition of ANOj with

nickel from Watts bath has been investigated. Urea added as a brightening
agent was detrimental to co-deposition [9]. Anionic surfactants like sodium
lauryl sulphate and sodium lignosulphate were useful to get uniform
dispersion of AKOv Cationic surfactants like cetyl. trimethyl ammonium
bromide and octadecyl trimethyl ammonium bromide resulted in brittle
deposits [10].

Joshi and Totlani [11] have shown that the co-deposition of ZrOi
particles increases the microhardness. yield strength and abrasive wear.

Electrodeposited Ni-SiC composites have been reported by Stott and

Ashby [12]. The introduction of fine SiC particles causes a significant
decrease in the oxidation rate. Nickel - glass composites were reported by

30
A.K. Bhargava and D.Kumar [13]. They were found to have increased
hardness and abrasion resistance.

Co-deposition of Yttria with nickel increases the room temperature

yield strength, ultimate tensile strength and hardness of the electroplates
[14].

Nickel - V2O5 composites were reported by G.N.K. Ramesh Bapu

and M.Mohammed Yusuf [15]. The composite coatings showed improved
corrosion resistance.

Ni-MoS; codeposits were reported [16] to posses good antifriction

properties. Vest and Bazzare [17] co-deposited MoS; with nickel from
sulphamate baths. Ni-MoS^ composite coatings exhibit a textured surface
which is considerably softer than pure nickel.

Eelctrolytic nickel PTFE composite coatings with non-stick

characteristics on moulds was developed by K.Naitoh et al.. [18]. Such
composites were also reported by Helle [19].

Refractory carbides and nitrides have been successfully

co-deposited with nickel which include TiC. WC. SiC and SiN and B4C.
The TiC particles increased the microhardness and were resistance of pure
nickel coatings [20].

Kedward et al. [21] observed that the wear resistance of Ni-WC

composite coatings was better than that of Ni-TiC and Ni-SiN composite
coatings.

Ni-ZrBi composites [22] showed enhanced hardness and good

oxidation resistance.

31
 Guglielmi and Icardi [23] observed that the yield strength and
ductilit\' decreased and the micro-hardness increased with increasing
amount of TiO: in the nickel composite coating.

Chromium based composites

Chromium is attractive as matrix metal because of its good wear and

oxidation properties.

Greco and Baldauf [24] successfully co-deposited Ti02 with

chromium from hexavalent baths and the hardness for the composite was
reported to be two times higher than that of pure chromium.

Chromium-ceria coatings with increased wear resistance and low

coetTicient of friction tlnd application in machines where galling is of
particular concern [25].

Chromium WB electrocomposites with improved corrosion

characteristics have been reported [26].

Skominas et al. [27] have reported the co-deposition of AKOj and

SiOi with chromium from hexavalent baths.

Addison and Kedward [28] has investigated both hexavalent and

trivalent electrolytes for codepositing AKOv

Various refractor\ carbides, and boride particles that have been

co-deposited with chromium include SiCB^C. B(,C. TiC etc. Diamond
particles have also been successfully co-deposited withchromium [29].
Data on the wear resistance of various composite chromium coatings have
been reported and it was found that next to diamond, inclusion of Bf,C was
most etTective in increasing the wear resistance of chromium coatings.
 Composite Cr-ZrBj [30] coatings exhibited good wear
characteristics between 300-400"C.

The feasibiHty of co-deposition of WC with chromium from

hexavalent chromium plating bath was reported by Raj Narayanan and
Singh [31].

Cobalt based composites

For dr> sliding wear, nickel cannot be used since it adheres to most
other metals and alloys. The nickel composites, though it performs better
than nickel coatings, is not the right type of material for certain high-
temperature applications for combating wear. Cobalt, on the other hand,
because of its CPH structure possess good wear and frictional properties.
Hence cobalt composite coatings with hard particle reinforcement exhibit
good wear properties.

SiC particles have also been co-depx^sited with cobalt by Gaigulas

and Sviculyte [32].

Cobalt-chromium oxide composite coating for high-temp)erature

wear resistance was studied by Martin Thoma [33]. The comp)osite coating
exhibits outstanding wear resistance from 300''C-700"C.

Highly oxidation resistant cobalt and cobalt-boronnitride composites

were reported by A.Iyer and S.K.Sheshadri [34].

The mechanism of co-deposition of SiC with cobalt is studied by

Bingand Cheng [35].

Copper based composites

Composite coatings using copper as the matrix metal have been

produced using acid sulphate [36] and alkaline cyanide baths [37] .AKO.:;

33
was difficult to codeposit from acid baths. But it was successful from
cyanide baths.

The use of the Tl* ion. added in the form of thallium sulphate as
promoter in copper baths has been reported [38]. It was shown that the
yield and ultimate tensile strength was increased and ductility decreased
[39] for Cu-a-ANOj composite coatings.

Chen et al. [40] successfully co-deposited rutile titania with copper

from acid baths in absence of promoters. Co-deposition of anatase titania
with copp)er from an acidic copper sulphate bath was studied in detail by
Athavale and Totlani [41 ]

It has been reported by Tomaszewski et al.. [37] that addition of

certain cationic promoters such as Cs*. Tf and Rb* ions to the plating
solutions will promote the co-deposition of inert particles with copper.

SiC dispersed in a copper matrix has been successfully deposited

from acid [42] and fluoborate [43] baths. The abrasion and oxidation
resistance improved as a result of the inclusion of SiC.

Konzina and Erganov [44] co-deposited MoS^ with copper. It had

practically no etTect on the co-efficient of friction.

Tomaszewski et al. [37] reported that graphite was co-deposited

with copper from acid baths, even in the absence of promoters.

C.G.Fink and J.D.Prince [45] produced self-lubricating copper

coatings, from acid copper sulphate baths containing embedded graphite
particles.

Cu-MoSi: composites with improved sliding wear is reported by

Y.Z.Wan et al.. [46].

34
Zinc-based composites

Zinc-SiC composite coatings have been reported by

Andrvushchenko and Kozlova [47]. Zn-B4C and Zn-AUO? composite
coatings were successfully produced by Young [48]. Addition of Tf ions
to the bath increased the amounts of B4C included in the matrix .

Zn-ANOi and Zn-ZrO: composite coatings have also been reported

[49].

The co-deposition of graphite particles with zinc [50] improved the

antifriction characteristics of zinc to a level comparable to that of
cadmium.

The deposition behaviour and the properties of electrodeposited

Zn-SiOi composite coatings [51] have been studied. The Zn-SiO^
composite coating showed excellent corrosion resistance and formabilit}.

Corrosion resistance and polymer adhesion of zinc-silica composites

[52] treated with silane coupling agents were reported by M.Hiramatsu and
H.Kawasaki.

Zn-SiC-ANOj [53] composites from alkaline electroKies showed

higher corrosion resistance and hardness.

Highly photocatalytic zinc coatings consisting of TiO: particles [54]

on steel was reported by Seishio Ito et al..

AUO} co-deposited on low C-steel from sulphate or amine- chloride

baths containing suspended a - AI2O3 has been reported [55]. The effect of
current density, temperature. AUOy concentration and stirring rate on the
micro hardness and corrosion resistance of the plate was studied.

35
 Co-deposition ot" Kaolin and M0S2 with zinc matrix was found to
obey Guglielmi's model as reported by GNKRamesh Bapu and
T.Thirchelvam [56].

The ductility and deposit structures of zinc and zinc composites are
reported by DeBonte et al. [57].

Other metal based composites

Silver-MoSi electrocomposiies with improved wear resistance has

been reported by M.Ramaswamy et al. [58].

Adherent uniform TiOi films have been obtained at ambient

temperature over aluminium cathodes [59].

SiC. SiO:- AI2O3. TiBi and BN were co-deposited with aluminium

by J.Fransaer et al. [60] from non-aqueous aluminium electrolytes.
S.K.Yen and C.C.Chang has reported on super alloys with AKOj
co-deposition [61 ].

Thermal fatigue resistance of aluminium containing graphite, silicon

carbide and fly ash particulates are found to be ver>' high. J.Sobczak et al.
have reported on such co-deposition [62].

Silver -corrundum composite coatings were studied by Saifullin

et al. [63]. The composite coatings had improved microhardness than that
of pure silver deposits.

Iron - AI2O3 composite coatings have been successfully produced

by various investigators [64]. The wear resistance of the composite
coatings was found to be twice that of pure iron deposits.

Lead-WC and Lead TiC composite coatings have been produced by

Pini and Weber [65].

36
 Gold is extensively used in electronic industn because of its ver\-
high tarnish resistance, its high electrical conductivity, and low contact
resistance. Gold-WC composite coatings from acid gold complex cyanide
and alkaline gold complex sulphite baths have been produced by Larson
[66]. The composite coatings exhibited higher hardness, tensile strength
and sliding wear resistance. Composite plating of gold from alkaline
cyanide baths and acid baths have been reported [67].

Electrical properties of zirconia-alumina composites were also

reported [68].

2.1.2. Additives for zinc plating baths

Zinc plating

For over 100 years zinc electroplating has been used to protect steel
from corrosion and enhance its appearance. Today, zinc remains the main
stav of the electroplating industn.'. The foremost concern that leads to the
use of zinc is cost etTectiveness for corrosion protection of steel. The end
use products are in building, construction, energy, power furniture,
agriculture and automobiles.

There are several different processes available for the electroKlic

application of zinc to various substrates.

The zinc cyanide system has been around the longest and was the
original process [69] for the electroplating of zinc. The deposit from the
cyanide bath has good ductility and the system is relatively easy to control.
Cyanide-based systems, however, have lost favour with the advent of
alternatives that avoid the use of cyanide, which is hazardous.

Hence the present work is to develop additives for acid and alkaline
zinc baths and the survey gives a brief account of such additives developed.

37
Acid zinc baths
The acid zinc plating process may be used to coat hardware, iron
and steel castings, and small manufactured parts. Its high plating rate and
low operating cost [70] make it attractive for these applications.

Continuous strip [71] and wire [72.73] are successfully

electrogalvanised from acid zinc plating baths. Acid zinc systems may be
classified by their chemical composition. They may be of sulphate,
chloride, mixed sulphate-chloride, fluoborates. phosphate and perchlorate
type.

Acid sulphate zinc baths [74-78] are considerably cheaper to operate

than cyanide solutions. It is used for the general purpose for
electrogalvanizing formed parts or castings. Deposits obtained are white in
colour and high current densities can be employed. One of the important
advantages of acid zinc plating is that the deposits obtained are much less
prone to hydrogen embrittlement.

Alkaline zinc baths

Emphasis on pollution control has stimulated efforts to deposit zinc

from cyanide-free solutions [79-83]. The most successful approach has
been the use of alkaline baths, using the hydroxide ion as the main ligand
for zinc. Without the use of organic additives it produces a deep black
powdery deposit over the entire range of current densities.

Additives for acid zinc baths

The development of addition agent for zinc plating was the subject
of continuing research. Most of the classic additives for the bath such as
dextrose, dextrin, glucose. P-naphthol. vegetable gums, gelatin, brewers
yeast and liquorice were extensively investigated [84.85].

38
 The use of organic compounds as additives can be treated back as
far as 1907 when Snowden [86] reported that formaldehyde in small
amounts had the effect of reducing grain size.

Colloids like gum Arabic [87] Licorice [88]. grapes sugar [89] and
mixture of additives such as starch, albumin and gelatin, double tartrates of
sodium and potassium, sucrose, gum arable, tannic acid and compounds
containing nitrogen atoms such as cyanide have been recommended in acid
baths [90].

Marino [91] suggested the use of alkaline metal salts of

borobenzoates to prevent anodic passivation.

Rice [92] made studies on the performance of acid baths with

glucose as additive. The deposits were brighter with additives.

EtTect of pyridine [93] in acid sulphate baths was found to increase

the throwing power.

The effect of a group of amines in acid suphate baths was studied by

Bra\ and Moral [94].

The use of thiourea and methyl thiourea in sulphate baths were

reported by Gockel [95].

Hydrolysed meat [96] of animal origin was found to produce

brightest deposit in acid baths. Polyethylene polyamine [97] is considered
to be one of the brighteners in acid baths where there is cathode rotation.

Additives of CTAB salicylaldehyde [98] together with cystine [99]

quaternary ammonium salts, molasses, napthol [100] have been repjorted
for producing bright finish from sulphate baths.

39
 The effect of glue and antimony were reported by various authors
[101-104] in zinc sulphate baths.

The effects of various organic compounds in the electrolysis of zinc

from sulphate, chloride and mixed electrolytes were studied by Dubiana
[105].

Bressen and Wiart [106. 107] have showed the effects of tetrabutyl
ammonium chloride, benzalacetone and lead acetate on the kinetics and
deposit morphology from acid baths using impedance measurements.

Adsorption behaviour of benzophenol [108-110] and its derivatives

as brightners in acid zinc sulphate bath was reported.

Furfural was found to give brighter deposits at a concentration of

lg/1 in sulphate baths [111.112].

a-amino acids, thiourea, dextrin, polyethylene polyamine in acid

baths are studied by Beresina et al. [113].

Anthranilic acid, dextrin, polyvinyl alcohol and formaldehyde were

shown to produce bright deposits from sulphate baths [114].

Mayanna et al. [115] have studied the effect of number of additives

like benzaldehyde. salicylaldehyde. cinnamic-aldehyde. furfaraldehyde.
methyl ethyl ketone, ethylene diamine, triethanol amine and thiamine
hydrochloride. They also obtained bright deposits with anthranilic acid and
formaldehyde [116] m-ntitrobenzaldehyde [117] thiourea and glycine
[118].

A reaction model for zinc electrodeposition in acidic sulfate

electrolytes containing Ge^* and Pb'" ions was proposed b> C.Cachet et al.
[119].

40
 Influence of sulfate ions on the formation of interphase layers in
acid zinc electrolytes was reported [120].

EfTect of organic additives like polyethylene glycol are reported to

produce low porosity in acid baths [121].

Use of vanillin, polyvinyl alcohol, triethanolamine. lactic acid,

thiamine hydrochloride [122] were reported as brightners in acetate acid
baths.

In acid sulphate baths Histidine and Ninhydrin were found to give

good quality deposit which would be used to plate zinc within an
industrially acceptable current densit\' range [123].

Benzylidene acetone was found to exhibit brightening property in

acid electrolytes [124].

Additives for alkaline zinc baths

An alkaline non-cyanide zinc bath without any addition agent will

produce a dull deposit and an amorphous powdery smut.

The synthesis of additives for non-cyanide zinc owe their birth to

the original winters patent [125] on the reaction products of primary
amines with epichlorohydrin.

Reaction products of nitrogen containing heterocylic compounds

with formaldehyde and epichlorohydrin [126] were patented additives for
alkaline baths.

Chelating agents [127] like EDTA. sodium gluconate. Rochelle salt

and triethanolamine additives were also reported.

41
 The reaction products of mixture of polyethylene amines, aromatic
aldehydes, aliphatic amines and epichlorohydrin [128] are additives of
non-chelating type.

Mixtures of aromatic and heterocyclic aldehydes, pxjlymers like

polyethylene glycol, triethanolamine [129]. furfural, lignin sulphonate and
gelatin [ 130] have also been reported.

Bukharecas [131] studied the effect of triethanolamine with

p-dimethylaminobenzaldehyde and polyepoxyamine on the capacitance of
the electrical double layer of a zinc electrode in zincate solution.

The effect of urea, diphenyl amine and furfural on the cathodic

polarization in zincate bath was reported by Nlcols et al. [132].

Cachet et al. [133] have studied the effects of organic additives

having the chemical formulation CftFi^CiRi (0C:H4)|20H and C12H25
(C2H4())i20H on the kinetics and deposit growth by means of impedance
studies.

New modified addition agents for alkaline baths were presented by

Biallozor and Lieder [ 134].

Addition of furfaraldehyde to alkaline plating baths have been

reported [135]. The furfaraldehyde molecules were adsorbed on the
growing zinc nuclei and prevented the growth of zinc deposition.

Effect of lead and perfluoro surfactants on hydrogen overpotential

of zinc electrodes in alkaline electrolyte has been reported [136].

The influence of macromolecular amines and poKletralkyl

ammonium salts on the cathodic deposition of zinc has been studied [137].
It was reported that with presence of macromolecular amines the

42
nucleation is instantaneous while in the presence of TAS the process is
progressive.

Glycol in alkaline bath is found to influence the electrochemical

efficiency, adherence and morphological characteristics [138].

Hydrogen evolution during zinc electrodeposition on a steel

substrate from zincate electrolylte containing Na-N-benzylnicotinate was
reported by M.Monev. et al.. [139].

Addition of alkaline earth oxides like SnO. Ni(OH)2 and Co(OH)2

were reported to bring about electrochemical changes [140]

Triethanolamine and furfuraldehyde are reported to act on the

hydrogen evolution and zinc deposition mechanisms [141] also urea
derivatives [142] in alkaline zinc plating baths was found to produce very
bright deposits.

2.2. SCOPE OF THE PRESENT WORK

Zinc is probably the leading metal dominating the electroplating

world. Zinc plating also referred to as eiectrogalvanising is widely used in
the automobile industry since last few decades.

The present research work is related to two main aspects of zinc

plating. The first part is to deal with the development of zinc composite
coatings. This type of plating was aimed, in order to obtain superior
functional performances over the traditional zinc electrodepositions.
Plating parameters affecting the formation of zinc composite coatings
using TiOi. CriO.^. MoSi and AI2O3 particles as dispersoids from sulphate-
acetate baths have to be examined

The second part of the work is to study the influence of some

carbonyl compounds and their thiosemicarbazone derivatives as additives
for the deposition of zinc from acid and alkaline non-cyanide baths. The
optimum conditions for the zinc electrodeposition in terms of the additive
concentration and other operating parameters are to be fixed.

The choice of the matrix, composite particles, plating baths,

additives, substrates and the techniques planned for studying the
composites and the influence of the additives are as sketched below.

2.2.1. Zinc composites

i) Choice of the matrix

Composite coatings prepared by electrolytic plating method have

attracted much attention in the metal finishing industries.

There has been considerable interest in the electroplated corrosion

resistant coatings on steel sheet used for automotive industn.. One of the
most important coatings for corrosion resistant applications is
electrodeposited zinc. The corrosion rate of zinc under atmospheric
exposure conditions is controlled bv the galvanic action of the substrate
and the coating characteristics.

The focus on industrial production of electrodeposited zinc based

alloys and composite coatings on steel substrates to enhance the corrosion
resistance is of recent origin. However, upto the present day only limited
informations have been published on the electrodeposition of zinc based
composite coatings ..

In view of the immense industrial applications zinc has been chosen

as the matrix metal to have better insight in to the realm of composites.

ii) Choice of the composites

The dispersion of fine non-metallic particles in the metal matrix
brings about an improvement in wear properties, strength, hardness,
improved lubricating properties and corrosion behaviour.

44
 The dispersion particles to be tried in the study are TiO;. CriO}.
M0S2 and AliOv

1. The co-deposition of most of the above particles from acid zinc

baths are not reported so far and their zinc composites could find
applications in various fields.
2. The particles could be easily maintained as suspensions in the
plating bath by suitable manipulation.
3. The particles are expected to be quite stable in the bath and may
not react with the matrix.
4. They are all easily available and relatively cheaper
5. With each one of them we can exjiect a marked improvement of
some of the important functional properties of the matrix.

Hi) Choice of the techniques

The corrosion resistance properties and mechanical properties of the

composites developed are to be evaluated by ditTerent techniques.

Weight loss studies, potentiodynamic polarization and impedance

measurements are to be carried out to study the corrosion resistance
properties of the zinc and zinc composites.

Mechanical properties like hardness and wear resistance in both as

plated and heat treated conditions are to be studied using Vickers hardness
tester and Taber abrader.

The electroplated pure zinc and composite surfaces are to be

examined by both optical and scanning electron microscopes. X-ray
analysis is to be employed to examine the distribution and to identify the
inclusions of the particles within the coatings.

45
2.2.2. Additives for zinc plating baths

Many organic compounds have been tried as additives to have

quality deposits.

i) Choice of the plating baths

Zinc can be deposited from allcaline cyanide, alkaline cvanide free,

acid sulfate, acid chloride, fluoborates and pyrophosphate baths.

Cyanide baths though widely used etTorts have been made for
change over to non-cyanide zinc systems owing to its toxicity. Fluoborate
and pyrophosphate baths are not well known and not widely used in
industries. Chloride baths inspite of their faster rate of deposition are
inherently corrosive and any electrolyte entrapped will severely corrode the
plated part.

Considering the above facts the two best alternatives possible are
acid zinc and alkaline non-cyanide (or) zincate system.

The acid baths are relatively cheap and non toxic. They could be
operated in wide range of compositions without affecting the deposit.

The zincate baths are also cheap and operating costs are low. The
bath may be employed in steel tanks and they exhibit excellent throwing
power.

Considering these facts, the present investigation is to focus on the

role of the additives mentioned in alkaline zincate solutions and acid
sulphate-acetate baths.

46
ii) Choice of the addition agents

In non-cyanide systems, the additives added to get desired

properties should be a weak complexing. non-chelating. addition agent that
could take the place of cyanide. It should not cause waste disposal
problem.

A thorough review of literature on addition agents in zinc plating

indicates that numerous addition agents are employed to get desired
structure and properties of zinc coating. Generally the addition agents
employed are organic in nature and contain sulphur, oxygen and nitrogen
atoms present either single or in combination. Various attempts have been
made by different workers to study the effect of each additives in acid and
alkaline zinc baths.

In the present study the role of some individual carbonyl compounds

and their thiosemicarbazones are to be examined. The synergism of the
reaction products could be compared with those of the individual
components.

Hi) Choice of the substrate

All the studies with zinc plating are to be done on mild steel
substrate, as zinc coating is mostly done on steel substrates for corrosion
protection and for decorative applications.

iv) Choice of the techniques

In order to understand the role of individual carbonyls.

thiosemicarbazide. and the thiosemicarbazones. the following techniques
are proposed.

47
 > Hull cell studies for optimizing the current densit\- ranges.
> Harring - Blum cell studies to measure the throwing power.
> Current efficiency measurements.
> Cyclic voltammetry studies.
> Weight loss studies, potentiodynamic polarization studies and
impedance method to evaluate the corrosion behaviour of the
substrate metal as well as the zinc deposit.
> SEM examination to studs the surface morphology.

In short the work is to focus on the development of some

electrozinc composites with the superior mechanical and corrosion
resistance properties and to obtain bright zinc deposits from acid and
alkaline plating baths with the use of thiosemicarbazones as brighteners.

48
REFERENCES
1. V.O.NwokoandL.L.Shreir. J. Appl. Electrochem.. 3(2). 137(1973).
2. V.P.Greco and W.Baldauf. Plating. 250 (1968).
3. F.K.Saulter. J. Electrochem. Soc. 110. 557 (1963).
4. E.A.Brandes and D.Goldthorpe. Metallurgia. 195-198 (Nov. 1967).
5. P.K.Sinha et al.. Plating 60( 1). 55-59 (1973).
6. M.Pushpavanam et al.. Proc. 14'*' Sem. Eelctrochem.. Karaikudi.
India. (1973).
7. D.W.Shimano and H.Otsubo. Kinzoku Hyomen. Gijutsu. 22(10).
513(1971).
8. D.Ramanauskene and J.Matutis. Liet. TSR Mokslu Akad. Darb.
Serb(l). 107(1971).
9. E.Broszeit. G.Heinke and H.Weigand. Metal.. 25 (5). 470 (1971).
10. N.Furukawa and T.Hayashi. J. Met. Finish. Soc. Japan. 28(10) 527
(1977).
11. M.N.Joshi and M.K.Totlani.. Know your Product. Nov.41. (1983).
12. F.H.Stottand D.J.Ashby. Corrosion Science. 18:183 (1978).
13. A.K.Bhargava et al.. Trans. Indian Inst, of Metals. Vol.33(6).
December. 451(1980).
14. M.N.Joshi and M.K.Totlani. Trans. Metal Finish, of Assn. India.
7(2) (1998).
15. G.N.K.Ramesh Bapu and M.Mohammed Yusuf. Materials
Chemistry and Physics. 36. 134 (1993).
16. G.N.K.Ramesh Bapu and V.S.Muralidharan. Bulletin of
Electrochem.. 8(8). 393 (1992).
17. C.E.Vest. and D.F.Bazzare. Met. Finish.. 65( 11): 52-58.
18. K.Naitoh. S.Matsumura. K.Araki. 10* Int. Cong. Metal Finish..
Proc. 224 (1980).
19. K.Helle. 10"^ Int. Cong. Metal Finish. Proc. 234 (1980).

