STUDIES ON THE ELECTRODEPOSITION OF

CHROMIUM AND ITS ALLOY FROM ECO-

FRIENDLY Cr(III) ELECTROLYTES AND ROOM
TEMPERATURE IONIC LIQUIDS-RTIL

THESIS SUBMITTED TO BHARATHIDASAN UNIVERSITY

FOR THE AWARD OF THE DEGREE OF
DOCTOR OF PHILOSOPHY

IN
CHEMISTRY
BY
G. SARAVANAN
18111/ Ph. D.1/Chemistry/Full time/Oct. 2009

Dr. S. MOHAN

(Research Supervisor)

EMFT Division
CSIR - Central Electrochemical Research Institute
Karaikudi – 630 006

December 2011
G. Saravanan Karaikudi 630 006
Senior Research Fellow (CSIR) Tamil Nadu, INDIA

Date:

DECLARATION

I hereby declare that the thesis entitled “Studies on the electrodeposition

of chromium and its alloy from Eco-friendly Cr(III) electrolytes and Room
Temperature Ionic Liquids-RTIL” has been originally carried out by me at
Central Electrochemical Research Institute-CSIR, Karaikudi 630 006, India under
the guidance of Dr. S. Mohan, Senior principal scientist, Central Electrochemical
Research Institute-CSIR, India. This work has not previously formed the basis for
the award of any Degree, Diploma, Associateship, Fellowship or other similar title
of Bharathidasan University or any other University.

(G. SARAVANAN)
 Acknowledgement

First and Foremost, I praise and thank the Almighty God for his countless

blessings that he showered upon me to complete my research successfully.

I would like to record my gratitude to Dr. S. Mohan, M. Sc., Ph. D., Senior

Principle Scientist, CSIR─Central Electrochemical Research Institute, for his

supervision, advice and guidance from the beginning of this research as well as making

me to gave extraordinary experience throughout the research work. Above all and the

most needed, he provided me constant encouragement and support in various ways. His

truly scientist instinct has made him as a constant oasis of ideas and passions in science,

which exceptionally inspire and enrich my growth as a student, a researcher and as a

scientist. I am indebted to him more than he knows.

I gratefully acknowledge Dr. Vijayamohanan K. Pillai, Acting Director, CECRI,

Dr. V. Yegnaraman, former Director, CECRI, Dr. N. Palaniswamy, Head Corrosion

Preotection, Dr. N. G. Renganathan, Head, Lithium Ion Battery, Dr. Shoba

Jayakrishnan, Head EMFT Division, Dr. GNK. Ramesh Bapu, Dr. K.L.N. Phani,

Chairman (SAC) and Dr. R. H. Suresh Bapu for their involvement with their originality

has triggered and nourished my intellectual maturity that I will benefit from, for a long

time to come. I am grateful to them in all possible way.

I am much indebted to Mr. R. Ravishankar, Mr. A. Rathishkumar,

Ms. S. Krithika, Dr. N. Radhakrishnan, Mrs. Nalini Thondiraj, Mr. P. Kamaraj,

Mrs. S. Bagyalakshmi and Dr. G. V. M. Kiruthika, for their help in using

instrumentation facilities. They were generous with their helpful comments and shared

their valuable time for discussions.

 I wish to express my sincere thanks to Dr. V. Raj, Associate Professor,

Department of Chemistry, Periyar University and Dr. G. Paruthimal Kalaignan,

Professor, Department of Industrial Chemistry, Alagappa University for having assessed

my research work during the doctoral committee meeting and making valuable

suggestions towards improving the scientific contents of the work.

I take great privilege in thanking those who have provided me personal

foundation, which has greatly influenced my professional life. I whole heartedly thank

my father Mr. Chinnaswamy Gengan, my mother Mrs. Kasthuri, my beloved brothers

and sisters Mr. G. Pughazanthi, Mr. G. Muthukumaran, Mrs. S. Vasugi and

Mrs. P. Suganthi for providing me the comfort and support on which my career is built.

It is because of their sacrifice, efforts and encouragement. I stand at this stage of my

professional life and without which I would have never achieved anything that I own

today as something great.

Collective and individual acknowledgments are also owed to my colleagues at

CECRI, Karaikudi whose encouragements are helpful and memorable. Many thanks go in

particular to Mr. RM. Gnanamuthu, Mr. J. Vijayakumar, Mr. N. Rajasekaran,

Mr. R. Pavulraj, Mr. J. Maharaja, Mr. C. Mohan, Mr. J. Vijay, Mr. K. Soundara

Pandian, Mr. P. Thangapandian and Mr. M. Vinoth Kumar, Mr. B. Venkata Rami

Reddy, Mr. M. Jeevan Kumar Reddy and Mr. V. Selvamani for giving me such a

pleasant time when working together with them at CECRI.

It is a pleasure to acknowledge Ms. C. Nithya, SRF, CECRI for constant

engagement and helpful during the preparation of my thesis.

 I would like to thank my CECRI scientist and friends, Dr. M. Selvam, Dr. V.V.

Giridhar, Dr. G. Radhakrishnan, Mr. N. Rajasekar, (S&T) Mr. T. Arun Kumar,

Mr. MV. Geathesh Menon, Mr. S. Varatharajan, Mr. A. Kumaravel,

Mr. M. Sankararao and Mr. P. Arunkumar.

Finally, I am thankful to all staff members of CECRI library, the administrative

staff of CECRI and Bharathidasan University for their support and the Department of

Science and Technology (India), and the Council of Scientific and Industrial Research

(India, CSIR–SRF) for the financial assistance, which has enlightened the task of this

tenure.

(G. SARAVANAN)
 TABLE OF CONTENTS

Abstract

Chapter 1.0 Introduction

1.1 Definition of electrodeposition 1

1.2 Principle 1

1.3 Factor affecting the electrodeposition process 4

1.4 Types of electrodeposits 6

1.5 Application of electrodeposition 6

1.6 Definition of alloys 7

1.7 Electro deposited alloy 8

1.8 Factor affecting the alloy deposition 8

1.9 Health and environmental effects of using hexavalent

chromium electrodeposition 11

1.10 Hexavalent chromium electroplating alternatives 13

1.11 Trivalent chromium electroplating 15

1.12 Electroplating in non-aqueous solution 18

1.13 Ionic liquids 20

1.14 Deep eutectic solvents 23

1.15 Applications of deep eutectic solvents 26

1.16 References 29

Chapter 2.0 Literature review

2.1 Chromium electrodeposition from Cr(VI) electrolyte 36

2.2 Decorative and hard chromium electrodeposition

using hexavalent chromium 37

2.3 Problems and developments in functional electrodeposition

using trivalent chromium 43

2.4 References 59

Chapter 3.0 Experimental procedure

3.1 Electrolyte preparation 65

3.2 DES preparation 65

3.3 Preparation of substrate 66

3.4 Electrodeposition methods 66

3.5 Characterization of electrodeposited metals and alloys 71

3.6 References 81

Chapter 4.0 Aim and scope of the research

4.1 Scope of research work 90

4.2 Methodology 91

4.3 References 93

Chapter 5.0 Electrodeposition of Fe-Ni-Cr alloy from deep eutectic system

containing choline chloride and ethylene glycol

5.1 Introduction 94

5.2 Experimental 95

5.3 Results and discussion 97

5.4 Conclusions 101

5.5 References 103

Chapter 6.0 Pulsed electrodeposition of microcrystalline chromium from trivalent

Cr−DMF bath

6. 1 Introduction 112

6. 2 Experimental 113

6.3 Results and discussion 114

6.4 Conclusions 118

6.5 References 120

Chapter 7.0 Structure, current efficiency and corrosion properties of

brush electrodeposited (BED) Cr from Cr(III)−

dimethylformamide (DMF) bath

7.1 Introduction 128

7.2 Experimental 129

7.3 Results and discussion 130

7.4 Conclusions 134

7.5 References 135

Chapter.8.0 Electrodeposition of Fe-Ni-Cr alloy from deep eutectic system

containing choline chloride and ethylene glycol

8.1 Introduction 145

8.2 Experimental section 146

8.3 Results and discussion 147

8.4 Conclusions 152

8.5 References 154

Chapter 9.0 Conclusions 159

List of publications 162

 ABSTRACT

Electrodeposition of chromium and its alloy from eco-friendly Cr(III) electrolyte

is an environmentally benign process for both decorative and functional applications. It

has been amply demonstrated that electrodeposited Cr by direct current (DCD) and pulse

current (PCD) on metal such as mild steel, can provide aesthetic appearance and

protection against corrosion. Glycine and dimethylformamide (DMF) used as Cr-

complexing agent, pulse and brush electrodeposition techniques have been used to

enhance current efficiency and deposit morphology. We obtained current efficiency

maximum of 36% using pulsed current which is two times higher than that of reported in

literature. Eco-friendly Cr(III) electrolyte with suitable complexing agent is a good

candidate to replace toxic Cr(VI) electrolyte. Ionic liquid/deep eutectic solvents have

been prepared using choline chloride and ethylene glycol (hydrogen bond donor) for

electrodeposition of Fe-Ni-Cr alloy. The influence of electrodeposition potential upon the

Fe, Ni, and Cr composition has been investigated. Ionic liquid/deep eutectic solvent

provides nanosized metal and alloy with negligible amount of H 2 evolution, therefore

current efficiency increased. Electrodeposit has been characterized mainly by using XRD,

SEM, AFM and EDS techniques. Anticorrosive property has been studied using

potentiodynamic polarization and electrochemical impedance spectroscopy.

 gF¡ß ·òÂïD
·u® ówK¦[ åâAç¦B Cr(III) t[Ãz¹l_ ÖòÍm
t[ªVuýBçkÝ>_ xçÅl_ ØÃÅ©Ã⦠z¼«VtBD \u®D ¶>[
c¼éVï ïéçk¥D, ·u®ówKÂz å[ç\ ÃBÂzD kçïlKD, ΩÃçª
\u®D ØÄB_ÃV| ïòsïÓÂzD ÃB[Ã|þÅm. ¼åì]çÄ \u®D m½©A
t[ûâ¦Ýç> ÃB[Ã|Ý] t[ªVuýBçkÝ>_ xçÅl_ ¨¹B
¨àþ[ *m ØÃÅ©Ã⦠z¼«VtB\Vªm sökVï sáÂï©Ã⦠Î[®
¼\KD ΩÃçªÂz, ¶ö\Vª >|©A ]Å窥D ¶¹ÂþÅm.

þçáE窥D \u®D ç¦Ø\Ý]_ àÃVì\ç\禥D,

z¼«VtBÝ][ ¶çª¡ ¼Äì\ºïáVï ÃB[Ã|Ý] t[û⦠ØÄB_]Å[
\u®D ýkÝ][ ¶ç\©¸Bçé ¶]ï©Ã|Ýmk>uz m½©A
x[ûâ¦D \u®D #öçï t[ªVu ýBçkÝ>_ Oâúï^
ÃB[Ã|Ý>©Ã⦪. m½©A t[ûâ¦Ýç> ÃB[Ã|Ý] ¶]ï\Vï 36%
t[û⦠ØÄB_]Åçª åVºï^ ïõ¦¤Í¼>VD, Öm \uÅ gF¡
¶¤Âçïï¹_ íÅ©Ãâ¦ç>s¦ Ö«õ| \¦ºz ¶]ï\Vï ÖòÂþÅm.

ØÃVòÝ>\Vª ¶çª¡ ¼Äì\ºïÓ¦[ ·w_ ‡ åâAØïVõ¦ Cr(III)

t[Ãz¹BVªm åâ·Ý>[ç\ ØïVõ¦ Cr(VI) Âz Ã]éVï Îò å_é
¼>ìkVï c^ám.

t[ªVuýBçkÝ>_ xçÅl_ Fe-Ni-Cr c¼éVï ïéçkçB ØÃÅ

ØïVçé[ z¼áVç«| \u®D ¨Ý]o[ þçáÂïV_ (çÇâ«Û[
¸çð©A) ~MçB ÃB[Ã|Ý] Àì\ ¶BM ¶_ém tï¡D
¨¹mòïç«©ÃV[ï^ >BVöÂï©Ãâ¦m. Fe, Ni \u®D Cr ïéçkl[ *m
t[ªVu ýBçkÂzD t[ûâ¦Ý][ >VÂïÝç> g«VB©Ãâ¦m.
çÇâ«Û[ Øk¹¼Bò>_ ¶á¡ A«ÂïMÂïÝ>Âï>Vï¡D tï OõèB
c¼éVï \u®D c¼éVï ïéçk ]«k ¶BM ¶_ém tï¡D ¨¹mò
ïç«©ÃV[ïáVï sáºzþÅm. gï¼k t[û⦠ØÄB_]ÅÐD
¶]ïöÂþÅm.

xÂþB\Vï XRD, SEM, AFM \u®D EDS Oâúïçá ÃB[Ã|Ý]

t[ªVuýkÝ][ Ã[äB©Ã|þÅm. t[ª¿Ý> \V®ÃV|
xçªkVÂïD \u®D t[¼k]lB_ t[\®©A WÅ\Vçé ïVâ½lBçé¥D
ÃB[Ã|Ý] ¶ö\Vª >|©A© Ãõçà ïõ¦¤B©Ãâ¦m.
Dedicated To My

Beloved Parents
CHAPTER I
 INTRODUCTION

1. 1 Definition of electrodeposition

Electrodeposition is process of coating usually metal onto a surface by passing the

direct current. This process is done by passing the direct current through the electrolyte

and it is associated with the movement through it of charged particles called ions. The

terminals leading the current are electrode.

1. 2 Principle

The electrodeposition was limited primarily to fulfilling decorative needs. But

today it is an important industrial process and it has the following functional properties

such as

 Corrosion resistance

 Wear and abrasion resistance

 Tarnish resistance

 Heat resistance

 Electrical resistance

 Oil retention surface

The metallic ions in salt carry positive charge and get attracted to the substrate

during passing negative current. When they reach surface of the substrate, it provide

electron to reduce the positive charged ions into metallic form. Figure 1. 1 shows

schematic diagram of electrodeposition cell.

1
 General reaction involves

At cathode

Mn+ + ne− M

At anode

In case of soluble anode

M Mn+ + ne−

In case of inert anode

H2O 2H+ + O2 + e−

2Cl− Cl2 + 2e−

The deposition reaction involves four types. They are

 Metal – solution interface as the focus of the deposition process.

 Kinetics and mechanism of the deposition process.

 Nucleation and growth process of the metal lattice.

 Structure and properties of the deposits.

Essential of plating should have the followings

 Cathode

 Anode

 Electrolytic solution

 An external circuit

Faraday’s Laws of electrolysis

They relate the current flow, time, and the equivalent weight of the metal with the weight

of deposit and may be stated as follows:

2
1. The amount of chemical change at an electrode is directly proportional to the quantity

of electricity passing through the solution.

2. The amounts of different substances liberated at an electrode by a given quantity of

electricity are proportional to their chemical equivalent weights.

Faraday’s Laws may be expressed quantitatively

I · t Eq

W = — (1)

where W = weight of deposit in grams

I = current flow in amperes

t = time in seconds

Eq = Equivalent weight of deposited element

F = Faraday, a constant, = ~96,500 coulombs

I · t is the quantity of electricity used (coulombs = ampere–seconds) and Eq (1) the

equivalent weight of the element, is the atomic weight divided by the valence change,

i.e., the number of electrons involved. If the current is not constant, then I · t must be

integrated

— (2)

From a practical standpoint, the weight of the deposit is converted to the more

meaningful thickness of the deposit using the relationship, W (gms) = volume

(cm3)/deposit density, with the volume of the deposit equal to the thickness (in µm) area

(in m2). The Faraday, F, can be experimentally determined by rearranging Eq. (1):

3
 I · t Eq

F = — (3)

WF

I·t = — (4)

Eq

permits the determination of the charge passing through a circuit by the known deposition

or dissolution of an element.

1. 3 Factors affecting the electrodeposition process

1. 3. 1 Effect of impurities

Impurities in the electrolyte can lead to unsatisfactory deposits. Insoluble

impurities such as dust and metal particles can attach physically to the cathode and cause

roughness of the plate. This is more likely if the electrolyte is agitated and the insoluble

particles are not allowed to settle as sediments.

Organic impurities may modify the deposit by the same mechanism as the

addition agents, with an unwanted effect.

1. 3. 2 Effect of Temperature

Increase in temperature of the electrolyte usually increases the solubility of the

metal and the conductivity of the solution. The temperature affects the nature of the

deposit and increase in temperature may lead to unsatisfactory plating. High temperature

also increases the problem of water evaporation and fumes. As with other parameters, the

4
most suitable temperature is usually determined empirically to give the best compromise

between plating rate and deposit quality.

1. 3. 3 Effect of agitation

Thermal convection current provides some stirring in plating electrolytes. Any

form of agitation increase the rate at which the metal ion reaches the cathode and thereby

reducing the concentration polarization. If hydrogen is co−deposited at the cathode the

bubbles leaving surface provide a very effective form of stirring. In other systems

introducing air bubbles from the bottom of the tank stimulates this effect. If the

electrolyte is not filtered, agitation can provide by keeping the solids in suspension.

1.3.4 Effect of leveling agent

Leveling is defined as the progressive reduction of the surface roughness during

deposition. Thus there are two types of leveling processes: (1) geometric leveling

corresponding to leveling in the absence of specific agents and (2) true or electrochemical

leveling corresponding to leveling in the presence of leveling agents. Theories of leveling

by additives are based on (1) the correlation between an increase in the polarization

produced by the leveling agents and (2) preferential adsorption of a leveling agent on the

high point (peaks of the substrate or flat surfaces) and by this inhibition (slowing down)

of deposition [1, 2].

1. 3. 5 Effect of brightening agent

The brightness of a surface is defined as the optical reflecting power of the

surface. It is measured by the amount of light peculiarly reflected Weil and Paquin [3]

showed a linear relationship between the logarithm of the amount of light peculiarly

reflected by a surface and the fraction of the surface having roughness of less than

5
1500A. Kardos and Foulke [2] distinguish three possible mechanisms for bright

deposition: (1) diffusion–controlled leveling, (2) grain refining, and (3) randomization of

crystal growth. Some fundamental aspects of brightening and leveling are reviewed by

Oniciu and Muresan [4].

1. 4 Types of electrodeposits

Electrodeposits are depending on the electrolyte composition, additional agents,

operating conditions such as pH, current density, temperature and agitation of the plating

electrolyte. Different types of electrodeposits are given below.

 Coarse or fine−grained deposit

 Microcrystalline

 Amorphous

 Compositionally modulated

 Multilayer

 Composite

 Nanocrystalline

 Powdery

 Bright/semi bright

 Dull/satin

 Black

 Soft/hard and Smooth/rough

1. 5 Application of electrodeposition

Electrodeposition is playing an important role in all walks of life. Some of the

important applications of electrodeposition are

6
  Household articles – Decorative items, wall clock, Fan Air conditioners, jewelers

etc.,

 Electronics – Control systems, radar instruments

 Computers

 Defense – missiles/ALH/remote controlled helicopter/fighter plane

 Aerospace

 Astronomy

 Communication – telephone wires

 Power station

 Solar energy conversion system

 Nuclear energy application

 Marine, mining industries etc.

1. 6 Definition of alloys

An alloy coating may be obtained by a co–deposition of the alloy constituents

from the electrolyte containing their ions. Deposited alloy may possess properties and

combination of properties, which are not achievable in the coatings of pure metals.

The aim of making alloys is to make them less brittle, harder, resistant to

corrosion, or have desirable color and luster.

Alloy may be either homogenous or heterogeneous.

1. Homogeneous (one phase alloy).

 Solid solution.

 Intermetallic compound.

7
2. Heterogeneous (two phase alloy)

 Solid solution

 Intermetallic compound

 Virtually unalloyed element

1. 7 Electro deposited alloy

They are similar to thermally prepared alloy in structure in that they usually

contain same phase. During deposition two are more metals deposited as alloy phases at

the cathode surface. These can be frequently achieved by electrolyzing a solution of

mixed salt at a sufficiently high current density.

1. 8 Factors affecting the alloy deposition

1. 8. 1 Role of electrode potentials in electrodeposition alloys

According to the Faraday’s law for electrodeposition binary alloy composed of

two metals M and A

WM = IM*t *μM/(nM*F)

WA = IA*t *μA/(nA*F)

Where

WM, WA – weights of the deposited metals M and A

μM, μA – weights of one mole of the metals M and A

nM, nA – numbers of electrons transferred by the ions M and A

F – Faraday’s constant (96485 Coulombs)

t – time.

Then the composition of the deposited alloy (molar concentration of A)

CA = IA/(IMnA/nM + IAnA/nA)

8
Under equilibrium conditions ions of a metal start to deposit on the cathode surface when

its potential is brought below the electrode potential calculated according to the Nernst

equation. In the real process the cathode potential, at which the deposition starts is even

below the equilibrium Nernst potential due to the electrode Polarization.

If the electrode potentials of the alloy components are different (EM > EA) then the

following conditions are possible:

 Ec > EM > EA (Ec is the cathode potential). Under these conditions no reduction

reactions occur.

No electric current is passing through the electrolyte.

 EA < Ec < EM. Only M is deposited. The electric current is a result of the

reaction Mn+ + ne– = M.

 Ec < EA < EM. Both M and A are deposited but the deposition of M is preferable.

The electric current is a result of the both reactions

Mn+ + ne– = M and An+ + ne– = A.

1. 8. 2 Effect of complexing agent

Electrodeposition of an alloy composed of metals with different electrode

potentials (more noble metal and more active metal) results in preferential of the metal

with higher potential (more noble metal). In order to obtain an alloy with the composition

similar to the ratio of the metals contents in the electrolyte their potentials should be

brought closer together.

Complexing agent (chelating agent) is a substance used for complexing particular

ions in the electrolyte. Ions of the complexing agent bind the simple metal ions forming

complex ions. Complexing agent not only approximates the metals potentials but it also

9
retains the more noble ions in the solution preventing their immersion deposition. In

order to achieve more stable effect complexing agent is commonly added to the

electrolyte solution in an amount higher than it is required by the stoichiometric

composition. The complexing agent in non–binded form is called free complexing agent.

A complexing agent may affect on only one of the metals shifting its electrode potential

to the negative side when the second metal stays in the form of simple ions. When a

complexing agent form complexes with both metal ions potentials of both of them are

shifted to the negative side but the difference between them decreases (they are getting

closer).

Sometimes two different complexing agents are added for complexing two different

metals.

Examples of complexing agents

 Potassium cyanide (KCN)

 Potassium tartrate (K2C4H4O6)

 Methanesulfonic acid (CH3SO3H)

 Glycine (C2H5O2N)

 Citric acid (C6H8O7)

 Thiourea ((NH2)2CS)

1. 8. 3 Effect of operating parameters

 Electric current density

Generally increase of current density results in an increase of the content of the less

noble metal in the deposited alloy.

10
 Temperature

Increase in temperature causes decrease of the cathode polarization. Activation

polarization decreases due to intensification of the gaseous hydrogen formation.

Concentration polarization drops as a result of increase of the metal concentration in

the diffusion layer at the cathode surface. Lower cathode polarization at increased

temperature results in increase of the content of the more noble metal in the alloy.

 Agitation

Agitation reduces the thickness of the cathode diffusion layer, which causes

decreased concentration polarization. Lower cathode polarization in agitated cathode or

electrolyte results in increase of the content of the more noble metal in the alloy.

 Additives (addition agents)

Additives (brighteners, leveling agents) act similar to complexing agents causing

increase of the less noble metal in the alloy. Addition agents are most effective in the

electrolytes containing simple (non–complexed) metal ions.

1. 9 Health and environmental effects of using hexavalent chromium

electrodeposition

Chromic acid, which is mainly used in chromium electroplating, has been

recognized as highly toxic and carcinogenic. There has been an increasing concern due to

environmental, health and safety considerations associated with the emission, handling,

storage and disposal of hexavalent chromium compounds [5]. Generally hexavalent

chromium electroplating baths generate trivalent chromium ions and hydrogen gas at the

cathode, while oxygen gas is the predominant product at the anode. These gases rise to

the top of the bath and then into the atmosphere. Workers can potentially inhale this mist

11
or it could potentially escape into the environment outside of the electroplating shop [6].

