13

CHAPTER 2
OVERVIEW OF THE PROCESSES AND LITERATURE
REVIEW
2.1 PLASTICS AND POLYMERS. 15
2.2 OVERVIEW OF COMPOSITES 16
2.2.1 Classification of Composites 17
2.2.1.1 Polymer Matrix Composites 18
2.2.1.2 Factors Affecting Properties of PMCs 19
2.2.1.2.1 Interfacial Adhesion 19
2.2.1.2.2 Shape and Orientation of Dispersed Phase
Inclusions (Particles, Flakes, Fibres, and
Laminates) 20
2.2.1.2.3 Properties of the Matrix Properties 20
2.2.1.3 Fabrication of Composites 23
2.2.1.4 Effect and Functions of Fillers 26
2.2.2 ABS Poly (Acrylonitrile, Butadiene, Styrene) 28
2.2.3 Nylon (Polyamides) 29
2.2.4 Wollastonite / Calcium Meta Silicate 36
2.2.5 Water Absorption Studies on Polyamide Composites 40
2.2.6 Mechanical, Electrical and Tribological Properties of
Polyamide-6 Composite Materials 44
2.3 METALLIZATION OF PLASTICS 50
2.3.1 Overview 50
2.3.2 Plating of plastics 52
2.3.2.1. Electroless plating 52
2.3.2.1.1 Composition of Electroless Plating Bath
53
2.3.2.1.2 Advantages of Electroless Plating 54
2.3.2.1.3 Applications of Electroless Plating 55
2.3.2.1.4 Electroless Plating of Copper 55
2.3.2.1.5 Electroless Nickel Plating 57
2.3.2.2 Electroplating 59
 14

2.3.2.2.1 Principles of Electrodeposition 60

2.3.2.2.2 Mechanism of Electrodeposition 61
2.3.2.3 Effects of Plating Variables 63
2.3.2.4 Components of Electroplating 69
2.3.2.5 Plating Process 71
2.3.2.6 Electroplating of Chromium 74
2.3.2.7 Electroplating of Copper and Nickel 76
2.3.2.8 Distinction between Electroplating and Electroless
Plating 78
2.3.2.9 Conductive Paints 78
 15

CHAPTER 2

OVERVIEW OF THE PROCESSES AND LITERATURE

REVIEW

2.1 PLASTICS AND POLYMERS

Plastics play a very significant role in our everyday life; many

vital products such as knee joints, disposable food utensils,

automotive components, etc. are fabricated with plastics. Since early

times, the polymeric materials have been used in various forms,

although there are no records to provide the evidence of their exact

usage. For instance, an observation about the use of natural rubber

balls for playing by the inhabitants of Haiti has been recorded by

Christopher Columbus in 1400s. In early 1900s, synthetic polymers

came into existence and were prepared using phenol and

formaldehyde to form resins known as Baekelands Bakelite [6].

Even after the development of synthetic polymers, scientists

were ignorant of the true nature of the materials they had prepared.

Scientists for many years assumed that they were colloids, but it was

in 1920s that Herman Staudinger explained that polymers were

macromolecules. Later in 1928, Carothers developed PAs.

Subsequently, Ziegler and Nattas work in 1950s, led to the

development of high-density, linear polyethylene, polypropylene, and

other stereo specific polymers [6].

Plastics exhibit a remarkable range of properties like lower

densities, thermal conductivities, moduli, etc. The properties of

 16

plastics can be customized by blending them with various additives

like fillers, fibres, plasticizers, etc. With the use of these additives the

compounder will be able to develop materials for specific applications.

Polymeric materials with lower densities benefit the applications

which require lighter weights. Conducting fillers, added into the

matrix of plastics, transform insulators into conductors and as a

result, they can be used in EMI/RFI applications. Plastics in

automotive area are used in fabricating interior and exterior

components. For instance, a swift glance inside an automotive vehicle

gives us an idea of the use of plastics. Components such as side view

mirror, headlight, bumpers, doors, wheel covers, trunk lids, hoods

and grilles.