49
20. L.I.Antropov et al.. Zashch. Metal. 10(4). 382 (1974).
21. E.C.Kedwardetal..Tribol. Int.. 7(5).221 1974).
22. Malathy Pushpavanam and S.R.Natarajan, Bulletin of Electrochem..
8(8). 396(1992).
23. N.Guglielmi and G.Icardi. Lametallurgia Italiana. 420-424 (1970).
24. V.P.Greco and W.Baldauf. Plating. 250-257 (1968)
25. R.Narayanan and S.K.Sheshadri. Plating Surf. Finish.. 87(11). 56
(2000).
26. GNK Ramesh Babu and RM.Krishnan. Int. Congress on Emerging
Corrosion Control Strategies for the New Millennium. Feb. 20-22.
New Delhi (2002).
27. V.Skominas et al.. Lict. TST Mokslu Akad. Darb. Ser. B (1).
101-106.(1971).
28. C.A.Addison and E.C.Kedward. Trans. Inst. Metal Finish. 55 (pt.2).
41-46(1977).
29. J.P.Young. NB SIR. 74. 615 (1974).
30. E.C.Kedward et al.. Brit. 1. 220. 331 (1971).
31. Rajnarayan and Surjit Singh. Metal Finish.. 81:45. (1983).
32. K.Gaigulas and B.Sviculvie. Electrokhim. Lit. SSR 99-104 (1976).
33. M.T.Martin Thoma, Plating and Surf Finish.. 71:51. (1984).
34. A.Iyer and S.K.Sheshadri. Sixth National Congress on Corrosion
Control. 22-24. May. Calcutta (1996).
35. Bing Joe Hwang and Cheng Sheng Hwang. J. Electrochem. Soc.
140(4) (1993).
36. E.A.Brandes and D.Goldthorpe. Metallurgia. 195-198 (Nov. 1967).
37. T.W.Tomaszewski et al.. Plating. 1234-1239 (1969).
38. J.Foster and AMJ. Kariapper. Trans. Inst. Metal Finish.. 50 (pt.5).
207-201 (1972).
39. G.R.Laksminarayanan et al.. Plat. Surf Finish.. (May 1976).
40. E.S.Chen et al.. Met. Trans.. 2(4). 937-942 (1971).

50
41. S.N.Athavale and M.K.Totlani. J. Electrochem. Soc. India, 31-34.
119(1982).
42. D.W.Snaith and P.D.Groves. Trans. Inst. Metal Finish.. 50(3),
95-101 (1972).
43. K.Masui et al.. Kinzoku Hyomen Gijutsu 25(12), 671-675 (1974).
44. T.P.Konzina and E.P.Erganov. Tr. Krasnodar. Politekh. Inst. 63.
253-259(1974).
45. C.G.Fink. J.D.Prince. Trans. Electrochem. Soc. 54. 315 (1928).
46. Y.Z.Wan et al.. Trans. IMF. 77( 1). 52 (1999).
47. Yu.I.Andryushchenko and L.A.Kozlova. Zashch. Metal. 12(6).
731-732(1976).
48. J.P.Young. NBSIR. 74. 615 (1974).
49. O.G.Popov et al.. Prikl Electrokhimiya. 6. 23-25 (1977).
50. W.A.Donakowski and J.R.Morgan. Plating and Surface Finishing.
Nov.. 48-51(1983).
51. Zinc-Based Steel Coatings Systems: Metallurgy and Performance.
Ed. By George Kauss and David K.Matlock. The Minerals. Metals
and Material Society. (1990).
52. M.Hiramatsu and H.Kawaski. Industrial Technolog> Centre of
Okayama Prefecture. Okayama. Japan (1987).
53. Arpiar Sachian et al.. Trans. IMF.. 75 (6) (1997).
54. Seishio Ito et al.. Electrochemical and Solid-State Letters. 2(9).
440-442(1999).
55. Y.N.Sadana and Z.Zhang. Metal Finish.. 85. July-Dec. 68 (1987).
56. GNK Ramesh Bapu and T.Thiruchelvam. Bull. Electrochem.. 17(9).
405-408(2001).
57. D.e.Bonte et al.. Galvanotechnik. 87 (8). 2492-2497 (1996).
58. M.Ramaswamy. G.Sheela and M.Pushpavanam. Trans. SAEST. 35.
July-Dec 144(2000).
59. J.Mater. Chem.. 12(9). 269 (2002).
60. J. Fransaer et al.. J. Applied Electrochem.. 32. 123-129 (2002).
61. S.K.Yen and C.C.Chang. Mater. Chem. And Phys.. 77(3). 2003.
62. J.Sobczak. et al.. J. Mater. Engg. and Perf.. 11(6). 595 (2002).
63. R.S.Sai Fullin et al.. Tr. Kanzankhim. Tekhnol. Inst. 40(1) 61-70.
(1964).
64. G.V.Guryanov. Tr. Kishinev. Sel'skokhoz" Inst. 59. 22-24. (1970).
65. G.C.Pini and J.Weber. Interfinish. 76. Tagungsberichtsband
Weltkongr. Oberflaschenbehandl. Met. 9"^ Paper. No.41 (1976).
66. C.Larson. Gold Bull.. 8(4). 127-130 (1975).
67. B.Bozzini. PL. Cavallotti and G.Giovannelli. Metal Finish.. 100(4),
50-60 (2002).
68. JCM" peko Solid State Ionics. 156. 1 -2. Jan:59 (2003).
69. Chris Johnston. Metal Finishing. August (1999).
70. "Modem Electroplating* Ed. By F.A.Lowenheim. John Wiley and
Sons Third ed.. p.442.
71. E.H.Lyons jr.. Trans. Eelctrochem. Soc. 80. 387 (1941).
72. E.H.Lyons. Jr.. Trans. Electrochem. Soc. 78. 317 (1940).
73. V.C.Tainton. J. Am. Zinc Inst.. 18. 42 (1937).
74. E.Raub and K.Muller. "Fundamental of Metals Deposition".
Elsevier Pub. Co.. Amsterdam. London. New York, p.82 (1967).
75. E.J.Smith "Modem Electroplating". F.A.Lowenheim ed. New York.
J. Wiley and Sons. p.396( 1963).
76. H.Geduld. Metal Finish.. 74(4). 27-31 (1976).
77. G.Storube. Galvanotechnik. 77(6). 1318-22 (1986).
78. H.Geduld. Metal Finishing Guide Book and Director). 84(1 A)
306-317.(1986)
79. C.J.Wemlund. Trans. Electrochem. Soc. 40. 257 (1921).
80. R.Wiswanath. S.Sampath and H.V.K.Udupa. J. Mines. Metals and
Fuels. 11. 15-18.(1961).
81. J. Paul Haricharik. Plating. 70(11). 28. (1983).

ST
82. V.G.Bushin. Zaschchita. Metallov. 14(5). 623-5 (1978).
83. W.Paatsch. Galvanotechnik. 70(8) 706-9 (1979).
84. S.A.Tucker and E.G.Thomssen, Trans. American Electrochem. Soc.
477(1909).
85. M.R.Thompson. Trans. American Electrochem. Soc. Vol. L.. p. 193
(1926).
86. R.C.Snowden. J. Phys. Chem.. 369 (1907).
87. R.Mare. J. Electrochem.. 19. 431 (1913).
88. S.A.Tucker and E.G.Thomssen. Trans. Am. Electrochem. Soc. 15.
477(1908).
89. S.E.F.Kem and P.S.Brown. U..S. Pat., 999. 568 (1971).
90. A.Classen. Brit. Pat.. 186. 459 (1921).
91. A.Marino. Fr. Pat.. 661. 863 (1928).
92. R.W.Rice. J. Inst. Metal. 43. 602 (1930).
93. L.C.Pan. Monthly Rev. Am. Electroplaters Soc. 18(5). (1931).
94. J.L.Bray and F.R.Moral. Trans. Electrochem. Soc. 78. 309 (1940).
95. H.Gockel. U.S.Pat.. 1.903.860(1933)
96. Kaui H. Lurdoman. U.S.Pat.3.285. 840
97. J.L.Bay and R.Haward. U.S.Pat.. 2. 393. 741.
98. K.S.Indira. K.Vasantha and K.S.G.Doss. Metal Finish.. 67(1). 7-3
(1969).
99. A.Jogarao and S.Guruviah. J. Sci. Industries. 19 B. 85 (1960).
100. K.S.Indira and H.V.K.Udupa. Metal Finish.. 71(5). 92 (1973).
101. E.B.Saubostoe et al.. Plating. 56(6), 691. (1969).
102. B.A.Lamping and T.Jo' Keefee. Metallurgical Transactions. 7B(12).
551-558(1976).
103. J.Robinson and T.J.O" Keefer. J. Appl. Electrochem.. 6. 1-7. (1976).
104. R.C.Kerby et al.. Metallurgical Trans.. 8B(12) 661-66 (1977).
105. N.M.Dubina, Chemical Abstract, 76, 9022p, (1972).
106. J Bressen and R.Wiart, J. Appl.. Electrochem.. 9(1). 43-53 (1979).

53
107. J.Bressen and R.Wiart. J. Electroanalchem.. 107. 233-245 (1980).
108. E.A.Wuchear. Electrochim. 14 (4). 555-60 (1978).
109. V.S.Kerevatovu. Zhpriklkhim. 51(71) 1563-9 (1978).
110. Granskov. Chem. Abstr.. 102: 69285 (1984).
111. S.Morisaki. Chem. Abstr.. 103 (18). 223175 (1984).
112. S.Morisaki et al.. Plating Surf. Finish.. 68(8). 55 (1981).
113. S.I.BeresinaetaL.ZashchMet. 21 (4). 572-6 (1985).
114. M.Hiramatsu et al.. J. Metal Finish. Japan. 37(2). 82-6 (1986).
115. S.M.Mayannaetal.. Metal Finish.. 85(7). 15(1987).
116. T.V.Venkatesha et al.. Metal Finish..83. 8. 33 (1985).
117. T.V.Venkatesha et al.. Metal Finish..84( 12) 29 (1986).
118. T.V.Venkatesha et al.. Plat, and Surf. Finish..74(6). 77-80 (1987).
119. C.Cachet et al.. Electrochem. Soc. 189"^ Spring Meeting Extended
Abstract. Los Angeles. California. 96-1. 5-10. 1176-7 (1996).
120. L.Grince Vichene and R.Vishumirskis. Metal Finish. 94(12). Dec.
13-6(1996).
121. L.Milkovaet al.. J. Applied Electrochem.. 31:647-654 (2001).
122. R.Sekar. C.Kala and RM.Krishnan. Trans. IMF. 80(5) (2002)
123. S.M.Mayanna. C.N.Tharamani and T.V.Venkatsha. Trans. IMF.
80(6) (2002).
124. D.Mockute and G.Bemoticne. J. Appl. Electrochem.. 27. 691-694
(1997).
125. J.B.Winters. U.S.Pat. 2791554. May 7 (1957).
126. W.Eckles, et al.. U.S.Pat.. 4188271. Feb.. 12 (1980).
127. C.F.Ruebensaal. U.S.Pat.. 2. 27768 (1942).
128. N.Creutz, U.S.Pat.. 3. 853. 718 (1974).
129. S.S.Yakobson et al.. Liet TSR mokslu Akad Parb'serb 4. 37 (1971).
130. T.Bereezky. Brit Pat.. 1. 228. 478 (1971).
131. V.Bukhaveckas. Chemical Abstracts. 79.486/8 (1973).
132. M.Nicolas. Metallurgia. 34(10). 546-8 (1982).

54
133. C.Cachet, et al.. Electrochim Acta. 32(3). 465-474 (1987).
134. Biallozor. Galvanotechnik. 85. 6. 1848-1851(1994).
135. Visalakshi Ravindran and V.S.Muralidharan. Bull. Electrochem..
16(2). pp.60-63 (200).
136. Shi J et al.. 46"^ Annual Meeting Extended Abstract. Xiansen.
Chinna. 2. 1995. Aug. 27-Sept.
137. V.N.Titova et al.. Bull. Electrochem.. 16(9). 425-429 (200).
138. Fabrio Galva and Irani A.CVarlos. Metal Finish.. Feb. (1997).
139. M.Monev et al.. J. Appl. Electrochem.. 28 1107-1112 (1998).
140. R.Renuka et al.. J. Appl. Electrochem.. 31:655-661 (2001).
141. A.John Rethinam. G.N.K..Ramesh Bapu and V.S.Muralidharan.
Trans, of SAEST. Vol. 37. No.3 & 4 July - Dec. 149-151 (2002).
142. G.N.K.Ramesh Bapu. Trans SAEST. 37 (3&4)) July-Dec. 119
(2002).

55
 CHMER-ffl

mRMEm mm
 CHAPTER-III

EXPERIMENTAL DETAILS

3.1. ELECTRO ZINC COMPOSITES

3.1.1. Materials, Chemicals and instruments used y^

Mild steel specimens were used as a base material for the deposition
of Zinc compxjsites. The mild steel specimens were given the following
sequential pretreatment before the electrodeposition.

1. Degreasing with trichloroethylene.

T Alkaline electro cleaning
(2 minutes cathodic followed by
1 minute anodic in the following composition)

Sodium hydroxide - 35g/l

Sodium carbonate - 25g/l
Current density 7A/dm-

3. Washed with running water.

4. Mild acid dip in 5% (v/v) hydrochloric acid for 10 seconds.
5. Washed with running water.
6. Distilled water dip.

The anode used was a zinc slab of high purity. All the chemicals
used for carrying out the experiments were of analar grade.

D.C. Regulated power supply (Aplab) was used as current source

for all dejDOsition studies. A motor attached with a stirrer was used for
stirring the electrolyte in order to keep the dispersed particles in
suspension. A hot plate was used for the maintenance of the temperature.

56
3.1.2. Plating procedure

a) Preparation and purification of bath

For any electroplating, proper method of preparing electrolyte and

preconditioning the solutions to remove metallic and other impurities is an
essential part to get good deposits of required phvsical and chemical
properties.

The plating bath of the following composition was prepared and

used in the present investigation for electrozinc composite developments.

ZnS04.7H:0 300 g/1

Na:S04 30 g/1
CHjCOONa 12 g/1 v/
pH 2-4
Current density l-4A/dm-
Temperature Room temperature

The operating variables were modified to examine the formation of

dispersion coatings.

b) Pretreatment and preparation of suspensions

The following particles were used as dispersoids.

Particles Density kg/m' Size i^m

TiO. 3.9 0.2
Cr.O., 5.23 0.2
MoS: 4.98 0.5
AI2O3 4.11 0.3

They were washed thoroughly with 2% H2SO4 solution to

remove soluble impurities. Then the particles were cleaned with

57
trichloroethylene to remove traces of residual organic impurities and
washed thoroughly with double distilled water, filtered and dried. The
particles were made in the form of slurr\' by mixing it with a little of bath
electroKle in a mortar to prevent the agglomeration of the particles. For
M0S2 0.1 gm of SLS was added as a wetting agent. The slurrv was then
transferred to the bath and blended for 2 - 5 hours to ensure good wetting
of particles by stirring the bath when an uniform suspension was obtained.

The composite plating was carried out in a two litre glass beaker.
Zinc slab of high purity was used as the anode and pretreated mild steel
specimen was used as the cathode. The experimental setup used for
electroplating zinc composite coatings is shown in Fig. (3.1.1).

c) Analysis of the dispersed particles /^

Zinc dispersion coatings plated on stainless steel were stripped

from the substrate and the incorporated particles in the coatings were
determined through gravimetry and zinc by standard volumetric method.

Initially the stainless steel specimens were weighed (W|)

accurately in an electrical balance. Then the composite plated samples were
weighed (W2) and the difference (W^ - W|) gives the weight of the deposit
on the substrate.

The deposits were stripped anodically in 50 ml of 20% HCl. The

stripped solution containing the dispersed particles were filtered through
G4 crucibles. They were dried and weighed.

From the weight of composite particles present and zinc present

in the deposits the volume percent of incorporation of the particles can be
determined as follows [1].

58
 Volume of zinc in the comix)site

Weight of zinc
V, =
Density of zinc

Volume of particles in the composite

Weight of the particles

V. =
Density of the particles

Total volume V= V, + V.

Volume percent content of particles = x 100

V

Triplicate analyses were made in each case and the average

values were reported.

d) Effect of operating variables on co-deposition

The extent of dispersed particles incorporation in zinc was

studied with respect to particle concentration ranging from 10 - 250 g/1 in
the bath, current density ranging from 1-15 A/dm", bath pH from 2-6 and
the bath temperature ranging from 30-60"C.

The stainless steel samples were coated for one hour and then
stripped in 20% HCl and analysed for the volume percent incorporation of
dispersed particles in the deposit.

3.1.3. Corrosion behaviour of zinc and zinc composites

The corrosion behaviour of zinc and the composites were studied by

weight loss method, potentiodynamic polarization and impedance method.

59
Fig.3.1.1. - Experimental Setup for Composite Plating

60
a) Weight loss method

One side of the steel specimens (7.5 x 5 \ 0.1 cm) were plated with
zinc or zinc composites. The\ were cleaned, weighed and suspended in the
test solution (5% NaCl) using glass hooks. After the test period at 24 hours
the specimens were removed, rinsed in distilled water, dried and weighed.
The weight loss was determined and the corrosion rate (CR) in mdd was
obtained.

Electrochemical methods

For the electrochemical corrosion studies a three-electrode cell

assembly was used. The zinc and zinc composite deposits were made on
mild steel substrates. The specimen was masked with lacquer to e.xpose just
1cm' area which served as the working electrode. A saturated calomel
electrode was used as the reference electrode. A rectangular platinum foil
served as the counter electrode. 5% NaCl solutions were used for the
corrosion test.

b) Potentiodynamic polarization method

The experimental setup for polarization studies is shown in

Fig.(3.1.2).

The corrosion measurement system BAS - 1OOA was employed and

the potential of the working electrode was varied. The specimens were
immersed in the test solutions and allowed to attain a steady potential
value. The dynamic fwlarization was carried out from -200 mV to
+200mV with respect to the OCP at a scan rate of lOmV/sec. The potential
E was plotted against log i. From the resulting E Vs. log i polarization
curves, the corrosion potential {^co„) and corrosion current densities (icon)
of the specimens were obtained using the Tafel extrapolation method.

61
Fig.3.1.2. - Experimental Setup for Polarization Studies
c) Impedance method

The experimental setup for impedance studies is shown in

Fig.(3.1.3). Impedance measurements were carried out at the corrosion
potential using the electrochemical impedance analyzer-EG&G(PAR-
USA) Model 6310.

An amplitude of lOmV was impressed over a wide frequency range

of 10 mHz to 100 KHz. Nyquist plot were made to get the value of charge
transfer resistance (R,) and the ieorr values were obtained using Stem-Geary
equation [2].

3.1.4. Characterization of the composite deposits

a) Adhesion

From the functional viewpoint the most fundamental requirement of

zinc plating is adequate adhesion of the coating to the substrate to which it
is applied. The degree of adhesion obtained in any particular case is
criticalK dependent on the correct choice of pretreatment.

To evaluate the adhesion of the composite plated steel specimens

bend test and heat quench, were employed. In this test the specimens were
bent back and forth through an angle of 180"C until fracture of the basis
metal occurs. Flaking or peeling of the deposit if an\ indicates poor
adhesion.

b) Microhardness

Hardness has been defined simply as the resistance to penetration

[3]. In order to measure this resistance to penetration a testing machine is
used to push a specific indenter into the test material with a specified force,
and the depth of penetration is used to derive a hardness number.

63
 ]6 171»19»!11! 1
.'J242S262:2« I

Fig.3.1.3. - Electrochemical Impedance Analyzer

64
 Micro hardness measurement for all the as plated and heat treated
samples at 400"C for 3 hours were made by Mitutoya Microhardness tester
with a load of 25 g. A diamond shaped indentation was made on each
sample. From this, the diagonal of the indentation was calculated on the
Vicker's scale. The hardness of each sample was calculated using the
formula

V.H.N. = (1854 X Load)/d-

Where d = diagonal of the indentor

At least three impressions were made a few microns apart and the
average diagonal length is taken for calculation.

c) Wear resistance

The abrasion resistance of the pure zinc and composite coatings

were measured through Taber abrader both in the as plated as well as heat
reacted conditions at 400"C hours for three hours.

The Taber abrader uses no lubricant and determines wear under dry
friction condition [4].For this measurement, mild steel coated specimens of
10 X 10 cm' area were used. The specimens were weighed accurately
before the experiment. The abrading wheels were allowed to rotate on the
coatings at a load of lOOOgms for 100 cycles.

3.1.5. Structural investigations

a) Optical microscopy /

A small portion of the zinc and zinc composite coated samples were
cut and the surface was examined by Nikon- Ephiphot image analyser. The
particle inclusion and distribution within the coatings could be identified
from the photomicrographs.

65
b) Scanning electron microscopy ^

Scanning electron microscopy analysis was used to provide

structural information in much finer detail than optical microscopy. A
small ix)rtion of the deposited mild steel specimen was cut and examined at
different magnifications of xlOOO. & x4000 using Scanning electron
microscope. Photographs were taken for pure zinc and zinc composite
coatings.
/
c) XRD studies
A portion of the coated sample was cut and subjected to XRD
analysis. X-ray diffraction analysis is widely used to ascertain the spacing
of atoms in a crystal and the orientation of unit cells.

3.2. ADDITIVES FOR ZINC PLATING BATHS

3.2.1. Synthesis of tbiosemicarbazones

The thiosemicarbazones were prepared as the condensation

products of the respective carbonyl compounds with thiosemicarbazide in
presence of 10% HCl as the catalyst [5]. Equimolar ratio of the two
compounds were mixed together and the reaction mixture was refluxed
with stirring for about three hours. Upon cooling, the precipitated products
were filtered off. washed with ethanol and ether and then dried in vacuum.
The products obtained were re-crystallized from ethanol twice [6]. The
characterization of the compounds have been reported in the earlier work
[7].

The structural formulae of the additives and their abbreviation used

are given below.

66
 List of additives used their structure and abbreviation

Name of the Structure Abbreviation

additive
S
Thiosemicarbazide II TSC
H,N NH C NH,

0
Acetophenone AcP
CH, C r H,

Cinnamaldehyde C H. CH CHCHO CnA

Crotonaldehyde CH, CH CHCHO CrA

Furfuraldehyde FrA
^o/ THO

OH
Salcylaldehyde X CHO SaA

Acetophenone
thiosemicarbazide ApTSCN
11
' \C = N NH C NH,

Cinnamaldehyde
II CnTSCN
HC ^ N NH C NH,
thiosemicarbazide <
C„H, CH==CH

67
3.2.3. Preparation and purification of the bath

a) Acid bath

All the bath constituents were dissolved in the double distilled water
and then treated with lg/1 of zinc dust to precipitate foreign metal ions. The
solution was filtered through Whattman - 42 filter pajjer. The bath was
carbon treated at 60"C in order to remove organic impurities.

Boric acid acted as a buffer while A 12(804)3 and NaCl were added to
improve the conduction of the solutions.

b) Alkaline bath V

Required amount of zinc oxide was made in the form of slurr>' with
minimum quantity of water. Caustic soda was added with continuous
stirring. Zinc dust at a concentration of 6 g/1 was then added to the bath and
stirred well. The bath was carbon treated to remove organic impurities and
then filtered.

Addition agent solution

All the additives are soluble in ethanol. The additives were

dissolved in a minimum quantity of ethanol and added to the baths.

3.2.4. Effect of additives in zinc plating baths

3.2.4.1. Hull cell studies

Hull cell experiments are ver\ much valued in the development of

plating bath solutions for industrial coatings [8]. A standard Hull cell of
267 ml volume made of perpex was used for the studies. Polished mild
steel panels of standard Hull cell size were mechanically polished and
degreased by trichloroethylene. Then the panels were alkaline cleaned

69
cathodically and washed well with tap and distilled water. Pure zinc was
used as the anode.

Studies were done to judge the qualit\ of electrodeposited zinc

under a variety of current densities, concentrations and temperatures. After
a number of experiments with the Hull cell the optimized bath whose
composition given below was obtained and it was used for studying the
effect of difterent additives.

Acid bath

Zinc sulphate 265gpl

Al2(S04)3 30gpl
H,BO., 30gpl
NaCl 15gpl
pH 4
Temperature 25" C

Alkaline bath

Zinc oxide 9.8gpl

NaOH 90gpl
pH 12-13
Temperature 30"C

The current density at any particular place was obtained by using

the formula [9]

CD = C X [5.1-5.24 log L] in A dm"-

Where C = Total current passing through the cell

L - distance in cm of the point of interest from the

near end of the cathode.

70
 Preliminary Hull Cell experiments were done to fix the optimum
concentration of the additives at which smooth fine grained zinc deposits
were obtained. Subsequent experiments were conducted with the standard
bath to study the etTect of changes in the Hull cell pattern with pH and
temperature. The pH was adjusted using 10% HCl or 10% NaOH. To see
the etTect of temperature on Hull cell experiments the Hull cell was placed
in a thermostat and filled with bath solution.

The operating conditions for Hull cell are given below:

Acid bath

Anode Zinc sheet

Cathode Mild steel
Total current - 1 A
Plating time - 10 mins

Alkaline bath

Anode Zinc sheet

Cathode Mild steel
Total current - 2A
Plating time - 10 mins

3.2.4.2 Throwing power studies

The throwing power of an electrolvlic cell describes its ability to

give deposition of uniform thickness over the entire cathodic area.

Standard Haring-Blum cell was used to determine the percent

throwing power ot" zinc plating baths with and without various addition
agents. The cell contains a perforated anode and two cathodes one placed

71
near the anode and the other at the far end of the anode in the distance ratio
of 15. Throwing power was calculated using the known Field's equation

(P-M) 100
T=
P + M-2

P - Ratio of the distance between near and the far cathode.

M - Ratio of the weight of the deposits at the near and far
cathode.