Hexavalent chromium ions are strongly suspected of causing lung cancer. Other effects to

health include burns, ulceration of the skin and the mucous membrane, and loss of

respiratory sensation (Surface Engineering Association, 1999). In addition to technical

difficulties experienced in the deposition of chromium, chromic acid has now been

classified as a carcinogen.

Existing regulations and legislations to control hexavalent chromium are as follows

Hexavalent chromium compounds (Chromates, bichromates and chromic acid)

have been classified as Category I carcinogens under the Hazard Information and

Packaging for supply regulations 3 (CHIP). The U.S Environmental protection agency

(EPA) has classified hexavalent chromium as one of seventeen kinds of highly hazardous

and toxic substances. Control of Major Accidents Hazards (COMAH) has reclassified

chromic acid from harmful to very toxic. Electroplating shop having more than 4000

litres of chromium electroplating solution will have to register as a tier 1 COMAH site,

similarly electroplaters having more than 16000 litres of chromium electroplating

solution will be a tier 2 COMAH site. Integrated Pollution Prevention Control (IPPC)

stated that the best available technology must be used to minimize and control pollution

in the electroplating industry such as that of hexavalent chromium. The End of Life

Vehicle Directive (ELV, Directive) has been designed to minimize the environmental

impact of vehicles, which have reached the end of their useful life and either recycled or

otherwise disposed of heavy metals such as lead, mercury, cadmium and hexavalent

chromium will be banned for use in manufacturing vehicles. The ELV Directive

regulation came into force in July 2007 and from that point onwards, no vehicle can be

12
introduced to the European market, which contains these elements. Occupational Safety

and Health Administration (OSHA) issued guidelines have significantly lowered the limit

on worker exposures to hexavalent chromium (VI). OSHA has amended the existing

standard that limits occupational exposure of hexavalent chromium Cr (VI) in the

electroplating shop from 52 µg/m3 to 1 µg/m3 as an eight hour time weighted average.

The European Parliament has recommended the average exposure level (PEL) from a

current PEL of 0.1 mg/m3 to 0.005 mg/m3. Electrodeposition of Cr from Cr(VI)-

electrolyte may be used in metal finishing, as long as it will not appear as Cr(VI) ion in

the final product. Cr(VI), which is a metal in ionic state, Cr electroplate is a metal in the

atomic state. In Cr plating, only the metallic form of chromium remains. Thus, articles

plated with the metal Cr are acceptable.

1. 10 Hexavalent chromium electroplating alternatives

It has now been established that conventional chromium electroplating using the

chromic acid process is extremely hazardous because it relies on hexavalent chromium,

which is highly toxic and has been classified as carcinogenic. However, there are also

technical difficulties experienced in the deposition of chromium from chromic acid

electrolytes. These have been summarized by Smart et al. [7] as follows

• Chromium electroplating using hexavalent chromium has a low efficiency i.e. 15–22 %

where 75–85 % of the applied current is used in hydrogen evolution.

• The average cathodic current densities is generally 10–15 Adm–2

• The process has poor covering power across low current density areas and also around

holes and slots of components.

• Burning is observed as grey deposits in high current density areas.

13
• Chromium electroplating has poor throwing power. It results in thick electrodeposits on

the edges and protruding parts of cathodes and thin deposits in recesses.

• Interruption of the current during electrodeposition produces milky deposits i.e. ‘white

washing’.

• Solid chromic acid has immediate detrimental effect on human tissue, burning the skin

particularly the eyes. Even dilute solutions have the insidious effect of causing ulcers,

either from splashes or inhalation of spray.

• Chromic acid is a strong oxidizing agent and therefore it is a potential fire hazard.

• High metal concentrations of chromium metal in chromic acid solution.

It has been recognized since the inception of industrial chromium electroplating

that the use of chromic acid presents many hazards in terms of the chemical reactivity

and toxicity of the chromium electroplating bath. Environmental, health and safety

considerations as well as disposal costs have prompted the electroplating industry to

consider other electroplating alternatives to hexavalent chromium. However, the problem

with hexavalent chromium electroplating process is not with the electroplating

technology but with the environmental, and health consequences associated with its use.

The ever–increasing regulatory requirements have therefore forced metal finishing

industries to look for acceptable and cost effective options [8]. The majority of industries

are relying on emission control technologies rather than switching to clean technologies

or waste minimization as a means of achieving compliance. In recent years there has been

a growing interest in alternative materials and deposition methods that reduce hazards

associated with hexavalent chromium. A novel technique can be used as a replacement

for hexavalent chromium if it matches the physical and mechanical characteristics of

14
hexavalent chromium. Trivalent chromium formulations can be used to replace

hexavalent bath formulations for decorative plating applications. Trivalent chromium is

at least 100 times lesser toxic to humans and the environment than hexavalent. Trivalent

decorative plating has been commercially available since 1975. As these formulation

have improved, they prove to not only be environmentally safer but can also result in

improved productivity and cost savings over hexavalent formulations. [9]. However,

promising alternatives for hexavalent chromium electroplating have been suggested

which include: Dry coating alternatives (physical vapour deposition, chemical vapour

deposition), Thermal spray technology (high velocity oxy fuel), Nickel based

alternatives, Ionic liquids and trivalent chromium electroplating [10, 11]. However, none

of these alternatives can match the unique properties of chromium electroplated from

hexavalent chromium. Trivalent chromium electroplating from trivalent electrolytes is

considered as a very promising technology to replace conventional hexavalent chromium

electroplating partly because Cr3+ ions are less toxic and therefore could serve as an

environmentally benign alternative. Trivalent chromium has now become a transitional

alternative for decorative applications. However, there is no commercially viable way of

producing thick deposits of chromium from electrolytes based on trivalent chromium.

Although more sensitive to impurities and more complex to operate, these baths are

gaining more and more acceptance due to their high tolerance to current interruptions and

lower toxicity.

1. 11 Trivalent chromium electroplating

The trivalent chromium electroplating process has been available to the metal

finishing industry since 1973. Jeffrey and Stanley [12] developed the first commercial

15
trivalent chromium bath based on chromium chloride, boric acid, ammonium chloride

and bromide ions [13]. This chloride based process was commercially used in the

electroplating industry as the only viable option to replace hexavalent chromium

electroplating. Barclay [14] produced a trivalent electrolyte based on chromium sulphate

and thiocyanate using a divided cell arrangement to prevent anodic oxidation of trivalent

chromium. In 1984, W. Canning Ltd worked with IBM in a collaborative project and

produced another sulphate–based bath [15]. All these trivalent chromium processes were

capable of depositing ≤ 0.5µm thick chromium layer. Chloride and sulphate based

trivalent chromium electroplating processes were used successfully in the electroplating

industry for decorative purposes. The deposition rate of the trivalent chromium process

using sulphate and chloride based electrolytes is similar to hexavalent chromium

electroplating but there was no commercially viable way of producing thick deposits for

hard chromium applications.

The trivalent chromium finish can be similar to the hexavalent chromium finish

when it is used for decorative application [16–21]. Ibrahim and Chisholm also observed

that deposits from trivalent electrolytes have similar properties to that of hexavalent

chromium electrolytes. The deposits were found to be micro cracked with a similar crack

density and hardness of between 800–1000 HV. Deposits from trivalent chromium baths

are inherently micro–discontinuous. The pore density in a micro–discontinuous deposit

was found to be about 20,000 to 60,000 pores/cm2 but it became micro cracked with

higher thicknesses. The normal hardness of the deposits from trivalent chromium baths is

700–1000 HV. The trivalent chromium bath also has the ability to tolerate current

interruptions without passivating or producing ‘white clouds’ and hazes in the deposit.

16
There are currently at least three basic types of trivalent chromium bath available. A

single electrolyte bath, chloride or sulphate based, using graphite or composite anodes,

and special additives to prevent oxidation of trivalent chromium at the anodes. Another

type of bath uses shielded anodes where conventional lead anodes are surrounded by

boxes sealed on one side by a selective ion membrane. The membrane prevents the

migrating trivalent chromium ions in the solution from reaching the anode, thus

preventing their oxidation to the hexavalent state. The sulphate based trivalent chromium

bath utilizes additives containing the trivalent chromium ion and a secondary additive

that contains grain refiners and brighteners [22]. When soluble chromium anodes are

used in trivalent chromium electroplating, they would cause a rapid buildup of chromium

in the electrolyte. Oxygen is produced at the insoluble anode surface and it is usually

sufficient to oxidize trivalent chromium to hexavalent chromium. This results in

deposition failure, because Cr(VI) contaminates trivalent electrolytes. There have been

several approaches proposed to prevent oxidation of Cr(III) to Cr(VI). Jeffrey and

Stanley [12] studied trivalent chromium electroplating using carbon anodes. The

electrolyte had oxidizable species at lower oxidation potential than oxidized trivalent

chromium. This build up of hexavalent chromium is prevented due to the difference in

potential between Cr(III) and oxidizable species in the bath. Smart et al., W. Canning Ltd

[23, 15] developed perfluorinated ion selective membrane in a divided cell arrangement

separating anolyte and catholyte. The chromium ions were thereby prevented from

coming into contact with the anode. Conductive metal oxide coated anodes also have

been successfully used in trivalent chromium electroplating. These developments have

solved some of the problems of anodic oxidation of trivalent chromium. A major problem

17
with the deposition from trivalent chromium electrolytes is associated with reactions

taking place at the cathode. In 1994 Shahin [24] suggested that electrodeposition of

chromium from trivalent baths involves two consecutive reduction steps of Cr 3+ species

to Cr2+ and then from the reduction of Cr2+ species to Cr(0). According to Lide [25], the

standard reduction potential for trivalent chromium ions is given according to the

following reactions

Cr3+ + 3e– → Cr Eo = –0.744V Vs SHE — (5)

Cr3+ + e–→ Cr2+ Eo = – 0.407V Vs SHE — (6)

Cr2+ + 2e– → Cr Eo = – 0.913V Vs SHE — (7)

2Cr2+ + 2H+→ 2Cr3+ + H2 — (8)

According to Lide, the net reaction process is thermodynamically expected to produce

hydrogen rather than chromium metal. Reduction from trivalent chromium metal is more

predominant than divalent reduction.

1. 12 Electroplating in non–aqueous solution

The first experiment to electrodeposits metal was carried out in 1805 by Luigi

Brugnatelli who used a Voltaic Pile to deposit gold [26]. Later improvements by John

Wright using KCN led to electrolytes for Au and Ag electrodeposits which are relatively

similar to those used today. While initially limited to the deposition of decorative metals,

more functional metals such as Cr and Ni were deposited by Bird in 1837 [27] and Junot

de Bussey in 1848 [28]. In depth study on the history of metal electroplating can be found

in several reviews [29, 30]. The electroplating industry is dominated by the deposition of

Cr, Ni, Cu, Au, Ag, Zn, Cd and some Cu and Zn–based alloys from aqueous solutions.

Other metals are usually deposited using chemical vapour deposition techniques (CVD).

18
While these are versatile in being able to coat any substrate (plastic, metal, ceramic, glass

etc.) they are difficult to apply to large and complex surfaces. Aqueous techniques have

dominated due to low cost, high solubility of electrolytes, high conductivities and good

throwing power, high solubility of metal salts, and high mass transfer rates. There are,

however, limitations of using water based electrolytes including limited potential

windows (1. 4V), hydrogen embrittlement, passivation of the anode or cathode, the use of

complexants such as cyanide and the environmental issues associated with treating large

volumes of water to remove metals and electrolytes before returning to the water course.

There are clearly a range of other solvents that could be used, ionic and molecular; polar

and non–polar. Ideally, to dissolve electrolytes polar solvents are the most desirable and

small solvent molecules will generally provide a high fluidity. Unfortunately all polar

molecules have electronegative elements which by their nature make them good electron

donors. These will strongly coordinate to metal ions making them difficult to reduce.

Some of the more electropositive metals have been plated from polar organic solvents but

these offer few technological advantages. Non–polar organic solvents, mainly aromatic

hydrocarbons have been used for metal deposition. These have the advantage of wide

potential windows but the obvious disadvantage of poor conductivity. The Alumiplate

process was developed in the late 1980s to plate aluminium from toluene [31, 32]

Triethyl aluminium was used as the source of aluminium but it is pyrophoric and this in

combination with a highly flammable solvent made the process difficult to run. A review

of electrochemistry in non–aqueous solutions is given by Izutsu [33].

19
1. 13 Ionic liquids

High temperature molten salts have long been used for extraction of metals such

as Al, Ti, Na and Li [34, 35]. The main limitation with high temperature molten salts is

clearly the operation temperature which makes difficult in operation and limits the range

of substrates that can be used. In an endeavour to reduce the melting temperature of salts

numerous studies focused on Li+/ K+/ AlCl3 eutectics which have freezing points close to

100°C [36]. The use of quaternary ammonium salts particularly pyridinium and

imidazolium salts has pushed the freezing point down to ambient conditions. The term

“ionic liquids” has been used to distinguish between high temperature and low

temperature systems. One of the key breakthroughs in the development of ionic liquids

came with the synthesis of a 1 mol. eq. N–ethylpyridinium bromide: 2 AlCl3 by Hurley

and Wier in 1951 [37] which was a eutectic liquid at 20°C. This was used for the

electrodeposition of aluminium [38] and therefore sparked a large amount of research for

metal deposition. Using molecular orbital theory, Wilkes and co–workers [39] developed

an ionic liquid, AlCl3: 1–ethyl–3–methyl–imidazolium, which had a room–temperature

liquid range between 33 and 67 mol% AlCl3. In addition these “first generation” ionic

liquids had a significantly lower viscosity than the corresponding pyridinium liquids and

it is the imidazolium cation that still dominates the ionic liquid literature. Discrete anion

or “second generation” ionic liquids are composed of simple anions, as opposed to a

mixture of anions in equilibrium. Their discovery is ascribed to Wilkes and Zaworotko

who produced 1–ethyl–3–methylimidazolium tetrafluoroborate and acetate for the first

time [40]. It is this class of ionic liquid which has dominated the literature ever since.

Anions such as BF–and PF6–were initially used because of their wide potential window

20
[41], however, they were found to slowly hydrolyze yielding HF [42] and liquids with

more hydrophobic anions such as tri–fluromethanesulphonate (CF3SO3–) and bis–

(trifluoromethanesulphonyl) imide [(CF3SO2)2N–] have subsequently become popular

[43]. The potential window of these liquids can be extremely large making it possible to

electroplate reactive metals. The properties of these liquids are covered in a series of

reviews [44, 45].

Ionic liquids are salts that have a melting temperature below 100°C. Generally one of

the ionic components is organic, most commonly the cation. The ions have a low degree

of symmetry. By careful choice of the components it is possible to tune the properties of

the liquid. In general ionic liquids

 Are good solvents for organic and inorganic materials.

 Are generally considered to be polar yet non–coordinating solvents.

 Immiscible with many organic solvents providing a polar alternative for two–

phase systems.

 Have low vapour pressures.

It is generally accepted that the first ionic liquid was [EtNH3][NO3], and had a

melting point of 12°C. Ionic liquids as a low temperature alternative are currently a

popular area of research. Ionic liquids are systems with an anionic and a cationic

component which are liquid below 100oC [46]. The definition is used to distance these

fluids with high temperature molten salts but is completely arbitrary. Ionic liquids have

been of great interest, due to them having many advantageous properties from molten

salts, yet negating the difficulties of high temperature. A variety of cations and anions are

described in the literature but for the application of metal deposition only a relatively

21
small quantity of ionic liquids has been used. These are shown in Table 1. 1. The

possibility to choose a possible ligand as the anionic component allows control over

speciation and thus redox properties of metal solutes to a much greater extent than in

aqueous media since extremely high activities of the ligands can be achieved.

Ionic Liquids have clearly been reported to be green solvents most notably for their

low vapour pressure compared to molecular alternatives. In the application of ionic

liquids to metal deposition the green credentials of this methodology could also come

from a significant reduction in the volume of low level aqueous streams that would need

to be processed. Today, it is generally recognized that this is only part of the picture since

many ionic liquids do have significant toxicity. Some ionic liquids have been designed to

contain ions which are known to have lower toxicity and these include functionalized

imidazoles [47], lactams [48], amino acids [49] and choline [50] although, it is only the

last of these which have been extensively applied to metal deposition.

Ionic liquids in electrodeposition initially the main drive to use ionic liquids was

the ability to obtain high concentrations of aluminium in a highly conducting aprotic

medium. The key advantages of the Ionic liquids are

 The wide potential windows

 High solubility of metal salts

 Avoidance of water and metal/water chemistry

 High conductivity compared to non–aqueous solvents.

The use of ionic liquids heralds not only the ability to electrodeposit metals that

have hitherto been impossible to reduce in aqueous solutions but also the capability to

engineer the redox chemistry and control metal nucleation characteristics. It is the latter

22
area that is only now being addressed and will no doubt be the focus of research over the

forthcoming decade. The main drive for using ionic liquids for metal plating has been the

ability to obtain wide potential windows which is the potential range of which the

electrolyte is neither oxidized nor reduced at the electrode surface. Some ionic liquids

have a very large potential window of up to 4.15 V for [Bmim (PF6)] at a Pt electrode

[51], and 5.5 V for [BMP(TF2N)] at a glassy carbon electrode [52]. The importance of

potential windows is well known from aqueous processes where hydrogen evolution can

be hazardous and lead to brittle electrodeposits (hydrogen embrittlement). Ionic liquids

may even be chemically altered and hence destroyed if potential limits are not

considered. The wide potential window of ionic liquids makes it possible to

electrodeposit elements with low redox potentials that cannot be reduced in other media

such as Al, Mg, Ge, and Si [53–55].

1. 14 Deep eutectic solvents

The requirements for ionic liquids to be used on a bulk scale for metal

deposition are that they need to be low cost, non–toxic and water insensitive. The

majority of discrete anions do not achieve all of these criteria and so it is more likely that

eutectic based ionic liquids will be more applicable for bulk scale electrodeposition. The

systems studied so far described can be expressed in terms of the general formula

Cat+ X–. z Y.

where Cat+ is in principle any ammonium or phosphonium cation, X is generally a halide

anion (usually Cl–). They are based on equilibria set up between X– and a Lewis or

Brønsted acid Y, z refers to the number of Y molecules which complex X –. The melting

point of two component mixtures is dependent upon the size of the interaction between

23
the components. For ideal mixtures (non–interacting components) the freezing point will

vary linearly with mole fraction whereas large negative deviations can occur when the

components interact strongly with each other. This is shown schematically in Figure 1. 2.

The composition at which the minimum freezing point occurs is known as eutectic point

and this is also the temperature where the phases simultaneously crystallize from molten

solution.

One of the key advantages of these types of ionic liquids is the ease of

manufacture. The liquid formation is generally mildly endothermic and requires simply

mixing the two components with gentle heating. Another key advantage is that they are

water insensitive which is very important for practical electroplating systems. The final

key advantage of eutectic based systems is that because they are simple mixtures of

known chemicals they do not have to be registered as new entities as they revert to their

constituent components upon excessive dilution in water. The ionic liquids described can

be subdivided into three types depending on the nature of the complexing agent used.

Eutectic Type 1 Y = MClx, M = Zn, Sn, Fe, Al [56–59]

Eutectic Type 2 Y = MClx.yH2O, M = Cr, Co, Cu, Ni, Fe [60]

Eutectic Type 3 Y = RZ, Z = CONH2, COOH, OH [61, 62]

To date the only Cat + species studied have been based on pyridinium,

imidazolium and quaternary ammonium moieties. In general, as with the chloroaluminate

and discrete anion systems, the imidazolium based liquids have the lowest freezing points

viscosities and higher conductivities. The depression of freezing point is related to the

strength of interaction between the anion and complexing agent although this has not

really been quantified as yet due primarily to a lack of thermodynamic data about the

24
individual components. A fourth type of eutectic has been described involving just a

metal salt and a hydrogen bond donor [63]. It was shown that ZnCl2 when mixed with

acetamide or urea could also form eutectics which had all the properties of ionic liquids.

The novelty of Type 3 eutectics is that they use a simple hydrogen bond donor to

complex the simple anion (usually chloride). The majority of the work to date has

focused on simple amides, alcohols and carboxylic acids. The first reported eutectics

were those formed between choline chloride and amides such as urea and acetamide.

These materials have been called Deep Eutectic Solvents (DESs) to differentiate them

from ionic liquids with discrete anions. A eutectic forms when there is a large interaction

between the two species in the mixture. An example of this is the choline chloride: urea

mixture. By themselves they have freezing points of 303˚C and 135˚C respectively. By

combining these two compounds in a ratio of 1:2 (choline chloride: urea), the product

formed has a freezing point of 12˚C which is a depression of freezing point is 178˚C. For

comparison the depression in freezing point for the choline chloride–zinc chloride system

was much larger (272˚C) [64] due to the covalent bonds formed in the metal chloride

case. The main reason behind choline chloride being such a useful quaternary ammonium

salt is to do with the fact that it is an asymmetric quaternary ammonium salt with a polar

functional group, but also small. The asymmetric nature of this molecule reduces the

freezing point of the ionic molecular liquid, as does the polar functional group. The group

of Abbott has published extensively on the subject of choline chloride

HOC2H4N+(CH3)3Cl–(ChCl) because it is non–toxic and readily available as a bulk

commodity chemical.

25
 The existence of hydrogen bonding in ChCl/urea eutectic mixtures can be

observed using NMR spectroscopy. HOESY spectra of HOCH2CH2N+(CH3)3F–

·2(NH2)2CO show intense cross correlation between the fluoride ion and the NH2 protons

on the urea molecule [50]. Some anion complexes have been identified using FAB–MS

and it is evident that the hydrogen bond donor (HBD) is sufficiently strongly coordinated

to the chloride anion to be detected by this technique. In a choline chloride: urea (1: 2)

mixtures the presences of Cl– with both one and two urea molecule were observed. The

freezing point of the HBD– salt mixtures will be dependent upon the lattice energies of

the salt and HBD and how these are counteracted by the anion–HBD interaction and the

entropy changes arising from forming a liquid. For a given quaternary ammonium salt,

the lattice energy of the HBD will be related to the anion–(HBD) interaction and hence to

a first approximation the depression of freezing point will be a measure of the entropy

change. It has been shown that the depression of freezing point correlates well with the

mass fraction of HBD in the mixture. The lowest viscosities and highest conductivities

are obtained with diol based HBDs. It is thought that the comparatively weak interactions

between the alcohol and the chloride mean that some free glycol is able to move

decreasing the viscosity of the liquid. The glycol based liquids tend also to have

comparatively large potential windows [65].

1. 15 Applications of Deep Eutectic Solvents (DESs)

Deep eutectic solvents are easy to synthesize, economically viable to produce

on a large scale, relatively insensitive to water, exhibit high metal solubility, hence it can

be used in metal plating, electro–polishing and metal recycling. Type III eutectics have

26
the ability to dissolve high concentrations of metal oxides which allows them to be used

for metallurgy. As a consequence they can be applied to large scale processes.

1. 15. 1 Electrochemical application

Deep eutectic solvents have been used for electrochemical application and these

have focused mainly on electrodeposition of metals. Choline chloride based liquids using

ethylene glycol as the hydrogen bond donor has been the most commonly used liquid.

The main advantage over aqueous media has been increased current efficiency (typically

> 70 %). Despite the short development time good reproducible surface finishes were

obtained.

1. 15. 2 Electrodeposition of metals

The electrochemical potential window of most DESs is typically in the range of

3V. This precludes applications such as lithium batteries and the deposition of

electropositive metals such as titanium and aluminium. The applications of deep eutectic

ionic liquids have focused on the deposition of metals and metal alloys such as Zn, Cu,

Ni, Ag, Cr, Sn, Zn-Sn, Zn-Ni and Ni-Sn alloys. While these can be deposited from

aqueous solutions, the studies to date have focused on the advantages that DES present

i.e. deposition on water sensitive substrates such as aluminium and the deposition of

specialized alloys. Zinc is one of the most important metals in the metal plating industry

due to its low cost, environmental compatibility and corrosion resistance. Abbott et al.

investigated the deposition of Zn from type II deep eutectic solvents (ChCl/ZnCl2) at

60°C and reported that the deposition morphology obtained is not different from

morphology reported by Sun [66]. The current efficiency was found to be 100 % and a

variety of Zn alloys can be deposited.