Many varieties of thermoplastics are used in packaging

applications which include carbonated beverage bottles to plastic

wrap. The requirements of plastics are different for different

applications, but fortunately, plastic materials can be modified to

meet up with the varied service conditions. The part designer has to

carefully select from the array of accessible thermoplastic materials to

cope up with the essential demands [6].

2.2 OVERVIEW OF COMPOSITES

Composite materials or composition materials are resources

prepared from two or more essential materials with unusual

physical or chemical properties. The materials when combined,

creates a new material with characteristics divergent from the

individual components. This combination material may be chosen for

 17

many reasons due to the benefits it offers like low weight, corrosion

resistance, high fatigue strength and faster assembly. These materials

are extensively used in building aircraft structures, electronic

packaging, medical equipments and space vehicles [7, 8].

The major demarcation between blends and composites is that

the two main constituents of the composites remain identifiable,

although these may not be decipherable in blends. Wood, ceramics,

concrete are some of the valuable materials used in our everyday life.

Surprisingly, the nature itself has gifted us with many polymeric

composites and these can be called as natural composites. For

example: The connective tissues found in mammals are a composite

material [8].

Composite materials are made of two or more distinct phases

known as a matrix and dispersed phase. The matrix phase is a

primary phase, which has a continuous character. It is more ductile

and is a less hard phase. Dispersed phase is a reinforcing phase,

usually stronger than matrix and is rooted in the matrix in a

discontinuous form [8].

2.2.1 Classification of Composites

Depending on the matrix phase, composites are classified as

metal matrix composites (MMCs), ceramic matrix composites (CMCs),

and polymer matrix composites (PMCs) (fig. 2.1) [7, 9].

According to the type of reinforcement, composites are classified

as either, particulate composites which are composed of particles,

fibrous composites which are composed of fibres and laminate

 18

composites which are composed of laminates. Fibrous composites are

further divided as natural / biofibre or synthetic fibre [7, 10]. Of late,

the market is concentrating on Bio-based composites which are

normally referred to as Green composites made from natural /

biofibre and biodegradable polymers. Green composites are further

divided into two types, viz., hybrid and textile composites [7, 8].

Fig. 2.1: Classification of composites [11]

2.2.1.1 Polymer Matrix Composites

Polymer matrix composites (PMCs) are prepared by mixing a

range of short and continuous fibres / whiskers / particles, etc. with

the organic polymers. The reinforcements added into the matrix of

PMCs offer high strength and stiffness to the material. These

reinforcements actually support the structure that is subjected to

mechanical loads [12]. The only difficulty with PMCs is its low thermal
 19

resistance and high coefficient of thermal expansion [7]. But

otherwise, put simply, they are exceptional materials with excellent

properties as listed in the ensuing literature.

Many of the commercially produced composites uses polymer

matrix material. There are numerous polymers available today

depending upon the raw materials. The most commonly known

polymers include polyester, polyamide, vinyl ester, epoxy,

polypropylene phenolic, polyimide, polyether ether ketone (PEEK) and

others. The reinforcement materials can be fibres, and can also be

minerals like calcium silicate, Calcium carbonate, graphite, etc. [7, 8].

In recent times, PMCs are gaining much importance due to their

low cost and uncomplicated fabrication techniques. The usage of

polymers in their unreinforced stage is limited due to the low-level of

mechanical properties. Polymers reinforced with fibres / additives are

characterized by the following properties: [7]

a) High specific b) High specific c) High fracture

strength stiffness resistance
d) Good abrasion e) Good impact f) Good corrosion
resistance resistance resistance
g) Good fatigue
h) Low cost
resistance

2.2.1.2 Factors Affecting Properties of PMCs

2.2.1.2.1 Interfacial Adhesion

Composite materials behaviour is generally explained based on

the collective behaviour of the polymer matrix, the reinforcing

materials, and the fibre / matrix interface. Superior mechanical

 20

properties are attained if the interfacial adhesion is strong. The

degree of interfacial adhesion is determined by anchoring the matrix

molecules to the fibre surface by chemical reaction or adsorption.