3.2.4.3 Current efficiency measurements

Mild steel specimens of size 5 x 2cm were mechanically polished

and degreased by trichloro ethylene. One side of the specimen was masked
with lacquer. The specimens were alkaline cleaned cathodically in the
alkaline cleaning solution for 3-5 minutes. The specimens were then
inserted in a 250 ml beaker containing the electrolyte. Pure zinc anode of
the same area as that of the cathode was used. Deposition was carried out at
current density of 2Adm"" and 4 Adm" for one hour using a constant
current regulator and held constant throughout the experiment. A coppjer
coulometer was used to follow the charge flown in the circuit. The
temperature was maintained at 30"C. The solution was agitated by a
mechanical stirrer. After deposition the cathode was removed, washed well
with distilled water, dried and weighed.

Experiments were carried out both in acid and alkaline bath

solutions with optimum concentration of the addition agents and without
addition agents and each experiments was repeated twice with a fresh
electrode.

From the difference in weight the cathode current efficiency was

calculated using the formula
 Actual gain
Current efficiency = x 100
Theoretical gain

Thus the influence of additives on the cathode current efficiency

was studied.

3.2.4.4. Cyclic voltammetry

CV studies were carried out with BAS lOOA electrochemical

workstation mentioned earlier.

It was shown that detailed examination of the CV results yield

considerable insight on the mechanism of the effects of additives during
zinc plating [10].

For the CV studies a cylindrical mild steel electrode embedded in

araldite with an exposed area of 0.3cm" was used as the working electrode.
Calomel electrode was used as the reference electrode for acid and alkaline
baths respectively.

The cyclic voltammetrv' studies were done at varying scan rates. The
sensitivity of the system was adjusted to be ImA/v. The range of potentials
used was from +2000 to -2000mV for alkaline baths and +700 to -700mV
for acid baths respectively.

The above three electrode cell assembly was used for the impedance
studies also. The working electrode for the corrosion studies in plating
baths was 0.3 cm' mild steel embedded in araldite.

3.2.4. 5. Weight loss method

For weight loss studies, mild steel specimens of size 5x2cm were
taken in both acid and alkaline baths containing different addition agents.
They were immersed in the plating bath by using glass hooks for a test

73
period of 24 hours. The specimens were removed, rinsed in distilled water,
dried and weighed. The weight loss was determined and the corrosion rate
(R) in mdd was obtained. The I^irT tor mild steel corrosion in the plating
baths was calculated using the equation.

Icorr (^A cm") = CR in mdd x 4 x 10'

3.2.4.6. Impedance measurements

The above three electrode cell assembly was used for the impedance
studies. The working electrode used for the corrosion studies in plating
baths was 0.3 cm" mild steel electrode embedded in araldite . The calomel
electrode was used as a reference electrode. A rectangular platinum foil
was used as a counter electrode. The working electrode was polished with
1/0. 2/0. 3/0 and 4/0 emer>' papers successively and degreased with
trichloroethylene.

The real part (Z") and the imaginarv' part (Z") of the cell impedance
was measured for various frequencies. Impedance measurements were
carried out both in acid and alkaline zinc baths with the optimum
concentration of the additives that give bright deposits in the Hull cell and
without the additives. An Ac amplitude of lOmV was impressed over a
wide frequency range of 10 mHz to 100 KHz. From the impedance
diagrams the charge transfer resistance values and double layer capacitance
values were calculated.

3.2.4.7. Potentiodynamicpolarization studies

The experimental setup for polarization studies is mentioned earlier.

A rectangular platinum foil was used as the counter electrode and

the working electrode was a cylindrical mild steel rod with an exposed area

74
of 1 cm". Saturated calomel electrode was used as reference electrodes for
acid and alkaline baths respectively.

A quantity of 150 ml of the test electrolyte was taken in the

polarization cell. The working electrode was polished with 1/0. 2/0. 3/0 and
4/0 emer> papers successively and degreased with trichloroethylene..
Experiments were carried out both in acid and alkaline baths in the
presence and absence of additives. The test solution was stirred well after
adding the additives.

The polarization studies were done from +200mV to -200mV with

respect to their rest potential at a scan rate of lOmV/sec.

3.2.5. Corrosion behaviour of the zinc deposits

3.2.5. J. Weight loss method

For weight loss studies, the deposit was obtained on a mild steel
samples of size 5x2cm from the bath containing different addition agents.
The coated specimens were immersed in 5% NaCl solutions by using glass
hooks. After the test period of 24 hours, the specimens were removed,
rinsed in distilled water, dried and weighed. The weight loss was
determined and the corrosion rate (R) in mdd was obtained. The Ic„rr for
zinc corrosion was calculated using the equation.

!,,,„ (^A cm-) = CR in mdd \ 3.42x10"^

3.2.5.2. Potentiodynamic polarization studies

For polarization studies zinc deposit was obtained on the mild steel
electrode of area I cm" from the bath containing different addition agents
at their optimum concentrations. A rectangular platinum foil was used as
the counter electrode. Saturated calomel electrode was used as the
reference electrode. A 5% NaCl solution was used as the test solution.

75
 The E Vs. log i plots were made from which the corrosion current
and corrosion potential were calculated.

3.2.6. Microhardness measurements

Hardness of the electrodeposited zinc surface with various additives

was measured using a LECO microhardness Tester model M400 by the
static indentation method. A diamond pyramid was pressed into the deposit
under a load of 50 gms for 15 seconds and the indentation diagonal
measured after the load was removed. Each electrodeposit used for this
measurement was of 30|am thickness. The micro hardness in kgmm"' was
determined in each case by using the formula.

HV= 1854 xL/d-

L being the load applied in grams and d the diagonal of the indentation in
micrometers.

3.2.7. Structural investigation

Mild steel specimens of size 2.5 x 5 cm were polished and

degreased by trichloroethylene. Then the panels were alkaline cleaned and
one side of the panel was masked. The other side of the specimen was
plated with Zinc deposit of 30 ^m thickness in the baths in presence and
absence of the best additive (FrTSCN). During deposition the solution was
agitated with magnetic stirrer.

From the plated specimen a small area was cut and examined at
magnifications of xlOO & xlOOO using scanning electron microscope.

76
 CHAPTER-IV

RESULTS AND DISCUSSION

4.1. Electro-zinc composites

The standard electrode potential of zinc is more negative than that of

iron. Hence, zinc has been wideh' used as an electrochemically protective
coating material for steel under ordinary' atmospheric conditions. Any
further improvement in the functional property of the metal is most
welcome owing to its wide range of applications. Improved properties are
shown by composite depx)sits containing inert particles on the metallic
matrix. The electrodeposition of inert particles from nickel, copper and
other baths [1-3] have already been well established. The present
investigation is on the co-deposition of particles like TiO:- Cr^O.^ AUOj
and M0S2 with zinc and on the evaluation of some of their functional
properties.

Standardization of the bath

Before making an attempt for the successful incorporation of inert

particles, the first prime job is to fix a standard plating bath that has
maximum throwing power and current efficiency. In the present
investigation sulphate-acetate zinc bath of composition mentioned in the
experimental section has been chosen and with this bath the operating
parameters were varied to ensure maximum incorporation of the particles
into the deposit.

Masaki Abe et ai.. [4] have successfully co-deposited SiO: particles

from such acid sulphate-acetate zinc plating bath. A detailed discussion on
the effect of operating parameters on the extent of co-deposition of the
above inert particles is presented below.

78
4.1.1. Effect of operating variables on co-deposition

An optimum choice of the bath parameters is needed to get a deposit

with maximum particles incorporated resuhing in improved functional
properties.

4.1. J. 1. Effect of bath loading

The most effective method of increasing the volume fraction of

dispersoid in the matrix is by increasing the particulate concentration in the
electrolyte.

i) Zn-TiO^ Electrocomposite

In the case of Zn-TiOn composites the bath loading was varied

between 10 and 80gpl. The curves obtained for the volume % of TiO:
co-deposited Vs TiO^ concentration in the bath is shown in Fig.( 4.1.1)

The vol.% of TiOi in the deposit is foiind to increase with increase

in the concentration of TiO: in the bath throughout the current density
range studied. With initial loading of the bath there is a linear increase of
TiOi in the deposit, but beyond certain concentration, the curves are
flattened indicating a saturation level in the deposit. This behaviour is
similar to Langmuir adsorption isotherm.

A maximum incorporation of 15.62 vol.% of TiO: was observed at

80 gpl and at a current density of 9 Adm". Further increase of the bath load
caused the TiO; particulates to agglomerate causing rough and nodular
deposits. V.P.Greco et al. [5] have reported a similar behaviour of TiOi
with nickel matrix.

ii) Zn-Cr^Oi Electrocomposite

In the case of Zn-Cr:©;, the bath loading was varied between 50 gpl
and 250 gpl. The plot of vol% of Cr^O^ co-deposited Vs bath loading in gpl
is presented in Fig. (4.1.2 ).

79
 •
•o
•o
s
E
o
o
"o
>

20 40 60 80
TiO, in the bath, gpl

Fig. (4.1.1 ) : Effect of bath load of TiO: on the vol.% inclusion in the deposit
(a)7Adm- (b)8Adm'- (c)9Adm"- (d)lOAdm-

25

„ 20
I
I 15 '

? 10
s«

> 5

0 100 200 300

CriO] in the bath, gpl

Fig. (4.1.2 ) : Effect of bath load of Cr203 on the vol.% inclusion in the deposit
(a)6Adm- (b) 7Adm " (c) 8Adm ' (d) 9Adm *

80
 Unlike TiO^ particles in the case of Cr^Ov co-deposition occurs
only from a higher bath load of 50 gpl onwards. At a concentration of 50
gpl the vol.% of co-deposited Cr^O;; was 5.11. A maximum incorporation
of 23.4 vol.% could be achieved at a bath load of 250 gpl. Any further
increase of Cr^O.^ particles resulted in settling of particles in the bath.

Hi) Zn-MoSj Electrocomposite

The bath load of MoS: was varied between 20 and 80 gpl. The
variation of bath load with vol% incorporation of MoS: in the deposit is
given in Fig. (4.1.3 ).

At a bath load of 30 gpl and at a current densit> of 6 Adm"' . an

incorporation of 9.73vol.% was observed. With further increase of MoSi
particles in the bath the incorporation increased and reached a maximum of
12.69 vol.% at a concentration of 50 gpl and at a current density of 7Adm"".
Still further increase in the bath load caused onl\ a decrease in the
incorporation of the particles in the deposit. At that stage the viscosity of
the bath was found to have increased and has also affected the nature of the
deposit. This may be due to the lubricating nature of the M0S2 particles.

iv) Zn-AliO) Electrocomposite

The bath load of AI2O3 was varied between 20gpl and 120gpl. The
variation of particle incorporation with bath loading of AKO^ is shown in
Fig. (4.1.4).

it is observed that at the lower concentrations of 20-40 gpl and at

lower current densities, the co-deposition observed was around 1.5 vol.%
only. A maximum co-deposition of 5.65% of AI2O3 was observed at 120
gpl and at a current density of 4 Adm",
 14

1 12

I« 10
o
=o 8

o
>

15 35 55 75
M0S2 in the bath, gpl

Fig. (4.1.3 ) : Effect of bath load of M0S2 on the vol.% inclusion in the deposit
(a)5Adm-^ (b)6Adni- (c) TAdm"^ (d)8Adm-

•o

5 5
•o
«
I 4
a 3
<
O /,

o
>
50 100 150
AI2O3 in the bath, gpl

Fig. (4.1.4): Effect of bath load of AI2O3 on the vol.% inclusion in the deposit
(a)2Adni^ (b)3Adm- (c)4Adm- (d) SAdm *

82
Forces effecting co-deposition /6 /

In order that the inert particles like TiO:. Cr:0^ AUO-, and MoS^
should codeposit with the plated metal at the cathode, these panicles have
to be transported to the cathode surface. Their mode of transport can be
either through electrophoretic or hydrodynamic forces. The plating solution
conductivities are normalK high and the field strengths become low. High
electrolyte concentrations lead to low zeta potential for the dispersoid
particles and the electrophoretic mobilities will be extremeh small of the
order of 10"^ cm/sec. Thus electrophoretic transport will be negligible as
compared to hydrodynamic transport.

A particle on reaching the cathode surface sia\s there for a sufficient

time for incorporation into the growing metal depKjsit. It seems necessarv to
explain this, as the electrolyte containing the inert particles is shaken up in
a beaker, and the particles do not sta\ there for an\ length of time at the
wall of the container. It is therefore, probable that some attractive force
exists holding the dispersoid particle at the cathode surface and it must be
large enough to overcome gravity and random agitation effects.

This is possible when there is a positive surface charge on these

inert particles. This positive surface charge arises because of adsprotion of
metal ions onto these particles. Herein comes the specificit\ in the
behaviour of the particles and this explains the varied extent of
co-deposition under ditTerent bath loading conditions.

4.1.1.2. Effect of current density

Effect of current density on the volume fraction incorporation of the

dispersoid is very significant. However its effect appears to be complex
and is still not clearK understood. Current densit\ used for co-deposition in
most of the systems consisting of Cu,Ni,Fe,Co and their allovs was
between 0.1 and 1.0 Adm". For chromium based systems it is reported to
range from 10 to 60 Adm''.

Current density had no signitlcant effect on co-deposition in Ni-

ANO;, [7].Ni-Ti02 [8] systems. An increase in incorporation with current
density was observed in Fe-Al.O, [9]. Ni-SiC (10] and Ni-TiO: [11]
systems. In systems like Ni-MoS;. Ni-Y:©;, [12] and Ni-TiO^ [13] decrease
in incorporation with current density was observed. At these point to the
fact that the effect of current densit\ is mostly centered around the specific
nature of the bath used.

Some systems, such as Cu-SiO: [14] Cu-AKOj [15] and Ni-TiO:

[16] showed an initial increase in incorporation of the dispersoid followed
by a decrease as the current density is increased, maximum incorporation
being achieved at a specific current density.

Many theories have been proposed to explain this behaviour.

According to one theor> [17] the strength of the interaction between the
particles and the cathode surface will determine whether co-deposition will
increase or decrease with current density. If the interaction is strong, the
co-deposition will increase with current density. If it is weak, the
incorporation will decrease. In another theory [18] the increase in
incorporation at lower current densities is attributed to the tendency for
absorbed particles to ride on the cathode surface ie.. metal continues to
deposit underneath the particles without encapsulating it. Desorption of
metal ions from the particle surface need a specific activation energy.
Therefore, the deposition of an adsorbed hydrated metal ion need more
activation energy than an free solvated ion. If this difference is significant,
then the particle may ride. As the current density increases, it is claimed
that the energy required to deposit a metal ion becomes insignificant as
compared with the proximity of the metal ion to the electrode and

84
therefore, the tendencv to ride diminishes. However, at ver\ high current
densities, particle arrival rate at cathode ma\ have a significant influence
on co-deposition. Consequently, the loose adsorption of particles may
become rate determining. Since this is always slower than metal deposition
rate, the incorporation decreases with increase in current densit\. A third
theory [ 19] was putforth to explain the co-deposition mechanism in copper
systems. According to it. at low current densities, the reduction of copper is
under charge transfer over voltage control, and the rate of co-deposition is
determined by the formation of a real contact between the dispersoid and
the cathode. This contact results from the reduction of copper ions
adsorbed on the particle surfaces and therefore, incorporation increases
with current density. Once, the reduction of copper ions is under the
control of concentration over voltage the amount of co-deposited
dispersoid decreases gradually with increasing current densit\.

In general it can be stated that the effect of current densit\ on

particle incorporation is purely dependent on the nature of the metal -
particle systems.

i) Zn-TiOi Electrocomposite

The variation of TiO^ incorporation in the deposit with the applied

current density is shown in Fig.( 4.1.5).

The current density was varied from 7 to 10 Adm". The amount of

co-deposited TiOi particles was found to increase and then decrease after a
critical current density. A maximum incorporation was achieved at a
current density of 9 Adm". With further increase of current density the
extent of incorporation was found to decrease to 13.46 vol.%. With all the
bath loads, a maximum incorporation was observed uniformK at 9 Adm".

85
 This trend is consistent with other metal particle composites
reported in the literature [17].

ii) Zn-Cr^Oj Electrocomposite

The incorporation of Cr20.:( particles increases and then decreases

as the current density was varied between 6 and 10 Adm' which is shown
in Fig.(4.1.6).

A maximum incorporation of 23.4% of Cr20.^ particles was

achieved with a bath load of 250 gpl at 8 Adm". With higher current
densities the vol.% of incorporation was found to decrease and affected the
nature of the deposit. At higher current densities above 9 Adm" the vol.%
of particles decreased to 4.0 even with the maximum bath load of lOOgpl.

in) Zn-MoSj Electrocomposite

The current density was varied between 5 and 8 Adm' for the
incorporation otjMoS: particles. The effect of current density on the vol.%
incorporation of MoSi particles is shown in Fig. (4.1.7 ).

At the optimum concentration of 50 gpl and 7 Adm'' a maximum

incorporation of 12.6 vol.% was observed. The concentration of the
incorporated particles were found to decrease slowly and reached a
minimum at 8 Adm"'. With further increase of current density there was no
further co-deposition. CE.Vest and DF.Bazarre [20] have reported a similar
trend for the incorporation of MoS: with nickel matrix.

iv) Zn-AliOji Electrocomposite

The effect of current density on the vol.% incorporation of ANOj

particles is shown in Fig. (4.1.8 ). The current density was varied between
2 and 5 Adm''.

86
 16

15

6 14
t-
"S
ss
Z 13
>

12
8 9 10 11
Current density, Adm'^

Fig. (4.1.5): Effect of current density on the vol.% inclusion of TiO^ in the deposit
(a) 70 gpl (b) 80 gpl (c) 90 gpl (d) 100 gpl

T, 25
«
1 20
E
« 15
O
O 10
o
35 5
"o
> n

7 9 11
Current density, Adm'^

Fig. (4.1.6): Effect of current density on the vol.% inclusion of Cr 2O3 in the deposit
(a) 100 gpl (b) 150 gpl (c) 200 gpl (d) 250 gpl

87
 14

1 "^
I 10

s 8

>

Current denisty, Adm

Fig. (4.1.7 ) : Effect of current density on the vol.% inclusion of M0S2 in the deposit
(a)40gpl (b)50gpl (c)60gpl (d)70gpl

•o
»
•a
I 5
E
»
d 4
mm
<
"5
s! 3
>

1.5 2.5 3.5 4.5 5.5

Current density, Adm''

Fig. (4.1.8 ) : Effect of current density on the vol.% inclusion of AI2O3 in the deposit
(a) 60 gpl (b) 80 gpl (c) 100 gpl (d) 120 gpl

88
 A maximum incorporation of 5.65% was achieved at a bath load of
120 gpl and at 4 Adm'' current density. At lower bath loads and current
densities, the vol.% of incorporated particles was ver\ less.

4.1.1.3. Effect of pH

Effect of pH on particulate incorporation is still not well established

and the incorporation trend seems to var\' from system to system.

With some systems, the incorporation of the dispersoids in the

matrix either remains same or increase with pH. But with most of the
systems the incorporation of the particles decreases after a critical pH. The
strength of the particle-cathode bond developed b\ metal deposition was
shown to be pH dependent, the strength being more at lower pH [21 J.
Some studies on the co-deposition of SiC with copper from acid copper
sulphate bath showed that there was no sudden change in zeta potential of
SiC as the pH of the solution was lowered [22].The absence of zeta
potential and an isoelectric point for alumina over a pH range of 0.5 to 5.0
in acid copper sulphate bath has also been reported [23].The studies imply
that hydrogen adsorption may not be the most likely explanation for
increased co-dep)osition at lower pH. On the basis of the above findings
some investigators suggested that the increase in incorporation with
decrease in pH might be due to a greater metal ion adsorption on the
particulates [24]. At verv' low pH. metal ion adsorption ma) decrease
thereby reducing the efficiency with which metal deposition form a
particle- cathode bond, causing the metal to get deposited underneath the
particle without incorporating it and thus lowering the incorporation [25].

i) Zn-TiO: Electrocomposite

The influence of pH on TiO: incorporation is shown in Fig. (4.1.9 ).

The pH was varied between 2 and 5 for TiO: incorporation.

89
 In the case of TiO; incorporation a remarkable influence of pH on
the co-deposition was observed. A maximum of 14.7 vol.% incorporation
could be achieved only at a higher pH of 5. When the pH was changed
between 2 and 4 there was no change in the vol.% of incorporation and it
remained constant around 11.0 vol.%.

Similar observation for the variation of pH between 2.0 and 5.0 with
little or no etTect on co-deposition for Ni-TiO: [26] system from Watts bath
has been reported by M.Pushpavanam et al..

ii) Zn-CryOj Electrocomposite

The dependence of vol.% incorporation of Cr^O^ particles on pH is

shown in Fig.(4.1.10). The pH was varied between 2 and 6 for Cr^Oj
incorporation.

At lower pH of 2 the amount of Cr^O^ co-deposited was found to be

just 18.8 vol.%.

However at a pH of 3 a maximum incorporation of 21.2% was

observed. Any further increase of pH upto 6 caused only a slight decrease
in incorporation.

iii) Zn-MoS; Electrocomposite

The effect of pH on the vol.% incorporation of MoS; is shown in

Fig. (4.1.11 ). The pH was varied between 2 and 6 for MoS: incorporation.
A maximum incorporation of 11.8 vol.% was observed at a pH of 2. With
further increase of pH to 6 there was a decrease in the incorporation of
MOST particles.

MoS: incorporation in nickel from a Watts* bath was found to

exhibit a similar trend as reported b> MD. Ghouse et al. [27].

90
 This kind of behaviour could be attributed to the fact that the
strength of the particle-cathode bond developed as pH dependent and the
strength being more at lower pH.

iv) Zn-AliOj Electrocomposite

The effect of pH on the vol.% incorporation of ANOi is shown in

Fig. (4.1.12 ). The pH was varied between 2 and 6.

An increase in incorporation was observed with increase in pH. A

maximum incorporation of 5.7% was found at a pH of 5. At a lower pH
there was a decreased incorporation.

M.Pushpavanam and BA.Shenoi [28] and T.W.Tomasweski et al..

[29] have reported an increase in particle incorporation with pH.

4.1.1.4. Effect of temperature

It is reported -that an increase in temperature to cause an increase in

metal ion adsorption and adsorption strength [30]. This happens upto
certain temperature of incorporation. Beyond that temperature desorption
of the adsorbed particles over ride the thermalK aided transport owing to
the weakening of the particle-metal bond strength.

i) Zn - Ti02 Electrocomposite

The eflect of temperature on TiOi incorporation is shown in

Fig.(4.1.13). With increase in temperature from 40"C to 80"C a maximum
incorporation of 15.33 vol.% was observed at 50"C. A further increase in
temperature caused a slight decrease in incorporation. At a maximum
temperature of 80"C the vol.% of incorporation was found to be 14.8%.

ii) Zn-Cr^i Electrocomposite

The effect of temperature of the bath on the vol.% inclusion of

Cr^O^ is shown in Fig. (4.1.14).

91
 It was observed that the temperature ot" the bath markedly
influenced the amount of CTIOT, particles co-deposited. It was found that at
a lower temperature of 30"C. the amount of CT20y co-deposited was found
to be 19.0 vol.%. whereas at a higher temperature of 40''C it got increased
upto 21 vol.%. Any further increase of temperature caused the decrease of
incorporated particles. At a ma.ximum temperature of 60"C only a 19.6
vol.% of CriOj was estimated in the deposit.

Hi) Zn-MoS; Electrocomposite

The effect of temperature on the vol.% incorporation of M0S2 is

shown in Fig. (4.1.15 ). The temperature was varied between 30 and 60"C
for M0S2 incorporation.