27
1. 15. 3 Chromium deposition

The deposition of chromium from aqueous electrolytes suffers from low current

efficiency and the use of toxic CrO3. Choline chloride forms eutectic mixtures with

CrCl3.6H2O, CoCl2.6H2O, and Zn(NO3)2.4H2O and these liquids are highly conducting.

Studies have shown that chromium and cobalt can be efficiently deposited from these

liquids. The high ionic strength prevents the water molecules acting as bulk water as they

are strongly coordinated to the ions and therefore they are not easily reduced at the

electrode surface. Accordingly the deposition of metals such as chromium can be carried

out with high current efficiencies. It was found that the addition of up to 10 wt % LiCl,

could lead to the deposition of black chromium which is amorphous in morphology hence

free from surface cracks. The process has been operated at pilot plat scale although no

reports about the improvement have been given in the open literature [67].

28
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64. A. P. Abbott, G. Capper, D. L. Davies, H. Munro, R. Rasheed, Inorg. Chem. 43

(2004) 3447.

65. R. C. Harris, PhD Thesis, University of Leicester, 2009.

66. Y. F. Lin, I. W. Sun, Electrochim. Acta 44 (1999) 2771.

67. A. P. Abbott, K. S. Ryder, U. Koenig, Trans. Inst. Metal Finish. (2008) 196

32
Table 1. 1 A selection of cations and anions used to make ionic liquids for metal

deposition.

Cations Anions

F O _ O
_ N
R3 B S S F
F
F F F
F O O
N F F F
R2
+
N
Tetrafluoroborate bis(trifluoromethylsulphonyl)imide
R1
[BF4]– [NTF]–
Imidazolium

R1
F
F _ F
N
P
+ R2
F F
F N C S

Pyridinium
Hexafluorphosphate thiocyanate

[PF6]– [SCN]–
R1

+
N
C2F5
R4 R2
F _ F
R3 _
P N

C2F5 C C
Quaternary ammonium C2F5
F N N

tris(pentafluoroethyl)
R1 trifluorophosphate dicyanamide

P
+ [FAP]– [DCN]–
R2
R4
R3

Phosphonium

33
 N

C
F
F _
O C
R1 R2 F C C
C
S+ _ N
O N

R3 Trifluoroacetate tricyanomethide

Sulphonium [ATF]– [TCM]–

R1, R2, R3 and R4 = alkyl group C

F O _
F B
C C
S _ C
F O N N

O N

Trifluoromethanesulfonate trtracyanoborate

[OTF]– [TCB]–

34
 Figure 1. 1 Schematic diagram of electrodeposition cell.

Figure 1. 2 Schematic representation of a eutectic point on a two component phase

diagram.

35
CHAPTER II
 LITERATURE REVIEW

2. 1 Chromium electrodeposition from Cr(VI) electrolyte

Chromium electrodeposition is one of the most widely used electrodeposition

processes in the electrodeposition industry due to attractive appearance, good adhesion,

high degree of hardness, good wear and corrosion resistance. Chromium is normally

deposited on a commercial scale from aqueous solutions of chromium trioxide (CrO 3)

which are commonly called chromic acid. However, chromium cannot be deposited from

an electrolyte containing only chromic acid, since another chemical, which acts as a

catalyst also needed. The most commonly used catalysts are sulphate and fluoride. They

are generally used in the complex form such as sulphuric acid, sodium sulphate,

flurosilicate and silicofluoride. The ratio of chromic acid to catalyst is maintained within

definite limits; preferably about 100: 1 in the case of sulphate [1, 2].

Generally, hexavalent chromium electrodeposition electrolytes are simple in

formulation, but are more complicated to operate than most electrodeposition

electrolytes, and they require rigorous control. Temperature, current density and

electrolyte composition affects the film characteristics and current efficiency, therefore

carefully controlled in order to obtain specific deposit properties and electrodeposition

rates. A dilute conventional formulation (250 g/L chromic acid and 2.5 g/L sulphate) is

extensively used in the electrodeposition industry to give good coverage, substrate

activation, and consistent current efficiency. The concentrated formulation (400 g/L

chromic acid and 4.0 g/L sulphate) gives better coverage and greater resistance to

impurities and requires a lower operating voltage. A critical point in all electrolyte

36
formulations is the requirement for close control of the CrO3/SO4 weight ratio needed to

produce consistent electrodeposition results. A low ratio of chromic acid to sulphuric acid

results in relatively poor throwing, covering power and increased limiting current density.

Higher ratios result in slow deposition rates which produce dull deposits, increased

covering power, and decreased limiting current density. Thicker deposits tend to be dull

and contain variable cracks [3]. The mechanism for chromium deposition from chromic

acid is complicated. Snavely et al. [4] suggested that the final reduction to metallic

chromium takes place via an intermediate hydride, of short but finite life at the cathode.

Ege and Silverman [5] found that additions of SO42– to the electrolyte results in the

formation of complexes, deposition ultimately takes place from a complex cation.

Variation of temperature, current density or electrolyte composition results in changes in

current efficiency and deposit characteristics. Chromium ions enter the cathode film in

the form of CrO42– anions forming complex chromium compounds. Raub et al. [6] and

Martayk et al. [7] claimed that the solution layer immediately adjacent to the cathode

must have mixed activation and passivation tendencies. Thus, if the chromium deposits

were too active, chromium would tend to redissolve in the strongly acidic electrolyte.

Conversely, if the chromium was too passive, it would tend to electroplate dull and in the

form of non–adherent layers flaking from each other, as frequently occurs when there are

current interruptions.

2. 2 Decorative and hard chromium electrodeposition using hexavalent chromium

Commercially, decorative and hard finish (functional) chromium electrodeposition

is categorized on the basis of thickness of the chromium, their applications and the

chemistry of the process. The hexavalent chromium electrolyte composition for

37
decorative applications depends primarily on whether the electrolyte is co–catalysed e.g.,

fluorides, fluorosilicates or fluoroborates [2, 8]. The presence of other oxides of metals

such as iron, copper and nickel combined with Cr 3+ affects electrolyte performance [9].

The phenomenological model for the deposition of Cr from hexavalent electrolyte was

proposed by Mandich and Hoare. According to these authors, the polychromates

decompose to chromous hydroxide and a dichromate which can polymerize back to a

trichromate by condensation with other chromates in the solution. The HSO 4– exerts its

catalytic activity by forming a chromousoxybisulfate complex through hydrogen bonding

with chromous oxide. With the successive transfer of two electrons to the specifically

absorbed chromousoxybisulfate complex on the cathode surface Cr(I) and finally metallic

Cr along with the regenerated HSO4–, ion are then obtained [10, 11]. Decorative

chromium electrodeposition is generally electroplated over a nickel resulting in tarnish

resistance, hardness and wear resistance, with an elegant blue metallic appearance [12].

Decorative chromium is not just a single chromium layer but it invariably has one or

more under layers of electroplated nickel, ranging from 5–50 µm thick. The visible top

layer is a thin chromium coating, typically with a thickness of 0.2–0.5 µm. For less

severe conditions, a single layer of bright nickel is adequate to afford the surface

improvement. This, combined with the chromium layer, provides sufficient product

durability. For severe conditions, multiple or single layers of nickel and copper can

precede the chromium deposit. Significant improvements can be achieved with two or

more different nickel layers and a special micro–discontinuous coating or strike layer

[13]. The basic formulations consist of chromic acid (H 2CrO4) and the sulphate ion

(SO4)2–. Single catalyst processes have about 12% chromium electrodeposition

38
efficiency. The remaining current goes towards the formation of hydrogen and trivalent

chromium Cr(III). The chromium deposition efficiency increases proportionally with

chromic acid concentration, up to 250 g/L and decreases thereafter. Usually, a CrO3/SO4

ratio of approximately 100: 1 is common. The inclusion of the second catalyst fluoride

can increase the average cathode efficiency to about 22%. The efficiency increases with

increasing chromic acid concentration up to 300 g/L but addition of fluoride catalyst

necessitates an adjustment in the CrO3/SO4 weight ratio. Co–catalyst (mixed catalyst) has

an increased electrodeposition speed, better coverage, wider brightness range, and more

tolerance to impurities. These processes are less sensitive to current interruption and can

electroplate substrates with reduced defects [14]. Tri–catalyzed chromium processes are

similar to co–catalyzed processes except for the addition of a third catalyst, a proprietary

organic catalyst. It improves the cathode deposition efficiency and coverage in the low

current density areas. Decorative chromium deposits are either micro–porous or micro–

cracked. Deposits from decorative chromium electrodeposition have approximately 10–

17 thousand pores/cm2 or 160 micro discontinuous cracks per linear cm (standard

requirement) deposits. These spread the corrosion reaction over many galvanic sites. In

decorative chromium electrodeposition, temperature is closely related to current density

in its effect on brightness and coverage by deposit. An optimum temperature range is

always established for a given concentration of chromic acid. Hard chromium

electrodeposition involves immersing the substrate to be coated into the chromic acid

electrolyte and the application of a current to provide driving force for the deposition of

the chromium ions from the solution. The deposits are extremely hard and for most

applications corrosion resistant. According to Newby [15], there are three generic

39
functional hexavalent chromium processes for the deposition of metallic chromium. The

earliest formulation is presently known as conventional or Sergent electrolytes which are

simply chromic acid (H2CrO4) and sulphate ions (SO42–) in approximately a 100:1 weight

concentration ratio. This formula was developed in the late 1920s and is still in

widespread use especially in small plating shops. The cathodic efficiency of this process

is of the order of 10–15%. Typically with a current density of 32 Adm–2 about 25 µm/hr

of deposition is obtained. In the 1950s a mixed catalyst system was commercialized in

which a fluoride ion source, typically a salt of fluorosilicic acid, was added to the

conventional electrolyte. This formula offered significant improvements both in cathodic

efficiencies of up to 22% and deposition rates up to about 50 µm/hr. It provides superior

wear and corrosion properties compared to conventional chromium deposits. Mixed

catalyst chemistry has been used successfully over thirty years in the electrodeposition

industry. In the mid 1980s a non–fluoride chromium (high speed) electrodeposition

electrolyte was introduced into the market which replaced the halogen ion with a

proprietary organic species. The process is capable of approximately 25% cathodic

efficiency and deposition rate up to 75 µm/hr. Deposits from this electrolyte are thought

to be the best in terms of wear and corrosion properties, surface finish available in the

chromium electrodeposition. This formulation consisting of chromic acid, sulphate ions,

fluorosilicic acid have now become the state of the art process and the solution is in

widespread use particularly where quality and productivity are of concern [8]. According

to Kirk Othmer [16] a thick layer of chromium is deposited directly on the base metal to

provide wear and corrosion resistance in hard chromium electrodeposition. The thickness

of the hard chromium coating varies in the range of 20–500 µm. Being very hard (~1000

40
HV) the chromium deposit will experience microcracking. This is quite normal and will

not usually affect the coating in most engineering applications. Hard chromium deposits

display high levels of internal stress and hardness up to 1000 HV with a micro cracked

structure varying from 15–200 cracks/cm2 [8, 9]. The cracks penetrate to the interface of

the base material and the chromium deposit. At high temperatures, smooth deposits with

less burning and nodulation are obtained. It has been observed that adherence and

roughness are the common defects in hard chromium electrodeposition. The high level of

tensile stress within the chromium deposit leads to spontaneous cracking of deposits

which can improve the oil retention properties of thicker deposits and this has many

engineering applications in lubricated wear situations [2].

Baraldi et al. observed during cyclic potentiodynamic curves of cathodic

polarization (from 0.00 to −1.25 V/SCE, 5 mV s−1) in chromic acid solution used by

industries, ARMCO iron undergoes pitting corrosion, while carbon steels undergo a

selective ferritic corrosion. Blisters of pure iron were also observed on ARMCO iron

electrodes surface. Baraldi also suggested a direct participation of the metal substrate to

the overall reaction of reduction of the chromic acid to chromium metal. Therefore, the

chemical nature of the electrode metal has been changed, in order to prove that the

chromium reduction goes on through an ECE mechanism involving a fast chemical

reaction between unstable intermediate chromium products and the metal substrate.

Cathodic potentiodynamic polarization curves were performed on copper electrodes and

the scans were stopped at four different potentials (−0.90, −1.00, −1.10 and −1.25 Vs

SCE). The copper surface undergoes a severe corrosion in all the experimental

41
conditions. The morphology of the attack depends on the polarization potential and in the

presence of additives, like iron sulphate [17].

The electroreductive behaviour of CrO3 + H2SO4 aqueous solution is studied on

poly–crystalline iron and copper cathodes. The electrochemical results have compared

with XPS, AFM and SEM. In the case of iron a main role is played by the passive state of

the electrodic surface caused by the presence of a protective mixed iron/chromium oxide

layer and by its electrochemical dissolution. This passive to active transition of the

electrodic surface and the occurrence of an irreversible reductive current peak, in a

potential range where the deposition of metallic chromium does not occur and this

suggests that the electrodic surface plays an active role in the electrochemical process. A

major difference is found between Fe and Cu cathodes, concerning the kinetic

mechanism of formation of adsorbed species [18].

Benedetto Bozzini reported the electrochemical reduction of bichromate from an

aqueous solution at a Pt(1 1 1) electrode and studies were done by voltammetry and

synchrotron–based photoelectron spectromicroscopy. Cathodic reduction is carried out at

potentials −1.5 and −2.0 eV in an electrochemical cell attached to the UHV chamber

hosting the scanning photoelectron microscope (SPEM). The Cr 2p and Pt 4f core level

spectra were used as fingerprints of the Cr lateral distribution and chemical state after

reduction. The Pt 4f and Cr 2p maps show inhomogeneous Cr distribution in microscopic

Cr–rich and Cr–poor islands. Analysis of the Pt 4f, Cr 2p photoemission peaks recorded

in these islands has disclosed that under both reduction conditions Cr(VI) is reduced

principally to Cr(III), with 10 % of Cr(0) localized in the Cr–rich islands. The presence of

42
an intermediate oxidation state has also been detected, that can be assigned to a transition

state from Cr(VI) to Cr(III) [19].

2. 3. Problems and developments in functional electrodeposition using trivalent

chromium

A major problem with deposition from trivalent chromium electrolyte is

associated with reactions taking place at the cathode as ligand formation is slow and

kinetically inert which hinders deposition [20, 21]. According to Bard et al. Howarth and

Pletcher [22, 23], the negative deposition potential from the trivalent chromium

electrolyte and slow ligand exchange gives low cathode efficiency with much of the

current going to produce hydrogen. High pH values of trivalent chromium electrolyte can

cause the production of oligomeric olated species, which will reduce the reducible

chromium. Benaben extensively studied about Cr deposition from trivalent electrolyte.

He states that by so doing he obtains a solution containing 30 to 50 g/l of trivalent Cr

together with Cl- ions. At a electrolyte temperature of 50˚C and a current density of about

100 A/dm2, he has demonstrated that deposits of at least 150 μm having a hardness of

about 950 HV can be obtained at an efficiency of about 30%. These deposits are semi-

bright in appearance with a slightly nodular appearance under the microscope. Increase of

hardness in trivalent Cr by heat treatment due to chromium carbide (Cr7C3) and oxide

(Cr2O3) formation during heat treatment (300-350˚C, 30 min), the microhardness was

increased to 1700-1800 HV [24–27]. El–Sharif et al. [28] observed that olation reactions

are catalyzed by Cr(II), however, Howarth and Pletcher [23] could not find any evidence

of Cr(II). Olation of the commercial electrolytes tend to lose efficiency with increasing

electrodeposition time. It was also observed that cationic species decreases but there are

43
an increase in anionic species [29]. Trivalent chromium has a marked tendency to form

various types of complexes in aqueous solutions. It is almost impossible to deposit the

chromium coating from a simple aqueous Cr(III) solution due to a very stable Cr(H2O6)3+

ion complex. The coordinate water molecules, OH– groups or other ligands may be

replaced by anions in solution. Anions that easily enter into the coordinate sphere and

displace OH–groups can effectively prevent olation [20, 12]. Some organic ligands

influence the electrodeposition rate and the quality of coatings due to the formation of

Cr(III) active complexes. Ibrahim et al. [30, 31] and El–Sharif et al. [28]. Handy et al.

[32] also confirmed that deposition rate and the quality of chromium deposits from

trivalent electrolytes are affected due to slow ligand exchange combined with

unfavourable reduction potentials. Zhenmi et al. (1993) [33] and Smith [34] (1994) found

that a rise in pH at the cathode surface is due to the evolution of hydrogen. As a result the

deposition rate from trivalent electrolytes falls rapidly and the process usually reaches a

limiting thickness of 3 to 4µm and also results in olation. Watson et al. [35] found that

the pH at the cathode surface is in the range of 3.8–4.5 compared to the bulk pH of the

electrolyte (2.3–3.8). At this pH value, coordinated water molecules may be converted to

OH– groups, which lead to the formation of bridge species. This reaction may continue

with the formation of larger molecules, where the chromium atoms are linked with OH –

groups (olated compounds) as shown in Figure 2. 1

Formation of olated compound chains of trivalent chromium [36] thus, in addition

to the slow ligand exchange processes, trivalent chromium has the characteristics of

forming short or long polymers by bridging via a water ligand and H +. Ibrahim et al. [30]

observed that the tendency to form olated species is in direct proportion with the pH of

44
the electrolyte. El–Sharif and Chisholm, [37] concluded that the presence of divalent

chromium accelerates not only ligand exchange kinetics but also the rate of formation of

olated species, particularly within the diffusion layer during electrodeposition. Song and

Chin [38] studied the effect of electrolyte composition, mass transfer and trivalent

chromium deposition from an electrolyte containing ammonium formate and sodium

acetate as the complexing agent and observed that the rate of chromium deposition

process is controlled by the transport of the Cr(III) complex ion to the cathode surface.

Maximum chromium thickness obtained from a commercial trivalent electrolyte is

generally less than 10µm, making the deposits unsuitable for functional applications.

Various studies [28, 30] described the failure of sustained deposition of Cr 3+ to the

formation of a stable and inert Cr 3+ complex, [(H2O)4Cr(OH)(OH)Cr(H2O)4]4+, in the

aqueous solution. The deposition rate is controlled by the diffusion of the complex Cr3+

ion to the cathode surface. Mandich [12] found that hydrolysis, olation, polymerization

and oxalation of trivalent chromium to metallic chromium occurred during trivalent

chromium electrodeposition. Song and Chin [38] also proposed that chromium coating is

inhibited by the formation of a film at the cathode composed of chromium hydroxide or

chromium oxide. Some of the organic ligands influence the electrodeposition rate and the

quality of the coatings due to formation of Cr(III) active complexes. Trivalent

electrodeposition has several problems such as low current efficiency and solution

instability. To minimize this problem an appropriate ligand capable of forming a Cr(III)

complex with optimum chemical and electrochemical reactivity is used [39]. Grace and

Spiccia [40] also confirmed that dimeric complexes and oligomeric species are present in

Cr(III) sulphate solution at pH 3.5–4.4 and the deposit obtained from such trivalent based

45
electrolytes is less bright compared to hexavalent chromium deposits. Ibrahim and

Watson [30, 35] found that such complex formation in the vicinity of the cathode is due

to a sharp increase in pH due to intensive hydrogen evolution. The inclusion of

oligomeric Cr(III) species into Cr deposit gives rise to a possible blackness in the

chromium deposit. Many researchers [37, 41] made a lot of effort to improve the

deposition of thick coatings from environmentally more acceptable Cr(III) electrolytes.

However, the most successful electrolyte systems have been developed by Ibrahim et al.

[30] to deposit at the rate of 1 µm/hr for prolonged electrolysis. Progress in the

development of Cr(III) electrolyte has been slow, largely due to the complex nature of the

chemistry and electrochemical nature of Cr(III) species in aqueous solutions. Recently, a

high speed electrodeposition system (300 µm/hr) for chromium coating based on the

more environmentally acceptable Cr(III) electrolyte has been developed by El–Sharif et

al. [42]. The deposits obtained have similar characteristics to hard chromium coatings.

Mcdougall et al. [43] found that hydrazine coating results in lower hardness, low current

efficiency and solution stability of Cr(III) electrolyte.

Nanocrystalline materials are of high technological and scientific interest because

their internal microstructure can affect many macroscopic properties like hardness,

corrosion resistance and magnetic properties. Narayanan et al. discussed the properties of

electrodeposited nanocrystalline (n–Cr) and amorphous (am–Cr) samples prepared by an

electrochemical method. The deposited n–Cr has crystallites with grain diameters of

about 30 nm. X–ray diffraction shows completely different atomic arrangements in n–

Cr and am–Cr, but the SANS results are very similar to each other. The microstructure of

46
both n–Cr and am–Cr can be described as a surface fractal with fractal dimension of

2.24(3) and 2.22(3) for n–Cr and am–Cr, respectively [44].

Fe–Cr alloy films were electrodeposited from the trivalent chromium electrolyte

containing glycine as complexing agent. The effects of electrodeposition parameters such

as current density, electrolyte pH and electrolyte concentration on the composition of

deposited films were investigated in detail. The magnetic properties of Fe–Cr deposited

films were measured by using VSM. The result indicated that the crystallographic

structures of deposited films are the α–Fe solid solution for deposited films with 3.1 at.%

Cr, the meta–stable phase for the deposited films with Cr content ranging from 4.5 to

22.4 at.%, and the amorphous phase for deposited films with Cr content ranging from

22.9 to 74.4 at.%. The magnetic measurement result indicated that the amorphous Fe–Cr

deposited film is a paramagnetic material [45].

The electrodeposition of quaternary Fe–Cr–Ni–Mo alloy was investigated in a

chloride electrolyte. The electrolyte was formulated to facilitate the deposition of

different alloy over a range of current density. Electrolytes containing trisodium citrate

and glycolic acid complexing agents showed possible synergistic effects, which was

beneficial to quaternary alloy deposition. It was observed that the chromium content of

electrodeposited alloy was increased with current density while the reduction of

molybdenum appeared to be associated with the induced codeposition of Ni and Mo. The

Fe–Cr–Ni–Mo alloy was deposited at a potential range from −1.2 to −1.9 V (saturated

calomel electrode). A scanning electron micrograph of electrodeposited quaternary alloy

showed that hydroxide particles were not present on the surface and that fine–grain,

smooth and compact Fe–Cr–Ni–Mo alloy deposits were obtained. The X–ray diffraction

47
pattern of the alloy deposits revealed that the alloy were either amorphous or

microcrystalline in structure [46]

A novel Ni90.4Cr9.6 nanocomposite film was prepared by co–electrodeposition of

Ni and Cr nanoparticles in an average size of 39 nm. The Cr nanoparticles were dispersed

in the electrodeposited nanocrystalline Ni grains (31 nm in average). The oxidation at

800°C showed that the as–deposited Ni–Cr nanocomposite film has a superior oxidation

resistance compared to the electrodeposited pure Ni film and the uncoated Ni matrix.

X–ray diffraction characterization and cross–sectional investigation indicated that a

continuous Cr2O3 scale formed on the electrodeposited nanocomposite film [47].

The effects of electrolyte composition and electrodeposition conditions on

structure, morphology, and composition of amorphous Fe–Cr–P–Co deposits on AISI

1020 steel substrate, earlier plated with a thin Cu deposit, were investigated. The increase

of charge density activates the inclusion of Cr in the deposit. The effect of charge density

on the content of Fe and Co is not clear. However, there is a tendency of increasing of Fe

content and decreasing of Co content with the raising of current density. The Co is more

easily deposited than the P and its presence results in a more intense inhibition effect on

the Cr deposition than the inhibition effect caused by P presence. Scanning electron

microscope (SEM) analysis showed that Co increase in the Fe–Cr–P–Co alloys does not

promote the susceptibility to microcracks, which led to a good quality deposit. The

passive film of the Fe–Cr–P–Co alloy shows a high ability of formation, high protective

capacity, and the results obtained by current density of corrosion, jcor, show that the

deposit with addition of Co, Fe31Cr11P28Co30, presents a higher corrosion resistance than

the deposit with addition of Ni, Fe54 Cr 21P20Ni5 [48].