Recent developments in atomic force microscopy (AFM) and nano

indentation devices have assisted in the investigation of the interface

[7].

2.2.1.2.2 Shape and Orientation of Dispersed Phase Inclusions

(Particles, Flakes, Fibres, and Laminates)

Bednarcyk [13] states that particles are mainly used to improve

properties and also to lower the cost of isotropic materials. Particles

have no preferred directions. Josmin P Jose et al. [7] and Tabiei [14]

explains that the shape of the reinforcing particles can be either

spherical, cubic, platelet, regular or irregular geometry and the

dimensions of particulate reinforcements are more or less same in all

directions. Particle-reinforced composites are divided into large

particle and dispersion-strengthened composites. Laminar composites

are made from two dimensional panels / sheets that are stacked and

subsequently bonded together to form high strength materials.

2.2.1.2.3 Properties of the Matrix Properties

Huang [15] explains that the matrix properties of different

polymers will decide the application to which it is suitable. The

principal advantages of polymers as matrix are low cost, easy

processability, good chemical resistance and low specic gravity.

Conversely, low strength, low modulus, and low operating

temperatures limit their usage. Varieties of polymers for composites

 21

are (a) Elastomers (b) Thermosetting polymers (c) Thermoplastic

polymers and their blends [7].

(a) Elastomers:

Polymers which possess the property of viscoelasticity are

known as Elastomers and these are amorphous polymers that exist

above their glass transition temperature. Elastomers remarkably have

low elastic modulus and high yield strain in comparison with other

materials. A classical example for this is a rubber. Rubbers are

reasonably softer and deformable at room temperatures. The youngs

modulus of rubber is approximately 3 MPa at room temperature and

rubbers are usually used in preparing seals, adhesives and moulded

flexible parts. Polybutadiene, butyl rubber, chloroprene rubber,

ethylene propylene rubber, natural rubber etc., are other examples of

elastomers [7].

(b) Thermosetting polymers:

According to Josmin P Jose et al. [7] thermosets are those

polymers that do not soften but decompose on heating and cannot be

restructured after solidification. Epoxies, silicone, polyesters, urea,

etc., are some examples of thermosetting polymers.

The viscosity of the thermosetting resins is usually low.

Nevertheless, these resins go through chemical reactions and finally

form a three dimensional network. These three-dimensional

structures have higher dimensional stability, superior resistance to

solvents and high-temperature resistance. In recent times, significant

 22

improvement has been made in enhancing the toughness and

maximum operating temperatures of thermosets [12].

(c) Thermoplastic polymers:

Thermoplastics are those polymers that can be restructured by

the application of heat and pressure [12]. Today, 85% of the polymers

made globally are thermoplastics [16]. Nylons, polyacetals,

polypropylene, polyvinyl Chloride (PVC), polyamideimide (PAI), etc. are

some examples of thermoplastic polymers [7, 12]. Some unique

polymers such as PEEK, polyimides, fluoropolymers and liquid-crystal

polymers are used in more sophisticated and high performance

application areas due to their high glass transition temperature Tg or

melting temperature Tm (290350 oC).

Depending on the type of their distinctive transition

temperature, thermoplastics are classified as either crystalline or

amorphous. Amorphous thermoplastics are distinguished from

crystalline thermoplastics by their Tg. The glass transition

temperature is the temperature beyond which the modulus of the

polymer reduces quickly and displays liquid-like properties;

amorphous thermoplastics are usually worked at temperatures well

beyond their Tg. For instance, the Tg for PVC may be as low as 65 oC

and for PAI, as high as 295 oC [16].