A ma.\imum incorporation of 12.9 vol.% of M0S2 was observed at a

temperature of 50"C. At a lower temperatures of 30"C and 40"C. the vol.%
of incorporation of MoS; was found to be 11.3% and 12.0% respectively.
The effect was not much pronounced when varied between 30''C and 50"C.
With further increase the amount of substance incorporated was found to
slightly decrease to 12.5% and increase in temperature affected the quality
of the deposits also.

iv) Zn-AliOjt Eelectrocomposite

The effect of temperature on the vol.% incorporation of ANOj is
shown in Fig. (4.1.16 ). The temperature was varied between 30 and 60"C.
It was found to have a little influence on the vol.% of particles incorporated
with a slight decrease being observed at a higher temperature of 50"C or
60"C. The co-deposition was found to be 5.2 vol.% at 60"C whereas it was
5.0 vol.% at 30"C. Similar insignificant effect of temperature [31] have
been reported by other researchers also.
 20 '
Temp =60°C
•o c.d. = 9 Adm'^

E
•14
1-
S5
O
>
8
4
1 3 5
PH
_>

Fig. (4.1.9 ) : Influence of pH of the bath on TiOi content of the deposit

22.5
Temp = 40°C
1 c.d. = 8Adm'^

I 21
E
o

u
•5 19.5
o
>
18
4 8
pH

Fig. ( 4.1.10): Influence of pH of the bath on CriOj content of the deposit

93
 12
1 Terrp =50''C
11.6 c.d = 7 Adm'.-2
E
11.2
o
S
10.8
10.4
o
10
>
4 8
pH

Fig. (4.1.11 ) : Influence of pH of the bath on M0S2 content of the deposit

Temp =40°C
•o • 4 Adm'
"S
1^
6
<
•S 4

>

0 4 8
pH

Fig. (4.1.12 ) : Influence of pH of the bath on Ai^Oj content of the deposit

94
 '
15.6
pH = 5
c d = 9 Adm'^

? 15
E

^14.4
"o
>

13.8
0 35 70 105
Temperature °C

Fig. (4.1.13 ) : Influence of temperature of the bath on TiOj content of the deposit

22
pH = 3
c.d. = 8 Adm"^
•a
o
•o
»
n
E 20
o
O
O

o
>

18 L
0 10 20 30 40 50 60 70
Temperature in "C

Fig. (4.1.14): influence of temperature of the bath on Cr^Oj content of the deposit

95
 pH=2
cd =7Adm'
1 12.5
E
i 12
s
!! 11.5
o
> 11
0 30 60 90
Temperature in °C

Fig. ( 4.1.15): influence of temperature of the bath on M0S2 content of the deposit

pH = 5
o cd. = 4 Adm'
•o
•o
o
E
«
O. 5

o
>

25 35 45 55
Temperature in °C

Fig. ( 4.1.16): Influence of temperature of the bath on AI2O3 content of the deposit

96
 C - concentration of the dispersoid particles in the bath in
volume percent
a - volume traction ot" the dispersoid particles in the
deposit.
W.d.n - atomic weight, density and valency of the
electrodeposited metal
F - Faraday's constant
K - is related to the intensity of interaction between
particles and the electrode,
io. r| - are the e.xchange current and over potential.

The equation (1) can also be expressed as

Wi.,B/A
log tgcj) = log + (1 -B/A) log i
nFdVj,

The parameters v„ and B are related to the particle deposition and

plays a symmetrical role with parameters !„ and A which are related to the
metal deposition. On plotting C/a against C a sheaf of straight lines having
the common intersection on the point 1/K of the C axis if obtained shows
that particle adsorpotion follows Guglielmi's adsorption model. Here in the
present investigation for all the above developed zinc composites
Guglielmi's adsorption model is verified experimentally.

in case of Zn-TiO^ electrocomposite Fig. (4.1.17 ) gives the results

plotted for C Vs C7a. The common intercept on the C axis has a value of
-0.7. The Fig.(4.1.17) for Zn-TiO; electrocomposites is quite similar to
Langmuir adsorption isotherm and it is clear that the co-deposition
mechanism is based on physical adsorption etTects.

98
 For Zn-Cr:0.i Fig. (4.1.18) gives the plot of C Vs C/a and we get a
similar sheaf of straight lines converging at a negative point on the x axis
with 1/k value of -2.5

Fig.(4.1.19) gives the plot of C Vs C/a values for Zn-MoS: system.

The experimental points can be satisfactorily grouped on a sheaf of
straight lines at 1/k of -0.5.

Fig.(4.1.20) gives the plot of C Vs C/a values for Zn-AKOj

electrocomposites. The 1/K value is found to be -1.4. The above results
show that the co-deposition for all the four systems agree with the model
proposed by Guglielmi. The difference in the 1/k values are due to the
difference in physical constants namely density, particle size etc. However,
some of the points do not fix exactly, possibly due to experimental errors
similar to that indicated by other researchers [32-34] for their system of
study.

4.1.3 Characterization of zinc composites

4.1.3.1 Adhesion

The adhesion of Zinc and Zinc composites are ven.- good.

Qualitative examination of bending, scrubbing, and heat/quench did not
cause any separation of the composite coatings from the base material.

4.1.3.2 Micro Hardness

Variation in the micro hardness VHN25 of electrocomposites of

thickness 30|im in the as plated and heat treated at 400"C for three hours
are noted.

99
 1.2
I/k = -0.7
1 . d
0.8 >XV/ a
jf ^ / ^ ^ C
: ^ 0.6
1o
0.4
0.2

0 > _i 1 1

n 9
1 4 9 14 1

C(vol. % of TiOz in the bath)

-J
Fig. (4.1.17): Variation of (C/a) as a function of (C) forTi02 codeposition
(a)7A/dm^ (b)8A/dm^ (c) 9A/dm^ (d) lOA/dm^

3.5
1/k = -2.5
A
25

/ .a
! ^
O
1.5
/ ^ ^'^ ^b

y' t / ^ ^ ^ ^ " ^
0.5

-5 0 5 10 15 20 25 30
C (Vol. % of CrzOs In the bath)
^

100
 f \

1.2
l/k=-0.5
1 ^ d
0.8

0.6

^ ' " 0.4

0.2
n 1 1 1
u
D 2 4 6 8
-2 (
C(vol. % of MOSj in the bath)
^

Fig. (4.1.19): Variation of (C/a) as a function of (C) for M0S2 codeposition

(a)5A/dm^ (b) 6A/dm^ (c) 7A/dm^ (d) 8A/dm^

C (Vol. % of AI2O3 in the bath)

^

Fig. (4.1.20): Variation of (C/a) as a function of (C) for AI2O3 codeposition

(a)2A/dni^ (b) 3A/dm^ (c) 4A/dm^ (d) 5A/dm^

101
 For Zn-TiOi. the micro hardness is taken at three difTerent vol.%
incorporation of TiO: particles. The results are summarized in the
Table (4.1.1). The hardness is found to increase with increase in TiOi
particles. The increased hardness in the case of the composite after the heat
treatment condition is due to the intermetallic diffusion. The dispersed
particles in the matrix act to obstruct the movement of dislocations and
resist the plastic flow of the matrix, thus improving the hardness. The
hardness of the composites are mainly influenced by the percentage of
embedded particles. In case of Zn-TiOi system with increase of TiOi
particles the hardness is also found to increase. Thus in comparison with
the singular zinc matrix, the electrodeposits show improved hardness, both
in as plated and heat treated condition at 400"C.

The variation of micro hardness values for as plated and heat treated
Zn-Cr^Oj composites at 400"C for 3 hours duration is presented in
Table(4.1.2). For a maximum incorporation of 22.7 vol.% of Cr^Oi
particles the hardness is found to be 140.8 VHN and 152 VHN before and
after the heat treatment.

The micro hardness values of electrodeposited Zn-MoS^ composites

are given in Table(4.1.3). The hardness was found to decrease with
increase of MOST particles in the deposit both in the as plated and heat
treated condition. The decrease in micro hardness is due to combined
action of two factors, namely softening of the matrix and particles growth.
Such growth of particles will lead to non-uniform distribution of the
particles in the zinc matrix with the result that large non-uniform
dislocation stress fields will be formed around the coarse particles with the
resultant shearing of the particles before effective hardening occurs [35].
The hardness values in such a case are thus expected to below.

102
 Table-4.1.1

Micro hardness of electrodeposited Zinc and Zinc - TiOj composites

Sl.No. System Vickers Hardness (Load 25 g)

As plated Annealed at 400*'C

1 Zinc 49 56.5

2 Zn-Ti02(14.4%) 70.9 83.9

3 Zn-Ti02(15.3%) 71.8 84.2

4 Zn-TiO:(15.6%) 72.8 87.3

103
 Table-4.1.2

Micro hardness of electrodeposited Zinc and Zinc - Cr203 composites

SI.No. System Vickers Hardness (Load 25 g)

As plated Annealed at 400°C

1 Zinc 49 56.5

2 Zn-Cr203(18.1) 115 129

3 Zn-Cr203(21.6) 129.2 138

4 Zn-Cr203(22.7) 140.8 152

104
 Table(4.1.4) gives the micro hardness values of electrodeposited
Zn-AKO.^ composites at different volume% of AKOj particles. The
hardness is found to be the maximum for AKO.^ (5.6%) after heat treatment
at 400"C has recorded a three fold increase when compared to the pure zinc
matrix.

4.1.3.3. Wear loss

The wear loss for zinc and zinc composites both in the as plated and
heat treated conditions are given in Table [4.1.5].

In the case of all the composite systems it was observed that there is
an increase in the wear resistance compared to the pure singular zinc
matrix. The wear resistance of the composites after heat treatment was
found to increase compared with the as plated ones. Among the composites
developed the wear resistance of Zn-MoSi system is the highest, with a
minimum wear loss of 0.007 gms after heat treatment.

Wear is a surface phenomenon which consists of the gradual

materials deterioration of contacting surfaces. Here the abrasive wear is
the removal of particles due to friction. The higher wear resistance of
Zn-MoS: system is attributed to the lubricating nature of the MoS;
particles. The wear loss is higher (0.036 gm) with Zn-AUOj system. This
may be due to the hard nature of the ANO^ particles which could have
increased the frictional resistance of the surface.

These results reveal that the wear resistance of composite coatings is

not directly proportional to their hardness [36]. It may be related to the
hardness ratio of matrix to particles.

4.1.4. Corrosion resistance characteristics of the zinc and zinc

composites

4.1.4.1. Weight loss method

The corrosion behaviour of zinc and its composites in 5% NaCl
obtained by weight loss method is presented in Table (4.1.6 ).

106
 Table-4.1.4

Micro hardness of electrodeposited Zinc and Zinc - AI2O3 composites

S1.N0. System Vickers Hardness (Load 25 g)

As plated Annealed at 4 0 0 T

1 Zinc 49 56.5

2 Zn-Al:03(4.6%) 118.2 123

3 Zn-Al203(5.1%) 122.3 154.9

4 Zn - AI2O3 (5.6%) 135.4 166.3

107
 Table-4.1.5

Wear loss of electrodeposited Zinc and Zinc composites

SI.No. System Wear Loss

As plated Annealed at 400''C

1 Zinc 0.438 0.236

2 Zn-TiO:(15.6%) 0.019 0.010

3 Zn - Cr.Oj (22.7%) 0.014 0.024

4 Zn-MOS:(12.4%) 0.035 0.007

5 Zn-Al203(5.6%) 0.036 0.017

108
 Table-4.1.6

Corrosion parameters of zinc and zinc composites in 5% NaCI obtained

by weight loss method

System Weight loss Icorr Efficiency

(mdd) (A/cm-) (%)

Zinc 4052 1.38x10-' -

Zn-TiO. 2342 8.00 xlO"" 42.20

Zn-Cr.Oj 3269 1.11 xlO-' 19.52

Zn-MoSi 4098 1.40 xlO"-^ *1.12

Zn-ANOj 3520 1.20 xlO'-' 13.12

Stimulation

109
 Among the different composites the corrosion resistance behaviour
is of the order of Zn-Ti02>Zn-Cr:03> Zn-AKOj. In the case of Zn-MoSi
instead of corrosion inhibition a sHght enhanced corrosion is noted. The
trend of corrosion inhibition is related to the micro structure of the
deposits. With TiO:. Cr^O; and Ai^O.^ particle incorporation, grain
refinement and compactness in the deposits are observed. This accounts for
improved corrosion resistance behaviour. With Zn-MoS^ deposits some
porosities are observed which is evident from SEM studies and this might
have caused a slight enhanced corrosion.

4.1.4.2 Potentiodynamic polarization method

The corrosion current for all the composites except Zn-MoS: is

found to be significantly decreased compared to the pure zinc matrix. The
Ij-orr values exhibit the following trend.

Zn-MoS: > Pure zinc > Zn-Cr.O.^ > Zn-ANO., > Zn-TiO;. Thus in
5% NaCI solution, zinc electro composites offer improved corrosion
protection except Zn-MoS2 deposits. A similar behaviour of MoS; particles
with Ni matrix has been reported [37]. In all these cases the cathodic
control of the corrosion reaction is inferred from the fact that b^ > ba.

Fig (4.1.21) shows the potentiodynamic polarization curves for pure

zinc and its composites in 5% NaCl. The linear segments of the
polarization curves were extrapolated to OCP to obtain the current density
(itorr)- The corrosion results obtained from potentiodynamic polarization
method is summarized in Table (4.1.7 ).

4.1.4.3. Impedance method

The results of impedance measurements for zinc and zinc-

composites are given in Table (4.1.8 ) and in Fig. (4.1.22 ).

ilO
o

-1200 -1100 -1000 -900 -800 -700

Potential (V)

Fig.4.1.21 Potentiodynamic polarization curves for Zinc and Zinc composites

obtained in 5% NaCI a) Zn, b) Zn-TiOj, c) Zn-CrjOj, d) Zn-MoSj, e) Zn-AljOj

11
 Table-4.1.7

Corrosion parameters of zinc and zinc composites in 5% NaCI

obtained by potentiodynamic polarization method

System E ^corr be Efficiency

mVVs A/cm* mV/dec mV/dec
(10')

Zinc -1061 3.63 170 197 -

Zn-TiO: -1044 1.05 165 178 71.07

Zn-Cr20j -969 1.09 161 205 69.97

Zn-MoSi -1058 3.75 169 179 *3.05

Zn-Al.O^ -1066 2.75 161 183 24.24

* Stimulation

12
 1 1 1 1 1 1 1 1
8.888

6.888 -
+b X -

X
6 +
O 4.888

N + X

2.888 * X 3K X
* X VK X a
••
>« + m

8.808
1 1 1 1 1 1 1 1
2.888 4.888 6.888 8.888 18.888 12.888 14.880 16.888

Z' (ohm)

Fig.4.1.22. Nyquist plots for the corrosion of Zinc and Zinc composites in 5%
NaCl
a) Znic, b) Zn-Ti02, c) Zn-Cr203, d) Zn-MoS2, e) Zn-AbOs

113
 Table-4.1.8
Corrosion parameters of zinc and zinc composites in 5% NaCI
obtained by impedance method

System Impedance Method

R, (ohm/cm~) Cdi (^F/cm-)

Zinc 3.32 54.15

Zn-TiO: 38.29 14.20

Zn-Cr203 7.191 45.10

Zn-MoS: 1.53 71.55

Zn-Al:0, 7.067 16.07

114
 As with weight loss and polarization results, the same trend of
inhibition is reflected from the R, values for the corrosion of the deposits in
5% NaCl. Except with Zn-MoS:. the Cji values have decreased for other
deposits indicating lesser charge in the interface. However in the case of
Zn-MoS: there is increased Cji value confirming the porous nature of the
deposit with entrapped charges. The Nyquistian plots in all the cases are
semicircles confirming the charge transfer control of the corrosion process.
Excepting in the case of M0S2 in other systems there is a rising portion at
the low frequency end suggesting a partial mass transfer control, in the
case of Zn- M0S2 two semi circles could be seen with the smaller one on
the lower frequency end. This suggests the adsorption of the ion of the
medium on the pores of the deposits as a slow process.

4.1.5. Structural investigation of the zinc electrocomposites

4.1.5.1. Optical microscopic studies

The optical micrographs of various zinc composites both in the as
plated and heat treated conditions were taken at different magnifications of
X 100.x 200 and X 2000.

The photomicrograph of as plated and heat treated pure zinc

coatings are given in Fig.(4.1.23)

The optical micrograph of Zn-TiOi system is shown in Fig. (4.1.24).

The grains have a nodular structure due to the incorporation of TiO:
compared to the plain zinc deposits. This nodular structure is due to the
control of lateral growth promoted by the adsorbed TiOj particles. In the
heat treated conditions the crystals are found to be arranged in a uniform
pattern. The optical micrographs of Zn-Cr^Oi system are shown in
Fig.(4.1.25). The incorporation of Cr^Oj particles as clusters in between
zinc crystalites could be seen. Fig.(4.1.26 ) shows the optical micrographs
of Zn- M0S2 system. The embedded M0S2 particles were shown as a dark
patch. Fig.(4.1.27) shows the optical micrographs of Zn-ANO^ system.

115
 (a) X 100 (b)X100

(a) X 200 (b)X 200

(a) X 2000 (b)X 2000

Fig.4.1.23 Optical micrographs of pure Zinc deposits obtained at different magnifications

a) As plated b) Head treated at 400°C for 3 hrs.

116
 (a) X 100 (b)X 100

(a) X 200 (b)X 200

(a) X 2000 (b)X 2000

Fig.4.1.24 Optical micrographs of Zn-TiOi deposits obtained at different magnifications

a) As plated b) Head treated at 400°C for 3 hrs.

117
 (a)X100 (b)X100

(a) X 200 (b)X 200

(a) X 2000 (b) X 2000

Fig. 4.1.25 Optical micrographs of pure Zn-Cr203 deposits obtained at different magnifications
a) As plated b) Head treated at 400°C for 3 hrs.

118
 (a) X 100 (b) X 100

(a) X 200 (b)X 200

(a) X 2000 (b)X 2000

Fig. 4.1.26 Optical micrographs of pure Zn-MoS2 deposits obtained at different magnifications
a) As plated b) Head treated at 400°C for 3 hrs.

119
 (a) X 100 (b)X 100

(a) X 200 (b)X 200

(a) X 2000 (b)X 2000

Fig.4.1.27 Optical micrographs of pure Zn-AhOs deposits obtained at different magnifications

a) As plated b) Head treated at 400"C for 3 lirs.

120
The grains of zinc are well defined and AKO.^ particles could be seen as
fine inclusion. In the heat treated condition it was found to be a compact
deposit.

4.1.5.2. Scanning Electron Microscopy

The scanning electron micrograph of zinc and zinc compxssites were

taken at difierent magnifications. The SEM photograph of Zn-TiO: system
is shown in Fig.4.1.28(a). It is clear from the photographs that in between
zinc crNslalites clusters of TiO: particles could be seen The distribution is
found to be uneven. The inclusion of TiO^ particles has led to the nodular
and uniform growth of zinc cr\stals. this in turn has improved the
properties of Zinc. The incorporation of CriO^ particles into the zinc matrix
has resulted in the layered structure of zinc shown in Fig.4.1.28(b).
Fig.4.1.29(a) shows the incorporation of M0S2 particles in zinc matrix
which has resulted in the porous structure for the deposit. Also the particles
have been shown as spherical ones giving oriented structures. The
incorporation may account the improved wear resistance and lubricating
propert>' of the deposit

The SEM of Zn-ANO^ composite is shown in Fig.4.1.29(b).

Uniform distribution of ANO.^ particles inducing oriented crsstal growth
could be seen.

121
 xlOOO
X4000

^^^i^i^'
xlOOO
x4000

Fig. 4.1.28 SEM of a) Zn-Ti02, b) Zn-CxiOy composites obtained at different

magnifications

122
 xlOOO x4000

xlOOO x4000

Fig.4.1.29 SEM of a) Zn-MoSi, b) Zn-AliOs composites obtained at different magnifications

123
4.1.5.3. XRD studies

XRD studies were made for the pure zinc deposit as well as for the
zinc composites developed to ascertain the incorporation of composite
particles in the zinc matrix. The results for pure zinc is presented in
Table(4.1.9) and in Fig.(4.1.30) . The calculated lattice parameters for the
zinc deposit suggest hexagonal structure with a = 3.033A and c = 5.676A.
The XRD parameters for Zn - TiO: composites is given in Table ( 4.1.10)
and the pattern in Fig. 4.1.31 (a). The TiO; used for co-deposition is
identified to be of anatase form. The calculated lattice parameters for
Zn-TiO: system are a = 3.8102A and c = 9.3108A with a tetragonal
arrangements. The results for Zn-Cr^O^ svstem are presented in
Table(4.1.11) & in Fig. 4.1.31(b). Hexagonal rhomb centered structure of
the deposit is inferred with lattice parameters a=5.0746A and c= 3.4970A.
The results for Zn-MoS: system are presented in Table(4.1.12) &. in
Fig.4.1.32 (a). The worked out lattice parameters value are found to be
ver\' high suggesting some amorphous nature for the deposit.

In the case of Zn-hhOy system the same crystallographic form as

that of zinc is inferred from the results presented in the Table(4.1.13) and
in Fig. 4.1.32 (b). The lattice parameters are a = 5.0532A and
c = 15.8082A. In this case the nature of AKO^ particles used for the
composite development was of a-form.

124
2000-

Fig. 4.1.30. XRD pattern for Pure Zinc deposit

125
 wA-.f^'W>~vi^^
20 30 m 50 60 70 so 9C
2©

Fig. 4.1.31. XRD pattern for a) Zn-TiOi b) Zn-CriOs electro composites

126
Fig. 4.1.32. XRD pattern for a) Zn-MoS2 b) Zn-A^Os electro composites

127
 Table-4.1.9

XRD - Parameters for electrodeposited zinc

Observed data PDF data

20 d 20 d

36.00 2.42 36.30 2.48

38.70 2.32 38.99 2.31

42.00 2.10 43.23 2.11

70.45 1.33 70.65 1.33

128
 Table-4.1.10

XRD - Parameters for electrodeposited Zn-TiOi

Observed data PDF data

26 d 26 d

37.45 2.40 37.84 2.39

38.65 2.33 38.60 2.33

47.70 1.90 48.07 1.91

54.00 1.69 53.95 1.69

Table-4.1.11

XRD - Parameters for electrodeposited Zn-CriOj

Observed data PDF data

26 d 26 d

24.56 3.67 24.25 3.69

36.21 2.50 35.90 2.50

41.50 1.34 42.85 2.11

76.84 1.22 76.85 1.24

129
 Table-4.1.12

XRD - Parameters for electrodeposited Zn-MOSj

Observed data PDF data

20 d 29 d

35.95 2.50 34.10 2.49

38.60 2.33 38.18 2.31

42.85 2.11 41.00 2.10

69.75 1.35 64.35 1.34

Table-4.1.13

XRD - Parameters for electrodeposited Zn-AliOj

Observed data PDF data

20 d 20 d

35.90 2.50 35.58 2.49

38.60 2.33 38.12 2.32

54.00 1.70 53.12 1.68

62.45 1.49 62.18 1.48

130
4.2. ROLE OF ADDITIVES IN ZINC PLATING BATHS

Zinc can be electrodeposited from alkaline cyanide, alkaline cyanide

free, acid sulphate, acid chloride, fluoborate and pyrophosphate baths.
Alternative to cyanide bath has become a necessity due to the very slow
rate of deposition and toxic effects. With acid and alkaline baths faster rate
of deposition compared to cyanide baths could be achieved. However,
these baths have very limited operational altitudes. Hence one has to
overcome these difficulties with suitable additives incorporated into the
bath.

The use of zinc sulphate baths as alternative to cyanide zinc baths is

on the increasing trend due to its relatively lou cost, safety features and
pollution control characteristics. The main disadvantages with such baths
are their poor throwing power and insufficient brightness of the deposit. To
overcome these difficulties many addition agents have been tried, among
them organic compounds [38-40] such as anthranilic acid, formaldehyde,
glycine, thiourea, m-dinitro benzaldehyde and furfaraldehyde need special
mention for their role as brighteners.

Alkaline zinc electrolytes are non-toxic and cheap. Triethanolamine.

furfaraldehyde. p-nitrobenzaldehyde. phenyl antranilic acid etc. are some
of the additives reported for alkaline baths [41].

In the present investigation the condensation products of some of

the carbonyl compounds with thiosemicarbazide have been evaluated for
their performance as additives in the reported acid [42] and alkaline [43]
baths.

The performance of some of the thiosemicarbazones in contrast to

the individual components on the Hull-cell pattern, cathode efficiency and
throwing power are discussed. The possible mechanism for the deposition

131
and dissolution of zinc in presence of the additives are examined tlirough
cyclic voltammetric studies and the results are discussed. Also the
corrosion resistance of the deposits in 5% NaCI solution was evaluated.
The deposit microstructures is reflected in their hardness values. This is
ver\ much controlled b\ the specificity' of the additives in plating bath.
These aspects are probed through SEM studies.

4.2(i). Hull cell studies

Hull cell studies are very useful to know the possibility of obtaining
smooth fine grained and bright zinc deposits under the influence of
additives at an optimum current densit\.

The legend for the Hull cell studies is presented in Fig (4.2.1).

The deposits obtained from plain acid bath was dull over a wide
current densitv range and burnt at the high current densitN areas, whereas
the deposits from plain alkaline bath was a gre\ deposit over the full range
of the Hull-cell panel. The effect of individual additives on the deposit
quality as revealed through Hull cell studies are discussed below.

Effect ofthiosemicarbazide

The concentration of TSC was varied from 0.1 to 0.4 gdm"' and 0.5
to 0.2 gdm" in the optimized acid and alkaline zinc plating baths
respectively. The corresponding Hull cell patterns are presented in
Figs.4.2.2(a)& 4.2.2(b).

in the case of acid bath at 0.1 gdm'' concentration a semibright

deposit was observed in the current densit\ range 0.3-5.5 Adm''. At low
current density area below 0.3 Adm'' the deposits obtained were dark grey
and pitted in nature. As the concentration was increased the deposit
obtained were found to be dull, powderv' and poorly covered.