48
 Nanocrystalline (nc) Ni films with and without dispersions of Cr nanoparticles

were electrodeposited from a nickel sulfate electrolyte. The grain size of the nc–Ni films

was reduced with increasing in the co–deposition content of Cr nanoparticles.

Potentiodynamic polarization tests showed that increasing in the co–deposition content

resulted in an enlarged passive region of the nc–Ni in 3.5% NaCl through reducing the

corrosion potential and increasing the breakdown potential. Scanning electron

microscopy (SEM) observation indicated that the polarized pure nc–Ni film exhibited

numerous large and deep pits. However, they became smaller and shallower when 4.5

wt.% Cr nanoparticles were co–deposited, and almost disappeared when 10.9 wt.%

Cr were co–deposited. X–ray photoelectron spectroscopy (XPS) analysis showed that the

different electrochemical corrosion performance was associated with the ability of the Cr

nanoparticles co–deposited nc–Ni film to form a continuous Cr–oxide passive film [49].

Cr–P coatings were prepared by electrodeposition from trivalent chromium

plating electrolyte using malonic acid as complexing agent. The influences of electrolyte

composition on the trivalent chromium electrodeposition process and deposited coating

properties were studied. The effects of plating parameters such as current density,

electrolyte pH and plating time on structure and morphology of deposited coatings were

investigated in detail. Results show that the composition, microstructure and surface

morphology of the Cr–P coatings depend on electrolyte composition and plating

conditions including electrolyte pH, current density, plating time, etc. Results of EDAX

and XPS indicate that the deposited coatings contain Cr(s), Cr(III), phosphorus, oxygen

and carbon. The optimum plating parameters for good–quality chromium deposited

coating are pH 2–3, current density 3–12 dm2, temperature 35°C and Ti/IrO2 as anode.

49
These results may be of great practical and theoretical significance for further

improvement of trivalent chromium plating process [50].

Nanocrystalline Cr–C layers with excellent anti–wear performance were prepared

by electrodeposition in Cr3+ electrolyte and subsequent annealing. X–ray diffraction

(XRD) shows that the crystalline structure of the Cr–C layer changed from amorphous to

nanocrystalline when the annealing was conducted. The hardness, Young's modulus and

wear rate of the Cr–C layer were measured. The results indicate that the 400°C annealed

nanocrystalline Cr–C layer exhibits a high ratio of hardness to Young's modulus and

excellent wear resistance. The excellent wear resistance can be attributed due to the

presence of hardness and roughness. The friction tests reveal that the friction coefficient

depends on the Young's modulus and the counterpart. Comparing wear with friction, no

obvious connection can be found between them [51].

Cr–Ni multilayers with thickness modulation of several tens of nanometers were

prepared by pulse–current electrodeposition from a Cr(III)–Ni(II) electrolyte at 30°C.

The Cr–Ni multilayers were composed of alternate amorphous Cr–rich and

nanocrystalline Ni–rich layers. This amorphous Cr–rich layer is attributed to a reduction

in the complex–formed Cr ion, which leads to the presence of C, a glass forming element,

in the Cr–rich deposit during electrodeposition. Twins were found in the nanosized Ni–

rich layer, in which stacking faults were frequently observed [52].

Chromium–phosphorus (Cr–P) coatings were electrodeposited from trivalent Cr

(III) electrolytes containing hypophosphite. The electrochemical corrosion behavior

of Cr–P coatings, traditional Cr coatings deposited in hexavalent Cr(VI) electrolytes, and

chromium–carbon (Cr–C) coatings deposited in Cr (III) electrolytes containing formate

50
were studied by measuring potentiodynamic polarization curves in a 10 wt% HCl

solution. The results of electrochemical tests showed that Cr–P coatings exhibit better

corrosion resistance than traditional Cr and Cr–C coatings, which is characterized by a

lower critical current density, lower passive current density, and lager passive potential

range. XPS and SEM analyses confirm that the excellent corrosion resistance of Cr–P

coatings is attributed to the formation of a phosphide passive film, which has high

stability and self–repairing ability, and can act as a “buffer” to reject the penetration of

chloride ions [53].

Fe–Cr–P amorphous alloys were electrodeposited in a trivalent chromium sulfate

electrolyte containing glycine as complexing agent. The effects of electrolyte

composition and electrodeposition parameters such as current density, electrolyte pH and

plating time on the structure, morphology and composition of the amorphous Fe–Cr–P

deposits were investigated. It showed that glycine is a suitable complexing agent to get

good quality of Fe–Cr–P amorphous alloys by trivalent chromium electrodeposition. It

was observed that the chromium content in the deposits increased with increasing the

cathodic current density. When current density exceeds specific value, the chromium

content in the deposit would decrease. Results of EDS and XPS indicate that the

deposited alloys contain chromium, iron, phosphorus, nitrogen, oxygen and carbon. The

XRD pattern reveals that the Fe–Cr–P alloy deposit has amorphous structure [54].

The chemical composition of the top layers of Cr–Co alloy electrodeposited

from Cr (III) formate–urea electrolytes with various concentrations of CoCl2 was studied

by the X–ray photoelectron spectroscopy method. The quantity of each element in at.%

was calculated from the single Cr2p3/2, Co2p3/2, C1s, O1s and N1s peak areas. Analysis

51
of XPS spectra has shown that the surface of Cr–Co alloy is covered with the thick oxide

film (about 20 nm) and the bulk of the deposit consists of two phases: carbide and

metallic of both chromium (about 60 at.%) and cobalt (about 3 at.%). A low percentage

(about 3 at%) of nitrogen in the bulk of the deposit suggests the presence of chromium

nitrides, which may be formed along with carbides during electrodeposition owing to

reduction of chromium–carbamide complexes and an extremely high electrocatalytic

activity of chromium in the cathodic processes [55].

Singh Raman et al. investigated nanocrystalline structure and concluded that Fe–

Cr alloys have oxidation resistance at much lower chromium contents. Discs of

nanocrystalline Fe–10% Cr alloy were produced by ball milling of Fe and Cr powders

and compact without considerable grain growth. Corrosion resistance of discs of

nanocrystalline and microcrystalline alloys were compared by subjecting them to

oxidation in air and post–oxidation characterization of the oxide scales by secondary ion

mass spectroscopy (SIMS). Nanocrystalline Fe–10% Cr alloy showed greater oxidation

resistance than the microcrystalline alloy of the same composition. Chromium content of

the inner scale formed over the nanocrystalline alloy was detected to be nearly five times

greater than that in the case of microcrystalline alloy, facilitating the formation of the

passive layer and providing an explanation for the greater oxidation of the former [56]

The effects of direct current and pulse current on composition and corrosion

resistance of Fe–Ni–Cr alloy coatings were studied. In both direct and pulse

current electrodeposition, increasing the current density has a decreasing effect on Fe and

Ni and an increasing influence on Cr. In pulse current electrodeposition, duty cycle has a

greater effect than frequency on composition of the alloy coating, particularly in the

52
range of 10–50%. In this range, by increasing the duty cycle, Ni decreases, Fe sharply

increase and Cr shows an increasing trend. Following a study of the microhardness of

coatings, it is determined that the microhardness increases about 1.5 times by pulse

current electrodeposition. The corrosion resistance of the alloy coatings (electrodeposited

by direct and pulse current) has been investigated in NaCl solution. The micro–cracks

of alloy coating can be decreased by using pulse current, which demonstrates a better

corrosion resistance than direct current coating [57].

Amorphous chromium coatings were electrodeposited from Cr(III)–based

solutions containing organic (HCOONa) or phosphorus–containing (NaH2PO2) additives.

Their structure was studied by a combination of X–ray diffraction (XRD), valence–to–

core X–ray emission spectroscopy (XES) and X–ray absorption spectroscopy (XAS) at

the Cr K–edge. Metalloid atoms (C or P) incorporated in electrodeposited structure are

chemically bonded to chromium. Upon annealing at elevated temperatures in vacuum,

these amorphous coatings crystallize into a mixture of phases containing metallic

chromium and chromium carbides or chromium phosphides. Quantitative analysis of

valence–to–core XES data demonstrates that the average local structure of chromium in

the amorphous coatings does not change significantly during crystallization [58].

Ni–Cr nanocomposite coatings with different Cr particles contents were

developed by electrodeposition method from a nickel sulfate solution containing different

concentrations of Cr nanoparticle with an average particle size of 40 nm. The

characteristics of the coatings were assessed by scanning electron microscopy and

microhardness test. The friction and wear performances of Ni–Cr nanocomposite coatings

and pure Ni film were investigated, with the effect of the Cr content on the friction and

53
wear behaviors to be emphasized. The results indicate the microhardness, friction and

wear behaviors of Ni–Cr nanocomposite coatings are closely related with Cr particles

content. The Ni–Cr nanocomposite coating with a lower Cr content of 4.0% shows

somewhat increased microhardness and wear resistance than the pure Ni coating, while

the Ni/Cr nanocomposite coating with a higher Cr content has much better wear

resistance than the pure Ni coating. The effect of Cr nanoparticles on the microhardness

and wear resistance were discussed [59].

Amorphous Cr–C alloy coatings were electrodeposited from a trivalent chromium

electrolyte containing formic acid. The effects of plating parameters such as pH and

current density on composition, structure, morphology and corrosion behaviour of as–

deposited coatings were investigated. Results showed that the suitable current density for

Cr–C alloy electrodeposition increases as the pH value decreases. Furthermore, by

decreasing the pH, higher amount of carbon was introduced into the coatings. The Cr–

C alloy coatings deposited at lower pH showed higher passive current density on Tafel

plot. By annealing the amorphous Cr–C alloy coatings at 300°C, a nanocrystalline

structure having higher hardness was obtained. However, the corrosion resistance was

seen to be impaired. Annealing at 600°C led to the precipitation of Cr23C6 which resulted

in a higher hardness. The formation of Cr23C6 enhanced the corrosion resistance of

coatings due to an increase in corrosion potential. However, formation of micro–cells

between the Cr23C6 precipitates and bulk chromium prevented the passive film formation

[60].

The mechanism of chromium metal deposition from a trivalent chromium electrolyte

containing formic acid and polyethylene glycol 1000 (PEG) was studied on an

54
electrochemical quartz crystal microbalance (EQCM). Reactions of PEG molecules with

trivalent chromium ions and their influence on the plating process of

trivalent chromium were investigated. EQCM studies at low trivalent chromium ion

concentrations show that chromium electrodeposition occurs via the formation of an

adsorption layer on the electrode surface, which is called a cathodic film. Cathodic films

hinder the penetration of ions from bulk solution to the cathode surface. In the inner

portion of the cathodic film and at the cathode surface, intermediate complexes were

formed during the deposition process. During electrodeposition, the PEG molecules

decreased the reductive current of hydrogen compared with solutions without PEG; an

effect that was also observed due to the pH on the electrode surface. PEG plays a decisive

role in the formation of intermediate compounds during electrodeposition [61].

Roberto Giovanardi studied an alternative plating process to obtain chromium

coatings through electrodeposition from electrolytes containing trivalent chromium, as

aqueous solutions of Cr (III) are significantly less dangerous, in terms of human health

and environmental impact, as compared to the traditional Cr (VI) electrolytes employed

for this purpose. In order to overcome problems regarding the reduction of Cr (III) in

aqueous solution, two approaches were followed: i) the possibility of co–depositing

chromium along with a second metal, which could help the process of discharge

of Cr3+ on the substrate; ii) the use of a specific ligand for the Cr3+ ion, which can

generate easily reducible complexes at the metal–solution interphase. Both approaches

led to interesting results: in particular, the co–deposition enabled us to obtain NiCr alloy

with a high percentage of chromium, and the deposition using specific complexing agents

55
allowed optimal electrolyte compositions to be developed both for decorative and hard

chromium plating [62].

Role of complexing agents were studied using the Cr(III)–formate, Cr(III)–

oxalate and Cr(III)–glycine electrolytes for the Cr coatings. The deposition rate and

brightness range of the electrodeposition process in these electrolytes were investigated.

The geometric structures of the Cr complex ions were optimized, using density functional

theory with General Gradient Approximation/Perdew–Wang 91 (GGA/PW91)

calculation. It was found that the deposition rate and brightness range significantly

depend on the geometric structure of the Cr(III)–ligand complex ions. The expansion of

the distance between Cr and H2O induced by introducing complexing ligand is a

necessary condition for the electrochemical reduction of Cr(III) to metal Cr. The

dehydration rate of Cr(III)–ligand complex ions determines the electrodeposition

characteristics of electrolytes. The ligand accelerates the electroreduction of Cr(III) in

Cr(III)-formate, due to expansion of the distance (r) between Cr and H2O as a result of

introducing ligand into complex ions. Cr complex ions with larger maximum ‘r’exhibit

the higher activation of electroreduction. Due to the relatively high pKa 1 of formate acid,

the active complex ions, [Cr(H2O)5CHOO]2+, in Cr(III)-formate electrolytes are rare.

Thus, during the plating process, as the [Cr(H2O)5CHOO]2+ ions are consumed rapidly to

achieve commercial acceptable thick Cr coatings [63].

Black chromium coatings were electrodeposited from a 1–butyl–3–

methylimidazolium tetrafluoroborate ([BMIm][BF4]) solution containing Cr(III) under

potentiostatic control on copper substrates. The electrochemical behavior of the

electrolyte was studied by cyclic voltammetry. The reduction of Cr(III) species in the

56
solution is a two–step process, from Cr(III) to Cr(II) and from Cr(II) to Cr(0). The

potential of each reaction shifts positively with the increase of the electrolyte

temperature. The parameters for the electrodeposition of black chromium films were

optimized. Homogeneous black chromium films with spectrally selective optical

properties were produced by applying a potential of −1.5 V for 1800 s, at an electrolyte

temperature of 85°C. The coatings consist of a mixture of chromium oxide/hydroxide and

metallic chromium. They are amorphous and present a sub–micrometric granular

structure [64].

Electrodeposition of chromium in a mixture of choline chloride and CrCl3·6H2O has been

reported recently [65]. Green viscous liquid is obtained by mixing choline chloride with

CrCl3·6H2O and the physical properties of this deep eutectic solvent are characteristic of

an ionic liquid. The eutectic composition was found to be 1:2 choline

chloride/CrCl3·6H2O. From this ionic liquid Cr could be electrodeposited efficiently to

yield a crack free deposit. Addition of LiCl to the choline chloride and CrCl3·6H2O liquid

was found to allow the deposition of nanocrystalline black–chromium films [66]. The use

of this ionic liquid might offer an environmentally friendly process for electrodeposition

of Cr instead of the current chromic acid–based electrolyte. However, some efforts are

still necessary to get shining Cr deposits which can compete with the conventional Cr(VI)

or Cr(III)–based aqueous galvanic process. Cr reduced via a Cr(II) state which forms an

insoluble intermediate at the electrode/electrolyte interface and the deposition process is

irreversible. Significant results reported by Benaben on hard Cr deposition using ionic

liquids (IONMET European research program), he obtained shiny metallic hard Cr with

57
thickness up to 50 100 μm using trivalent chromium salts. Using a mixed solution of

CrCl3·6(H2O) and choline chloride, hard chromium layers were deposited on steel [67].

The addition of up to 10 wt.% LiCl leads to a matt black, amorphous Cr layer is free of

surface cracks, unlike samples deposited using aqueous Cr(III) and Cr(VI) which are

highly crystalline with cracked surface [66]. When the samples were electrolyzed in

1.1 M KNO3 solution for 2 min they were found to have excellent corrosion resistance.

The samples withstood > 1600 hr in a salt spray test without any visible sign of corrosion.

The black coloration of the film was due to the deposits being nanoparticulate and XRD

analysis showed that the Cr(110) and Cr(211) were the predominant crystal faces present.

The deposit thickness, adherence and morphology could be further improved using

pulse–plating [68]. Solid particles of primarily hard substances, solid lubricants, ductile

metals or their alloys and/or molten polymers are embedded in a network of cracks of

hard chromium coatings to attain improved physical characteristics, primarily to increase

wear resistance, sliding behavior, ductility and corrosion resistance. The network of

microcracks in the chromium coating is widened and solid particles are embedded within

the cracks. Preferred uses are as coatings on the bearing surfaces of piston rings or

cylinder bearing sleeves for internal-combustion engines [69, 70].

58
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63
 OH2 OH

Cr + H+
Cr

OH2 OH2

H
OH O

Cr Cr Cr + 2H2O
2

OH2 O
H

H H H
O OH O O

Cr Cr Cr Cr Cr

O O O
H H H

Figure 2. 1 Reactions of polymeric olated Cr(III) complexes.

64
CHAPTER III
 EXPERIMENTAL PROCEDURE

3. 1 Electrolyte Preparation

The compositions of the electrolytes used for Cr electrodeposition were shown in

Table 3. 1. All components were purchased from Across Organics and were weighed

using a Contech precision CB–Series balance. Chromium (III) chloride, glycine and

methanol were mixed in one beaker and the other components were mixed in another.

Each beaker was filled with half of the required volume of deionized (DI) water and then

both solutions were mixed and heated in a water bath with reflux condenser. The

chromium (III)–glycine solution and the solution containing the other components were

heated at 67˚C and 35˚C, respectively, for 30 minutes. Then, both solutions were mixed

together and allowed to cool to room temperature. The purpose of using complexing

agents is to 1) to obtain lower potential reduction of Cr 3+ to metallic state, and 2) to

prevent the formation of hexaaquo–coordinated trivalent chromium complexes.

3. 2 DES preparation

Choline chloride [HOC2H4N(CH3)3Cl] (ChCl) (Acros organics 99 %) was dried

under vacuum prior to use. Ethylene glycol (EG) (Fisher scientific 99 %), was used as

received. The mixtures were formed by stirring the two components together (in a 1: 2

molar ratio of ChCl: EG at 60˚C until a homogeneous, colourless liquid formed. The

metal halide salts are; CrCl3·6H2O (Acros organics 98 %), NiCl2·6H2O (Acros organics

98 %), FeSO4·7H2O (Acros organics). The concentrations of metal salts were 0.79 mol

dm–3 of CrCl3·6H2O, 0.39 mol dm–3 NiCl2.6H2O and 0.03 mol dm–3 FeSO4·7H2O.

65
3. 3 Preparation of substrate

Surface Treatment Process

The Cr and its alloy electrodeposition process involved the following steps

Degreasing (1min)

Rinsed with distilled water (1min)

Activated by immersion in electro–cleaning solution

(35g/l Na2CO3 + 25g/l NaOH) for 2 min

Rinsed with distilled water (30 s)

Acid dipping in 5% H2SO4

Rinsed with distilled water (30 s)

Electrodeposition of Cr and its alloy for various time and current densities

Rinsed with distilled water (1min)

Dried in air.

3. 4 Electrodeposition Methods

3. 4. 1 Comparison of DC and PC electrodeposition

Pulse electrodeposition–charging of the electrical double layer (EDL) at the metal–

electrolyte interface

In pulse electrodeposition (PED) [1–3] the potential or current is alternated

swiftly between two different values. This results in a series of pulses of equal amplitude,

duration and polarity, separated by zero current. Each pulse consists of an On–time (tOn)

during which potential and/current is applied, and an Off–time (tOff) during which zero

current is applied as shown in Figure 3. 1. It is possible to control the deposited film

composition and thickness in an atomic order by regulating the pulse amplitude and

66
width [4–7]. They favour the initiation of grain nuclei and greatly increase the number of

grains per unit area resulting in finer grained deposit with better properties than

conventionally plated coatings.

Modern electronics and microprocessor offers the flexibility of programming of

the applied current waveform. The latter is of two groups: (1) unipolar, where all the

pulses are in one direction (with no polarity) cathodic pulse followed by a period without

current (or an anodic pulse), (2) bipolar, where anodic and cathodic pulses are mixed.

Cathodic pulses followed by anodic pulses and (3) direct current (DC) with superimposed

modulations. In electroplating, a negatively charged layer is formed around the cathode

as the process continues. When using DC, this double layer charges to a defined thickness

and obstructs the ions from reaching the part. In PED, the output is periodically turned

off to cause this layer to discharge somewhat. This allows easier passage of the ions

through the layer and onto the part. High current density areas in the bath become more

depleted of ions than low current density areas. During tOff, ions migrate to the depleted

areas in the bath. When pulse t On occurs, more evenly distributed ions are available for

deposition on the substrate.

In the conventional DC plating there is only one parameter, namely current

density (i), which can be varied. But in PED, we have many independent variables, viz.,

(i) on–time (ton), (ii) off–time (tOff) and (iii) peak current density (ip). In PC, the duty

cycle (γ) corresponds to the percentage of total time of a cycle and is given by [8]

γ (duty cycle) = t On / (tOn + tOff) — (1)

where f is frequency, defined as the reciprocal of the cycle time t Total

f (frequency) = 1/ (tOn + tOff) — (2)

67
 In practice, pulse plating usually involves a duty cycle of 5% or greater and tOn

from µs to ms. PC will deposit metal at the same rate as DC provided the average pulse

current density equals the latter. The average current density (ia), in pulse plating is

defined as [9]

Average current (ia) = peak current (ip) X duty cycle (γ) — (3)

The charges are provided to electrical double layer (EDL), to raise its potential to the

value required for metal deposition at the rate corresponding to (ia). The (ip) supplied

consists of two parts, (1) a capacitive current, which charges the double layer and (2) a

faradic current (iF), which corresponds to the rate of metal deposition. The charging time

(tC) of EDL is the time required for the iF, to reach 99% of ip [10] while discharge time

(tD) is the time required to decrease iF to 1% of ip. The rapid method for selection of tC

and tD values in relation to the applied ip [11] is given below.

tC = 17/ ip — (4)

tD = 120/ ip — (5)

3. 4. 2. PED vs. DC deposition

The pulse parameter were selected such that in all cases the pulse on–time was

less than the transition time, τ (the time required for the interfacial concentration to reach

zero [12] and much longer than the charging time, t C in microseconds, of the double layer

as calculated from Eq. (4) and Eq. (6), respectively [13].

τ = {πD (CbzF)2}/4 ip2 — (6)

Where ip is the peak current density (A cm–2), z is the number of electrons (3, for the case

of chromium), F is Faraday’s number (96,500) coulombs), C b is the bulk concentration of

Cr3+ ions (mol L–1) and D is the diffusion coefficient of Cr 3+ (cm2 sec–1). In addition, the

68
pulse off–time was selected such that the shortest pulse off–time was several order of

magnitude longer than the discharge time, t D, of the double layer as calculated from

Eq.(5) [13].

Ibl [10] observed that the deposit properties obtained with PC at high frequency

are similar to those obtained by DC plating. They believed that deposition at high

frequency during off–time is independent of the primary current distribution because no

external electric field is applied during off–time. PC makes the deposition more uniform

than by DC plating at the same current density. The uniformities of PC at high frequency

are even better than that of DC plating at 10 mAcm–2, as can be shown by a Wagner

number analysis. The Wagner number, assuming Tafel kinetics [11, 14] is defined as

follows.

RTK

WαT = — (7)

αcFL|i*avg|

where L is a characteristic length of the system, K is the specific conductivity of the

electrolyte solution, and iavg * is the average current density which is dependent on the

primary current distribution. The value of Wagner number is an index of the relative

influence of solution conductivity and surface kinetics over deposition distribution.

The electrode response at high frequency approaches that of a DC signal due to

charging and discharging the double layer as shown in Figure 3. 1. The current

discharging from the double layer is independent of the primary current distribution

according to Holmbom and Jacobsson [15]. The iavg * of PC at high frequency is iavg* =

69
iavg x duty cycle, and equal to 20 x 0.5 = 10 mAcm–2. Hence, the Wagner number of PC at

high frequency is the same as that of DC at 10 mAcm–2 as other parameters in Eq. 7

should be considered constant. With equal Wagner number, the current distribution of PC

at high frequency should predictably be the same as that of DC at 10 mAcm–2.