Crystalline thermoplastics or, put simply, semicrystalline

thermoplastics are usually processed or worked beyond the melting

temperatures Tm of thermoplastic polymers. The degree of

crystallinity ranges between 20 90 %. Melting temperatures for

 23

polymers such as low-density polyethylene (LDPE) may be as low as

110 oC and for polyetherketone (PEK) may be as high as 365 oC. [16]

Thermoplastics have high resistance towards cracking and

impact damage. Some of the recently developed thermoplastics like

PEEK, which are semicrystalline in nature, demonstrate exceptional

high temperature strength and solvent resistance. The time involved

in heating and cooling of thermoplastics is faster and hence the curing

time in comparison with thermosets is low. This is very much

essential for automotive industries that need materials fabricated at a

faster rate to reduce the production time and maximize the profits.

Thermoplastics reinforced with discontinuous fibres are in high

demand these days and there is also scope for thermoplastics

reinforced continuous fibres and thus, these plastics will proffer a

huge scope in the future from the manufacturing and design

viewpoint. As an example, the thermoplastic composites could replace

thermosetting composites (epoxies) in many of the fighter aircrafts

[12].

2.2.1.3 Fabrication of Composites

There are various methods available for fabricating composite

components. Some of the methods were developed to meet specific

design and manufacturing needs and some were borrowed. However,

selection of a particular method depends on the materials, the part

design, and the end-user applications [17].

 24

Some of the important processing methods are (a) Hand lay-up

(b) Bag moulding process (c) Filament winding (d) Pultrusion (e) Resin

transfer moulding (f) Injection moulding [7].

(a) Hand Lay-Up

Hand lay-up technique has been used in the manufacture of

reinforced (small and large) products. It is one of the simplest and

normally used techniques for fabricating laminate composites. This

method uses plastics, wood, metal or a combination of these to

fabricate materials [7].

(b) Bag Moulding Process

According to Josmin P Jose et al. [7] and Tay [18], the bag

moulding process is a very flexible type of composite fabrication

technique known to the mankind till date. It is a process wherein the

laminates are laid up or stacked up in a mould and resin is spread in

between them. A flexible diaphragm is spread over the stacked layers

and cured by applying heat and pressure. Once, the curing cycle is

complete, the materials take the shape of the mould itself. There are

three basic moulding method involved viz., pressure bag moulding,

vacuum bag moulding and autoclave moulding.

(c) Pultrusion

Josmin P Jose et al. [7] describes pultrusion as an automatic

process of fabricating composite materials into unbroken, regular

cross-section profiles. Pultrusion involves pulling the product from the

die rather than being forced out by pressure as in the extrusion. Using
 25

appropriate dies, materials in the form of rods and tubes are

produced.

(d) Filament Winding

Filament winding is a method of creating surfaces of revolution

such as pipes, tubes, and cylinders. The method is normally used in

the construction of large tanks, pipes and tubes for industrial

purposes. The filament winding method is based on the principle of

laying down continuous reinforcements at high speeds in pre-specified

patterns [7].

(e) Resin Transfer Moulding

Resin Transfer Moulding (RTM) involves fabrication of large,

high performance products. In this process, a tool is manufactured

either from metals or composites and the resin is injected into the

tool. The reinforcements are also placed in the tool and due to the

injection the resin will come in contact with the reinforcements. RTM

can offer distinct advantages, particularly if the temperature

controlled tooling is used. The advantages include increased

productivity through the use of higher injection pressures and heated

moulds, improved quality, improved product consistency due to better

process control and improved dimensional tolerances [7].

(f) Injection Moulding (IM)

Wakeman et al. [19] describes IM as a method of manufacturing

both thermoplastic and thermosetting plastic materials. Materials

(matrix and reinforcement) are fed into a heated barrel, churned and

pushed into a mould cavity where it cools and hardens and finally
 26

takes the shape of the mould cavity. Through IM, many materials

such as mobile phone cases, spike busters, internet dongles, etc., are

produced today. IM method is suitable for producing same objects in

larger quantities, since the cost involved in manufacturing dies is

more.

Josmin P Jose et al. [7] lists some of the pros and cons of IM

such as high production rates, repeatability, high tolerance, knack to

use a broad range of materials, low labour costs and minimal scrap

losses, but the tools and equipments involved are expensive; the need

to design mouldable parts and potentially high running costs makes it

suitable for producing articles in larger volumes.