132
 MIRROR BRIGHT DEPOSIT

BRIGHT DEPOSIT

SEMI BRIGHT DEPOSIT

v\\\\\\\\\\\S\\\\\\S>
DARK GREY DEPOSIT
ILXVVVW^^>>V>^^X>..>^U

POWDERY DEPOSIT

SATIN WHITE
f^^^^^^r^r^r^r^r^

STREAKS

DULL DEPOSIT

BURNT DEPOSIT

FFST^FTTTTTn

•«••••••••'
POROUS
»••••••••••

NO DEPOSIT

GREY DEPOSIT

Fig. (4.2.1) Legend for Hull Cell Studies:

133
TSC gdm-^

—» » • »• ' — : r y
a. 0.0 1 •- • '•

h n 1 >• -

ft 7 * 1

- •
, ,

• •
•

H n^

p Hi
I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
80 60 50 40 3024 2 0 1 6 1 2 0806040201

Fig.4.2.2(a) Effect of TSC concentration in acid bath

TSC gdm ^

a. 0.0

ytw j« y j jf^ ;» ^•jtjry jr;»y y r

b.0.5 ^»^>>^>i->g

c. 1.0

n 1 \ \ 1—I—I—I—I 1—I—I—I—r
40 30 25 20 15 12 100806 040302 0 1 0 05

Fig4.2.2(b) Effect of TSC concentration in alkaline bath

134
 In the case of alkaline bath a lower concentration of 0.5 gdm'"'
produces mostly a streaky deposit over a wide current density range. At a
concentration of 1.0 gdm"" bright deposits are obtained over a narrow
current densitv range ot 0.6-1.2 Adm". Further increase in the
concentration of the additive yields grey and porous deposits and are
sometimes pitted also. At 2.0 gdm" concentration there was no deposit
towards the low current density end.

Effect offurfaraldehyde

The concentration of FrA was varied between 0.1 mldm" and

0.4mldm'" in acid bath and from 0.5 to 2.0 mldm" in the case of alkaline
bath. The results are presented in Figs.4.2.3.(a) & 4.2.3.(b) respectively.

At the additive concentration of 0.1 mldm' in the case of acid bath,

a bright deposit was observed in the current density range 1.6 to 4.0 Adm'".
An\ further increase in concentration causes mostK streak), dull and burnt
deposits for the full length of current densities.

As with acid bath, in the case of alkaline bath also we get bright
deposit for 2.0mldm" concentration but only over a limited current density
range of 1.0 - 2.5 Adm''.

Effect of salycylaldehyde
A
The concentration range tried was the same being 0.5 to 2.0 mldm
in both acid and alkaline baths. The Hull cell patterns are shown
Fig.4.2.4(a) & 4.2.4(b) respectively. There was no bright deposit in both
the medium for the full range of concentration tried, over the entire current
density range. In the case of acid bath at a concentration of 0.5ml dm"' a
semibright deposit could be obtained for the current densitv range 1.6 to
2.4 Adm'". However with alkaline bath we get a satin white finish for
1.0 mldm'"* concentration in the current density range 0.4 to 1.2 Adm'".

135
 FrA mldm -3

a. 0.0

b.0.1

c.0.2

d.0.3

e.0.4 ' ^r^r^r2rz^n:^^-M^rzrzr2rz'^'^^r2r^r2r2r2rz'^'zrz:z'^rz:^'^'^'^nsi

I 1 1 \ 1 1—I—I—I—I 1—I—I—I—r
80 60 50 40 3024201612 0806040201

Fig 4.2.3(a) Effect of FrA concentration in acidic bath

FrA mldm -3

a. 0.0

b.0.5

c. 1.0

' v T " - - •,..-•' •

d. 1.5

e.2.0
I 1 1 \ 1 1—I—I—I—I 1—I—I—I—r
40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 0 1 0 05

Fig4.2 J(b) Effect of FrA concentration in all^aline bath

136
 SaA mldm -3
I I V' , ,» r.

a. 0.0 - -^ •' si.

h. n.s

r. 1.0

H. 1.5

e. 2.0

1 1 1 1 1—\—I—I—I \—I—I—I—I—I
80 60 50 40 3024 201612 080604 0201

Fig 4.2.4(a) Effect of SaA concentration in acidic bath

SaA mldm'

a. 0.0

b.0.5

c. 1.0

;» ; » P » » > > » » » » > » i m > » » » » > » » » > » > » » t m m

I******* »*« «l
d. 1.5 ^t^tlllltl*?t?**»»?»??>t«»«?t»l»»»tt>t»«S«l

V';. .•:•'? -'

e. 2.0 /-^^^~^y.^^^y^^^^^^^^^^^^^Z^^^^^^^^^^^^^^^^^^^^^U

~l I I I 1 — I — I — I — I 1 — 1 — I — I — 1 — I
40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 010 05

Fig 4.2.4(b) Effect of SaA concentration in alkaline bath

137
Effect of cinnamaldehyde

0.5 to 2.0 ml dm" concentrations have been tried in both acid and
alkaline plating baths and the results are presented in Figs 4.2.5 (a) &
4.2.5(b) respectiveK. No bright deposit could be located in presence of the
additive. At the best onh a semibrighi deposit could be obtained at
1.5ml dm" concentration in alkaline bath in the current densit> range
1.5 to 2.5Adm''. With 0.5 ml d m ' concentration of the additive in the acid
bath a dull deposit could be obtained in the current densit\ range of 1.2 to
2.0 Adm'-.

In both the media with higher concentration of the additive at higher

current density ranges uniformly burnt deposits are observed.

Effect of crotonaldehyde

With crotonaldehyde the concentration range tried was same in both

acid and alkaline baths which varied between 0.5 ml d m ' and 2.0 ml dm".
The Hull cell patterns for both the plating baths are shown in Figs 4.2.6 (a)
and 4.2.6 (b).

In the case of acid bath at 0.5 ml dm " concentration ue get a dull

deposit covering the current density range of 4.0 to 5.0 Adm"'. With the
higher concentration of 2.0 ml dm"' there is no deposit over the major
current density range covering upto 8.0 Adm"". Beyond that at still higher
densities as usual we get a burnt deposit. For the highest concentration of
2.0 ml dm""' in the case of alkaline bath we get a semi-bright deposit
covering the current density range of 1.2 to 2.0 Adm"'. Beyond this
maximum current there were onU burnt deposits.

138
 CnA mldtn'^

a. 0.0

b.0.5

c. 1.0

d. 1.5 iiliii
.. r—r-p- • - ; J (•-. • .,

e.2.0
-l 1 1 1 1 — I — I — I — I 1 — I — \ — I — I —
80 60 50 40 3024 201612 080604 0201

Fig 4.2.5(a) EfTect of CnA concentration in acidic bath

CnA mldm'

a. 0.0

b.0.5

c. 1.0

d. 1.5

e.2.0
I 1 1 \ 1 1—I—I—I—I \—I—I—I—I—I

40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 0 1 0 05

Fig 4.2.5(b) EfTect of CnA concentration in alkaline bath

139
CrA midm ^

a. 0.0 N M ^•.*' it-X-I-I-X-:

b.0.5

c. I.O ** *^ «* i/» n^ »» »A i/i » • V •!* w* •A •". w* »/» V* 1^ »* ^^ , ^ I

d. 1.5

e.2.0
~i 1 1 1 1—I—I—I—I 1—\—\—I—r
80 60 50 40 3024 201612 0 8 0 6 0 4 02.0 1

Fig 4.2.6(a) Effect of CrA concentration in acidic bath

CrA mldm -3

a. 0.0

b. 0.5

C. 1.0

d. 1.5

e.2.0
-I 1 1 1 1—I—I—I—I 1—I—\—I—r

40 30 25 20 15 12100806 040302 0 1 0 05

Fig 4.2.6(b) Effect of CrA concentration in alkaline bath

140
Effect of acetophenone

The concentration of acetophenone was varied between 0.1 ml dm'"'

and 0.4 ml dm" in the case of the acid bath and from 0.5 to 2.0 ml dm'' in
the case of alkaline baths. The corresponding Hull cell patterns are
presented in Figs. 4.2.7 (a) & 4.2.7(b) respectively.

The best quality deposit we could get was only a dull deposit for the
concentration of 0.2 ml dm ' in the current density range 3.0 to 4.0 Adm'".
With the lower or higher concentrations of the additive we get mostly
powdery or streaky deposits only. In the case of alkaline bath with 1.5 ml
dm" concentration we get a grey deposit in the low current densit) region
of 0.8 to 1.2 Adm"'. With lower or higher concentration of the additive for
the full range of current density mostly we get dark grey or burnt deposits
only.

Effect of the condensation products of the above carbonyl compounds

with thiosemicarbazide

After having studied the effect of individual carbonyl compounds

and thiosemicarbazide separately as additives in acid and alkaline zinc
plating baths on the Hull cell pattern, it was then proceeded with their
condensation products.

Effect of the furfarldehyde thiosemicarbazone

The concentration of FrTSCN was varied from 0.3 ml dm ' to

0.6 ml dm'' in the acid bath and from 0.5 ml dm " to 2.0 ml dm"' in the case
of alkaline bath and the results are presented in Figs. 4.2.8(a) & 4.2.8(b)
respectively.

In the case of the acid bath even with low concentration of

0.3mldm"' we are able to get a mirror bright deposit covering a wide
spectrum of the current density range starting from 0.2 Adm'' to 8.0 Adm"'.

141
 AcP mldm"^

I •j.'v , .' I-.-.-.-.-.-.---.---.-.

a. 0.0 J.'.. ;.V.:' • rxXi-xX:::-::;

r9*7t770<W*9*7779'79*7799(77^9!^9*9*77t>*9(9n^7777^9(:n79
b.0.1

» . 1 V '—,. ^ ; <. ,
r. (1.2 v.-!^ v . w : / . . ^ :, {-:-
---•-•-"-• ••••••«••••>*«•••«>«•««••••»••••«•••
>••••••••••••••»•«••••••««••••>•••••
,'' •• .». .^ • - i i ' I--

rt. n..^

e. n.4
I 1 1 1 1 1—1—I—\—I 1—I—\—I—I—

8 0 6.0 5.0 4.0 3.0 2 4 2 0 1 6 1.2 0.8 0 6 0 4 0.2 0.1

Fig 4.2.7(a) Effect of AcP concentration in acidic bath

AcP mldm'

a. 0.0

r7"<ir^^wro"'W!;^^r^w?twjjwTOrTOiKW?«WTO:^^w^rr^rwrK!jw^^^^
h. 0..S

.VVVVKV§«»«««»>»« • » • • • • » • • • • I
c. 1.0

d. 1.5

e.2.0

n 1 1 1 1—I—I—I—I 1—I—\—I—r
40 3.0 25 20 15 12 1.0 0.8 0.6 0 4 0.302010.05

Fig 4.2.7(b) Effect of AcP concentration in alkaline bath

142
FrTSrN mlHm'^

a. 0.0 :-:-:-x-:-:-x-:-:-:%-:-:-:-:-:-:-x<<-:-x-:-:-:-:-x-x<-:-x<-:-:-:->x-x^^^^

b.0.3

c. 0.4

1 . ' V , ^ - • • • T - - - ••,
d.0.5

e. 0.6
1 1 1 1 1 1 1 1 1 i 1 1 1 1
80 60 50 40 3024201612 0806040201

Fig 4.2.8(a) Effect of FrTSCN concentration in acidic bath

FrTSCN mldm -3

a. 0.0

b.0.5

c. 1.0

d. 1.5

e.2.0
1 1 1 1 1—I—i—I—I 1—I—I—I—I—I
40 30 25 20 15 12100806 0 4 0 3 0 2 0 1 0 05

Fig 4.2.8(b) Effect of FrTSCN concentration in alkaline bath

143
 With the increase in concentration of the additive we move on to
bright, semibright and grey deposits successively.

In the case of the alkaline bath, the concentration of the additive was
varied from 0.5 ml dm'" to 2.0 ml dm"'. With 1.5 ml dm"' concentration we
get a mirror bright deposit in the current density range of 0.4 to 4.0 Adm"".
With further increase in the concentration of the additive we get only dull
or semi bright deposits for the entire current density range.

Effect of salycylaldehyde thiosemicarbazone

In the case of the acid plating bath the concentration range of the
additive tried was between 0.1 ml dm"' and 0.4 ml dm""* while it was in the
range of 0.5 ml dm'" to 2.0 ml dm"' in the case of the alkaline bath. The
Hull cell results of the acid and alkaline baths are shown in Figs. 4.2.9 (a)
& 4.2.9(b) resjjectively.

The optimum concentration of the additive in the acid bath was

0.2ml where we get a bright deposit for the current density range of 0.8 to
4.0 Adm"'. With increase in concentration we get semibright and powder,
deposits only at high current density areas and no deposit zones in the low
current density end. In the case of the alkaline bath the optimum
concentration was found to be 0.5 ml dm" and we get bright deposit for the
current density range 0.2 to 1.5Adm'". For the same concentration on the
higher current density side we get semi bright and burnt deposits. Also
with increase in concentration we get only semi bright, burnt or powdery
deposits. At the highest concentration of 2.0 ml dm'" the major portion of
the Hull cell panel remains uncovered.

Effect of C'mnamaldehydethiosemicarbazone

The Hull cell patterns obtained for the additive CnTSCN in acid and
the alkaline baths are shown in Figs.4.2.10(a) & 4.2.10(b) respectively.

144
SaTSCN midm -3

a. 0.0

b.0.1 ^^•>.^.>..^^^_^.^_^.^.^-*_^^.>.^^.^.^r}-

/• ^ V* . * V* V* •'* v*

c.0.2

d.0.3

e.0.4
I \ 1 \ 1 1—I—\—\—I 1—I—I—\—r
80 60 50 40 3 0 2 4 2 0 1 6 1 2 0 8 0 6 0 4 0 2 0 1

Fig 4.2.9(a) Effect of SaTSCN concentration in acid bath

SaTSCN mIdm

a. 0.0

b.0.5 .vf.
• -

c. 1.0

d. 1.5

e.2.0

—1 1 1 1 1—I—I—I—I 1—1—I—I—r-
40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 0 1 0 05

Fig 4.2.9(b) Effect of SaTSCN concentration in alkaline bath

145
CnTSCN mldm -3
' • • • • • • • • • • • • • i T M ' W M wrw M^' m wn m'^w B ^ • y ••'•'^ • • ^ • T T ' B ' M g w • ^m •
' • ' V", '—T-T"
a. 0.0

b.0.1

c.0.2

— ' V' >• '—r.J" '• V'' --I 1 =

d.OJ

e.0.4

"I 1 1 1 1—I—I—I—\ 1—I—\—I—I—I

80 60 50 40 3024 2 0 1 6 1 2 0806 04 0 2 0 1

Fig 4.2.10(a) Effect of CnTSCN concentration in acid bath

CnTSCN mldm ^

a. 0.0

b.0.5

c. 1.0

\\\\\>.\\\\\\\\\\\\\\S\\\VN\\\\\\\\\\VNN\\V\\\\\V\VN\V\NN\\\V\NW

d. 1.5

e.2.0 • •

I 1 1 1 1 1—I—\—I—I 1—I—I—1—I—
40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 0 1 05

Fig 4.2.10(b) Effect of CnTSCN concentration in alkaline bath

146
With acid bath, the concentration range tried was from 0.1 mi dm'" to
0.4ml dm'" while it was in the range of 0.5 ml dm'" to 2.0 ml dm'" with the
alkaline bath.

The optimum concentration in the acid bath being 0.3ml dm'"'

covering the current density region 1.6 to 4.0 Adm'". while it was
1.5 mldm'"' with the alkaline bath and corresponds to the current density
range of 1.2 to 3.0 Adm''. In both the media with the lower concentration
of the additive we get dull or semi bright deposits and at higher
concentrations we get burnt, powder, or streaky deposit.

Effect of Crotonaldehydethiosemicarbazone

The results for the acid and alkaline baths are presented in
Figs. 4.2.11 (a) & 4.2.11 (b) respectively.

The working range of concentration of the additive in both the baths

are the same being 0.5 ml dm"" to 2.0 ml dm'"'. Further the optimum
concentration (1.5 ml dm'"') for the quality deposit is the same in both the
baths. With this concentration in the acid bath we get a bright depxjsit for
the current density range 1.0 to 3.0 Adm'' and in the case of the alkaline
bath we get only a dull deposit for nearly the same current densits range.

Effect of Acetophenonethiosemicarbazone

Figs.4.2.12 (a) & 4.2.12(b) represent the Hull cell pattern for the
acid and alkaline baths with the additive ApTSCN.

In the case of the acid bath the concentration of the additive was
varied from 0.1 ml dm'' to 0.4 ml dm ". The optimum concentration
required was found to be 0.3 ml d m ' with which we get semibright deposit
over the narrow current density range of 1.2 to 2.4 Adm". With other
conditions we get mostly porous, streaky or dull deposits only.

147
CrTSCN midm-

a. 0.0

b.0.5 x-:-:-x-!->>!-x-:-x->x-x-:-:-x-;->:-:-:-:-:-:-;-:-:-:-:-:-:-:-:-

c. 1.0 >»«»»»«»»>««»»»••«•«••«»••«•••>««<
;Aj^^ »•••»••»•••>••••••••••••«••••••••<

d. 1.5
- - - •* L - - - - - - . . . . - - « . , . , - - -

e.2.0

80 60 50 40 3024 201612 080604 0201

Fig 4.2.11(a) Effect of CrTSCN concentration in acid bath

CrTSCN mIdm

a. 0.1

h n.S t • T " ~ * ' ' - - * * * ' ~ ' ' * * * * * * * * * * * * ' * * * ' ' ' - ' ' * - * '

in V'l x::-:-x-x-x-:-.-.-.-.-.-.-:-.-.-.-.-.-.
• •^•^•f.i^M,^.^. I, • • ^ .. I . . . •• ^ r - - - * - ' - - - ' - * - -" '-^-'-^-'-'s's'-'r^T'.-.

rt. l.S
-- lAAA^^A^^AA^^^kAAA^A^^kAA^^^

e.2.0 'k:
-] 1 1 1 1—I—I—I—I 1—I—I—I—r-
40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 0 1 0 05

Fig 4.2.11(b) Effect of CrTSCN concentration in alkaline bath

148
 -3
AcTSCN mldm
a. 0.0 'f,'v—r:T-

b.0.1 «»*••>>••••••*•••«••»«»
— *—
. U J i.L 1 IL . . - X 1 . . 4 . ^ J . l . a L « J ( I A L a
••>««•••••••••««•»•««
-»-2 iasi 4« «••••••••»»•••••••••

d.0.3

e.0.4

I 1 1 ] \ \—I—\—\—\ 1—I—\—I—r
80 60 50 40 30 24 2 0 1 6 1 2 080604 0201

Fig 4.2.12(a) Effect of ApTSCN concentration in acid bath

AcTSCN mldm -3

a. 0.0 >«>tvtVt>^>pp^V><v^^tM>^M><!>^^^iypO'&a^^Qi;^^

b.0.5

c. 1.0
P^R?i.1
d. 1.5

e.2.0

I I I I I \ I I I I \ I I I I
40 30 25 20 15 12100806 040302 0 1 0 05

Fig 4.2.12(b) Effect of ApTSCN concentration in alkaline batb

149
In the case of the alkaline medium the concentration range tried was from
0.5 ml dm"' to 2.0 m ml d m \ The best quality deposit we could get with
this additive was a dull deposit for the concentration 0.5 ml dm' covering
the current density range of 0.8 to 1.5 Adm"". For higher current density
range we usually get either burnt or streaky deposits only.

A comparative account of different additives from Hull cell studies

In the absence of any additive we get a matt white deposit for the
full current density range in the case of acid bath and a grey deposit with
the alkaline bath. The addition of thiosemicarbazide or carbonyl
compounds individually to both the bath was helpful in getting a bright,
semibright. grey or dull deposits which are adherent and pore free. Further
the operational current density to get such deposits were also found to be
widened covering lower to higher current densities. The performance of the
condensation products are found to be sujierior than the individual
components wherein we get mostK mirror bright and bright deposits only.
With few compounds we get semibright. dull or grey deposits. Also, it is
noted that the performance of the compounds are found to be slightly better
in acid baths than in alkaline baths. The presence of additives in plating
baths has shown to influence the physical and mechanical properties of the
deposits such as grain size, brightness, internal stress, pitting and even
sometimes the chemical composition [44]. It is predicted that the additives
get adsorbed onto the electrode surface partialh and cause decrease in the
number of available active sites and controls the nucleation and growth
step of the deposition process resulting in control of the grain size and
refinement [45]. Thus the performance of the above additives reflected in
the Hull cell studies should be related to be the basic adsorption process
and in turn with their molecular structures and reactivity of the polar
centers of the adsorption site. A detailed discussion on the mechanism of
the electrodeposition process in presence of the additives will throw light

150
on the grading of the additives in terms of their performance. This will be
taken up at the end of this chapter.

Influence of operating parameters on the performance of the best

additive

It was found that FrTSCN was the best additive both in acid and
alkaline baths where in we could get mirror bright deposits. The effect of
operating parameters such as temperature and pH were studied on the acid
and alkaline baths in presence of the optimum concentration of the
additive. The Hull cell pattern for the temperature etTect is presented in
Figs.4.2.13(a) & Fig .4.2.13(b) respectively.

In both the media with increase in temperature the mirror bright

deposits change into bright deposit with narrowed current density ranges.
At a ma,ximum of 55"C we get semibright powder\' or porous deposit only.
Thus it is concluded that the additives give the best performance at the
ambient temperature. At elevated temperatures, the faster thermally aided
transport hinders the grain refinement and impedes the nucleation rate
resulting in poor quality deposits.

The influence of pH is presented in Figs.4.2.14(a) & 4.2.14(b) for

the acid and alkaline baths respectively. It is evident from the Hull cell
studies that lower or higher pH"s than the optimum pH is not helpful in
getting a quality deposit. The optimum H" or OH" concentration of the bath
may help in stabilizing surface concentration of the additive which in turn
controls the quality of the deposit.

4.2. (ii). Throwing power studies

Throwing power of acid and alkaline baths were calculated in

presence of various additives and the results are presented in Table (4.2.1).

151
Temperature ("C)

a. 25 ,v-f, ,

b.35 I' > » ' v •- , . . ^ -—'

C.45

• • • • • • • • • • • ^ • • • • • ^ • • • »
«•••••••»•••»»••»«•«•
d.55 ••«•>•••>•»•••»••••»»
.•••••••*•«••••••»•>>•
b I fc—•— ^ • ' • ' ' • ^ ' ' • • ' - • • ' ' ' ' ' ' ' ' ' ' ' *

I 1 1 1 1 1 \—i—I—I 1 i 1 1 T"
80 60 50 40 30 24 2 0 1 6 1 2 08 0 6 0 4 0 2 0 1

Fig 4.2.13(a) Effect of temperature on the performance of FrTSCN in

acid bath

Temperature ("C)

a. 25

b.35

c.45

..•».'•• I . • v 'e
d.55 '»'K''/.

n 1 1 1 \—I—I—I—\ 1—1—\—\—n
40 30 25 20 151210 0806 04 0 3 0 2 01 05

Fig 4.2.13(b) Effect of temperature on the performance of FrTSCN in

alkaline bath

152
pH

a. 2

L i l t ^'w waTi • ^ » M ' x ^ * » » > * J i « i i ' » i

b.3

C.4

d.5
ti.
7^
I I \ I I I I I I i I I I I I 1
80 60 50 40 30 24 2 0 1 6 1 2 080604 0201

Fig 4.2.14(a) Effect of pH on the performance of FrTSCN in acid bath

pH

a. 10

"T^
b. 11 » •. .

^^•^^^^^^^^^P^n^^^^^^^«^m^^^^^pa»av<^V^^

c. 12
^---- -.---- ^.^ ^ ^.^.. ^ ^
f^^^^9ryvf^v^^vrffV9'^^^i»9'V^^ww'9'^\

d. 13
1 1 1 1 1 — I — I — I — I 1 1 — I — I — I — I
40 30 25 20 15 1 2 1 0 0 8 0 6 0 4 0 3 0 2 0 1 0 05

Fig 4.2.14(b) Effect of pH on the performance of FrTSCN in alkaline bath

153
 Table-4.2.1

Throwing power of acid and alkaline baths in presence of various

additives

Throwing Power

Sl.No. Name of the additives

Acid Bath Alkaline Bath

1 Pure bath 15.7 33.6

2 ISC 19.8 38.0

3 AcP 16.8 12.0

4 CnA 9.0 15.0

5 CrA 10.3 16.0

6 FrA 18.4 19.0

7 SaA 14.9 17.0

8 FrTSCN 32.0 48.0

9 SaTSCN 25.0 42.0

10 CnTSCN 22.0 39.0

11 CrTSCN 19.0 37.0

12 ApTSCN 16.2 34.0

154
It was noted that the throwing power of the acid and alkaline plating baths
are in the reported range of values [46]. It is clear from the results that the
condensation products as well as TSC are seen to give a slightly better
throwing power than the corresponding carbonyl compounds. This may be
attributed to their adsorption through the sulphur atom of the >C=S group.
With FrTSCN it has become possible to reach the maximum throwing
power of 32% in acid bath and 48% in alkaline bath which are closer to the
ma.ximum reported values.

4.2.(ui). Cathode current efficiency measurements

Values of cathode current elllciencies of acid and alkaline baths in

the presence of various additives at two different current densities are given
in Table(4.2.2). The current efficiencies of both the acid and alkaline baths
are by themselves high. The additives in both the baths further slightly
improve the current efficiencies at both lower and higher current densities.
The plating rate observed with these additives are in the range of
28-35^m/hr at 2Adm" current density in both the baths. The best plating
rate is observed with FrTSCN and the least in the case of AcP. High
plating rate and current efficiencies will tell upon the economy of the
plating process.