A longer on–time of 40 ms may be explained in terms of the redistribution of the

partial currents for reduction of Cr and hydrogen ions. At such a long on–time, it is

believed that a larger portion of the applied current is consumed by the hydrogen ion

reduction reaction leading to lower efficiency for Cr deposition. The moderate on–time of

16 ms enhances the formation of very thin pulsating diffusion layer shown in Figure 3. 2,

from which mass transfer and diffusion of ions occurred very effectively. It is reasonable

to assume that the off–time (24 ms) is sufficient for replenishment of the Cr 3+ ions at the

pulsating diffusion layer. Therefore, there is a plenty of replenished Cr 3+ ions getting

deposited without significant amount of hydrogen evolution which leads to higher current

efficiency [16–19].

3. 4. 2 Brush Electro Deposition (BED) techniques

BED equipment includes power packs, solutions and plating tools, anode covers

and auxiliary equipment. Microprocessor–controlled selectron power pack Model 150 A–

40 V was used to transform AC current to DC current. The schematic of the brush plating

system is given in Figure 3. 3. The power packs have two leads, one is connected to the

plating tool and the other is connected to the work piece to be electrodeposited. The

anode is covered with an absorbent material, which holds the solution. The operator dips

the plating tool in the solution and then brushes it against the surface of the work piece to

70
be finished. When the anode touches the work surface a circuit is formed and deposits

produced.

3. 5 Characterization of electrodeposited metals and alloys

3. 5. 1 X–Ray Diffractometry (XRD)

Principle

In this technique the primary X–rays are made to fall on the sample substance

under study. Because of its wave nature, like light waves, it gets diffracted to a certain

angle. This angle of diffraction, which differs from that of the incident beam, will give

the information regarding the crystal nature of the substance. The wavelength of the X–

rays can be varied for the application by using a grating plate. Phillips diffractometer

with CuK (2.2 kW)

Instrumentation

It consists of X–ray tube for the source, monochromatic and a rotating detector are shown

in Figure 3. 4.

Applications

The diffraction of X–rays is a good tool to study the nature of the crystalline

substances. In crystals the ions or molecules are arranged in well–defined positions in

planes in three dimensions. The impinging X–rays are reflected by each crystal plane.

Since the spacing between the atoms and hence the planes can’t be same or identical for

any two chemical substances, this technique provides vital information regarding the

arrangement of atoms and the spacing in between them and also to find out the chemical

compositions of crystalline substances. The sample under study can be of either a thin

layer of crystal or in a powder form. Since, the power of a diffracted beam is dependent

71
on the quantity of the corresponding crystalline substance; it is also possible to carry out

quantitative determinations.

3. 5. 2 Scanning Electron Microscopy (SEM)

Principle

In this technique, an electron beam is focused onto the sample surface kept in a

vacuum by electro–magnetic lenses (since electron possesses dual nature with properties

of both particle and wave an electron beam can be focused or condensed like an ordinary

light) (Hitachi 3000H). The beam is then scanned over the surface of the sample. The

scattered electron from the sample is then fed to the detector and then to a cathode ray

tube through an amplifier, where the images are formed, which gives the information on

the surface of the sample.

Instrumentation

It comprises of a heated filament as source of electron beam, condenser lenses,

aperture, evacuated chamber for placing the sample, electron detector, amplifier, CRT

with image forming electronics, etc are shown in Figure 3. 5.

Applications

Scanning electron microscopy has been applied to the surface studies of metals,

ceramics, polymers, composites and biological materials for both topography as well as

compositional analysis. An extension (or sometimes conjunction to SEM) of this

technique is Electron Probe Micro Analysis (EPMA), where the emission of X–rays,

from the sample surface, is studied upon exposure to a beam of high energy electrons.

Depending on the type of detectors used this method is classified in to two as: Energy

Dispersive Spectrometry (EDS) and Wavelength Dispersive Spectrometry (WDS). This

72
technique is used extensively in the analysis of metallic and ceramic inclusions,

inclusions in polymeric materials, diffusion profiles in electronic components.

Disadvantages

The instrumentation is complicated and needs high vacuum for the optimum

performance.

3. 5. 3 Energy–dispersive X–ray spectroscopy (EDS)

Energy dispersive X–ray spectroscopy (EDS) is an analytical technique used for

the elemental analysis or chemical characterization of a sample (Hitachi 3000H). It is one

of the variants of XRF. It relies on the investigation of a sample through interactions

between electromagnetic radiation and matter, analyzing X–rays emitted by the matter in

response to being hit with electromagnetic radiation. Its characterization capabilities are

due in large part to the fundamental principle that each element has a unique atomic

structure allowing X–rays that are characteristic of an element's atomic structure to be

identified uniquely from one another. Schematic diagram of EDS are shown in Figure

3. 5.

To stimulate the emission of characteristic X–rays from a specimen, a high energy

beam of X–rays is focused into the sample being studied. At rest, an atom within the

sample contains ground state (or unexcited) electrons in discrete energy levels or electron

shells bound to the nucleus. The incident beam may excite an electron in an inner shell,

ejecting it from the shell while creating an electron hole where the electron was. An

electron from an outer, higher–energy shell then fills the hole, and the difference in

energy between the higher–energy shell and the lower energy shell may be released in the

form of an X–ray. The number and energy of the X–rays emitted from a specimen can be

73
measured by an energy dispersive spectrometer. As the energy of the X–rays is

characteristic of the difference in energy between the two shells, and of the atomic

structure of the element from which they were emitted, this allows the elemental

composition of the specimen to be measured.

3. 5. 4 Atomic force microscope (AFM)

Principle

This technique operates by measuring the forces between the sample and the tip,

and the sample need not be a conducting material. Here, the tip is brought close enough

to the sample surface to detect the repulsive force between the atoms of the tip material

and the sample. The probe tip is mounted at the end of a cantilever of a low spring

constant and the tip–to–sample spacing is held fixed by maintaining a constant and very

low force on the cantilever (Molecular Imaging, Picoscan 2000). Hence, if the tip is

brought close to the sample surface, the repulsive force will induce a bending of the

cantilever. This bending can be detected by a laser beam, which is reflected off the back

of the cantilever. Thus by monitoring the deflection of the cantilever, the surface

topography of the sample can be tracked. Since the force maintained on the cantilever is

in the range of inter–atomic forces (about 10–9 Newton), this technique derived the name

“atomic force” microscopy. Schematic diagram of AFM are shown in Figure 3. 6.

AFM operates at two modes

Repulsive or contact mode ─ which detects the repulsive forces between the tip and

sample;

Attractive or non–contact mode ─ which detects the van der waals forces that act

between the tip and sample.

74
Applications

AFM find applications widely in material sciences especially for surface studies

on a nano scale range. AFM finds its applications in measuring the hardness of materials.

Sometimes, AFM can be used in the study of “depth profile” of the deposited oxide layer

on to a material.

Disadvantages

These methods require special sample preparation techniques, which are tedious,

like, thin sectioning, electopolishing, various mechanical cutting and polishing

techniques, etc.

3. 5. 5 Hardness measurements

Microhardness of the Cr deposited on suitable substrate was evaluated by using a

MH6 Everyone hardness tester with Vickers intenders. A dwelling time of 5s and a load

of 50g were used for the measurement. Schematic diagram of Everyone hardness tester

are shown in Figure 3. 7.

3. 5. 6 Thickness and Current Efficiency

Initial and final weights were taken for all the samples. By knowing the

Electrodeposited weight, from which thickness and current efficiency were calculated by

the following formulae.

Thickness (µm) = Weight of deposit X 10000 / (Area X Density) — (8)

Current Efficiency = (Actual weight of deposit X 100) /Theoretical weight of deposit— (9)

Theoretical weight of deposit = (M x I x T) / (Z x F)

M  Molecular weight of metal (Zn)/alloy (Zn–Cr)

I  Current Passed in Ampere

75
 T  Time in (Sec)

Z  No. of electrons

F  Faraday's constant (96500C)

3. 5. 7 Electrochemical studies on anticorrosive properties

3. 5. 7 (A) Potentiodynamic polarization studies

The principal aim of the present investigation was to study surface degradation

resulting from electrochemical processes, and this necessitated in analysis of the surface

deposit left after electrochemical reactions. The potentiostatic polarization experiments

provided some idea of the electrochemical activity of the material. The studies were

carried out using PARSTAT 2273 electrochemical impedance analyzer. However, this

necessitated scanning across a wide range of electrode potentials so that the surface of the

material at the end of such polarization was the result of cumulative effects at different

potentials. To analyze the surface, the material was subjected to potentiostatic

polarizations, one specified potential being impressed on the material at a time. The

potentials were either anodic or cathodic with respect to the primary electrochemical

process occurring on the surfaces as indicated by the potentiodynamic polarization

curves. The schematic polarization curve shown in Figure 3. 8 current and potential of the

corroding electrode is related by

I=Icorr(e2.3η/ba – e2.3η/bc) — (10)

where I corr is corrosion current; η is over potential (E–Ecorr), ba and bc are anodic and

cathodic Tafel slopes.

At higher overpotentials, i.e.

η ≥RT/F — (11)

76
I=Icorr e2.3η/ba — (12)

logI = logIcorr + η/ba — (13)

In the plot η vs. logI, extrapolation of linear line to corrosion potential gives a

straight line and the slope gives both ba and bc and the intercept gives the corrosion

current. The Ecorr and Icorr values have been calculated using the Tafel extrapolation

method.

3. 5. 7 (B) Electrochemical impedance spectroscopy

EIS Electrochemical Impedance Spectroscopy or EIS is a powerful technique for

the characterization of electrochemical systems (PARSTAT 2273 electrochemical

impedance analyzer). The promise of EIS is that, with a single experimental procedure

encompassing a sufficiently broad range of frequencies, the influence of the governing

physical and chemical phenomena may be isolated and distinguished at a given applied

potential. In recent years, EIS has found widespread applications in the field of

characterization of materials. It is routinely used in the characterization of coatings,

batteries, fuel cells, and corrosion phenomena. It has also been used extensively as a tool

for investigating mechanisms in electrodeposition, electrodissolution, passivity, and

corrosion studies. It is gaining popularity in the investigation of diffusion of ions across

membranes and in the study of semiconductor interfaces.

3. 5. 7 (C) Principles of EIS measurements

The fundamental approach of all impedance methods is to apply a small

amplitude sinusoidal excitation signal to the system under investigation and measure the

response (current or voltage or another signal of interest). In the following figure, a non–

linear I–V curve for a theoretical electrochemical system is shown in Figure 3. 9. A low

77
amplitude sine wave ∆Esin(ωt), of a particular frequency, is superimposed on the dc

polarization voltage E0. This results in a current response of a sine wave ∆Isin(ωt+φ)

superimposed on the dc current I0. The current response is shifted with respect to the

applied potential. The Taylor series expansion for the current is given by

ΔI = (dI/dE) E0, I0 ΔE+1/2 (d2I/dE2) E0, I0 ΔE2+ ······· — (14)

If the magnitudes of the perturbing signal ∆E is small, then the higher order terms

1/2 (d2I/dE2) E0, I0 ΔE2+ ········ — (15)

the first equation can be assumed to be negligible. The impedance of the system can then

be calculated using Ohm’s law as,

ΔE(ω)

Z(ω) = — (16)

ΔI(ω)

This ratio is called impedance, Z(ω), of the system and is a complex quantity with a

magnitude and a phase shift which depends on the frequency of the signal. Therefore by

varying the frequency of the applied signal one can get the impedance of the system as a

function of frequency. Typically in electrochemistry, a frequency range of 100 kHz – 0.1

Hz is used. The impedance, Z(ω), as mentioned above is a complex quantity and can be

represented in Cartesian as well as polar co–ordinates. In polar co–ordinates the

impedance of the data is represented by,

Z(ω) = |Z(ω)|eφ(ω) —(17)

78
where |Z| is magnitude of the impedance and φ is the phase shift. In Cartesian co–

ordinates the impedance is given by

Z(ω) = Zr(ω) + jZj (ω) —(18)

where Zr is the real part of the impedance and Zj is the imaginary part and j = −1

The plot of the real part of impedance against the imaginary part gives a Nyquist

Plot, as shown in Figure 3. 10. The advantage of Nyquist representation is that it gives a

quick overview of the data and one can make some qualitative interpretations. While

plotting data in the Nyquist format the real axis must be equal to the imaginary axis so as

not to distort the shape of the curve. The shape of the curve is important in making

qualitative interpretations of the data. The disadvantage of the Nyquist representation is

that one loses the frequency dimension of the data. One way of overcoming this problem

is by labeling the frequencies on the curve. The absolute value of impedance and the

phase shifts are plotted as a function of frequency in two different plots giving a Bode

plot, as shown in Figure 3. 11. This is the more complete way of presenting the data. The

relationship between the two ways of representing the data is as follows:

|Z|2 = (Zre)2 + (Zim)2 — (19)

Zre

Ø = tan–1 — (20)

Zim

Zre = |Z|cosø — (21)

Zim = |Z|sinø — (22)

For this simple process, the model circuit is that shown in Figure 3. 12. The

circuit is a resistor, Rp, is parallel with a capacitor, C. The entire parallel circuit is series

79
with another resistor, Rs. The utility of AC impedance lies in the fact that Rs equals the

solution resistance uncompensated by the potentiostat and Rp equals the polarization

resistance.

80
References

1. M. Ghaemi, L. Binder J. Power Sources 111 (2002) 248.

2. A. Marlot, P. Kern, D. Landolt, Electrochim. Acta 48 (2002) 29.

3. K. M.Yin, S. L. Jan, C. C. Lee, Surf. Coat. Technol. 88 (1997) 219.

4. S. Kainuma, S. Ishikura, K. Hisatake, J. Magn. Soc. Jpn. 21 (1995) 889.

5. T. Houga, A. Yamada, Y. Ueda, J. Jpn. Inst. Met. 64 (2000) 739.

6. Y. Ueda, N. Hataya, H. Zaman, J. Magn. Magn. Mater. 156 (1996) 350.

7. M. Alper, K. Attenborough, R. Hart, S.J. Lane, D.S. Lash- more, C. Younes,

W. Schwarzacher, Appl. Phys. Lett. 63 (1993) 2144

8. S. D. Beattie, J. R. Dahn, J. Electrochem. Soc. 150 (2003) A894.

9. J. C. Puippe, N. Ibl, J. Appl. Electrochem. 10 (1980) 775.

10. N. Ibl, Surf. Technol. 10 (1980) 81.

11. J. C. Puippe, F. Leaman, Theory and practice of pulse plating, 1st edn. American

Electroplaters and Surface Finishers Society, Orland, FL, 1986, p 247–257

12. A. M. El–Sherik, U. Erb, J. Page, Surf. Coat. Technol. 88 (1996) 70.

13. S. K. Ghosh, A. K. Grover, G. K. Dey, M. K. Totlani, Surf. Coat. Technol. 126

(2000) 48.

14. A. C. West, C. C. Cheng, B. C. Baker, J. Electrochem. Soc. 145 (1998) 3070.

15. G. Holmbom, B. E. Jacobsson, Surf. Coat. Technol. 35 (1988) 333.

16. S. I. Kwak, K. M. Jeong, S. K. Kim, J. Electrochem. Soc. 143 (1996) 2770.

17. S. Roy, Ind. Eng. Chem. Res. 51 (2012) 1756

19. M. Datta, D. Landolt, Surf. Coat. Technol. 25 (1985) 97.

81
 Table. 3. 1 Electrolyte composition for electrodeposition of chromium

Solution composition Glycine electrolyte DMFelectrolyte (g/l)

(g/l)

CrCl3 6H2O 212 212

NH4Cl 26 26

NaCl 36 36

B(OH)3 20 20

Glycine 75 –

DMF – 200 ml

CH3OH 200 ml –

Figure 3. 1 A typical time dependence of applied current in pulse wave form where t On is

the On–time, tOff is the Off–time, ia is the average current density, ip is the peak current

density and iF is the Faradaic current.

82
Figure 3. 2 Concentration profiles of the two diffusion layers in pulse electrolysis at the

end of pulse. The broken line (– – – – –) shows the recovery of the concentration in the

pulsating diffusion layer during the Off–time. (T <t1<t2<θ.) δs is the Outer stationary

diffusion layer, δN is the Nernst diffusion layer, and δp is the Pulsating diffusion layer: C0

is the Bulk concentration, Ce is the concentration at electrode surface.

Absorbant wrap

Graphite anode
Deposit
Build-up solution Stylus handle

Leads
_

Substrate DC Power pack

Figure 3. 3 Schematic of brush electroplating process

83
 Figure 3. 4 Schematic diagram of X–ray Diffraction system.

Figure 3. 5 Schematic diagram of a Scanning Electron Microscopy system

84
Figure 3. 6 Schematic diagram of Atomic Force Microscopy system

Figure 3. 7 MH6 Everyone hardness tester with Vickers intenders

85
Figure 3. 8 Anodic and cathodic Tafel curves for corrosion of metal.

86
Figure 3. 9 A non–linear I–V curve for a theoretical electrochemical system is shown.

Figure 3. 10 Nyquist Plot for a Simple Electrochemical System

87
 Figure 3. 11 Bode Plot for a Simple Electrochemical System

Figure 3. 12 Equivalent circuit diagram of impedance spectra for simple

electrochemical system.

88
CHAPTER IV
 AIM AND SCOPE OF THE RESEARCH

Environmental pollution is an important aspect to be considered in Cr plating.

Until now, the quasi totality of Cr plating is realized through hexavalent Cr electrolyte.

This is now classified as a Class – I carcinogen, and strict environmental regulations have

been reinforced [1]. However, the hard chromium deposit has so many engineering

applications, that it still could not be replaced with any other coating effectively. It

provides a tarnish resistant surface finish. The maximum allowed pollution level is 0.05

mg/L for Cr (VI) where as it is 3 mg/L for Cr (III). The developed baths should have

better current efficiency, throwing power and better physical characteristics (micro

hardness, wear and corrosion resistance) than hexavalent Cr deposits. Chromium exhibits

very sluggish ligand exchange behavior. This leads to an inertness in the higher

oligomeric olated µ–hydroxo bridged Cr3+ ions, formed in the electrolyte. The process is

said to be catalyzed by the formation of transient divalent chromium at the cathode

surface [2]. The chromium oligomers formed have a disastrous effect on the deposit,

since they are selectively adsorbed on the crystal growth sites, blocking further growth of

the deposit, thereby acting like a poison. A second problem encountered at the cathode is

the shift of the standard potential to more negative values. The normal value is –1.38 V,

whereas with the oligomeric complex formation setting in, this value shifts to as much as

–1.91 V. This value is very close to the reduction potential of water, and in turn poses a

serious threat to the cathodic efficiency. To overcome these problems, several organic

additives like methanol, formic acid, glycine and carboxylic acids have been suggested

[3]. These additives delay the formation of the oligomers, enabling an increase in the

89
deposition rate by one or two orders of magnitude. Due to hydrogen evolution CE

decreases in Cr(III) bath. So in order to eliminate the hydrogen evolution of ionic liquid

(IL) have been chosen so that we can obtain maximum CE of 60–75%. Cr deposited from

ionic liquids will be having higher thermal stability, higher hardness and corrosion

resistance properties.

4. 1 Scope of research work

The main aim of this study is to develop chromium and its alloy electrodeposition

on mild steel and to explore the option of ionic liquids/trivalent chromium electrolyte as

an alternative to hexavalent chromium electrodeposition in the wake of an impending

legislation. The electrodeposition of Cr and its alloys are very important in the field of

automobile, aerospace and engineering tools as decorative as well as functional

applications. Electrodeposition from chromic acid is widely used but Cr(VI) ion is highly

toxic, carcinogenic and not environmentally benign process. So efforts were taken to

develop more eco–friendly green electrolyte such as Cr(III) based electrolytes and ionic

liquid/deep eutectic solvent for electrodeposition of Cr and its alloy. We prepared

different Cr(III) based electrolytes and deep eutectic solvent from which both Cr and its

alloy were deposited. United States Environmental Protection Agency (EPA) insist not to

use Cr(VI) based electrolyte because of its toxicity. Therefore, our electrolytes are a very

good candidate for both decorative and functional application with high current

efficiency of 20–35%. In order to increase current efficiency further to maximum extent

ionic liquids are used. Ionic liquids are superior media for the electrodeposition of metals

and have an exceptional potential to revolutionize electrodeposition. Key advantages that

enable them to overcome the limits imposed by common aqueous media are their wide

90
electrochemical window, spanning up to 6 V in some cases; extremely low vapour

pressures, which allow deposition at temperatures well below 100°C. Processes that are

competitive reaction between hydrogen evolution with lower current efficiency metal

such as Cr and its alloy become viable if ionic liquids are used. Cr having a deposition

potential conflicting with water decomposition, in order to avoid metal water complexity

and to improve thickness, hardness and current efficiency ionic liquids can be used.

This process has shown an interesting cation effect: in one ionic liquid, the

deposited metal is nanocrystalline, with grain sizes of around 50 nm; with a different

cation the grain size is, under practically the same conditions, around 5 μm [4]. It is

remarkable that just variation of the ionic liquid leads to different morphologies, without

the addition of any brightener or grain refiner. This effect results from the solvation

layers forming at the interface between the electrode and the ionic liquid; these vary from

liquid to liquid and depend upon the metal salt dissolved. A further advantage over

aqueous plating baths is that many ionic liquids are benign media without toxicity issues

in comparison with the chromic acid and cyanides that are involved in many aqueous

systems (for example H2CrO4 and [Ag(CN)2]–, which is used in Cr and silver

electrodeposition) [5].

4. 2 Methodology

Direct current (DCD), brush (BED) and pulse current electrodeposition technique

were used to prepare Cr and its alloy. Aplab regulated dual DC power supply (CBPS

32/20 D), for DC deposition and Microprocessor–controlled selectron power pack Model

150A–40 V were used for BED. Pulse electrodeposition was done using Dynatronix

(USA) model DPR20–5–10. Crystallographic phases of electrodeposited metal and alloy

91
were identified using Phillips diffractometer with CuK (2.2kW). Surface morphologies

and grain size of electro deposits were characterized by scanning electron microscopy

(SEM) employing Hitachi 3000H. The surface topography of brush electrodeposited Cr

was studied using atomic force microscopy (AFM). Microhardness of the Cr deposited on

suitable substrate was evaluated by using a MH6 Everyone hardness tester with Vickers

intenders. Electrochemical impedance spectroscopy of as obtained metal and alloy were

studied using Princeton Applied Research electrochemical analyzer (PARSTAT 2273)

with in–built software package (power SUITE).

92
References

1. A. Lozano–Morales, R. P. Renz, J. J. Fortman, E. J. Taylor, ECS Trans. 6 (2007)

51.

2. N. V. Mandich, Plat. Surf. Finish. 84 (1997) 108.

3. M. El–Sharif, S. Ma, C. U. Chisholm, Trans. Inst. Metal Finish. 77 (1999) 139.

4. S. Zein El Abedin, E. M. Moustafa, R. Hempelmann, H. Natter, F. Endres,

Chem. Phys. Chem 7 (2006) 1535.

5. M. Armand, F. Endres, D. R. MacFarlane, H. Ohno, B. Scrosati, Nat. Mater. 8 (2009)

621.

93
CHAPTER V
 CORROSION BEHAVIOR OF Cr ELECTRODEPOSITED FROM Cr(VI) AND

Cr(III)–BATHS USING DIRECT (DCD) AND PULSE ELECTRODEPOSITION

(PED) TECHNIQUES

5. 1 Introduction

Hexavalent chromium [Cr(VI)] plating was commercialized many years before.