2.2.1.4 Effect and Functions of Fillers

The solid additives normally added into the matrix of polymers

are termed as fillers [20]. Fillers can be classified into two types viz.,

Inert and Reinforcing fillers. Inert fillers are added from the

economical point of view. Even though termed inert, inert fillers can

nevertheless have influence on other properties of the composite,

besides cost. Adding them into the matrix may increase the density of

the prepared material, improves hardness and reduces shrinkage.

China clay (kaolin), talc, and calcium carbonate are some examples of

inert fillers. On the other hand, reinforcing fillers are added from the

strength point of view. They actually increase the mechanical

properties of the compound, increase heat deflection temperature,

reduce shrinkage of the composite, and bring improvements in creep

behaviour.
 27

The properties of the composites are altered and improved by

the reinforcing fillers using several mechanisms. A bond (chemical) is

formed linking the polymer and the filler, in some cases and in other

cases, the properties of the thermoplastics is affected by the volume

occupied by the fillers. Consequently, interaction amongst the filler

and the thermoplastic and the surface properties are of greater

significance. The particle shape and size, the surface chemistry of the

particles also administrates the behaviour of composites. The smaller

particles lead to the greater improvements in the mechanical strength.

Particles of larger size may offer reduced properties in comparison

with virgin thermoplastics. It has also been observed that the shape of

the particles has a larger influence on the properties, for instance,

fibrous particles or plate-like particles results in anisotropic properties

with proper orientation of particles during processing. Calcium

carbonate is sometimes used with thermoplastics for strength

enhancement. Calcium carbonate is a natural product and has a

particle size of 1 m [20]. Glass spheres, Talc, Kaolin, and Mica are

used as fillers in thermoplastics.

Glass spheres can be either solid or hollow, and talc, kaolin,

and mica usually have lamellar shapes [20]. Other fillers include

calcium meta silicate, barium sulphate, metal powders and silica.

Rubber industry usually uses carbon black as filler, but

thermoplastics use carbon black for conductivity, protection from

ultra violet radiations, and also as a pigment.

 28

Thermoplastics often use fibres as fillers. Carbon, wood flour,

cotton, and fibreglass are some types of fibres used in thermoplastics.

Table 2.1 presents some typical fillers and their forms. Table 2.5

presents a summary of some characteristic fillers, and their effect on

properties of composites. Significant research interest is shown

towards inclusion of nanoscale fillers into polymers [6].

Table 2.1 Forms of various fillers [6]

Spherical Lamellar Fibrous

Sand/quartz powder Mica Glass fibres
Silica Talc Asbestos
Glass spheres Graphite Wollastonite
Calcium Carbonate Kaolin Carbon fibres
Carbon black Whiskers
Metallic Oxides Cellulose
Synthetic fibres

2.2.2 ABS Poly (Acrylonitrile, Butadiene, Styrene)

ABS is basically a terpolymer of Acrylonitrile, Butadiene

and Styrene [21]. A terpolymer is a copolymer consisting of three

distinct monomers. It is produced by making acrylonitrile and styrene

react with polybutadiene. Acrylonitrile is made from ammonia and

propylene; butadiene is produced by steam cracking; and styrene is

produced from ethyl benzene [22].

ABS plastic is used for its impact resistance and toughness and

these are considered as the most important mechanical properties.

Alterations with respect to impact resistance, toughness, and heat

 29

resistance can be made by incorporating certain fillers and

reinforcements into the matrix of ABS. ABS polymers are known for

their resistance towards vegetable oils, hydrochloric acid, mineral and

animal oils, alcohols, etc. But show least resistance towards

concentrated nitric and sulphuric acids. Apart from being used in

mechanical related applications, ABS also possesses electrical

properties that are reasonably constant over a broad range of

frequencies. ABS at high temperatures could be flammable, and are

damaged when exposed to sunlight. Table 4.3 indicates the various

properties of ABS.