4.2.1. Cyclic voltammetry studies

Number of organic compounds with polar functional groups have

been tried as additives in zinc plating baths, as they are known to affect
nucleation and growth step of zinc deposition and dissolution. In
understanding their participation, their involvement in the discharge step of
the metal ion/hydrogen ion is important, besides the knowledge of the
kinetics of metal dissolution and adsorption of the additives at the metal/
solution interface. The cyclic voltammetric technique is widely used to
study the electrochemical behaviour of such processes.

155
 Table - 4.2.2

Current efTiciency of acid and alkaline baths in presence of various

additives

Name of Acid bath Alkaline bath

the
Sl.No. additives
2 Adm"' 4 Adm* 2 Adm - 4 Adm""

1 Pure bath 85 80 91 90

2 TSC 91 89 93 92

3 AcP 84 78.8 85 82

4 CnA 87 83 93 92

5 CrA 87 84.1 94 91

6 FrA 90 87 96 94

7 SaA 89 86 93 91

8 FrTSCN 99 98 98 97

9 SaTSCN 97 95 97.3 95.2

10 CnTSCN 90 87.2 95 93

II CrTSCN 89 86.4 94 91

12 ApTSCN 86 83.3 89 87

156
Role of additives in acid zinc plating baths

The deposition and dissolution characteristics of Zn*' ions in acidic

zinc bath in the absence and presence of the carbonyl compounds at their
optimum concentration at a scan rate of lOOmV/s is given in Table(4.2.3)
& in Fig.(4.2.15). The CV results for the condensation products and TSC at
different scan rates at their optimum concentration is given in Table(4.2.4).
It is noted that the introduction of the carbonyl compounds into the acid
plating bath has not altered the electrochemical spectrum in the sense that
there is only one anodic and one cathodic F>eak appearance. Herein both the
anodic and cathodic peak potentials have been altered. In the case of the
anodic peak potential there is a significant negative shift and in the case of
cathodic peak potentials there is a negative shift, but not to a very
significant extent. Both the anodic and cathodic peak currents are reduced
in presence of the carbonyl compounds due to the adsorption of these
compounds on to the electrode surface impeding the corresponding
electrochemical reactions. Also in the presence of the compounds, the
hydrogen evolution rate is marginally diminished with negative shift of the
hydrogen evolution potential. The study on the hydrogen evolution and
permeation into steel during zinc plating in presence of polyethyleneglycol
of high molecular weights has revealed low hydrogen coverage on the steel
and to the low porosity of the coating [47]. Such type of adsorption by
some of the aldehydes in acidic zinc plating bath has been reported [48].
The adsorption process has been quantified on plated surface to follow
Langumuir adsorption isotherm. The shift of cathodic peak potential values
to more cathodic values had been reported [49] in the case of
polyethoxylated additives on the electrodeposition of zinc from acidic
solutions.

157
8E-002

-8E-002

-2000 -1000 1000 2000

Potential (mV)

Fig. 4.2.15. Cyclic voltommogram of mild steel electrode in acid bath with
different additives at a scan rate of 100 mV/s
a) Plain b) FrA, c) SaA, d) CnA, e) CrA, f) AcP

158
 Table ^ 4.2.3

Cyclic voltammetric results obtained for mild steel in acid bath at a

scan rate of 100 mV/s obtained with optimum concentration of
different additives

Dissolution Deposition

Name of the
additives Ep 'P Ep

(Acm'^) («nV) (Acm"^) (mV)

Plain 4.30x10-- -160 1.39x10"* -5459

FrA 3.11 .\10'- -359 1.87x10-^ -673

SaA 3.08x10-^ -:>24 5.56x10- -551

CnA 3.58x10-^ -340 6.36x10- -571

CrA 3.62x10-' -340 6.54x10- -583

AcP 1.83 X10-' -351 1.18x10-' -609

159
 w fN in 00
o •5t
o o o o
« in >n
00 00 in oo O
o^
1
' t

u e o o o
c
U 1 r>4

b b b b b b b b b b b b b
<*1

c
u 1 —
C^'E

<
y in
00
X

m
X
o
so
X
X X
r-
X X
00
q
fN
X X
in <N
fN
X
m
fN
X
SO
X
00
1 1 1

so
iri

R o
"1
"5t fN <N fN fN
fN fN (N fN fN fN 1 1 1
so sO

i
in in m sO
>

IN (N (N <N
b b b b b b b b b b b b b
e
_o
1 —
^'E
w
X
00
X
O
q
X
in
X
VO
X
vO
C>
X
00
(>
o
X X
• * _
X
X
f<n
q
X
00
X
q
1 1 1

"*» < (N fN fN fN
C9 fN
U
•*«
c
in >n 00
fN fN fN
m
m m
o
so
o
so m m
sO sO
V in sO sO vO sO SO sO vO sO
1 1 1 1 1 1 1 >o 1 1 1

1
1
u 1 1 1
c
o
u

1
-T -r 7 -T

s b b b b b b b b O b b b b b b b
X X X X X X X X X X X X
3 — ^ CM OJ
X X X
00
X
oo 00
< *^ o q fN 00
E fN o^ <n sq
in
I o iri
in
JZ
z ^••s
o o (N fN 00 CN m m m 00 00
es ?> fN m 00 00 00 00 00 00 SO so sO
1 1 1 1 rn *N
1
(N
1
fN
1 1
fN
1
(N
1 (N fN fN
1 1 1 1

1-
1 1 1

!2
'3 3
R

1 —
CL'E
y
o o o o o o
X
r-
X

in
o
X X
00
X
*n
X
O
X
00
o
so
X
O
X
so
00
in
O
X
fN
sd
O
X
00
O
X
fN
rr
in
O
X
r>
so
O
X
so
o o
X
00
X
r-
sO
mi in
•a
E ij
o O O m o O m o O m o o m O o m O
m o o in O m O
o o m
en

E
S Z Z Z Z Z
R at u U
"o •£
u CO
c 'CL.
o sj
<
u
E
R

z
160
 The positive anodic peai< potential in the case of the plain bath
indicates the spontaneity of the anodic reaction while a negative shift of
peak potentials obtained with the additives are illustrative of their
inhibitive nature for the metal dissolution process which has been
confirmed from the corrosion studies.

The role of additives has been suggested to act at the interface

creating a barrier in the proximit\ of the electrode surface that has a
blocking effect on the electrodeposition. Therefore additional energy is
required to discharge metal ions. This explains the decrease in the current
density of the cathodic peak.

The effect of TSC additive in the acid plating bath have been
studied. It is noted that the electrochemical spectrum in presence of TSC is
ver> much changed compared to the plain bath and this could be
understood from cyclic voltammogram shown in Fig.(4.2.16). In the case
of TSC additive, besides the usual anodic and cathodic peaks, there is a
broad adsorption peak at 1365 mV Vs. SCE immediateK following the
anodic peak and it corresponds to the formation of adsorbed surface
complex of Zn (II) . In the reverse scan this surface complex gets desorbed
at a less positive potential. This phenomenon which is absent with other
carbonyl compounds should characterize the adsorption through the
specific >C=S group of TSC. Uniformly such adsorption-desorption peaks
have been obtained with number of thiosemicarbazones presented
subsequently. The formation of the surface complex has been confirmed
from UV studies in one of the representative case of FrTSCN which is
presented in the following section .

The CV results for thiosemicarbazones at varsing scan rates are

presented in Figs.(4.2.17) -(4.2.21).

161
 2E-001

1E-001

c
I 5E-002

OE+000

-5E-002

-2000 -1000 1000 2000

Potential (mV)

Fig. 4.2.16. Cyclic voltammograms obtained on mild steel in acid bath at a sweep rate of lOOmV/s
a) Plain b) Thiosemicarbazide (TSC)

162
 3E-002

2E-002

S 1E-002

OE+000

-1E-002

-2000 -1000 1000 2000

Potential (mV)

Fig.4.2.17 Cyclic voltammograms obtained on mild steel in acid bath with FrTSCN at various sweep rates
a) 50 mV/s, b) 75mV/s, c) lOOmV/s

16-
3E-002 —T

-1E-002

-2000 -1000 1000 2000

Potential (mV)

Fig.4.2.18. Cyclic voltammograms obtained on mild steel in acid bath with SaTSCN at various sweep rates
a) 50 mV/s, b) 75mV/s, c) lOOmV/s

164
 3E-002

2E-002

i 1E-002
3
o

OE+000 —

-1E-002

-2000 -1000 1000 2000

Potential (mV)
Fig.4.2.19 Cyclic voltammograms obtained on mild steel in acid bath with CnTSCN at various sweep rates
a) 50 mV/s, b) 75niV/s, c) lOOmV/s

165
 4E-002

2E-002

OE+000 —

-2E-002

-2000 -1000 1000 2000

Potential (mV)

Fig.4.2.20. Cyclic voltammograms obtained on mild steel in acid bath with CrTSCN at various sweep rates
a) 50 mV/s, b) 75mV/s, c) lOOmV/s

166
 0.12

0.08

0.04 —

c
0)
3
o

-0.04

-0.08

-2000 -1000 1000 2000

Potential (mV)

Fig.4.2.21. Cyclic voltammograms obtained on mild steel in acid bath with ApTSCN at various sweep rates
a) 50 mV/s, b) 75tnV/s, c) lOOmV/s

167
 With all the thiosemicarbazones. the dissolution potential has shown
a negative shift with respect to the plain acid bath. Also the dissolution
current is decreased compared to the plain acid values. In the case of the
deposition potentials the> have shown, a negative shift. Further the
deposition current is also decreased uniformly with all the additives and
such decrease in the deposition current is understandable when the
additives are adsorbed at the active cathodic sites. The hydrogen evolution
potential has uniformly shown a negative shift to a smaller extent. The
hydrogen evolution rate is also decreased in presence of the additives. The
electrochemical behaviour of the thiosemicarbazones except ApTSCN is
similar to the behaviour of TSC. In all these cases besides the anodic and
cathodic peaks, there is a one broad adsorption and complementary
desorption peaks at some positive potentials above 1.2V. The occurrence of
this adsorption peak is supposed to be due to surface adsorbed
Zn(II)-thiosemicarbazide/ thiosemicarbazone complexes. As suggested
earlier the adsorption is through >C=S polar center of the molecule. This
has been confirmed by active formation of the surface complex with
FrTSCN additive in the zinc plating bath on mild steel b} holding the
potential corresponding to the anodic adsorption jseak for about 5 minutes.
Then the formed surface complex was anodically stripped in dil HCl
solution and the UV spectrum was taken which shown in Fig.(4.2.22). In
this case relativeK one strong peak at /.n,a\ 304nm and one weak peak at
244 nm have been obtained. This UV spectrum was compared with that
taken for FrTSCN in HCl without the presence of Zn'* ions. The additive
FrTSCN gives one predominant peak at /.max 323.5nm corresponding to
>C=S adsorption and one shoulder at >.max 241 nm for >C=N group. The
>C=N group being free there is no change in its >.max at 241 - 244 nm.
However as >C=S is weakly complexed with Zn'* there is a shift in the
absorption peak of >C=S from 323.5nm to 304nm confirming the

168
formation of some surface complex in the oxidized state of Zn at some
highly positive potential. However such complexes are not formed between
the Zn'* and FrTSCN in the solution phase in the bath.

The scan independent nature of the adsorption/desorption potentials

and their closeness in values indicate the non-charge transfer nature of the
adsorption surface-complex formation step. On the contran. the scan
dependence of potentials and currents for the dissolution/deposition of
ZnlZn'* emphasizes the charge transfer control of such processes. As
expected with increased scan rate both anodic and cathpdic currents have
increased. The dissolution and deposition potentials are not affected by the
scan rate. Similar is the case with all the other thiosemicarbazones except
with ApTSCN. In the case of ApTSCN shown in Fig.(4.2.21) like plain
acid zinc plating bath or acid zinc plating bath in presence of carbonyl
compounds, there is only dissolution and deposition peaks. The
adsorption/desorption peaks corresponding to the formation of the surface
additive complex is absent. It is surprising that though >C=S group is
present in acetophenone thiosemicarbazone additive, it is not involved in
the >C=S....Zn'* complex formation. The possible reason for this could be
the steric shielding of the sulphur atom by the methyl group of the phenyl
ring. Such hindrance to reactivity of sulphur atoms of sulphides by the
proximity bulky groups is reported in the literature [50].

Role of additives in alkaline zinc plating bath

The CV results of the above mentioned additives along with plain

zinc plating bath are presented in Figs.(4.2.23) & (4.2.24) as a
representative case for lOOmVs"' scan rate and in the Tables (4.2.5) &
(4.2.6) for different scan rates.

169
 0.4

1 A
0.3

c
(0
-S
o 0.2
in
<

0.1

I ' t
200 400 600 800
Wavelength (nm)

Fig. 4.2.22. UV-Visible spectra to indicate the formation of surface complex

of Zn(ll) with FrTSCN

170
 1E+002

OE+000

c
0)

-1E+002 —

-2E+002

-1.6 -1.2 -0.8 -0.4

Potential (V)

Fig.4.2.23. Cyclic voltammograms of mild steel electrode in alkaline bath with different additives
at a sweep rate of 100 mV/s
a) Plain b) Fra c) SaA d) CnA e) CrA f) AcP

171
 1E+002

OE+000 —

c
3
o

-1E+002 —

-2E+002

-1.6 -1.2 -0.8 -0.4

Potential (V)
lMg.4.2.24. Cyclic voltammograms of" mild steel electrode in alkaline bath with different additives
at a sweep rate of 100 mV/s
a)TSC b)FrTSCN c) SaTSCN d)CnTSCN e)CrTSCN f) AcTSCN

172
 Table - 4.2.5

Cyclic voltammetric results of mild steel in alkaline bath with

optimum concentration of different additives at different scan rates

Dissolution peak Deposition

Name of Scan rate peak
the
mVs' Epi ip2 Ep2 'p Ep
additives
(mA) (mV) (mA) (mV) (mA) (mV)

50 59.67 -1.32 85.17 -1.07 -82.0 -1.81

Plain
75 65.82 -1.29 87.57 -1.07 -97.90 -1.85

100 83.17 -1.30 89.02 -1.07 -118.8 -1.75

50 87.64 -1.21 95.61 -1.02 -84.28 -1.70

FrA
75 87.0 -1.23 96.68 -1.01 -98.02 -1.74

100 93.66 -1.19 97.56 -1.97 -107.4 -1.72

50 80.81 -1.29 90.57 -1.06 -83.79 -1.72

SaA
75 91.22 -1.28 95.78 -1.03 -105.9 -1.77

100 95.37 -1.24 96.59 -1.4 -119.1 -1.80

50 53.34 -1.37 47.64 -1.15 -86.14 -1.80

CnA
75 71.11 -1.34 51.06 -1.12 -86.22 -1.78

100 86.84 -1.31 62.77 -1.10 -87.53 -1.72

50 39.59 -1.27 56.26 -1.05 -64.51 -1.78

CrA
75 56.67 -1.18 63.99 -1.02 -73.16 -1.82

100 56.73 -1.20 64.39 -1.03 -73.20 -1.66

50 35.60 -1.26 72.20 -1.00 -77.11 -1.76

AcP
75 46.83 -1.29 80.98 -1.00 -89.31 -1.79

100 54.15 -1.27 81.47 -1.00 -94.19 -1.81

173
 Table - 4.2.6

Cyclic voltammetric results of mild steel with optimum concentration of

different additives in alkaline bath at different scan rates

Dissolution peak Deposition

Name of Scan rate peak
the
mVs' 'pi Epi »P2 Ep2 'P Ep
additives
(mA) (mV) (mA) (mV) (mA) (mV)

50 61.23 -1.20 98.38 -1.02 -103.1 -1.82

TSC
75 64.95 -1.21 99.52 -1.01 -104.9 -1.81

100 71.06 -1.21 99.97 -1.01 -105.4 -1.82

50 91.87 -1.22 99.85 -1.02 -85.74 -1.68

FrTSCN
75 93.83 -1.22 103.6 -1.01 -103.3 -1.70

100 94.39 -1.21 105.5 -1.03 -107.0 -1.71

50 63.42 -1.28 80.01 -1.04 -59.06 -1.67

SaTSCN
75 75.55 -1.28 89.96 -1.00 -79.65 -1.70

100 78.71 -1.28 88.14 -1.00 -84.93 -1.74

50 33.09 -1.37 29.19 -1.16 -34.57 -1.67

CnTSCN
75 34.40 -1.37 31.14 -1.14 -47.58 -1.67

100 59.27 -1.37 56.02 -1.13 -48.04 -1.69

50 32.35 -1.24 58.92 -1.14 -64.92 -1.35

CrTSCN
75 32.35 -1.25 62.84 -1.16 -65.93 -1.35

100 32.75 -1.25 73.81 -1.44 -65.98 -1.35

50 43.82 -1.25 46.26 -1.02 -31.40 -1.83

ApTSCN
75 48.94 -1.26 68.46 -1.03 -71.83 -1.86

100 61.55 -1.25 70.90 -1.06 -82.40 -1.85

174
 Considering the cyclic voltammograms presented in the above
mentioned Figures and tables for mild steel in zincate baths in the absence
of any additive, one can understand the zinc dissolution/deposition
mechanism over mild steel substrate. The two anodic peaks in the potential
range of-1.3V and -1.0 V Vs. SCE. correspond to the anodic oxidation of
zinc and the subsequent dissolution of the oxidized product as per the
following mechanism [51. 52].

Zni,.,nk • Znad (1)

Znad + 20H- • [Zn(OH).fad (2)

[Zn(OH):]',d ^ [Zn(OH)2]3d + 2e- (3)

[Zn(0H)2]ad • [Zn(OH);]d,ss (4)

[Zn(0H)2]d,ss + 20H- • [Zn(0H)4f- (5)

The above mechanism explains the anodic behaviour of zinc

electrode in alkaline solutions.

Reaction (3) may proceed via two one electron steps and the same
finding has been reported while discussing the effect of organic additive on
electrodeposition and dissolution of zinc from zincate solutions [53].

The first anodic peak occurring at around -1.3V corresponds to

reaction (3) of the above mechanism and the second anodic peak at around
-l.OV corresponds to reactions (4) and (5). the dissolution of the oxidized
product of Zn and this is a non-charge transfer process unlike reaction (3).
Hence this peak potential has not shown much of shift with scan rate and
so is the trend in the current.

The cathodic peak which corresponds to the discharge of Zn"*

occurs around -1.7V to -1.8V Vs. SCE and this being a charge transfer

175
step is sensitive to scan rate variations. With increase in scan rate the
cathodic peak currents are on the increase.

The dependence of Ip^ on the square root of the potential scan rate is
of linear nature shown in Fig.(4.2.25) (with R' =0.98) for the additive
FrTSCN. this points to the presence of diffusion limitations in the
reduction of zinc ions in alkaline medium as indicated in the earlier studies
[48].

From the CV results in presence of different additives in the alkaline

zinc plating bath it becomes clear that the electrochemical spectrum was
not altered as compared to that in the plain bath. In all the cases uniformly
we have two anodic peaks and one cathodic peak. The first anodic f)eak
which corresponds to oxidation of zinc being charge transfer step is more
sensitive to scan rate and the peak currents show an increase in trend with
scan rate. The second anodic peak was not ver\ sensitive to the scan rates
as it was a non-electrochemical step leading to the formation of soluble
zincates. As with plain bath the cathodic peak currents show increasing
trend with scan rate. Uniformly with all the additives it was noted that in
their presence the anodic and cathodic peak currents are decreased
indicating the adsorption of the additives at the energetically active sites.
Such adsorption of furfuraldehyde molecules on the growing zinc nuclei
reducing the cathodic discharge current and enhanced hydrogen evolution
has been reported [54]. As regards the anodic and cathodic peak potentials
there was not much of significant shift in presence of the additives.

The performance grading of the additives can be understood when

we consider the limiting current of zinc ion reduction presented in
Table(4.2.7). The best additive was seen to increase the cathodic
polarization and raises the limiting current of zinc-ion reduction.
Polyethylene polyamine (PEPA) has been ranked as the best additive from

176
among a group of 13 additives for quality zinc deposit from zincate
electrolytes based on these parameters [55].

4.2.2. Corrosion behaviour of the mild steel substrate in the plating

baths - Role of the additives as inhibitors

The substrate iron metal is susceptible to corrosion in the acid and

alkaline zinc plating baths with the risk of contaminating them. This would
intum tell upon the quality of the deposit. In the event. H:0: treatment is
recommended as a trouble shoot. Hence studies on the corrosion behaviour
of the mild steel in the acid and alkaline zinc plating baths in the absence
and presence of the additives at their optimum concentrations through
weight loss, potentiodynamic polarization and impedance methods have
become relevant.

4.2.2.1. Weight loss studies

i) Acid plating bath

The weight loss results for the corrosion inhibition of mild steel in
acid plating bath in the absence and in the presence of additives are
presented in Table (4.2.8). The order of corrosion inhibition offered by
them are as follows:

(i) For the carbonyl compound:

FrA>SaA>CnA>CrA>AcP

(ii) For the thiosemicarbazone derivatives :

FrTSCN>SaTSCN>CnTSCN>CrTSCN>AcTSCN>TSC.

It is noted that the condensation products offer only reduced

inhibition compared to their counter part carbonyl compounds. Also TSC is
found to give the least inhibition among the additives tried.

177
 \
r 1 UU
R^ = 0.9801
75
^—•

S 50

25

0 1 1 1 1 1
j
5 6 7 8 9 10 11
v"^ mV/s
V J

Fig. 4.2.25 Dependence of Ipc on scan rate from CV studies of FrTSCN

system in alkaline platting bath

178
 Table - 4.2.7

Limiting deposition current values for zinc on mild steel in alkaline

bath

Additives Limiting deposition current

(mA)

Plain 85.42

TSC 98.26

FrA 92.62

SaA 88.91

CnA 89.31

CrA 78.33

AcP 76.71

FrTSCN 138.3

SaTSCN 116.2

CnTSCN 112.3

CrTSCN 108.3

AcTSCN 106.6

179
 Table - 4.2.8

Weight loss measurements for mild steel in acid bath with optimum
concentration of different additives

Corrosion rate 'corr EfTiciency

Additive
(mdd) xlO^ (Acm-) (%)

Plain 8286 3.31 -

TSC 4325 1.73 47.73

FrA 490 0.196 94.07

SaA 590 0.236 92.87

Can 872 0.349 89.45

CrA 892 0.356 89.24

AcP 897 0.359 89.15

FrTSCN 959 0.384 88.39

SaTSCN 1905 0.762 76.97

CnTSCN 2651 1.060 67.97

CrTSCN 3407 1.362 58.85

ApTSCN 3602 1.440 56.49

180
ii) Alkaline plating bath
The weight loss results for the alkaline plating bath in the case of the
ditTerent additives are presented in Table(4.2.9). The trend of inhibition is
the same as in the acid bath, but the inhibition in the alkaline bath is overall
very much lower than in the acid bath.

All the thiosemicarbazone derivatives. TSC and AcP show

practically very little corrosion inhibition. Other carbonyl compounds seem
to perform better.

4.2.2.2. Potentiodynamic polarization studies

i) Acid plating bath

The Tafel polarization results of mild steel in acid plating bath

without and with the presence of a set of carbonyl compounds at their
optimum concentration recommended for quality deposit, is presented in
Table(4.2.IO) and in Fig.(4.2.26). It is noted that all the carbonyl
compounds are able to reduce the corrosion of mild steel considerably. The
corrosion potential has shown mostly an overall slight negative shift. There
is a good matching in the inhibition efficiency values between the weight
loss results and the polarization measurements. However, the corrosion rate
from polarization measurements are 3-4 orders less compared to weight
loss results. This indicates that the perturbation electrochemical
measurements are able to judge the steady state corrosion reactions only to
a limited extent. Neverthless. the electrochemical techniques are ver\
useful for instantaneous corrosion rate measurements and for predicting the
mechanism of inhibition. It is ver> ditTicult to get reproducible results for
Tafel slopes with highly active metal like iron in acidic plating bath. Hence
the mode of inhibition by the additives is fixed by considering the
reduction in the partial currents (anodic and cathodic) of the corrosion
process at a common reference [X)int in the Tafel region (Ea>rr± 100 mV)
compared to that with the control.
 Table-4.2.9

Weight loss measurements for mild steel in alkaline bath with optimum
concentration of different additives

Corrosion rate ^corr Efficiency

Additives
(mdd) xlO"' (Acm -) (%)

Plain 4862 1.94 -

TSC 4701 1.88 3.09

FrA 998 0.399 79.43

SaA 1522 0.609 68.60 .