A Cr(VI) plating bath operates at an elevated temperature and produces a mist of

chromic acid. Since Cr(VI) plating produces hazardous air emissions, all Cr(VI) electro

depositors must control and monitor the bath surface tension periodically. Cr(VI) widely

recognized as a human carcinogen was reported to cause increased incidences of lung

cancer. A United States Environmental Protection Agency (EPA) report [1] implicates

Cr(VI) as a Group A known human carcinogen. The EPA also found that Cr(III) is much

less toxic, classifies as a Group D carcinogen not classifiable as to carcinogenicity in

humans. Cr(III) is rather insoluble and does not oxidize organic materials, poorly

absorbed from gastrointestinal tract and is not considered to be a carcinogen. Cr(VI) is

very reactive and causes ulceration of nasal septum and other tissues upon exposure as

well as reproductive and gastrointestinal effects. The use of Cr(III) in industrial and

commercial processes is preferred over Cr(VI) on the basis of comparison of the

toxicities. Chromium is used in industry because of its excellent wear, corrosion

resistance and attractive appearance [2, 3]. The main advantage of Cr(III) plating bath

in comparison with a Cr(VI)–bath is that Cr3+ ions are nontoxic and environmentally

benign [4]. However, it is almost impossible to deposit the Cr coating from a simple

aqueous Cr(III) solution due to a very stable [Cr(H2O)6]3+ complex [5]. According to the

94
published data [6] the slow deposition rate in Cr(III) chloride electrolyte is related to the

appearance of very stable 1–hydroxobridged oligomeric species of Cr(III). To

destabilize the strong hexaaqua chromium(III) complex, some of the complexing agents

(glycine, urea, dimethyl formamide, formic acid, acetate, sodium citrate, DL–

aspartic acid, etc) may be used [7–11]. Chromium plating from Cr(VI) solution is now

under scrutiny due to its toxicity and carcinogenicity; therefore, significant efforts have

been applied to the development of alternative process for chromium plating from

Cr(VI) solution [12]. The present work was important in terms of a Cr(VI)–free process,

using Cr(III)–glycine solution as an alternate bath. Therefore, in the present work the

aim was to compare the DC and PE–deposited chromium using a Cr(III)–glycine bath

with Cr(VI)–bath. The microstructure and corrosion behavior were analyzed in 3.5%

NaCl solution using potentiodynamic polarization and EIS.

5. 2 Experimental

5. 2. 1 Materials preparation

Chromium coatings were electrochemically deposited from Cr(VI)–bath

consisting of 250 g/L CrO3, 2.5 g/L H2SO4 and Cr(III)–bath consisting of 212 g/L

CrCl3·6H2O, 26 g/L NH4Cl, 36 g/L NaCl, 20 g/L B(OH)3, 75 g/L glycine and 200 ml

methanol. AR grade chemicals and double distilled water were used to prepare the

solution. The coatings were deposited on polished and electrocleaned substrate of mild

steel. The pH value of 2 ± 0.2 was maintained for Cr(III)–bath and stirred by mechanical

stirrer. Graphite and lead were used as the anode for Cr(III) and Cr(VI)–baths

respectively, mild–steel plates were used as the cathode. The samples obtained for mild

steel, DC and PE–deposited chromium from Cr(VI) and Cr(III) were represented by

95
(MS), Cr–(DCD)/MS from Cr(VI)–bath, Cr–(DCD)/MS from Cr(III)–bath, Cr–

(PED)/MS from Cr(VI)–bath, and Cr–(PED)/MS from Cr(III)–bath, respectively. Pulse

plating was done by using Dynatronix (USA) DPR20–10–5 Model. The pulse parameters

used are given in Table 5. 1 [13]. The formula used in pulse plating is given below

ON time

% Duty cycle = X 100 ― (5.1)

ON time + OFF time

ON time

Average current = X Peak current ― (5.2)

Total time

Average current

Peak current = X 100 ― (5.3)

Duty cycle

The surface morphologies of the electrodeposits were characterized by SEM, and grain

size and texture were assessed by X– ray diffraction (XRD) technique.

5. 2. 2 Corrosion resistance measurements

5. 2. 2 (A) Cell apparatus

Corrosion measurements were performed in a three electrode cell with the volume

of 150 ml. The samples (MS), Cr–(DCD)/MS from Cr(VI)–bath, Cr–(DCD)/MS from

Cr(III)–bath, Cr–(PED)/MS from Cr(VI)–bath, and Cr–(PED)/MS from Cr(III)–bath

were used as the working electrodes (WE). A platinum foil and a saturated calomel

electrode (SCE) were used as the auxiliary electrode and reference electrode respectively.

96
The electrodes were connected to a potentiostat (PARSTAT 2273). The corrosion

resistance parameters were obtained with inbuilt software package (powerCORR). All

potentials in this work are referred to SCE.

5. 2. 2 (B) Electrochemical procedures

Corrosion behavior was examined in neutral 3.5% NaCl solution at 30 ± 1°C.

Potentiodynamic polarization curves were measured for all the samples between 0.9 and

0.2 V at a scan rate of 5 mV/s. Impedance spectra were conducted at open circuit

potential over a frequency range from 105 Hz to 10–2 Hz. The amplitude of potential

modulation was 5 mV. All the recorded impedance spectra were shown as Bode and

Nyquist diagrams.

5. 3 Results and discussion

5. 3. 1 Microstructural characteristics

The morphology of chromium deposits on mild–steel substrate was examined

under a scanning electron microscopy (SEM). Figure 5. 1A, B and 5. 2A, B, are the

surface structure of pure chromium from Cr(III) and Cr(VI)–baths. Figure 5.1A and B

are the SEM images of DC electrodeposited chromium at 35 Adm–2 for 30 min from

Cr(III) and Cr(VI)–baths, respectively. Both deposits have a small nodular deposit with

the particle size of about 2–2.5 µm with micro cracks. The micro cracks formed during

electrodeposition is due to the adsorbed hydrogen gas. Similarly, Figure 5. 2A and B is

the SEM images of PE–deposited chromium at an average current density of 10.4 Adm–2

for Cr(III) both and 20 Adm–2 for Cr(VI)–bath in 30 min. Both the deposits have a very

small nodular size with the particle size of about 1–1.4 µm. In the PE deposition, the

peak current density is higher than average current density, this leads to a decreased

97
grain size. The decreased porosity and denser packed surface are due to the desorption of

hydrogen during the off time of pulse cycle [14].

5. 3. 2 X–ray diffraction analysis

Chromium may be electrodeposited in various phases (α–, β– and γ–phase) [15].

The phases obtained are dependent on plating conditions. α–Chromium [16,17] is the

most predominant and stable phases; however, β–chromium only deposits under certain

conditions and converts eventually to α–chromium over time or with annealing. Figure

5. 3 shows the X–ray diffraction pattern of the chromium deposited from hexavalent and

trivalent chromium baths. The α–Cr(1 1 0) peak was obtained at 2θ = 44.6992 and 2θ =

44.2276 from trivalent and hexavalent chromium baths respectively. Similarly,

α–Cr(2 0 0) peaks were obtained at 2θ = 65.0869° and 2θ = 64.7460° for trivalent and

hexavalent chromium baths, respectively. Intensity of α–Cr(1 1 0) peak is higher in

trivalent, whereas α–Cr(2 0 0) peak is higher in hexavalent chromium. The α–Cr(1 1 0)

plane is having higher intensity in BCC structure from trivalent bath. Therefore, the

α–Cr deposits tend to grow with the plane of highest intensity. In contrast to α–Cr(1 1 0),

the preferred orientation in hexavalent chromium bath is α–Cr(2 0 0). The crystallite

sizes of Cr coatings were calculated from Scherer’s equation. The values of texture

coefficient TC[ø] and grain size are tabulated in Table 4. 2A and B.

0.94 X λ

D= ― (5.4)

β cosθ

where D is the grain size, β is the full width at half maximum (FWHM) of the

diffraction peak, λ is the wavelength of the incidental X–ray (1.54 Å), and θ is the

98
diffraction angle. Based on Eq. (1), the average crystallite sizes were found to be 71.33

nm for α–Cr(1 1 0) and 32.08 nm for α–Cr(2 0 0) in trivalent chromium bath. Similarly,

the average crystallite sizes were found to be 11.86 nm for α–Cr(1 1 0) and 10.67 nm for

α–Cr(2 0 0) in hexavalent chromium bath respectively. The preferred growth orientation

was determined using texture coefficient TChkl. This factor can be calculated by using

TChkl = I/I0 1/N{Σ[I/I0]} ― (5.5)

where TChkl is the texture coefficient of the plane, I hkl is the measured intensity of the

(hkl) plane, I0(hkl) corresponds to the recorded intensity in the JCPDS data file and N is

the number of preferred directions of the growth. The TC110 was found to be 65.08 and

92.89 from trivalent and hexavalent chromium baths.

5. 3. 3 Corrosion resistance studies

5. 3. 3 (A) Potentiodynamic polarization tests

Figure 5. 4 shows potentiodynamic polarization curves for electrodeposited

chromium in 3.5% NaCl solution. All the curves display the active passive behavior

between 0.9 and 0.2 V. It indicates that the mechanism of activity and passivation is

similar in essence for all electrodeposits. The current density increases with the

increasing potential at the activation region. And then the electrode passivates and

displays high stability, as characterized by the low and steady value of passive current

density. The corrosion current density (Icorr) and corrosion potential (Ecorr) are calculated

from the intercept of the Tafel slopes. The corrosion rate (CR) in mils per year was

estimated from the polarization curves, and is given in Table 5. 3. Among all the

samples, Cr–(PED)/MS from Cr(VI)–bath and Cr–(PED)/MS from Cr(III)–bath exhibit

the lowest values of Icorr and CR than that of samples Cr–(DCD)/MS and mild steel

99
(MS). From the values, sample Cr–(PED)/MS from Cr(III)–bath has the smaller

differences of I corr and CR than that of Cr–(PED)/MS from Cr(VI)–bath. Therefore,

PE–deposited chromium from Cr(III)–bath is suitable to replace carcinogenic, non

eco–friendly Cr(VI)–bath, which is attributed to the compact microstructure.

5. 3. 3(B) Electrochemical impedance spectroscopy measurements

The measured impedance spectra for the electrodeposits in 3.5% NaCl solution

are shown as Bode and Nyquist diagrams in Figure 5. 5B and 5. 5C. The impedance plots

exhibit depressed semicircles. The equivalent circuit as shown in Figure 5. 6 is used to fit

the corrosion resistance parameters. Rct and Cdl represent the charge–transfer resistance

and double layer capacitance, respectively. The fitted impedance spectra are in good

agreement with the impedance spectra recorded during the measurements as shown in

Figure 5. 5. The calculated values of circuit elements are listed in Table 5. 4. It is found

that all fitted corrosion parameters of the electrodeposits vary with the changes of the

microstructure. The corrosion resistance (R ct) of Cr–(PED)/MS from Cr(III)–bath and

Cr–(PED)/MS from Cr(VI)–bath have higher values than that of DC–deposited

chromium and mild steel (MS). The increased R ct values and decreased Cdl values for Cr

deposits clearly confirm the better corrosion resistance of these Cr–(PED)/MS from

Cr(III)–bath than that of DC deposited and bare mild steel as observed from the high

frequency region of the impedance spectra.

5. 3. 3 (C) Porosity of DC and PE–deposited systems

It is possible to determine the porosity of a coating using an electrochemical

measurement technique that determines the ratio of the current density through the pores

and the coating [18]. Using the facts that when determining the porosity, in most cases

100
the cathodic current is negligible, and the current density is inversely proportional to the

polarization resistance. Elsener et al. [19] estimated the porosity of TiN–coated mild steel

from the shift of the corrosion potential caused by the presence of the coating (ΔEcorr)

and from the individual polarization resistance of the coatings (Rp) and the substrate

materials (Rp,s) as given below

P = (Rp,s/Rp) X 10 –|ΔEcorr|/ba ―(5.6)

Using this equation, and the values of (Rp,s) (63 Ω cm2) and ba (0.483 V/decade)

determined from the separate measurement on an uncoated mild–steel (MS) substrate

in 3.5% NaCl solution, we calculated the porosity of DCD and PED deposited Cr from

Cr(VI) and Cr(III) baths. For this purpose, the Ecorr of the mild steel was determined to

be 702 mV Vs SCE. The coating porosity determined in this way is given in Table 5. 4.

From these values, Cr–(PED)/MS from Cr(III)–bath (P = 0.013%) differs only 1.5

times of Cr–(PED)/MS from Cr(VI)–bath (P = 0.00813%). Therefore, PE–deposited

chromium from the Cr(III)–bath is having better corrosion resistance and a good choice

to replace conventional hexavalent chromium plating process.

5. 4 Conclusions

Eco–friendly Cr(III)–glycine–based electrolyte was developed from which

microstructure and electrochemical corrosion behavior of DCD and PED Cr coating were

studied and compared to the microstructure and electrochemical behavior of Cr coating

from Cr(VI)–bath.

1. Using potentiodynamic test, the current density of DC and PE deposited, uncoated

substrate and differences in their corrosion potentials (E corr) were determined. In all the

cases, the (Ecorr) shifted to a more positive potential when the coatings were applied.

101
The PE–deposited substrate had a better corrosion resistance than DC and mild–steel

substrate. Corrosion properties of PE–deposited chromium from Cr(III)–bath differ only

1.5 times (higher positive potential, lower current density (I corr) and lower corrosion

rate than that of PE deposited chromium from Cr(VI)–bath.

2. EIS data for DC and PE–deposited chromium from Cr(III) and Cr(VI)–baths showed

that the values of charge–transfer resistance (Rct) and double layer capacitance (Cdl) of

PE deposited from Cr(III) bath were not much different from those of Cr(VI)–bath.

3. The porosities of both DC and PE–deposited chromium on the mild–steel substrate

from Cr(III) and Cr(VI)–baths were quantitatively estimated. Among the porosity values,

PE deposited chromium from Cr(III)–bath differs only 1.5 times. Therefore, the structure

and corrosion properties of PE–deposited chromium from Cr(III)–bath are comparable to

those of Cr(VI)–bath. So developed trivalent chromium coatings are very good choice to

replace toxic, carcinogenic Cr(VI)–bath by Cr(III)–bath.

102
References

1. A. Lozano–Morales, R. P. Renz, J. J. Fortman, E. J. Taylor, ECS Trans. 6 (2007) 51.

2. Z. Zeng, J. Zhang, Surf. Coat. Technol. 202 (2008) 2725.

3. K. S. Nam, K. H. Lee, Sh. Ch. Kwon, D.Y. Lee, Y. S. Song, Mater. Lett. 58 (2004)

3540.

4. S. C. Kwon, H. J. Lee, J. K. Kim, E. Byon, G. Collins, K. Short, Surf. Coat. Technol.

201 (2007) 6601.

5. B. Li, A. Lin, F. Gan, Surf. Coat. Technol. 201 (2006) 2578.

6. S. K. Ibrahim, D. T. Gawne, A. Watson, Trans. Inst. Metal Finish. 76 (1998) 156.

7. S. Surviliene, V. Jasulaitiene, O. Nivinskiene, A. Cesuniene, Appl. Surface

Sci. 253 (2007) 6738.

8. J. Y. Hwang, Plat. Surf. Finish. 78 (1991) 118.

9. M. El–Sharif, S. Ma, C. U. Chisholm, Trans. Inst. Metal Finish, 77 (1999) 139.

10. Y. B. Song, D. T. Chin, Electrochim. Acta 48 (2002) 349.

11. N. V. Mandich, Plat. Surf. Finish. 84 (1997) 108.

12. M. El–Sharif, C. U. Chisholm, Trans. Inst. Metal Finish. 75 (1997) 208.

13. G. Devaraj, S. K. Seshadri, Plat. Surf. Finish. 83 (1996) 62.

14. K. Haug, T. Jenkins, J. Phys. Chem. B 104 (2000) 10017.

15. H. Dasarathy, C. Riley, H. D. Coble, J. Electrochem. Soc. 141 (1994) 1773.

16. D. Sherwood, B. Emmanuel, Cryst. Growth Des. 6 (2006) 1415.

17. H. Okada, T. Ishida, Nature 187 (1960) 496.

18. W. Tato, D. Landolt, J. Electrochem. Soc. 145 (1998) 4173.

19. B. Elsener, A. Rota, H. Bohni, Mater. Sci. Forum 29 (1989) 44.

103
Table 5. 1 Pulse parameter used for pulse electrodeposition of Cr from Cr(III)-glycine

and Cr(VI) electrolyte.

Duty Pulse frequency and pulse on–off Current density (Adm–2)

cycle times (ms)

(%) 10 Hz 25 Hz 50 Hz 100 Hz Cr(III)–bath Cr(VI)–bath

Peak Average Peak Average

10 10–90 4–36 2–18 1–9 104 10.4 200 20

20 20–80 8–32 4–16 2–8 52 10.4 100 20

40 40–60 16–24 8–12 4–6 26 10.4 50 20

80 80–20 32–8 16–4 8–2 13 10.4 25 20

Table 5. 2 (A and B) Texture coefficient and crystallite size of Cr from Cr(III)-glycine

and Cr(VI) electrolyte obtained from XRD pattern.

hkl 2θ D[Å] I/I0 Tc[ø] Crystallite

size(nm)

α–Cr(110) 44.6992 2.0274 1 65.08 71.33

α–Cr(200) 65.0869 1.4319 0.5365 34.91 32.08

α–Cr(110) 44.2276 2.0479 0.3825 7.10 11.86

α–Cr(200) 64.7460 1.4386 5 92.89 10.67

104
 Table 5. 3 Corrosion resistance parameters of Cr from Cr(III)-glycine and Cr(VI)

electrolyte obtained from polarization studies in 3.5% NaCl electrolyte.

Sample Ecorr VS ba bc Icorr (A/cm2) Corrosion

SCE (V/decade) (V/decade) rate (mpy)

(mv)

MS panel –0.702 0.483 –0.043 8.47 X 10–5 3.91 X 101

Cr on MS (DCD) Cr(III)– –0.629 0.150 –0.225 5.01 X 10–5 1.56 X 101

bath

Cr on MS (PED) Cr(III)– –0.588 0.182 –0.421 2.70 X 10–5 8.43

bath

Cr on MS (DCD) Cr(VI)– –0.619 0.555 –0.302 3.41 X 10–5 1.04 X 101

bath

Cr on MS (PED) Cr(VI)– –0.556 0.112 –0.495 4.8 X 10–6 1.50

bath

105
 Table 5. 4 Corrosion resistance parameters and porosity obtained for Cr from Cr(III)-

glycine and Cr(VI) electrolyte from impedance measurements by Nyquist plots.

Sample OCP (V) Rct(Ω*cm2) Cdl(F/cm2) Porosity

(%)

MS panel –0.511 63 8.75 X 10–4

Cr on MS (DCD) Cr(III)–bath –0.580 111.5 6.78 X 10–2 0.399

Cr on MS (PED) Cr(III)–bath –0.582 2807 5.44 X 10–4 0.013

Cr on MS (DCD) Cr(VI)–bath –0.597 116.9 12.2 X 10–2 0.362

Cr on MS (PED) Cr(VI)–bath –0.543 3860 7.03 X 10–4 0.0081

106
Figure 5.1 (A and B) SEM surface morphology of DC–deposited chromium at

35 Adm–2 in 30 min from Cr(III)-glycine and Cr(VI)–baths.

Figure 5. 2 (A and B) SEM surface morphology of PE–deposited chromium at an

average current density was 10.4 Adm–2 and 20 Adm–2 from Cr(III)-glycine and

Cr(VI)–baths in 30 min.

107
Figure 5. 3 XRD pattern of chromium coatings from Cr(III)-glycine and Cr(VI)–baths.

108
Figure 5. 4 Polarization studies of MS panel, Cr on MS (DCD) and Cr on MS (PED)

from Cr(III)-glycine and Cr(VI)–baths in 3.5% NaCl electrolyte.

109
Figure 5. 5 Impedance spectra of MS panel, Cr on MS (DCD) and Cr on MS (PED) from

Cr(III)-glycine and Cr(VI)–baths: (A) Bode plot; (B) Nyquist plot.

110
Figure 5. 6 Equivalent circuit diagram of for electrodeposited chromium in 3.5% NaCl

electrolyte.

111
CHAPTER VI
 PULSED ELECTRODEPOSITION OF MICROCRYSTALLINE CHROMIUM

FROM TRIVALENT Cr–DMF BATH

6.1 Introduction

Electrodeposition of chromium is carried out in aqueous solution containing

Cr(III) ions as a metal component for anticorrosion surface modification of suitable

substrate using square–wave pulsed electrolysis. Shunsuke Yagi et al. [1] recently

reported formation of Fe–Cr alloy through pulsed electrodeposition. Pulse plating can

be defined as current–interrupted electroplating. Figure 6. 1 shows a typical

oscilloscope trace of a square–wave attainable with existing pulse equipment.

However, the figure does not show a pure square–wave because there is a gradual

curvature to both the ascending and descending current flows. The curvature on the

rising flow is intentionally induced electronically to avoid an instantaneous rise and

current overshoot. This type of pulse process is suggested as a means of obtaining

smooth and bright deposits. If, for example, the duty cycle flows for 40 ms and is

interrupted for 60 ms between periods of flow, there is greater opportunity for

replenishment of the cathode film through diffusion and convection. Cathode

polarization is increased, and cathode efficiency may be increased. Consequently, a

high current density can be used and a desired thickness can be deposited in shorter

time, even though the current is not flowing continuously. In pulse electrolysis,

selection of the electrolyte, peak current density, on–time, and off–time determines the

physical characteristics of the deposits [2]. Chromium plating is widely applied in

various fields such as aerospace, automotive, and general engineering industries, since

112
chromium plating has excellent abrasion resistance, corrosion resistance [3], and

hardness. Chromium was first deposited from hexavalent chromic acid solution by

Geuther 150 years ago [4]. Later, plating solutions based on chromic acid were

investigated and produced on a commercial basis [5, 6]. Improvement in surface

appearance and mechanical properties were reported using normal pulsed electrolysis

with regard to Cr [7] and Cr alloy plating [8, 9]. However, chromium plating from

Cr(VI) solution is now under pressure due to its toxicity and carcinogenicity; therefore,

significant efforts have been applied to the development of alternative process for

chromium plating from Cr(VI) solution [10, 11]. The present work i s also important

in terms of a Cr(VI)–free process, using Cr(III) solution as an alternate bath.

6. 2 Experimental

6. 2. 1 Materials preparation

Electrodeposited chromium was prepared from a dimethylformamide bath

consisting of 212 gL–1, CrCl3.6H 2O, 26 gL–1, NH4Cl, 36 gL–1 NaCl, 20 gL–1 B(OH)3,

and 189.4 gL–1 (200 mLL–1) dimethylformamide. AR grade chemicals and distilled water

were used to prepare the solution. Electrodeposits with thickness of about 7 µm were

obtained at average current density of 15 Adm–2 for 10 min. The solution was

maintained at pH 2 ± 0.2 and temperature 30±1°C, and stirred by mechanical stirrer.

Graphite and brass plates were used as the anode and cathode respectively. The samples

obtained for mild steel, DC–deposited chromium, and PE–deposited chromium are

represented by (MS), Cr–(DCD)/MS, and Cr–(PED)/MS respectively. Pulse plating was

done by using Dynatronix (USA) model DPR 20–5–10. Surface morphologies of

electrodeposits were characterized by scanning electron microscopy (SEM) employing a

113
Hitachi 3000H. Crystallite size was assessed by X–ray diffraction (XRD) technique using

a Phillips diffractometer with CuKα (2.2 kW maximum) as source. Crystallite size was

calculated using Debye–Sherrer formula.

6. 2. 2 Corrosion resistance measurements

6. 2. 2(A) Cell apparatus

Corrosion measurements were performed in a three electrode cell with volume of

150 mL. (MS), Cr–(DCD)/MS, and Cr–(PED)/MS samples were used as the working

electrode (WE). Platinum foil and saturated calomel electrode (SCE) were used as the

auxiliary and reference electrode, respectively. The electrodes were connected to a

potentiostat (PARSTAT 2273). Corrosion resistance parameters were obtained with

built–in software package (powerCORR). All potentials in this work are referred to

SCE.

6. 2. 2 (B) Electrochemical procedures

Corrosion resistance behavior was examined in neutral 3.5% NaCl solution at

30±1°C. Potentiodynamic polarization curves were measured for all the samples

between – 0.8 and –0.2 V at scan rate of 5 mVs–1 . Impedance spectra were conducted at

open circuit potential over a frequency range from 105 to 10–1 Hz. The amplitude of

potential modulation was 5 mV. All the recorded impedance spectra were shown as

Bode diagram.

6. 3 Results and discussion

6. 3. 1 Effect of duty cycle on thickness, current efficiency, and hardness of Cr

deposits

Figure 6. 2 (A) shows the effect of pulse duty cycle on the thickness of Cr deposits

114
obtained for various frequencies at average current density of 15 Adm–2. From this

figure, it is observed that the thickness of the chromium deposit increases with

increasing pulse duty cycle. As the duty cycle increases, current on–time increases and

off–time decreases. At lower duty cycle, the peak current is flowing for less time and so

the overall amount of deposition is less than for higher duty cycle. Also at very high duty

cycle and high frequencies the pulse current is very low, and so correspondingly

reduced thickness is obtained. The maximum thickness of 7.3µm was obtained at 40%

duty cycle for lower pulse frequencies (10 and 25 Hz) at current density of 15 Adm–2

[12].

Figure 6. 2 (B) shows the effect of pulse duty cycle on current efficiency of Cr

deposits obtained for various frequencies at its average current density of 15 Adm–2.

The maximum current efficiency is obtained at 40% duty cycle at lower pulse

frequencies (25 and 50 Hz). As pulse frequency increases, the pulses are very short

and they produce very thin pulse diffusion layers. Diffusion of metal ions from the bulk

of electrolyte to the electrode surface depends on gradient of metal ions concentration.

So at 40% duty cycle at lower pulse frequencies enhancement of migration of ions

increases the nucleation rate, uniformity of deposit [13], and deposition rate, and

hence current efficiency is increased.

Figure 6. 2 (C) shows the effect of pulse duty cycle on the hardness of Cr

deposits obtained for various frequencies at average current density of 15 Adm–2. The

hardness of the Cr deposit was found to increase with increase of duty cycle [14]. A

maximum hardness value was obtained at 40% duty cycle at low frequencies (10 and

25 Hz) when the average current density was 15 Adm–2 because at low pulse duty cycle

115
a high peak current is passed, this produces powdery or burnt deposits with poor

adhesion and considerable porosity. This porosity leads to a decrease in hardness of the

deposit. However, at 40% duty cycle, the peak current is lower due to the formation of a

smooth fine–grained deposit. Improved surface coverage with denser built up of grains

is to be expected [2]. At higher frequencies (100 Hz) the pulse current appears to be

almost equal to that of DC deposition because there is no sufficient relaxation time for

reestablishment of equilibrium between the ions in the bulk solution and the electrode

surface, which leads to the formation of porous deposit. So hardness of the deposit

decreases beyond 40% duty cycle.

6. 3. 2 Microstructural characteristics

Morphology of chromium deposits on brass substrate was examined under

scanning electron microscopy (SEM). Figure 6. 3(A) shows a SEM photograph of

the chromium deposit obtained after 10 min with 40% duty cycle at average

current density of 15 Adm–2. The deposits exhibited columnar [15] nodular structures

with nodular size ranging from 3 to 8 µm. Deposits were brighter and smoother with

microcracks. The decreased porosity and denser packed surface are due to the

desorption of hydrogen during the off–time of the pulse cycle.

The XRD patterns of electrodeposited chromium are shown in Figure 6. 3 (B).

All the electrodeposits consist of grains with weak Cr(110) plane and strong Cu(200),

Cu(220) plane due to lower thickness (less than 16 µm) of chromium coatings.

Crystallite size of Cr(110) at 10%, 20%, and 40% duty cycle are 31.9, 51.1, and 63.9

nm, respectively. When duty cycle increases, on–time increases and off–time

decreases and this leads to insufficient supply of reacting species and hence reduced

116
nucleation rate and increased grain size during electrodeposition. It has been reported

[16] that coarse–grained electrodeposition due to concentration depletion occurred as

on–time increased. A large grain size therefore results from the evolution of more

hydrogen at the cathode interface [17].

6. 3. 3 Corrosion resistance studies

6. 3. 3 (A) Potentiodynamic polarization tests

Figure 6. 4 (A) shows potentiodynamic polarization curves for electrodeposited

chromium in 3.5% NaCl solution. All the curves display active–passive behavior

between – 0.8 and –0.2 V. This indicates that the mechanism of activity and passivation

is similar in essence for all electrodeposits. The current density increases with increasing

potential at the activation region, then the electrode passivates and displays high

stability, as characterized by a low and steady value of passive current density. The

corrosion current density (Icorr) and corrosion potential (Ecorr) are calculated from the

intercept of the Tafel slops. The corrosion rate (CR) in mils per year was estimated from

the polarization curves, and is tabulated in Table 6.1. Among all the samples Cr–

(PED)/MS exhibits the lowest values of Icorr and CR than that of samples Cr–(DCD)/MS

and mild steel (MS). Therefore, sample Cr–(PED)/MS exhibits the best corrosion

resistance [3], which is attributed to the compact microstructure.

6. 3. 3 (B) Electrochemical impedance spectroscopy measurements

The measured impedance spectra for the electrodeposits in 3.5% NaCl solution

are shown as Bode diagrams in Figure. 6. 4 (B). The equivalent circuit (Figure 6. 5) is

used to fit the corrosion resistance parameters. Rct and Cdl represent the charge transfer

resistance and double layer capacitance respectively. The fitted impedance spectra are in

117
good agreement with the impedance spectra recorded during the measurements, as shown

in Figure 6. 4. The calculated values of circuit elements are listed in Table 6. 1. It can

be found that all fitted corrosion parameters of the electrodeposits vary with the changes

of the microstructure. The corrosion resistance (Rct) of PED chromium (C) is greater than

that of other samples. The increased Rct values and decreased Cdl values for Cr deposits

clearly confirm the better corrosion resistance of these PED and DC deposit compared

with bare mild–steel substrates.

6. 3. 3 (C) Porosity of Cr–(DCD) and Cr–(PED) systems

Detailed procedure for calculation of porosity of electrodeposits are given in

chapter 5, section 5. 3. 3 (C) [18, 19].

P = (Rp,s/Rp) X 10 –|ΔEcorr|/ba

Using this equation, and the values of Rp,s = 263 Ω cm2 and ba = 0.483 V

decade–1) determined from separate measurement on an uncoated mild steel (MS)

substrate in 3.5% NaCl solution, we estimated the porosity of the Cr–(DCD) and Cr–

(PED) systems. For this purpose Ecorr of the mild steel was determined to be –702 mV Vs

SCE. The coating porosity determined in this way was approximately 0.2724% for the

Cr(DCD) system and 0. 0256 % for the Cr (PED) system in 3.5% NaCl solution. From

this value the PED Cr coating system had ten times lowers porosity than the DCD Cr

system. Therefore PED Cr has better corrosion resistance than the DCD Cr coating

system.

6. 4 Conclusions

The microstructure and corrosion behavior of electrodeposited chromium

prepared at different peak current densities, duty cycles, and frequency were studied.

118
The following conclusion can be drawn: Grain size increases with decreasing peak

current density during electrodeposition. The maximum thickness, current efficiency,

and hardness of electrodeposited chromium are obtained at 40% duty cycle. All the

chromium samples exhibit active–passive polarization characteristics. Electrodeposited

chromium prepared at 40% duty cycle exhibited the best corrosion resistance. The

corrosion behavior of electrodeposited chromium in 3.5% NaCl solution is well described

by the equivalent system of charge transfer resistance (Rct) and double layer capacitance

(Cdl).

119
References

1. S. Yagi, K. Murase, T. Hirato, Y. Awakura, J. Electrochem. Soc. 154 (2007) D304.

2. J . C . Puippe, F. Leaman, (1986) Theory and practice of pulse plating, 1st edn.

American Electroplaters and Surface Finishers Society, Orland, FL, 247 pp

3. J . H . Qui, Mater. Sci. Forum 211 (2003) 437.

4. M . Kishi, Hyomen Gijutsu 37 (1986) 159

5. M . Selvam, Met. Finish 81(1983) 7.

6. T . Morikawa, S. Eguchi, Hyomen Gijutsu 37 (1986) 341.

7. J . C . Saiddington, Plat. Surf. Finish. 65 (1978) 45.

8. T . A . Eckler, B . A . Manty, P. L. McDaniel, Plat. Surf. Finish. 67 (1980) 60.

9. M . H . Gelchinski, L. Gal–Or, J. Yahalom, J. Electrochem. Soc. 129 (1982) 2433.

10. T . Hirato, T. Terabataka, E. Watanabe, Y. Awakura, Hyomen Gijutsu 47 (1996)

245.

11. M . El–Sharif, Trans. Inst. Metal Finish.75 (1997) 143.

12. G . Devaraj, S. K. Seshadri, Plat. Surf. Finish. 83 (1996) 62.

13. T . Pearson, J. K. Dennis, J. Appl. Electrochem. 20 (1990) 196.

14. T . Pearson, J. K. Dennis JK, Surf. Coat. Technol. 42 (1990) 69.

15. Y . B . Song, D. T. Chin, Electrochim. Acta 48 (2002) 349.

16. E . Toth–Kadar, I. Bakonyi, L. Pogany, A. Cziraki, Surf. Coat. Technol. 88 (1996)

57.

17. F . Ebrahimi, Z. Ahmed, J. Appl. Electrochem. 33 (2003) 733.

18. W . Tato, D. Landolt, J. Electrochem. Soc 145 (1998) 4173.

19. B . Elsener, A. Rota, H. Bohni, Mater. Sci. Forum 29 (1989) 44.

120
 Table 6. 1 Corrosion parameters obtained from polarization studies and impedance

measurements of electrodeposited Cr from Cr(III)-DMF bath by Bode and Nyquist

plots in 3.5% NaCl solution

Sample Ecorr vs ba bc Icorr Corrosion OCP (V) Rct Cdl

SCE (mV) (V/dec) (V/dec) (A/cm2) rate (mpy) (cm2) (F/cm2)

MS panel –0.702 0.483 –0.043 8.5X101 3.9X101 –0.511 263 0.060

Cr on MS (DC) –0.620 0.279 –0.157 8.3X101 2.6X101 –0.545 654 0.049

Cr on MS (PC) –0.589 0.145 –0.181 1.4 X101 4.6 –0.537 1006 0.014

121
 Figure 6. 1 Square–wave pulsed current with curved flow

A B

122
 C

Figure 6. 2 A, B and C Effect of duty cycle on: A thickness, B current efficiency, and C

hardness of electrodeposited Cr from Cr(III)-DMF bath.

123
 A

Figure 6. 3 (A) Scanning electron microscopy (SEM) of electrodeposited Cr from

Cr(III)-DMF bath at 40% duty cycle at peak current density of 3.7 Adm–2 .

124
 B

Figure 6. 3 (B) XRD patterns of electrodeposited Cr from Cr(III)-DMF bath prepared at

different duty cycles.

125
A

126
 B

Figure 6. 4 (A) Polarization curve of electrodeposited chromium from Cr(III)−DMF bath

in 3.5% NaCl solution. Impedance spectra for electrodeposited chromium in 3.5% NaCl

solution. (B) Bode diagram

Figure 6. 5 Equivalent circuit diagram of impedance spectra for electrodeposited Cr from

Cr(III)−DMF bath in 3.5% NaCl solution.

127
CHAPTER VII
 STRUCTURE, CURRENT EFFICIENCY, AND CORROSION

PROPERTIES OF BRUSH ELECTRODEPOSITED (BED) Cr

FROM Cr(III)DIMETHYL FORMAMIDE (DMF) BATH

7. 1 Introduction

Chromium is used in industry because of its excellent wear, corrosion resistance,

and attractive appearance [1, 2]. The main advantages of Cr(III) electroplating bath in

comparison with a Cr(VI) bath is that Cr3+ ions are non–toxic and environmentally

benign [3]. However, it is almost impossible to deposit the Cr coating from a

simple aqueous Cr(III) solution due to a very stable [Cr(H2O)6]3+ complex [4].

According to the published data [5], the slow deposition rate in Cr(III) chloride

electrolyte is related to the appearance of very stable µ–hydroxo–bridged oligomeric

species of Cr(III). To destabilize the strong hexaaqua chromium(III) complex, some

of the complexing agents [dimethylformamide (DMF), urea, formic acid, acetate,

glycine sodium citrate, DL–aspartic acid, etc.] may be used [6–10]. Chromium plating

from Cr(VI) solution is now under pressure due to its toxicity and carcinogenicity;

therefore, significant efforts have been applied to the development of alternative

process for chromium plating from Cr(VI)–bath [11–13]. LDC–HTC [14] chrome is a

first trivalent chrome that produces longer lasting deposits, increased solution life,

improves parts wearability and is environmentally friendly. LDC–HTC chrome does not

contain or produce hexavalent chrome. This reduces costs and difficulties associated

with the disposal of hexavalent waste. This study is important in terms of a Cr(VI)–free

process, using Cr(III)DMF–bath as an alternate bath. Therefore, the aim of this study

128
was to develop brush electrodeposition (BED) Cr using a Cr(III)DMF–bath. The

corrosion behavior was analyzed in 3.5% NaCl solution using potentiodynamic

polarization and electrochemical impedance spectroscopy.

7. 2 Experimental

7. 2. 1 Electrolyte and BED

BED Cr was prepared from a DMF bath consisting of 212 gL–1 CrCl3.

6H2O, 26 gL–1 NH4Cl, 36 gL–1 NaCl, 40 gL–1 B(OH)3, and 200 ml of DMF. AR grade

chemicals and distilled water were used to prepare the solution. The effect of current

density and time on thickness and current efficiency were studied. The pH of these

solutions was adjusted to 2±0.2 by adding HCl/KOH. BED equipment includes power

packs, solutions and plating tools, anode covers, and auxiliary equipment.

Microprocessor controlled selectron power pack Model 150A–40V was used to

transform AC current to DC current. The schematic of the brush plating system is given

in Figure 7. 1. The power packs have two leads, one is connected to the plating tool and

the other is connected to the work piece to be electrodeposited. The anode is covered with

an absorbent material, which holds the solution. The operator dips the plating tool in the

solution and then brushes it against the surface of the work piece that is to be finished.

When the anode touches the work surface a circuit is formed and deposit is produced.

The brush deposits with the thickness of about 15 µm were obtained at current density of

24 Adm–2 in 20 min. Mild steel (MS) and BED Cr were represented by (MS) and Cr–

(brush)/MS.

129
7. 2. 2 Corrosion resistance measurements

7. 2. 2(A) Cell apparatus

Corrosion measurements were performed in a three electrode cell with the volume

of 150 ml. The samples (MS) and Cr–(brush)/MS were used as the working electrode. A

platinum foil and a saturated calomel electrode (SCE) were used as the auxiliary

electrode and reference electrode, respectively. The electrodes were connected to a

potentiostat (PARSTAT 2273). The corrosion parameters were obtained with in–built

software package (powerCORR). All potentials were measured with reference to SCE.

7. 2. 2 (B) Electrochemical corrosion stud ies

Corrosion behavior was examined in neutral 3.5% NaCl solution at 30±1°C.

Potentiodynamic polarization curves were measured for all the samples between – 0.8

and –0.2 V at a scan rate of 5 mVs–1. Impedance spectra were conducted at open circuit

potential over a frequency ranging from 105 to 10–2 Hz. The amplitude of potential

modulation was 5 mV. All the recorded impedance spectra were shown as Bode and

Nyquist diagrams.

7. 3 Results and discussion

7. 3. 1 Effect of current density and time on thickness and current efficiency of Cr

deposits

Figure 7. 2A shows the effect of current density on the thickness of Cr deposits

obtained for various time intervals. From this figure, it is observed that the thickness of

the chromium deposit increases with increasing current density and time. When current

density and time increased, the amount of current flowing is also increased and so

the overall amount of deposition is increased. The maximum thickness (15 µm) was

130
obtained at a current density of 32 Adm–2 in 20 min. From this figure, the optimum

current density and plating time can be fixed for appropriate thickness required. Figure

7. 2 B shows the effect of current density on the current efficiency of Cr deposits

obtained for various time intervals. From this figure, it is observed that the current

efficiencies (18) reach maximum at 24 Adm–2 in 20 min. In BED system, hydrogen

evolution is somewhat low; most of the current supplied is utilized for deposition of

chromium, so current efficiency increases with increasing time. When current density

increased beyond 24 Adm–2 burnt deposits occurred. Therefore, from Figure 7. 2 B, we

concluded that 24 Adm–2 is the optimum current density for obtaining maximum current

efficiency.

7. 3. 2 Microstructural characteristics

Morphology of BED Cr on MS substrate was examined under a scanning

electron microscopy (SEM). Figure 7.3 A is an SEM photograph of the brush plated

chromium after 20 min of deposition and at a current density of 24 Adm–2. The deposits

exhibited fine grained, smooth surface nodular structures with nodular size ranging from

1 to 2 µm. Deposits were brighter, smoother with microcracks. The smaller grains are

due to low hydrogen evolution during deposition process [15]. The surface topography

of brush plated Cr was studied using atomic force microscopy (AFM). An AFM picture

scanned over an area of 191 µm2 is shown in Figure 7. 3B. The advantage of AFM is its

capacity to probe minute details to the individual grains and intergrain regions. Figure

7. 3B shows the deposit consists of many small spherical particles may be conditioned

by progressive nucleation and very low hydrogen evolution during deposition

process. From the horizontal cross section analysis, the minimum and maximum

131
globule size was estimated to be in the range of 5 to 15 nm.

The XRD patterns of electrodeposited chromium are shown in Figure 7. 3 C. All

the electrodeposits consist of grains with strong Cr(110) plane and weak Cr(211) plane

for Cr coatings. Crystallite size is assessed by the Debye Scherrer equation. The values of

texture coefficient TC (ø) and grain size are tabulated in Table 7. 1. In addition, a

relatively strong (110) texture is associated with smaller grain size. The nucleation and

growth interface by hydrogen changes the surface energy and growth mechanism, and

then facilitates the formation of smaller grain size [15].

7. 3. 3 Corrosion resistance studies

7. 3. 3(A) Potentiodynamic polarization tests

Figure 7. 4A shows potentiodynamic polarization curves for BED Cr in 3.5%

NaCl solution. All the curves display the active passive behavior between –0.8 and

–0.2 V. It indicates that the mechanism of activity and passivation behavior for Cr–

(brush)/MS. The current density increases with increasing potential at the activation

region. And then the electrode passivates and displays high stability, as characterized by

low and steady value of passive current density. The corrosion current density (Icorr) and

corrosion potential (Ecorr) are calculated from the intercept of the Tafel slops. The

corrosion rate (CR) in mils per year was estimated from the polarization curves, and is

given in Table 7. 2. Among both the samples Cr–(brush)/MS exhibit the lowest

values of Icorr and CR than that of samples MS. Therefore, sample Cr–(brush)/MS

exhibits the best corrosion resistance, which is attributed to the compact

microstructure.

132
7. 3. 3 (B) Electrochemical impedance spectroscopy measurements

The measured impedance spectra for the electrodeposits in 3.5% NaCl solution

are shown as Bode and Nyquist diagrams in Figure 7. 4B, C. The impedance plots

exhibit depressed semicircles. The equivalent circuit as shown in Figure 4d is used to

fit the corrosion resistance parameters. Rct and Cdl represent the charge transfer

resistance and double layer capacitance, respectively. The fitted impedance spectra are

in good agreement with the impedance spectra recorded during the measurements as

shown in Figure 7. 4. The calculated values of circuit elements are listed in Table 7. 3. It

can be found that all fitted corrosion parameters of the electrodeposits vary with the

changes of the microstructure. The corrosion resistance (Rct) of Cr–(brush)/MS is

greater than that of MS samples. The increased Rct values and decreased Cdl values for

Cr–(brush)/MS deposits clearly confirm the better corrosion resistance than the MS

substrates. Also it is observed a more pronounced semicircular region in the case of Cr–

(brush)/MS has maximum corrosion resistance than MS as observed from the high–

frequency region of the impedance spectra.

7. 3. 3(C) Porosity of Cr–(brush)/MS systems

Detailed procedure for calculation of porosity of electrodeposits are given in

chapter 5, section 5. 3. 3 (C) [16-18].

P = (Rp,s/Rp) X 10 –|ΔEcorr|/ba

Using this equation, and the values of (Rp,s) (102.5 X cm2) and ba (0.483 V/decade)

determined from separate measurement on an uncoated MS substrate in 3.5% Nacl

solution, we estimated the porosity of the Cr–(brush)/MS systems. For this purpose, the

Ecorr of the MS was determined to be –702 mV Vs SCE. The coating porosity

133
determined in this way was approximately 0.162% for the Cr (brush)/MS in 3.5% Nacl

solution. From this value, BED Cr coating system is having lower porosity than that

reported in the literature [18]. Therefore, Cr–(brush)/MS have better corrosion resistance

system than that of MS substrate.

7. 4 Conclusions

(1) Cr(III)DMF–based electrolyte was developed from which effect of current density

and plating time were studied. Thickness and current efficiency is increased because of

lower hydrogen evolution. Thickness and current efficiency of Cr deposit reached

maximum of 15 μm at 32 Adm–2 and 18 μm at 24 Adm–2, respectively.

(2) Corrosion resistance measurements show appreciable increase in corrosion

resistance for BED Cr from Cr(III) DMF bath than that of the MS.

(3) SEM, AFM, and XRD images of BED Cr show fine grained nodular and

microcrystalline deposit.

134
References

1. Z . Zhixiang, Z. Junyan, Surf. Coat. Technol. 202 (2008) 2725

2. K . S . Nam, K. H. Lee, S. C. Kwon, D. Y. Lee, Y. S. Song, Mater. Lett. 58 (2004)

3540.

3. S . C . Kwon, H . J . Lee, J . K . Kim, B . Eungsun, C . George, S . Ken, Surf.

Coat. Technol. 201 (2007) 6601.

4. B . Li, A. Lin, F. Gan, Surf. Coat. Technol. 201 (2006) 2578.

5. S . K . Ibrahim, D. T. Gawne, A. Watson, Trans. Inst. Metal Finish. 76 (1998) 156.

6. S . Surviliene, V. Jasulaitiene, O. Nivinskiene, A. Cesuniene, Appl. Surf. Sci. 253

(2007) 6738.

7. J . Y . Hwang, Plat. Surf. Finish 78 (1991) 118.

8. M . El–Sharif, J. McDougall, C. U. Chisholm, Trans. Inst. Metal Finish, 77(4)

(1999) 139

9. Y . B . Song, D. T. Chin, Electrochim. Acta 48 (2002) 349.

10. N . V . Mandich, Plat. Surf. Finish. 84 (1997) 108.

11. M . El–Sharif, C. U. Chisholm, Trans. Inst. Metal Finish. 75 (1997) 208.

12. J . J . B . Ward, I. R. A. Christie, Trans. Inst. Metal Finish. 49 (1971) 148.

13. B . Robert, AES 10th plating in the electronics industry symposium, San

Francisco Hilton, San Francisco, CA, 1–2 February 1983, pp 199–205

14. www.ldcbrushplat.com

15. K . Haug, T. Jenkins, J. Phys. Chem. B 104 (2000) 10017.

16. W . Tato, D. Landolt, J. Electrochem. Soc. 145 (1998) 4173.

135
17. B . Elsener, A. Rota, H. Bohni, Mater. Sci. Forum 29 (1989) 44.

18. D . K . Merl, P . Panjan, M . Cekada, M . Macek, Electrochim. Acta 49 (2004)

1527.

136
 Table 7. 1 Texture coefficient and crystallite size of brush electrodeposited Cr from

Cr(III)-DMF bath

Hkl 2 D[Å] I/IO TC [ø] Grain size

(nm)

Cr(110) 44.6230 2.0306 1 71.65 47.4

Cr(211) 82.3499 1.1700 0.3956 28.34 47.5

Table 7. 2 Corrosion resistance parameters obtained for electrodeposited Cr from

Cr(III)−DMF bath from polarization studies in 3.5% NaCl solution

Sample Ecorr vs ba (V/dec) bc (V/dec) Icorr (A/cm2) Corrosion rate

(SCE/mV) (mpy)

MS panel –0.702 0.388 –0.056 2.5X102 7.6X101

Cr–(brush)/MS –0.587 0.214 –0.214 5.6X101 1.7X101

Table 7. 3 Corrosion resistance parameters obtained fo r electrodeposited Cr from

Cr(III)−DMF bath from impedance measurements by Bode and Nyquist plots

Sample OCP(V) Rct ( cm2) Cdl (F/cm2)

MS panel –0.547 102 163.4

Cr–(brush)/MS –0.543 194 25.8

137
 Absorbant wrap

Graphite anode
Deposit
Build-up solution Stylus handle

Leads
_

Substrate DC Power pack

Figure 7. 1 Schematic of brush electroplating process

16
5 min
10 min A
14
15 min
20 min
12
Thickness (µm)

10

15 20 25 30 35 40
2
Current density (A/dm )

138
 19
5 min
18
B 10 min
15 min
17
20 min
16

Current efficiency (%)

15

14

13

12

11

10

15 20 25 30 35 40
2
Current density (A/dm )

Figure 7. 2 A and B Effect of current density on thickness and current efficiency of

electrodeposited Cr from Cr(III)−DMF bath in different time.