Can 2978 1.191 38.60

CrA 3638 1.455 25.0

AcP 4233 1.693 12.73

FrTSCN 4082 1.633 15.82

SaTSCN 4191 1.676 13.60

CnTSCN 4558 1.823 6.03

CrTSCN 4735 1.894 2.61

ApISCN 4791 1.916 1.46

182
 -400 -200

Potential (mV)

Fig. 4.2.26. Potentiodynamic polarization curves for mildsteel in acid bath with optimum concentration
of different additives,
a) Plain, b) CrA, c) CnA, d) AcP, e)SaA, f)FrA

183
 Table-4.2.10

Potentiodynamic polarization results for mild steel in acid bath with

optimum concentration of diflerent additives

AtE„„±100mV Reduction in
Name of t-COIT b. b.
the (mV) i< Anodic Cathodic
(A) (mVdec') (mVdec')
additives current current
(A) (A)
(%)

Plain -528 1.99\10" 108 160 4.21x10"' 1.3x10"-' - -

FrA -569 1.0x10' 59 110 5.62x10" 8.1 xlO" 99.87 99.37

SaA -540 3.02x10'' 6fB 155 7.08x10' 1.2x10* 99.83 99.03

CnA -535 3.16x10"' 60 150 3.63 xlO* 2.5x10"" 99.14 98.07

CrA -531 3.98x10' 63 172 7.90x10* 3.7x10"" 98.11 97.15

AcP -539 4.36x10' 75 157 5.50x10* 4.0x10* 98.69 96.87

184
 It is clear from the results that the carbonyl compounds act as mixed
inhibitors by controlling both the anodic and cathodic currents of the
corrosion process to almost equal extent. Such method of predicting the
mode of inhibition is already reported [56-58]. This method is nothing but
in a sense comparing the Tafel slopes at a point in the Tafel region.

Another set of additives starting from TSC to its condensation

products with above carbonyl compounds were tried as additives in the
acid plating bath. Their inhibition property with respect to the substrate
metal mild steel are presented as polarization results in Table(4.2.11) &
Fig.(4.2.27).

It is clear from the results that all the thiosemicarbazones as well as

TSC are not effective inhibitors as their counterparts namely the carbonyl
compounds. The mixed mode of inhibition offered by the compounds is
evident from the results presented.

ii) Alkaline plating bath

The polarization results for the mild steel in alkaline plating bath in
the presence and absence of the carbonyl compounds are presented in
Table(4.2.12) & in Fig.(4.2.28). All the carbonyl compounds have shown a
negative shift of Etorr values with respect to the plain bath value indicating
the cathodic control of the corrosion reaction. This is again confirmed
when we consider the reduction in the partial current at E^orr ± lOOmV
presented in Table(4.2.12). Unlike the performance of the carbonyl
compounds in the acid plating bath, here in the alkaline medium their
performance is not ver\ impressive. A maximum etTiciency of 65% is
obtained for the best performing furfuraldehyde.

185
 -3

-8
1
-700 -600 -500 .400 -300 -200
Potential (mV)
Fig. 4.2.27. Potentiodynamic polarization curves for mildsteel in acid bath with optimum concentration
of different additives,
a) TSC, b) FrTSCN, c) SaTSCN, d) CnTSCN, e)CrTSCN, f)AcTSCN

186
 Table-4.2.11

Potentiodynamic polarization results for mild steel in acid bath with

optimum concentration of different additives

AtE„„±I0OmV Reduction in
R
Name of *-»C«MT •corr b. be
the (mV) i» Anodic Cathodic
X !0'*(A) (mVdec') (mVdec"')
additives current current
(A) (A)
(%) (%)

TSC -533 1.67 112 230 3.91x10' 1.2x10"' 7.12 7.69

FrTSCN -575 1.26 42 I")-* 3.6 .\I0- 3.9x10-" 91.38 96.95

SaTSCN -563 1.44 47 140 1.2x10"' 3.9x10* 71.49 96.95

CnTSCN -565 1.44 65 102 6.9x10* 9.7x10" 98.36 92.50

CrTSCN -537 1.58 63 132 4.7xl0-- 1.0 xlO' 88.83 92.33

ApTSCN -533 1.66 79 136 2.5x10"' 0.81 xlO"* 40.40 37.69

187
 n

-3.5

-4.5
o

-5

-5.5 -

-6

-1400 -1200 -1000 -800 -600 -400

Potential (mV)

Fig. 4.2.28 Potentiodynamic polarization curves for mildsteel in alkaline bath with optimum concentration
of different additives,
a) Plain, b) FrA, c) SaA, d) CnA, e)CrA, f)AcP

188
 Table - 4.2.12

Potentiodynamic polarization results for mild steel in alkaline bath with

optimum concentration of different additives

AtE„„±l(K)mV Reduction in

Name of 'corr b, be
the
E-corr in Anodic Cathodic
(mV) X 10"' (A) (mVdec"') (mVdec') current
additives current
xlQ-*
(%) (%)
(A) (A)

Plain -967 3.187 175 110 6.309 1.778 - -

FrA -997 1.115 169 132 6.160 1.023 2.36 42.46

SaA -1046 1.334 176 166 5.495 1.63 12.98 8.32

CnA -1031 1.429 178 131 2.630 1.380 58.31 22.38

CrA -995 1.995 172 148 6.079 1.047 3.78 41.11

AcP -1010 2.239 167 132 6.160 1.62 2.36 8.66

189
 The polarization results for TSC and its condensation products with
the carbonyl compounds are presented in Table(4.2.13) & in Fig.(4.2.29)
As with weight loss results the poor inhibition of the TSC and carbazones
are revealed here also. The negative shift in the corrosion potential values
indicate the cathodic control of the corrosion reaction. The reduction in the
partial current values also confirm this.

From the above studies it is clear that the carbonyl compounds act
as better corrosion inhibitors than their carbazone derivatives in both the
media. This could be due to the strong adsorption made b\ the former
through the >C=0 compared to the relatively weak adsorption by >C=S
group of the thiosemicarbazide and carbazones at iron/solution interface.

4.2.2.3. Impedance studies

Studies with acid plating bath

Impedance studies are very effective tool to understand the

influence of additives as corrosion inhibitors, be it a conducting or a
resistive medium. With Nyquist plots the R, values are calculated as the
X-intercept of the impedance real axis where the semi-circle cuts this axis.
The double layer capacitance Cji is calculated using the expression.

Cd,=
2 TiFmavR,

The equivalent circuit in the case of corrosion inhibitors where

adsorption is the main process is represented as

Rs Cdi.ln.

-V^WVWWA^

R,

190
 -3.5 —

•5, -4-5
o

-5 —

-5.5

-6

-1600 -1200 -800 -400

Potential (mV)

Fig. 4.2.29. Polentiodynamic polarization curves for mildsteel in alkaline bath with optimum concentration
of different additives,
a) TSC, b) FrTSCN, c) SaTSCN, d) CnTSCN, e)CrTSCN, f)AcTSCN

191
 Table-4.2.13

Potentiodynamic polarization results for mild steel in alkaline bath obtained

with optimum concentration of different additives

AtE„,r±100mV Reduction in

Name of li-corr 'corr b. be

the (mV) i. ic Anodic Cathodic
additives X IQ-' (A) (mVdec') (mVdec') current current
xlO-'(A) xlO-' (A)
(%) (%)

TSC -1003 2.309 ISO 152 7.94 8.51 25.89 52.13

FrTSCN -1015 2.371 163 125 5.75 6.91 8.79 61.09

SaTSCN -1020 2.512 168 144 3.1 7.07 50.86 60.23

CnTSCN -1018 2.671 172 156 2.75 6.49 56.4! 63.46

CrTSCN -992 2.985 179 162 6.106 6.16 3.22 65.35

ApTSCN -1031 3.09 168 157 5.88 7.07 6.80 60.23

192
 The impedance results for mild steel [59-63] in acid bath in presence
of different carbonyl compounds are presented in Table(4.2.14). and in
Fig.(4.2.30) as Nyquist plots. In most of the cases, the impedance plots are
semi circles indicating the charge transfer control of the corrosion process.
The occurrence of the rising portion on the low frequency end in few cases
indicate the partial diffusion control of the corrosion reaction in the plating
bath. The occurrence of the Warburg impedance [64.65] in the low
frequency end is seen as loop in few cases. This confirms the partial
diffusion control of the corrosion process. The increase in R, values and
decrease in Cdi values are indicative of the corrosion inhibition offered by
the carbonyl compounds in the acid bath.

The impedance results for the corrosion of mild steel in the acid
plating bath in presence of different thiosemicarbazones and TSC are
presented in Fig.(4.2.31) and Table (4.2.15). As with carbonyl compounds
thiosemicarbazones give rise to semicircular plots indicating the charge
transfer control of the corrosion process. The increased R, and decreased
Cdi values are inline with their inhibition performance.

Studies with alkaline plating bath

The impedance results for mild steel in alkaline plating baths for
carbonyl compounds and their thiosemicarbazone derivatives are presented
in Figs.(4.2.32) & (4.2.33) and in Tables(4.2.16) & (4.2.17) respectively.
All the additives (both carbonyl compounds and thiosemicarbazones) were
found to increase R, values and decrease Cji values confirming their
inhibition performance. The compound TSC is not effective as inhibitor
both in acid and alkaline baths. The decreased Cdi values in presence of the
additives are indicative of less charge in the interface due to diminished
metal dissolution. The ia,rr values calculated using R, values of the
impedance studies and the Tafel slopes of polarization studies are in close
agreement with the Tafel extrapolation results.

193
 1 •• I I 1 1 1 1 1

188 a
b)

lie 8 - -

IBS 8 - -

68 8 - • -

- -
28 8
1
•J-
1 1 1 1 1 J 1 1
9 888 12 888 15 B88 18.888 21888 »
-1Z8 8 -18 8 IB 8 128 8 zee I
Z' (koln) r (kohn)

1 1 1 1 1 1 1 1 1 1 1 1
^ eee , 1 1 1 1
~ 18 88
c) d)
3 888 - ~
38 88 -
2 888 • -
1
N
1 888 -
\
% 28 88 - .
• . Ki
f" IB 88
' •.
-1 888 - 1
1 t 1 1 1 1 1 1 a 88
1 1 1 1 1 1 1 1
-5 88 5 88 IS 88 2S 88 3S 88 15 88 55 88 65 88 75 I
588 IS 88 2588 3588 IS 88 5588 6588 751
V (koha)
2' (koha)

— r - • 1 - • 1 • 1 1 1 1 1 T 1 1 1 1 1 r
18 88 1588 8
e) f)
38 88 1888 8

\
'g ZB 88 - I see 8

18 88 . • •

a 88
1 1 1 1 1 1 I J

-1 I I L. _l L.
588 15 88 ZSae 3588 15 88 55 88 65 88 751
8 eae 3 eee 6 aee 3 see tz see is eee le eee _!_
zi aee 211
Z' (koln)
r (kohm)

Fig.4.2.30 Nyquist plot for mildsteel electrode in acid plating bath with different
additives
a) Plain bath, b) FrA, c) SaA, d) CrA, e) CnA and f) AcP
194
 Table-4.2.14
Impedance measurement for mild steel in acid plating bath with
optimum concentration of different additives

R. Cdi 'corr
Name of the additives
(K ohms) (^Fcm•^) xlO-* (Acm-^)

Plain 11.20 82.52 2.500

FrA 65.83 32.10 0.253

SaA 67.34 12.60 0.249

CnA 36.28 21.25 0.513

CrA 43.16 17.42 0.465

AcP 59.29 14.58 0.372

195
 ••I •• 1 T - 1 1 1

888.a a) -

lee.a _ . •• - i. lea.e -

a.B ..y SB .8

-488.8 -
1 1 1 I 1 1
4.88 8.88 12.88 16.88 28.88 24.6

Z' (koha)

1 1 1 1 1 1 1 1 1

16.888

12.888 - d) -
<; 8.888 -
o
r 4.888
N
• ,
8.888
• . . I J.

-4.888
1 1 1 1 1 1 1 1 1
S.ee IB.88 15.88 28.88 25.88 38.88 35.88 48. 6.88 14.88 22.88 38.88 38.88 46.88
2' (koln) 2' (koha)

T 1 1 T "T 1 r

e)

58.8

-588.8 -

_j I t 1 I 1 I [_
IS.a 28 a ZS.8
V (koha)

Fig.4.2.31 Nyquist plot for mildsteel electrode in acid plating bath with different
additives
a) TSC, b) FrTSCN, c) SaTSCN, d) CrTSCN, e) CnTSCN and f) AcTSCN

196
 Table-4.2.15

Impedance measurement for mild steel in acid plating bath with

optimum concentration of ifferent additives

R. Cdi 'corr
Name of the additives
(K ohms) (^Fcm"^) xlO"* (Acm"^)

TSC 21.10 46.75 1.550

FrTSCN 45.27 19.89 0.303

SaTSCN 25.81 35.96 0.796

CnTSCN 14.98 66.78 1.153

CrTSCN 14.66 67.20 1.263

ApTSCN 14.18 62.32 1.526

197
 1 1 1 1 I r -1
1 1 1 1 r i l l
6.eee
i.ee ; • a) - b)
^ . i.eee -
a.ee '
, . •
Jl
- •-
I. 1 ee - S 2z.eee
/' •
-E.ee - - a.eee

-3.ee - - -z.eee
1 1 1 1 r i l l r i l l 1 1 1

zee I.ee 6.ee e.ae ie.ee iz.ee ii.ee ]6.( -i8.ee 18.88 za.es 3a88 i8.ee SB.BB bB.ee 78.i
Z' (koha) Z' (koha)

1 1 1 1 1 • 1 •• 1 ••• I —
ze ee
45.86 -
d)
35.88 - -

25.86 _

15.86 . • . -

5.86

i5.ee 45.ee 75.88 185.ee

/ 1 1 1 1 J 1 L.. ,1 .
18.68 Ze.88 38.86 48.86 58.86 66.66 78.86
Z' (koha)
Z' (kohn)

1 1 1 1 1 1 1 1 1 zze.e "T 1 1 1 1 1 1 1 r
16.686 -
188.8
e) f)
iz.eee -
HB.e
^ B.Heu - - £
1 S
- lee.e
=N * - ^ ' . •
• . . ^ - . . '

ZB.B
-i.BBB -
r 1 1 1 1 1 1 J 1 _i I I I I I I I L.
-ze.a
6.ee H.ee zz.ee ae.ee 3a.ee 46.i -48.8 48 8 1Z8.B Zte.B

Z' (koha) Z' (koha)

Fig.4.2.32 Nyquist plot for mildsteel electrode in alkaline plating bath with different additives
a) Plain bath, b) FrA, c) SaA, d) CrA, e) can and f) AcP

198
 1 1 1 1 1 1 1 1 "T 1 1 1 1 r
iza.ea - iB.eee
a) b)
88 ae - -
J Bl
10.88 -

0 88 /"

-n.ee -
1 1 1 1 1 1 1 J
_i 1 1 1 1 J 1 1 i_
-SB se IS B 28 1 -18.86 l e 88 28 88 38 I 48.88 S8 I

2' (kohn)

158,88 -

-188 88

IS B 2S 8 IS B Z5.e
2' (kohn) 2' (koha)

38 88 18 1
2' (kolui)

Fig.4.2.33 Nyquist plot for mildsteel electrode in alkaline plating bath with different additives
a) TSC, b) FrTSCN, c) SaTSCN, d) CrTSCN, e) CnTSCN and f) AcTSCN

199
 Table-4.2.16

Impedance measurement for mild steel in alkaline plating bath with

optimum concentration of different additives

R, Cdi 'corr
Name of the additives
(K ohms) (liFcm'^) xlO"* (Acm"^)

Plain 14.46 71.55 2.030

FrA 75.64 14.20 0.426

SaA 71.66 16.07 0.518

CnA 26.61 45.10 1.232

CrA 25.51 46.21 1.356

AcP 18.08 57.25 1.786

200
 Table-4.2.17

Impedance measurement for mild steel in alkaline plating bath with

optimum concentration of different additives

Icorr
Name of the additives
(K ohms) (^Fcm"^) xlO"* (Acm ^)

TSC 19.02 56.84 1.54

FrTSCN 17.58 58.42 1.75

SaTSCN 20.63 54.15 1.63

CnTSCN 20.57 55.12 1.72

CrTSCN 18.88 59.20 1.95

ApTSCN 21.63 51.13 1.63

201
Mechanism of corrosion inhibition of mild steel in plating baths

As regards the role of the additives, as inhibitors in the plating baths

for the corrosion of the substrate metal mild steel, it is concluded that the
carbonyl compounds act better than their thiosemicarbazone derivatives.
The simple reason for this could be due to the strong adsorption through
the carbonyl group rather than the weak adsorption through the >C=S
group in the iron/solution interface. The performance ordering among them
is purely governed by their electronic structure that facilitates adsorption
through the electron rich center.

Besides the adsorption, control of the partial current values of the

corrosion process is also a contributing factor to the corrosion inhibition
process.

4.2.3. Mechanism on the role of additives as brighteners

The role of additives which allow bright and homogenous deposits

to be obtained is explained in many ways. In one of the approaches, the
over potential for the metal deposition process is explained as the
additional energy required for the discharge process due to the blocking
effect on the electrodeposition process by the additives. The overpotential
is computed as the difference between the deposition potential (Ecp) and the
cross over potential (E^o).

Cross over potential with polyethoxilated additive of high molecular

weight that gives bright zinc deposit from acidic solution is reported [66].
In the present investigation, all the additives are seen to increase the
deposition potential with respect to the control in the more negative
direction subscribing to the above view. The effect of glycine and thiourea
as brightener in acid zinc sulphate bath has also been explained based on
this principle [41].

202
 In another approach, the additives are explained to meddle with the
nucleation mechanism of the deposition process. Scharifker et al [67] have
proposed the model for 3D instantaneous and progressive nucleation
process controlled by diffusion. In the case of instantaneous nucleation. the
model assumes ver\ high nucleation rate and instantaneous coverage of all
the active sites by the nuclei. The following equation describes the current
transient under chronoamperometry performed in the potential range of the
deposition process.

1.9542 -1.2564
1 -e.\p
t t
I-

J
In the case of progressive nucleation process, the number of nuclei
is assumed to be time dependent form and the corresponding equation is

.2254 2.3367
-exp ^
_t^ t
tma\ t„

V J
The type of nucleation is decided by the slope of the i-t transient and
is actually the exponent of the i versus t^' dependence [68]. When p = 0.5. it
denotes instantaneous crystallization. (5=1.5 progressive, but P=l supposes
both types of crystallization.

For the deposition of zinc from zincate bath, it is suggested that the
process follows instantaneous nucleation in presence of macromolecular
amines and progressive nucleation with poKtetralkyl ammonium salts .

203
 A transition between the two nucleation mechanism has also been
reported for nucleation and growth processes controlled by mass transfer
[69-71]. Ultimately whether it is instantaneous or progressive nucleation
that decides the grain size of the deposition.

From the impedance measurements for the control of dentritic

growth of zinc electrodeposit. it has been suggested that the additive
modifies the rates of some of the elementan,- reaction taking place at the
interface and seems to decrease the importance of the autocatalytic step in
the reaction mechanism [72]

The type of nucleation process is proposed with stable electrodes

like platinum or glassy carbon and not with active metal surfaces like Fe or
Zn. Anyway it is reasonable to assume the same type of nucleation process
may be followed with these interfaces also.

The order of performance in getting bright zinc deposits in both acid

and alkaline plating baths is TSC and thiosemicarbazones > carbonyl
compounds. Among the carbonvi compounds, the order of performance is
FrA>SaA>CnA>CrA>AcP and among the thiosemicarbazones the order
being FrTSCN>SaTSCN>CnTSCN>CrTSCN>AcPTSCN>TSC.

In the case of the carbonyl compounds the adsorption is through the

carbonyl group which is strong compared to the adsorption through >C=S.
For the performance as good inhibitor, the essential requirement is very
strong adsorption, but for the performance as brightner. it is desirable that
the adsorption should be neither weak nor strong but moderate in nature
which is met in the adsorption through >C=S group. Hence, the
performance as brightners of thiosemicarbazones as well as TSC is better
than the corresponding carbonyl compounds. The electron releasing ability

204
of the different moieties is furfuryl>ortho-hydroxy phenyl>methyl>phenyl
planked with methyl group.

In the case of ortho-hydroxy phenyl group the intra molecular

hydrogen bond formation between OH group and lone pair electron of
nitrogen atom nullifies the electron withdrawing p)ower of OH group and
this account for its better performance than the simple phenyl moiety.

In the FTIR spectrum of SaTSCN. the -OH stretching appears at

3172.58 cm"' instead of a normal phenolic -OH expected at 3373 cm"'
which confirms this. The poor performance of the AcP/ApTSCN among
their respective groups may be due to the shielding of the polar >C=S
center by the methyl group as indicated below.

H3C ^N

H H

4.2.4. Evaluation of the corrosion resistance behaviour of the zinc

deposits

Zinc electrodeposition in both alkaline and acid media is reported to

give successively spongy compact and dendritic deposits controlled by the
current density. This property is reported to be due to an autocatalyiic step
in the reaction mechanism which leads to multiple steady states. [73] and
to local over intensities that give rise to an irregular growlh [74]. In this

205
context the role of small amounts of additives such as lead acetate that is
able to prevent heterogeneous growth of zinc dejX)sits is most promising
from platers point of view. According to electroplating principles it is
possible to obtain fine grained smooth and pore free deposits by adding
suitable addition agents to the plating bath. In most cases the addition
agents (brighteners) are adsorbed on the surface of the cathode and from
thin film that control the deposition process.

In the present investigation a set of carbonyl compounds and their

thiosemicarbazone derivatives have been tried as additives in the acid and
alkaline zinc plating baths. The presence of these additives is bound to tell
upon the quality of the zinc deposits obtained. The corrosion behaviour of
such deposits in the common 5% NaCl electroKle will reflect on the extent
of grain refinement and pore free structure that has bearing on the
performance of the additive in the bath as brighteners.

4.2.4,1. Studies with deposits from acid plating baths

The corrosion resistance behaviour of the zinc deposit is evaluated

through weight loss and polarization measurements.

i) Weight loss studies

The weight loss results for the zinc deposits obtained from acid zinc
plating bath in the absence and in presence of different carbonyl
compounds in 5% NaCl medium is presented in Table (4.2.18). It is found
that the corrosion resistance property of the deposits obtained in presence
of the carbonyl compounds is not much different from that obtained from
the plain bath. This reflects the fact that the carbonyl compxjunds are not
etTective as brightners. The weight loss results for the zinc deposits
obtained from the plating bath containing the thiosemicarbazones of the
above carbonyl compounds is presented in Table(4.2.19).

206
 Table-4.2.18

Weight loss results in SVo NaCI for zinc deposits obtained from acid
bath with different additives

Corrosion rate 'corr Efficiency

Name of the additives
(mdd) xlO-^ (A) (%)

Plain 4700 1.607 -

FrA 4211 1.440 10.40

SaA 4255 1.455 9.46

CnA 4409 1.508 6.19

CrA 4511 1.543 4.02

AcP 4569 1.562 2.78

207
 Table-4.2.19

Weight loss results for zinc deposits in SVo NaCl obtained from acid
bath with optimum additive concentrations

Corrosion rate 'corr EfTiciency

Name of the additives
(mdd) (A) (%)

TSC 4627 1.58.\10"- 1.50

FrTSCN 867.1 2.96x10-' 20.6

SaTSCN 150.3 5.14 \10"' 68.02

CnTSCN 185.5 6.34x10- 54.04

CrTSCN 198.3 6.78x10' 48.04

ApTSCN 252.7 8.64x10' 33.5!

208
It is noted that the deposits from the plating baths containing
thiosemicarbazones give unitbrmK better inhibition than from those
containing carbonyl compounds. Further, it is also noted that the simple
thiosemicarbazide does not have any effect on the qualitv of the zinc
deposit reflected from the negligible corrosion resistance obtained in
presence of it.

ii) Potentiodynamic polarization studies

The Tafel polarization results with zinc deposits obtained in

presence of carbonyl compounds and their thiosemicarbazone derivatives
are presented in Tables(4.2.20) & (4.2.21) and in Figs.(4.2.34) & (4.2.35)
respectively. As with weight loss results, the better performance of the zinc
deposits from plating baths containing the carbazone derivatives compared
to those from the baths with carbonyl compound additives is reflected here.
The cathodic control of the corrosion reaction of the zinc deposit obtained
from different baths, in NaCl medium is inferred from the fact that almost
in all the cases K>bd.

4.2.4.2. Studies with deposits from alkaline plating bath

I) Weight loss studies

The weight loss results for the two sets of above compounds are
presented in Tables(4.2.22) & (4.2.23). As with deposits from acid plating
baths here also the same trend of performance is revealed (ie.) deposits
from bath with carbazone derivatives show better corrosion resistance
behaviour. Also there is overall improved corrosion resistance for zinc
deposits from alkaline plating baths than those from acid bath.

209
 -1

-1.5

-2

- -2.5
o

-3.5 —

-1700 -1600 -1500 -1400 -1300 -1200

Potential (mV)
Fig. 4.2.34. Potentiodynamic polarization curves in 5%NaCI solution for electrodeposits
obtained from acid bath with different additives
a) Plain, b) FrA, c) SaA, d) CnA, e) CrA and f) AcP

210
o

-1700 -1600 -1500 -1400 -1300 -1200

Potential (mV)

Fig. 4.2.35. Potentiodynamic polarization curves in 5%NaCI solution for electrodeposits

obtained from acid bath with different additives
a) TSC, b) FrTSCN, c) SaTSCN, d) CnTSCN, e) CrTSCN and f) ApTSCN

21
 Table - 4.2.20

Potentiodynamic polarization results for zinc deposits in 5% NaCI

from acid bath with optimum additive concentrations

Name of 'corr be EfTiciency

the
additives (mV) xlO"^ (A) (mVdec"') (mVdec') (%)

Plain -1455 6.026 209 251 -

FrA -1467 4.335 206 269 28.30

SaA -1466 4.46 206 253 26.24

CnA -1461 4.57 200 242 24.40

CrA -1458 4.78 218 251 20.50

AcP -1460 4.78 248 260 20.50

2i;
 Table-4.2.21

Potentiostatic polarization results for zinc deposits in 5% NaCI from

acid bath with optimum additive concentrations

Name of the 'corr b. be EfTiciency

additives (mV) xlO"^(A) (mVdec"') (mVdec"') (%)

TSC -1473 5.49 218 248 8.81

FrTSCN -1461 2.11 215 269 64.98

SaTSCN -1464 2.63 200 281 56.35

CnTSCN -1459 2.89 208 242 52.04

CrTSCN -1464 3.02 218 224 49.88

ApTSCN -1471 3.80 212 256 36.93

213
 Table - 4.2.22

Weight loss results in 5% NaCI for zinc deposits obtained from alkaline
bath with different additives

Corrosion rate 'corr Efficiency

Name of the additives
(mdd) (Acm'^) (%)

Plain 4499 1.53x10- -

FrA 2044 6.99x10"-' 54.55

SaA 2499 8.54x10"' 54.40

CnA 3353 9.41 xlO"- 38.83

CrA 3519 1.20x10"- 21.76

AcP 3647 1.24x10"- 18.93

214
 Table - 4.2.23

Weight loss results for zinc deposits in 5% NaCI obtained from alkaline
bath with optimum additive concentrations

Corrosion rate 'corr EflTciency

Name of the additives
(mdd) (Acm"^) (%)

TSC 3500 1.19x10- 2219

FrTSCN 310 1.42 xlO-' 90.75

SaTSCN 415 1.45 .\I0-' 89.33

CnTSCN 425 1.64 \ I 0 ' 88.05

CrTSCN 479 1.86 .\ 10' 87.4

ApTSCN 543 1.06x10- 30.72

215
ii) Polarization studies

The Tafel polarization results for the corrosion of zinc deposits from
alkaline zinc plating baths containing carbonvi compounds and their
thiosemicarbazone derivatives are presented in Tables(4.2.24) & (4.2.25)
and in Figs.(4.2.36) & (4.2.37) respectively. These studies also confirm the
better performance of the zinc deposits from baths containing
thiosemicarbazone derivatives than those from bath containing carbonvi
compounds. The fact that b o b a and shift of corrosion potential in the
negative direction suggest the cathodic control of the corrosion of zinc in
5%NaCl medium..

4.2.5. Microhardness studies on the zinc deposits

Normally with zinc deposits its corrosion resistance behavior is

more important than its hardness property particularly for application like
cathodic protection. But in automobile spare parts, the latter property is
more demanding. The additives of the plating bath control the quality of
the deposit which is related to the hardness. Hence the microhardness
studies assume importance in the present context. The results are presented
in Table(4.2.26).

It is clear from the results that a better quality deposit is obtainable

from bath containing thiosemicarbazone derivatives rather than with the
carbonyl additives, be it from acid or alkaline plating bath. The enhanced
microhardness should be the result of grain refinement of the deposition
process controlled by the additive of the plating bath.

4.2.6. Morphology of the deposits

The structures of the zinc deposits obtained from acid and alkaline
baths were examined by scanning electron microscopy. The SEM
photographs for the plain acid bath without additive and with the best

216
additive FrTSCN taken at xlOOO. x4000 are shown in Figs.(4.2.38)
&.(4.2.39) respectively.

It is observed that the morphology of the deposits are controlled by

the additives in the bath. With the addition of FrTSCN to both the baths
there is significant grain refinement of the zinc deposit.

The deposit from acid bath without the additive is ver\ irregular and
loosely packed and that of from alkaline bath has a random nodular
appearance.

It has been proposed [75] that brightners are adsorbed at points of

low over potentials, and inhibit lateral growth and as a result influence the
grain structtires.

The addition agent FrTSCN has produced uniform zinc platelets

from acidic bath and a more compact layered structure in the case of
alkaline bath. This most ordered and refined structure is responsible for the
better corrosion resistance and improved hardness of the deposits.

217
-1700 -1600 -1500 -1400 -1300 -1200
Potential (mV)

Fig. 4.2.36. Potentiodynamic polarization curves in 5% NaCI solution for electrodeposits

obtained from alkaline bath with different additives
a) Plain, b) FrA, c) SaA, d) CnA, e) CrA and f) AcP

218
 -1 -
a

-1.5 —
"~\^^^^^0\ X ^
" \ ^ x^\ \ / ^^-''"'"^ e

-2 —

- -2.5 -A

-3 —

-3.5 -^

A
-*» 1 1 1 1 1 1 1 1
-1700 -1600 -1500 -1400 -1300 -1200
Potential (mV)

Fig. 4.2.37. Potentiodynamic polarization curves in 5% NaCl solution for electrodeposits

obtained from alkaline bath with different additives
a) TSC, b) FrTSCN, c) SaTSCN, d) CnTSCN, e) CrTSCN and f) ApTSCN

219
 Table - 4.2.24

Potentiostatic polarization results for zinc deposits from alkaline bath

with optimum additive concentrations in SVo NaCI

Name of the •^corr Icorr b. be EfTiciency

additives (mV) xlO"^ (A) (mVdec') (mVdec') (%)

Plain -1430 5.012 187 218 -

FrA -1458 2.88 181 254 42.5

SaA -1450 3.65 154 281 27.17

CnA -1472 5.01 193 221 3.99

CrA -1473 4.57 188 251 8.81

AcP -1476 4.81 187 263 4.03

220
 Table - 4.2.25

Potentiostatic polarization results for zinc deposits from alkaline bath

with optimum additive concentrations in 5Vo NaCl

Name of the ticorr 'corr b. be Efficiency

additives
(mV) xlO"' (A) (mVdec') (mVdec') (%)

TSC -1500 3.86 190 219 22.92

FrTSCN -1453 1.34 186 242 73.26

SaTSCN -1457 1.50 193 218 70.07

CnTSCN -1454 1.51 185 236 69.80

CrTSCN -1451 1.78 189 263 64.48

ApTSCN -1455 2.11 187 236 57.90

221
 Table - 4.2.26

Microhardness values for the zinc deposits of 30 ^m thickness obtained

with different additives from acid and alkaline baths

VHN (Load 50 gm)

Additives
Acid Alkaline

Plain 77.2 80.5

TSC 32.3 39.9

FrA 38.6 48.9

SaA 37.9 47.3

Can 38.4 39.9

CrA 38.1 37.2

AcP 32.6 35.4

FrTSCN 96.2 110

SaTSCN 94.2 108

CnTSCN 93.2 100

CrTSCN 91.5 98.3

AcTSCN 89.9 97.2

-)~)1
 xlOO xlOOO

xlOOO x4000

Fig.4.12.38. SEM photographs of Zinc deposits from acid bath a) plain bath
b) with FrTSCN at different magnifications

223
 xlOO xlOOO

xlOOO x4000

Fig.4.2.39. SEM photographs of Zinc deposits from alkaline bath a) plain bath
b) with FrTSCN at different magnifications

224
REFERENCES

1. R.Narayanan and B.H.Narayana. Review in Coatings and Corrosion.

4(2). (1981).

2. J.P.Celis and J.R.Roos. Reviews in Coatings and Corrosion. 5(1-4).

(1982).

3. B.J.Hwang and C.S.Hwang. J. Electrochem. Soc. 140(4). 979

(1993).

4. Masaki Abe, Yukimtsu. Shihohara and Akiyoshi Okada. Zinc Based

Steel Coating Systems. Edited by George Krauss and David
K.MaHock. The Mineral. Metals and Materials. Society. (1990).

5. V.P.Greco and W.Baldauf. Plating. March. 250-257 (1968).

6. S.N.Athavale and N.K.Totlani. J. Eelctrochem. Soc. India. 31-4. 119

(1982).

7. F.K.Satter. J. Electrochem. Soc. 110. 557 (1963).

8. M.N.Joshi and M.K.Totlani. Proc. l" National Conf. Electroplating
and Metal Finishing. Dec. New Delhi. Published by National
Productivity Council. Delhi. Oct.. p. 185(1981).

9. TP.Konzina. R.S.Saifullin and M.F.Skalozab Blest>'ashchie Komb

Metal Pokrytiya. 2. 88 (1967).

10. M.Viswanathan. Metal Finish. 71-11. 38 (1973).

11. GNK. Ramesh Babu. V.S.Muralidharan and K.l.Vasu. Plating Surf.
Fin.. 78(5). 126(1991).

12. M.N.Joshi and M.K.Totlani. Trans. Of the Metal Finisher's

Association of India. Vol.7. No.2. April-June. (1998).
13. Naoji Furukowa and Tadao Hayashi. Surf. Finish. 85. Proc 71*'
AES Annual Tech. Conf July 16-20. New York (1984).

225
14. R.V.Williams and P.W.Martin. Proc. 6* International Conf.
Electrodeposition and Metal Finishing, p. 182 (1964).
15. J.P .Cells. J.R.Roos and C.Buelens. J. Electrochem. Soc. 134. 6.
1402(1987).
16. E.C.Kedward. CA Addison and AAB Tennett. Trans. Inst. Metal
Finish.. 54. 8(1976)
17. N.Guglielmi. J. Electrochem. Soc.. 119. 1009 (1972).
18. C.White and J.Foster. Trans. Inst. Metal Finish. 59. 8 (1981).
19. J.P.Cells. J.R.R00S and C.Buelens. J. Elctrochem. Soc. 1346.
1402(1987).

20. CE.Vest and DF bazano. Met. Fin.. 65( 11). 52 (1967).

21. C.White and J.Foster. Trans. Inst. Metal Finish. 56. 92 (1978).

22. D.W.Snaith and P.D.Groves. Trans. Inst. Metal Finish. 50. 95

(1972).

23. J.E.HolTmann and C.L.Mantell. Trans. TMS-AIME. 236. 1015

(1964).

24. M.Pushpavanam et al.. Metal Finish. 72-10. 46 (1974).

25. C.White and J.Foster. Trans. Inst. Metal Finish.. 59. 8 (1981)

26. M.Pushpavanam et al.. Metal Finish. 72-10 . 46 (1974).

27. M.D.Ghouse. M.Viswanathan and EG.Ramachandran. Metal Fin..

78(4). 44(1980).

28. M.Pushpavanam and BA.Shenoi. Metal Finish. 77. 38 (1977).

29. T.W.Tomaszewski. LC.Tomaszewski and H.Brown. Plating. 1234

(1969).

30. C.White and J.Foster. Trans. Inst. Metal Finish. 59. 92 (1978).

226
31. F.K.Sautler, Electrodeposition of Dispersion Hardened Nickel-
alumina Alloy. Report No AD 225956. Office of Technical
Services. US Dept. ofCommerse. Washington. DC 25 (1962).

32. R.V.Williamsn and P.W.Martin. Proc. 6"^ International Conf. on

Electrodepostion and Metal Finishing. 182 (1964).

33. C.A.Brandes and D.Goldthorpe. Metallurgia. 76. 195(1967).

34. AMJ. Kariapper and J.Foster. Trans. Inst. Met. Finish. 52.87 (1974).

35. R.W.Guard. "Strengthening Mechanisms in A.S.M. Metals Park.

Ohio (1960)

36. Y.Z.Wan et al.. Trans. IMF. 77(1) 52 (1999).

37. G.N.K.Ramesh Babu and V.S.Muralidharan. Bulletin of

Electrochemistry 8(8) August, pp.393-395 (1992).

38. T.V.Venkatesha et al.. Metal Finishing. 83. 33. Aug. (1985).

39. T.V.Venkatesha et al.. Metal Finishing. 84. 29. Dec. (1986).

40. Shigeyoshi Morisaki. Tatemimori and Sakae Tajima. Plating and

Surface Finishing. 55-63 (1981).
41. T.V.Venkatesha. J.Balachandra. S.M.Mayanna and R.P.Dambal.
Plating and Surface Finishing. June. 77-80 (1987).

42. S.M.Mayanna et al.. Metal Finish.. 85. 33 (1987).

43. A.John Rathinam. GNK. Ramesh Bapu and V.S.Muralidharan.

Trans. SAEST. Vol.37 (3&4). (2002).
44. G.Trejo, H.Ruiz and Y.Meas.. Journal of Applied Electrochemistry.
31:685-602.(2001).
45. L.Mirkova. G.Maurin. I.Krarter and C.Tsvetkova. J. Applied
Electrochem.. 31:647-654. (2001).
46. S.Shabana Begam et a!.. Portugalie Electrochim. Acta. 19. 121
(2001).

227
47. Y.Arthoba Naik. T.V.Venkatesha and P.Vasudeva Nayak. Bull.
Electrochem.. 16(11). 481 (2000).
48. V.N.Titova et al.. Bull. Electrochem.. 16(9). 425 (2000).
49. Visalakshi Ravindran and V.S.Muralidharan. Bull. Electrochem..
16(2). 60-63 (2000).
50. M.Jamal Abdul Nasser. Ph.D. Thesis submitted to Bharathidasan
University. (2001).

51. J.P.G.Faur and N.A.Hampson. J. Electroanal. Chem.. 13. 433

(1967).
52. J.P.G.Faur and N.A.Hampson. Trans. Faraday Soc. 62. 3493
(1966).
53. V.S.Muralidharan. Trans. SAEST. 37(3&4). July-Dec. (2002).

54. D.Kardos and D.G.Foulke. Advances in Electrochem. And Electro

Engg..2. 145(1962).

55. V.l.Potapova. P.M.Vyacheslovov and O.A.Nikitina. Zhumal

Prikladnoikhimii. 50(12). 2698. Dec. (1977).

56. R.Shivakumar. G.Paruthimal Kalignan and T.Vasudevan. J. Surface.

Sci. Tech.. 13.99(1997).
57. R.Shivakumar. G.Paruthimal Kalaignan and T.Vasudevan. J. Power
Sources. 55. 53(1995).

58. T.Vasudevan et al.. Corros. Sci.. 37(8). 1235 (1995).

59. M.S.Morad. Corros. Sci.. 42. 1307 (2001).

60. P.Li. J.Y.Lin. K.L.Tan and J.Y.Lee. Electrochemica Acta. 42(4).
605(1997).

61. Metikos-Hukovic et al.. J. Appl. Electrochem.. 2418. 772 (1994).

62. C.Desiowis et al..J. Electroanal. Chem.. 107. 1993 (1980).

63. C.Desiowis et al.. J. Electroanal. Chem.. 129. 107 (1982).

228
64. W.Werburg. Ann. Phy.. 6. 125 (1901).
65. G.Gabriellli. Identification of Electrochemical Processes by
Frequency Response Analysis Solatron. Franborough. U.K. 62
(1980).

66. G.Trejo. et al.. J. Appl. Electrochem.. 31:685-693 (2001).

67. B.R.Scharifker and G.Hills. Electrochim. Acta. 28. 879 (1983).
68. JA.Harison and HR.Thrisk. Electroanalytical Chemistr> : A series of
Advances. (Ed.) A.J.Bard. New York. Marcel Dekker. 5. 67(1988).

69. G.Gunawardena. G.Hills and I.Montenegal. J. Electroanal. Chem..

184.371(1985).
70. G.Gunawardena et al.. J. Electroanal. Chem.. 138. 225. (1982).
71. M.Sanchuz Cruz. F.AIonso and J.M.Palacios. J. Appl. Electrochem..
23.364(1993).

72. J. Bressan and R.Wiart. J. Appl. Electrochem.. 505-510. (1977).

73. l.Epelboin. M.Ksouri arid R.Wiart. J. Electrochem. Soc. 122. 1206

(1975).
74. J.ldem. J. Electroanal. Chem.. 65. 373 (1975).
75. R.AIbalat et al.. J. Applied Electrochem.. 21. 44-49 (1991).

229
mpiER • 1/

mmm
 CHAPTER-V

CONCLUSIONS

Zinc being the most widely used metal with lot of applications, it is
always desirable to see whether its functional properties like mechanical
and corrosion resistance, could be improved. This is achieved when some
electrozinc composites are developed with the incorporation of suitable
inert particles in the metal matrix. Another important aspect with zinc
plating is the quality of the plating which is mainly controlled by the
additives added to the bath. Hence in the present investigation these two
aspects are studied in detail and the important conclusions drawn from the
studies are presented below.

5.1. ELECTRO-ZINC COMPOSITES

1) After optimizing the bath parameters with acetate-sulphate zinc

plating bath. Zn-TiO^. Zn-Cr^Oj. Zn-MoS; and Zn-AUO:,
electrocomposites were developed. The optimized bath parameters
specific to each composite is mentioned below.

System pH Temperature Current density Bath load

rc) (Adm-) (epi)
TiO: 5 60 9 80

Cr.O, 3 40 8 250

MoS: 2 50 7 50

Al.O., 5 40 4 120

2) The incorporation of the inert particles is explained based on

electrostatic attraction (function of adsorbed charge densitv on the
particles and the potential field in the interface) physical bond formed

130
 between the particles and the electrode which is weak in the initial
stages and that is transformed into a strong bond subsequently, and on
some of the mechanical interaction factors like size and density of the
particles and the rate of agitation.

3) The validity of adsorption mechanism for the electrodeposited zinc

composites is explained based on the model proposed by Guglielmi
where in plots of C/a Vs C yielded a sheaf of straight lines
converging on a common intersection point on the negative side of
the abscissa. Thus the incorporation of the inert particles into the
metal matrix is similar to Langmuir adsorption isotherm and the co-
deposition mechanism is based on physical adsorption effect.

4) The microhardness measurements made with the composites at a

constant thickness of 30fim in the annealed condition at 400"C for
3 hrs help to grade them in the order of performance as

Zn-Al203>Zn-Cr.03>Zn-Ti02>Zn-MoS:>Zn

Whereas under as plated condition there is a slight change in the order

with Zn-Cri03 taking the first place. The hardness of the composite
will be related to the hardness of the particles and grain refinement of
the matrix metal. MoS^ being the softest particle naturally Zn-MoSi
has the least micro hardness but still better than pure zinc deposit.

5) Wear loss measurements were made for 100 cycles at a load of 1kg
indicate that Zn-MoSi offers the least wear loss followed by Zn-TiO^.
Zn-CriOs and Zn-TiO; exhibit more or less the same wear loss. The
best wear resistance exhibited by Zn-MoS: system is due to the
lubricating nature of the M0S2 particles and the layered structure of
the Zn-MoSi matrix.

231
6) The corrosion resistance behaviour of the composites in comparison
with the pure zinc deposit is monitored in 5% NaCl medium through
weight loss. Tafel polarization and impedance measurements. The
order of their corrosion resistance behaviour is as follows

Zn-TiO: > Zn-Cr.O., > Zn-ANOj > Zn - MoS.

The improved corrosion resistance in the case of the composites with

respect to pure zinc is related to compactness and grain refinement of
the deposits. The poor corrosion resistance of Zn-MoSi is due to its
porous structure.

7) The surface morphology of the composites developed is examined

through optical microscope and for better clarity through scanning
electron microscope. The nodular oriented, layered and relatively
amorphous and porous structures with respect to Zn-TiOi. Zn-AKOj.
Zn-CriOj and Zn-MoSi deposits respectively were photographed.

8) The XRD studies of zinc and zinc composites were made. These
studies clearly indicate the incorporation of the composite particles
into the zinc matrix. The lattice parameters of the respective
composites are predicted.

5.2. ROLE OF ADDITIVES IN ZINC PLATING BATHS

The additives of the plating bath have a great influence in controlling

the quality of the deposit. A set of carbonyl compounds and their
thiosemicarbazone derivatives have been tried as additives in acid and
alkaline zinc plating baths.

9) The summarized results of the Hull cell studies of the acid and
alkaline plating baths are given below:

232
Current density ranges for various deposits obtained with different
additives in acid bath
Additive Concentration Nature of Current
(ml/I) deposit density range
(Adm"^)
TSC 0.1* Semibright 0.3-5.5
FrA 0.1 Bright 1.6-4.0
SaA 0.5 Semibright 1.6-2.4
CnA 0.5 Dull 1.2-2.0
CrA 0.5 Dull 4.0-5.0
AcP 0.2 Dull 3.0-4.0
FrTSCN 0.3 Mirror bright 0.2 - 8.0
SaTSCN 0.3 Bright 0.8-4.0
CnTSCN 0.3 Bright 1.6-4.0
CrTSCN 1.5 Bright 1.0-3.0
AcTSCN 0.3 Semibright 1.2-2.4
* gdm
Current density ranges for various deposits obtained with different
additives in alkaline bath
Additive Concentration Nature of Current density
(mldm"') deposit range (Adm*)
TSC 1.0* Bright 0.6-1.2
FrA 2.0 Bright 1.0-2.5
SaA 1.0 Satin white 0.4-1.2
CnA 1.5 Semibright 1.5-2.5
CrA 2.0 Grey 1.2-2.0
AcP 1.5 Grey 0.8-1.2
FrTSCN 1.5 Mirror bright 0.4 - 4.0
SaTSCN 0.5 Bright 0.2-1.5
CnTSCN 1.5 Bright 1.2-3.0
CrTSCN 1.5 Dull 1.0-2.5
AcTSCN 0.5 Grey 0.8- 1.5
* gdm

233
10) The throwing power and current efficiencies of both the baths in
presence of the additives are measured and reported. The
thiosemicarbazone derivatives are noted to improve the throwing
power of both the baths better than their carbonyl counter parts. So is
the current efficiency trend.

11) There is always some risk, of the substrate metal mild steel corroding
over a period of time in the plating bath resulting in poor quality zinc
deposit. The corrosion inhibition power of the additives with respect
to mild steel corrosion in the plating baths are monitored through
weight loss polarization and impedance measurements. It is noted that
the carbonyl compounds offered better corrosion inhibition than their
corresponding thiosemicarbazone derivatives. The order of inhibition
among them being FrA>SaA>CrA>TSC>AcP and FrTSCN>
SaTSCN>CnTSCN>CrTSCN>AcTSCN. The strong adsorption
through the carbonyl group in the case of the former compounds than
the weak adsorption though > C=S centre with the latter group
accounts for the above observation. The performance ordering among
them in the respective groups is purely governed by the structure
related electronic effects that controls the prime adsorption process
through the electron rich center. The Tafel polarization measurements
help to identify the control of the corrosion process in presence of the
additives. The reduced double layer capacity values measured through
impedance method confirm the inhibition offered by the additives.

12) The cyclic voltammetric studies carried out with mild steel electrode
in acid and alkaline plating baths in the absence and presence of the
additives at their optimum concentration help to identify the
mechanism of the discharge of Zn*"" ions and the role of the additives
tried. The function of the additives as brighteners through adsorption

234
 at the energetically active sites resulting in decreased cathodic
currents is highlighted. The electrochemical spectrum in presence of
the additives is not altered compared to that of the plain bath
suggesting that there is no change in the basic deposition/ dissolution
of zinc in the plating baths. The best additive is seen to increase the
cathodic polarization and raise the limiting current of zinc ion
reduction to the maximum extent.

13) The corrosion resistance behaviour of the zinc deposits obtained from
acid and alkaline zinc plating baths in the absence and presence of the
additives is examined through weight loss and polarization
measurements in 5% NaCl. The deposits from both the baths
containing the thiosemicarbazone derivatives shows better corrosion
resistance behaviour than that obtained with carbonyl additives. The
corrosion resistance behaviour is closely related to the micro structure
of the deposits obtained. With compact and fine grained structures
there will be least corrosion.

14) The microhardness measurements made with different zinc deposits

obtained from acid and alkaline plating baths in the absence and
presence of the additives indicate that there is improved hardness with
deposits obtained with baths containing thiosemicarbazone derivatives
than from those with carbonyl additives. As with the corrosion
resistance the hardness improvement is again related to the surface
morphology.

15) The surface morphology of the deposits obtained from both the acid
and alkaline baths without any additive and from them with the best
additive FrTSCN. were examined through SEM. This indicates the
role of the additive in the plating bath in getting compact and grain
refined deposits.

235
From the studies of the composites Zn-AliOj could be chosen as the
best composite with maximum hardness and fairly good corrosion
resistance property. Zn-MoS: composite may find application where
wear loss is of important consideration. With the use of
thiosemicarbazone additives as brighteners. bright zinc deposit could
be obtained and FrTSCN is the best of all the additives tried with
which even mirror bright deposits are possible. Whether it is the
composite or the pure deposit it is only the microstructure of the
deposit that ultimately governs both the mechanical and corrosion
resistance property. The optimum choice of the bath parameters
besides the suitable additive will enable the achievement and this is
the focus of the study.

236
SCOPE OF THE FUTURE WORK

Recently some new domains have been explored in which

electrochemical synthesis of composites is of great interest in order to
better cope with the requirements of new application fields.

The present work carried out was aimed at almost entirely on the
production of wear and corrosion resistance coatings, self lubricating layers
and dispersion strengthened coatings. Zinc has wide industrial applications
and hence the preference of this matrix.

It is possible to have alternative matrix materials like conducting

polymers, oxides and salts in order to produce composites with properties
that appropriates their use in electrocatalysis. fabrication of photoactive
devices and energy storage.

In developing additives for zinc plating baths, the synergistic effect

of thiosemicarbazones with some other brighteners can be evaluated.

237