139
 B

Figure 7. 3 SEM (A) AFM (B) of BED Cr from Cr(III)−DMF bath at 24 Adm–2 (C)

XRD patterns of brush–plated chromium at 24 Adm–2

140
 A

Figure 7. 4 (A) Polarization curve of brush electrodeposited Cr from Cr(III)−DMF bath

in 3.5% NaCl solution.

141
B

142
 C

Figure 7. 4 Impedance spectra for BED Cr from Cr(III)-DMF bath in 3.5% NaCl solution

(B) Bode diagram and (C) Nyquist diagram.

143
 D
\
D

Figure 7. 4 (D) Equivalent circuit diagram of impedance spectra for brush

electrodeposited Cr from Cr(III)-DMF bath in 3.5% NaCl solution.

144
CHAPTER VIII
 ELECTRODEPOSITION OF Fe–Ni–Cr ALLOY FROM DEEP EUTECTIC

SYSTEM CONTAINING CHOLINE CHLORIDE AND ETHYLENE GLYCOL

8. 1 Introduction

Fe–Ni–Cr alloy is a widely used in many areas due to its good corrosion resistance,

magneto resistive, and mechanical properties [1–4]. Resistance towards aggressive media

and its biocompatibility would make the alloy an excellent candidate for developing

cheap biodevices, [5] composition equivalent to stainless steel is reported by M. R. El–

Sharif et al. [6–7] and it would allow advantage to aforementioned properties and for

fabrication of electroformed structures with complex shapes. Electrodeposition of alloy

such as Fe–Cr [8], Fe–Ni–Cr [7, 9], and Fe–Ni–Cr–Mo [10], were reported in the

literature but t hey are limited to producing thin layers in aqueous based electrolytes.

Due to the complexity of producing a ternary alloy by electrochemical means, the

presence of Cr in high quantity in the deposits is a challenge by itself [11]. First of all,

Cr(III) aqua–species, Cr(H2O)63+, being a very strong Lewis acid, undergoes a rapid

olation reaction between unprotonated forms in aqueous electrolyte, annihilating Cr

deposition. To prevent this phenomenon, we will be investigating Cr

electrodeposition from DES based on choline chloride without any complexing

agent [12]. Additionally, the presence of Cr in the alloy decreases the quality of the

structure by the formation of cracks, low thickness, and increase of internal stress. In

order to overcome this problem, the addition of an organic additive such as saccharine

[13] will reduce the stress and may help to get a better deposits quality. On the other

hand, these additives are known to prevent the formation of a passivated oxide layer at

145
the surface, thereby decreasing the corrosion resistance of the alloy [14]. In aqueous

based electrolyte, the reduction of water into hydrogen runs with very low overpotential

on transition metal [15] deposits and leads to free H2 and OH– anions. This reduction of

water decreases the cathode efficiency and the hydroxide increases the pH, which

precipitates the iron and nickel as their insoluble hydroxides. The precipitation of Cr(III)

species into the deposits is also a problem [16].

In this study, a novel DES based electrolyte is developed allowing the deposition

of Fe–Ni–Cr alloys [17]. This work is very important in terms of free from aqueous

electrolyte, complexing agent, additive like saccharine and H2 reduction. Effect of

electrodeposition potential on the composition, structural morphology, and corrosion

resistance properties of alloy deposits were investigated.

8. 2 Experimental section

8. 2. 1 Preparation of Deep Eutectic Solvent and Electrochemical Deposition

The deep eutectic solvent (DES) was prepared by mixing choline chloride – 4.4

g, CrCl3·6H2O – 8.5 g, NiCl2·6H2O – 3.8 g, FeSO4·7H2O – 0.33 g , KCl – 1.5 g, ethylene

glycol – 44.4g, at 65°C until a homogeneous, green liquid is formed [18]. Potentiostatic

electrodeposition was carried out using three electrode cell connected to a

potentiostat/galvanostat PARSTAT 2273. Constant potential deposition was carried out

in an undivided cell at potential from –1.3 to –1.5 V. The working electrode (area, 1cm2)

was either copper or mild steel, counter and reference electrode were platinum foil and

saturated calomel electrode directly immersed in DES. The sample was degreased in

acetone, electro cleaned in alkaline solution, rinsed with 5% H2SO4 and finally rinsed

with double distilled water.

146
8. 2. 2 Microchemical and Microstructural analyses

Structural morphology and elemental composition of deposits were carried out by

using scanning electron microscopy and energy dispersive X–ray spectroscopy (Hitachi,

3000H) respectively. X–ray diffraction pattern of alloy phases were measured using a

Phillips diffractometer, 2θ from 20 to 100° using CuKα, λ = 0.1540 nm.

8. 2. 3 Corrosion resistance studies

The electrochemical measurements were carried out using a PARSTAT 2273

advanced electrochemical system (Princeton Applied Research Company, USA). A

saturated calomel electrode (SCE) was used as the reference electrode and a large

platinum plate as the counter electrode. The mild steel (MS) and Fe–Ni–Cr alloy

obtained at –1.5 V on MS were the working electrodes. The corrosive medium in the

test was 3.5% NaCl [19]. Potentiodynamic polarization curves were measured for both

substrate and electrodeposited alloy between –0.25 and 0.25V at scan rate of 5 mV/s.

The corrosion parameters were obtained with inbuilt software package (Power Suite).

EIS were conducted at open circuit potential over a frequency range from 105 to

10–2 Hz. The amplitude of potential modulation was 5 mV. All the recorded

impedance spectra were shown as Nyquist diagram. ZSimpWin (3.21) software was used

to fit the EIS experimental data.

8. 3 Result and discussion

8. 3. 1 X–ray diffraction analysis

Figure 8. 1 shows a typical X–ray diffractogram for the electrodeposited alloy.

As can be seen, this alloy exhibits sharp lines characteristic for poly crystalline nature.

The peaks were observed at diffraction angle of 43.4, 50.4, 73.9, 89.8 and 94.9º

147
corresponding to (111), (200), (220), (311) and (222) crystal planes and Fe–Ni–Cr phases

were polycrystalline. All peaks can be indexed as the Fe–Ni–Cr face–centered cubic

(FCC) phases based on the standard data of the JCPDS (Card No. 33–0945) file. The

average crystallite size was estimated at 35.5 nm using Scherer formula [20, 21].

8. 3. 2 Microstructural characteristics and elemental composition

Deposition potential has an important effect on deposit brightness,

microstructure and composition of alloy deposits on copper substrate. In the present

studies, the SEM images and EDAX patterns show differences on the samples obtained

by potentiostatic deposition technique. Figure 8. 2A and 8. 2B shows the morphology of

alloy deposited at –1.3V and the corresponding EDAX pattern reveals the presence of

Fe–53.7% Ni–41.7% and Cr–4.5%. Deposits were darker than one obtained at –1.4

and –1.5V, nodular grain sizes ranging from 0.3–0.7μm with agglomeration of particles

formed are seen.

Figure 8. 2C and 8. 2D shows the SEM and EDAX results of alloy obtained at

–1.4V, these deposits were brighter than those obtained at –1.3V with grain sizes ranging

from 0.2–0.5μm. Deposits were denser and compact layer containing spherical particles

were formed as small clusters. The compositions of alloy atomic percentage were Fe–

60.9% Ni–34.3% and Cr–4.7% as shown by EDAX analysis. SEM and EDAX results of

alloy deposits obtained at –1.5V and these results were shown in Figure 8. 2E and 8. 2F.

Deposits were brighter, homogeneous, dense and very small nodular grains with an

average size of 0.2μm. Bright deposits could be due to increasing of Cr percentage in the

alloy composition, EDAX shows that the atomic percentages of alloy were Fe–54.6%,

Ni–30.8% and Cr–14.5%. From the analysis of alloy deposits morphology and

148
composition under different potentials, it appears that the type of deposits and

composition gradually changed from darker to bright and from deviated [22] to close

stainless steel [23] compositions [24]. The electrical double layer structure in DES may

be expected to be different from that in the conventional media containing molecular

solvent dipole and supporting electrolyte, because DES is composed of ions and they are

directly in contact with the electrode surface. Compact–layer effect [25, 26] on the

electrical double layer structure in DES would facilitate diffusion of ions.

8. 3. 3 Potentiodynamic polarization tests

The results from the potentiodynamic polarization measurements of the

Fe54.62Ni30.87Cr14.5 alloy deposits on the mild steel substrate in 3.5% NaCl aqueous

solution are shown in Figure 8. 3A. The curves representing the mild steel (MS) and a

Fe54.62Ni30.87Cr14.5 electrodeposits obtained at –1.5V on mild steel were shown for

comparison. The earlier studies [27–29] indicate that transpassivation is always

accompanied by an increase in the anodic current density. In most cases, it is

consider that the indication of the onset of transpassivation is a sudden increase in the

anodic current density with increasing electrode potential. Figure 8. 3A shows, that the

current density of the Fe–Ni–Cr deposits increased rapidly when the potential

reached –0.146V (SCE), and there is no obvious localized corrosion on the surface

of alloy deposits. Therefore it is proposed that transpassivation of alloy deposits

occurs at this potential. In the whole transpassive region the current density of the alloy

deposits is much smaller than that of the mild steel substrate. Corrosion potential (Ecorr)

of mild steel and Fe54.62Ni30.87Cr14.5 alloy are –0.671 V and –0.385 V (SCE) respectively.

This increasing Ecorr indicates that after applying an alloy deposits a better corrosion

149
protection is obtained. Corrosion protection is normally proportional to the corrosion

current density (Icorr) measured via polarization. The very lower (Icorr) values for the

Fe54.62Ni30.87Cr14.5/mild steel (1.1X10–5) [23] than that of bare mild steel (71X10–5) could

indicate that the Fe54.62Ni30.87Cr14.5 alloy electrodeposits is more protective than the

mild steel substrate. Corrosion rate in mmpy was estimated from the polarization curves,

and is given in Table 8. 1. Very lower corrosion rate is obtained for alloy deposits than

that of bare substrate.

8. 3. 4 Electrochemical impedance spectroscopy measurements

The polarization resistance and double layer capacitance of Fe–Ni–Cr deposits in

a corrosive medium could provide information regarding the ongoing corrosion reaction

process. EIS data provides additional information about the deposits/solution and

substrate/solution interface. The simple RC combination can be used to model several

components of an electrochemical cell. For example, the bulk electrolyte and a deposits

on the electrode surface each has an associated resistance and capacitance. However, it

should be noted that the semi–circle for the bulk electrolyte is often not seen since it

typically occurs at higher frequencies than those that can be used in an impedance

experiment. Therefore, only the low frequency limit can be measured. This parallel

combination can also be used to model the interfacial region; C is double–layer

capacitance (Cdl) and R is the charge transfer resistance (Rct). The rationale for

representing the charge transfer reaction as a resistance is derived from the small

overpotential limit of the Butler–Volmer equation [30, 31]

Where

150
 It should be stressed that this linear relationship only applies at low overpotentials

between 5 to 10 mV. Hence, the A.C. amplitude used in electrochemical impedance

experiments is limited to 5 to 10 mV. The other fundamental component of an

electrochemical cell that must be considered is mass transport. Semi–infinite diffusion

can be modeled using the Warburg impedance Zw, which is given by the following

equation.

This element has a constant phase angle and yields a strait line in the Nyquist

plot at an angle of 45°. The equivalent circuit for an electrochemical cell, in which

solution species involved in the charge transfer reaction can be constructed from the

components discussed above, is shown as inset in Figure 8. 3B and 8 . 3C. The

semicircle at high frequencies indicates charge transfer control; however, at lower

frequencies, the rate of mass–transfer become the rate limiting factor and is reflected by

the transition from a semi–circle to a straight line.

Figure 8. 3B and 8 . 3C shows the experimental and simulated impedance

response of bare mild steel and Fe–Ni–Cr alloy deposits on mild steel substrates in a

Nyquist representation. At low frequencies the interception with the real axis was

ascribed to the charge transfer resistance Rct at the corrosion potential. The Rct value of

Fe54.62Ni30.87Cr14.5/mild steel was several order magnitude higher than that of bare mild

steel substrate. The value of fitted parameters of the equivalent circuit, together with the

corrosion potentials Ecorr as a function of Fe54.62Ni30.87Cr14.5 alloy electrodeposits on mild

steel substrate were presented in Table 8. 1. Porosity of Fe54.62Ni30.87Cr14.5 alloy

electrodeposits on mild steel substrate were calculated based on our previous studies [32,

151
33]. Table 8. 1 shows that the diffusion impedance value (Zw = 287 Ω cm2) of the

deposited alloy is higher than the charge transfer resistance of mild steel substrate (Rct

= 116 Ω cm2). This shows that diffusion process can dominate the whole corrosion

process for the deposited alloy and also means that the uncoated mild steel substrate

easily suffers from attack by aggressive substance like CO2 and chloride ions. Both Rct

and Zw values of the deposited alloy are much larger than those of the bare mild steel

substrate. This suggests that electrochemical reaction is difficult on the deposited

electrode surface and Fe–Ni–Cr alloy deposits presents better corrosion resistance. The

lower the porosity values suggest the better corrosion protection and the less defects are

in the alloy electrodeposits. The double layer capacitance parameter Cdl was another

parameter that could provide information about the polarity and the amount of

charge at the alloy deposits/solution interface. Higher Ecorr, Rct, Zw and lower Icorr, Cdl

values of Fe54.62Ni30.87Cr14.5 alloy electrodeposited on mild steel substrate showed better

corrosion resistance properties than that of bare substrates.

8. 4 Conclusions

We developed a novel DES for the electrodeposition of Fe–Ni–Cr alloy without

H2 evolution. The major advantages of DES are free from Cr–complexing agent,

brightener and stress reducer. The effect of electrodeposition potential on the structural

morphology and composition of Fe–Ni–Cr alloy was successfully studied by SEM and

EDAX techniques. From these results potential for electrodeposition of Fe–Ni–Cr alloy

compositions is optimized. We obtained higher Cr% in alloy composition without Cr–

complexing agent at –1.5V; whose structural morphology is fine grained dense nodular

deposit. The Potentiodynamic polarization and Electrochemical Impedance Spectroscopy

152
results showed Fe54.62Ni30.87Cr14.5 alloy deposited at –1.5V is having very high Rct, Zw

and lower Icorr than that of bare mild steel substrate.

153
References

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139.

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Corros. Sci. 37 (1995) 709.

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3769.

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154
 Table 8. 1 Corrosion parameters obtained for Fe–Ni–Cr alloy from potentiodynamic

polarization and electrochemical impedance measurements by Nyquist plot in 3.5% NaCl

solution.

Sample Ecorr V ba bc Icorr Corrosion Rct Zw Cdl Porosity

(SCE) (V/decade) (V/decade) (A/cm2) rate (mmpy) ( cm2) ( cm2) (F/cm2) (%)

MS substrate –0.671 0.373 –0.061 7.1X10–4 8.42 116 – 1.0 X10–3 –

Fe–Ni–Cr/mild –0.384 0.228 –0.260 1.1X10–5 0.1213 3053 287 1.7 X10–3 0.2237

steel

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 Fe-Ni-Cr

(111)
800

600
Intensity (a.u)

(200)
400

(311)

(222)
200

(220)
0

40 50 60 70 80 90 100
2 (degrees)

Figure 8. 1 XRD pattern of Fe–Ni–Cr alloy deposited at –1.5 V in deep eutectic solvent

based on choline chloride and ethylene glycol.

A B

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 C
D

E
F

Figure 8. 2 SEM images and EDAX patterns of Fe–Ni–Cr alloy deposits prepared under

different conditions: (A and B) Fe53.74Ni41.73Cr4.52 electrodeposited alloy at –1.3 V; (C

and D) Fe60.92Ni34.39Cr4.68 electrodeposited alloy at –1.4 V; (E and F) Fe54.62Ni30.87.Cr14.5

electrodeposited alloy at –1.5 V.

157
 A

B C

Figure 8. 3 (A) Typical Potentiodynamic polarization curves of electrodeposited alloy

and bare substrate in 3.5% NaCl solution. (B and C) Electrochemical impedance

spectroscopy both ( ) experimental and ( ) simulated Nyquist plot for mild steel (MS)

and Fe54.62Ni30.87.Cr14.5 alloy on mild steel (Fe54.62Ni30.87.Cr14.5 / MS) (insert Equivalent

circuit diagrams for impedance spectra.

158
CHAPTER IX
 CONCLUSIONS

The study carried out has described the development of a methodology for

electrodeposition of Cr and Fe-Ni-Cr from eco-friendly Cr(III) electrolytes and ionic

liquid/deep eutectic solvents. The study has produced the following conclusions:

 Eco-friendly Cr(III)-glycine electrolyte was developed from which microstructure

and electrochemical corrosion behavior of DCD and PED Cr coating were studied

and compared to the microstructure and electrochemical behavior of Cr coating

from Cr(VI)–bath.

 Using potentiodynamic polarization test, the corrosion current density of DC and

PE deposited, uncoated substrate and differences in their corrosion potentials

(Ecorr) were determined. In all the cases, the (E corr) shifted to a more positive

potential when the coatings were applied. The PE–deposited substrate had a better

corrosion resistance than DC and mild–steel substrate. Corrosion properties of

PE–deposited chromium from Cr(III)–bath differ only 1.5 times (higher positive

potential, lower corrosion current density (Icorr) and lower corrosion rate than that

of PE deposited chromium from Cr(VI)–bath.

 EIS data for DC and PE–deposited chromium from Cr(III) and Cr(VI)–baths

showed that the values of charge–transfer resistance (Rct) and double layer

capacitance (Cdl) of PE deposited from Cr(III) bath were not much different

from those of Cr(VI)–bath. Therefore, the structure and corrosion properties of

PE–deposited chromium from Cr(III)–bath are comparable to those of Cr(VI)–

bath. So developed trivalent chromium coatings are very good choice to replace

toxic, carcinogenic Cr(VI)–bath by Cr(III)–bath.

159
 The microstructure and corrosion behavior of electrodeposited chromium

prepared at different peak current densities, duty cycles, and frequency were

studied. The following conclusion can be drawn. Grain size increases with

decreasing peak current density during electrodeposition. The maximum

thickness, current efficiency, and hardness of electrodeposited chromium are

obtained at 40% duty cycle.

 All the chromium samples exhibit active–passive polarization characteristics.

Electrodeposited chromium prepared at 40% duty cycle exhibited the best

corrosion resistance. The corrosion behavior of electrodeposited chromium in

3.5% NaCl solution is well described by the equivalent system of charge transfer

resistance (Rct) and double layer capacitance (Cdl).

 Cr(III)DMF–based electrolyte was developed from which effect of current

density and plating time were studied. Thickness and current efficiency is

increased because of lower hydrogen evolution. Thickness and current efficiency

of Cr deposit is reached maximum of 15 μm at 32 Adm–2 and 18 μm at 24

Adm–2, respectively.

 Corrosion measurements show appreciable increase in corrosion resistance for

BED Cr from Cr(III) DMF bath than that of the MS. SEM, AFM, and XRD

images of BED Cr show fine grained nodular and microcrystalline deposit.

 In choline chloride based DES having negligible gas evolutions at

anode/electrolyte interface. Even small amount of Cl2 gas formed reacts at a faster

rate with the DES and thus has no time to escape from the solution. From all the

160
 above advantages properties of DES can be used as environmentally benign

electrolyte for electrodeposition of metals*.

 We developed a novel DES for the electrodeposition of Fe–Ni–Cr alloy without

H2 evolution. The major advantages of DES are free from Cr–complexing agent,

brightener and stress reducer. The effect of electrodeposition potential on the

structural morphology and composition of Fe–Ni–Cr alloy was successfully

studied by SEM and EDAX techniques. From these results potential for

electrodeposition of Fe–Ni–Cr alloy compositions is optimized. We obtained

higher Cr% in alloy composition without Cr–complexing agent at –1.5V, whose

structural morphology is fine grained dense nodular deposit. The

Potentiodynamic polarization and Electrochemical Impedance Spectroscopy

results showed Fe54.62Ni30.87Cr14.5 alloy deposited at –1.5V is having very high

Rct, Zw and lower Icorr than that of bare mild steel substrate.

* Kurt Haerens, Edward Matthijs, Koen Binnemans, Bart Van der Bruggen,

Green Chem. 11 (2009) 1357

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 LIST OF
PUBLICATIONS
 LIST OF PUBLICATIONS

1. G. Saravanan, S. Mohan, “Corrosion behavior of Cr electrodeposited from Cr(VI) and

Cr(III)-baths using direct (DCD) and pulse electrodeposition (PED) techniques”, Corros.

Sci. 51 (2009) 197-202. (Related to chapter 5)

2. G. Saravanan, S. Mohan, “Pulsed electrodeposition of microcrystalline Chromium

from trivalent Cr-DMF bath”, J Appl Electrochem. 39 (2009) 1393-1397. (Related to

chapter 6)

3. G. Saravanan, S. Mohan, Structure, “Current efficiency and corrosion properties of

Brush electrodeposited (BED) Cr from Cr(III)Dimethyl formamide (DMF)-bath”, J Appl

Electrochem. 1 (1) (2010) 1-6. (Related to chapter 7)

4. Gengan Saravanan, Subramanian Mohan, “Electrodeposition of Fe-Ni-Cr alloy from

Deep Eutectic System containing Choline chloride and Ethylene Glycol’’, Int. J.

Electrochem. Sci., 6 (2011) 1468-1478. (Related to chapter 8)

5. RM. Gnanamuthu, S. Mohan, G. Saravanan, Chang Woo Lee, “Comparative study on

structure, corrosion and hardness of Zn-Ni alloy deposition on AISI 347 steel aircraft

material”, J. Alloys Compd. Doi: 10.1016/j.jallcom.2011.10.078.

6. M. Ilayaraja, S. Mohan, R.M. Gnanamuthu, G. Saravanan. “Nanocrystalline zinc-

nickel alloy deposition using pulse electrodeposition (PED) technique. Trans. Inst. Metal

Finish, 87 (3) (2009) 145-148.

7. S. Mohan, V. Ravindran, B. Subramanian, G. Saravanan. “Electrodeposition of zinc–

nickel alloy by pulse plating using non-cyanide bath”, Trans. Inst. Metal Finish, 87(2)

(2009) 85-89.

162
8. A. Balasubramanian, D.S. Srikumar, G. Raja, G. Saravanan, S. Mohan. “Effect of

pulse parameter on pulse electrodeposition of copper on stainless steel”, Surf Eng. 25(5)

(2009) 389-392.

9. S. Mohan, J. Vijayakumar, G. Saravanan, “Influence of CH3SO3H and AlCl3 in the

direct and pulse current Electrodeposition of trivalent chromium”, Surf Eng. 25(8)

(2009) 570-576.

10. G. Saravanan, S. Mohan, RM. Gnanamuthu J. Vijayakumar, “Effect of AlCl3,

CH3SO3H on thickness, current efficiency and corrosion properties of brush plated Cr(III)

formate urea baths”, Surf Eng. 24(6) (2008) 458-463.

11. S. Mohan, G. Saravanan, N. G. Renganathan, “Comparison of chromium coatings

and electrochemical behaviour with direct current and pulse current deposition in

trivalent chromium formate urea bath as alternative to conventional Cr coatings”, Surf

Eng. 27(10) (2011) 775-783.

163