The light weight of ABS and its ability to get it injection moulded

makes it extremely handy in fabricating products such as kitchen

utensils, bathroom accessories and fittings, automobile components,

electronic and electrical assembly enclosures, domestic appliances,

toy manufacturing, and even in fabricating musical instruments [22].

Fig. 2.2: Molecular Structure of acrylonitrile-butadiene-styrene (ABS)

2.2.3 Nylon (Polyamides)

Nylon is one of various man-made materials for plastics. Plastic

materials are organic solids that are either synthetic / semi-synthetic

with a wide range of properties that can be moulded into a desired

 30

shape and size. Plastics are either natural or man-made. Chemically,

plastics are composed of chain-like molecules of high molecular

weight, called polymers, which usually have been built up from

simpler chemicals called monomers. Various monomers and an

amalgamation of different monomers are used to produce a different

combination of polymers. Many different kinds of polymers are

available to us today. For example: PVC, PP, PEEK, PAs, epoxy, etc.

Undoubtedly, polymers have made a great impact on our

society. They are rapidly reinstating many metals for making objects.

Chemical Structure of Polymers

Fundamentally, a polymer is made up of many repeating

molecular units formed by sequential toting up of many monomer

molecules to each other. Many monomer molecules of A, say one

thousand to one million, link themselves mutually to form a new

gigantic polymeric molecule.

An example of this type of polymer is the polyethylene, as shown

in the ensuing literature. In this case the monomer is ethylene.

Countless numbers of these molecules connect themselves together

into a long chain polymeric molecule by breaking the double covalent

bond and creating new single covalent bonds between the monomers.
 31

This reaction is promoted by heat, pressure, and a chemical catalyst.

Another type of polymer uses two different monomer molecules,

A and B, to produce a polymer of alternating A and B. Again, this

polymer may have one thousand to one million units linked together.

An example of this type of polymer is nylon.

In the above reaction, HCl is lost and a covalent bond is formed

in its place. The new substance is given the trade name nylon, but

chemically it is known as a polyamide because of the type of linkage

which occurs at regular intervals.

 32

Nylon is prepared by mixing hexamethylenediamine, water,

sodium hydroxide, adipoyl chloride and cyclohexane [23].

P.A.Mahanwar and Suryakanti Bose [24] have discussed about

the usage of N6 / PAs in various fields ranging from automobiles to

consumer applications. They report that PAs possess excellent

mechanical properties and at the same time have certain limitations

such as low heat deflection temperature, high water absorption and

dimension instability which makes them less usable in applications

related to structural components. They also report that by adding

inorganic fillers such as aluminatrihydrate, montmorrilonite, clays,

talc, mica, silica, flyash, kaolin, etc., one can make them usable in

many areas such as automobile, electrical, electronic, packaging,

textiles, etc.

Several different types of nylons are produced and marketed

worldwide, of these, nylon 6 (Polyamide 6), nylon 6/6 nylon 6/10,

nylon 6-6/6, nylon 6/12, nylon 11 and nylon 12 are the most

common ones [25]. Nylon6 and nylon 6/6 are the ones that are being

used in most of the applications as discussed in the previous

literatures. The typical molecular structure of polyamide series is as

shown in fig. 2.3.

The numbers 6, 6/6, 11, 12, etc., refers to the number of

methyl units (-CH2-) occurring on each side of the nitrogen atoms

 33

(amide groups). It is understood that these methyl units have a strong

influence on the properties of various PAs in use. For instance, it is

noted that nylon 6/12 has a lower melting point, lower strength, lower

hardness, lower modulus, lower thermal distortion than nylon 6/6.

But, one relationship which does not conform is price, i.e., nylon 6/12

is more costly than nylon 6/6. The property which gives nylon 6/12

its efficacy is moisture absorption, which is just about half of that of

nylon 6/6 [25].

Similarly, N6 has some advantages over N6,6. To begin with, the

synthesis of N6 is cheaper than N6,6 and secondly, N6 has a better

attraction towards acid dyes than N6,6 [26]. The properties that make

N6 superior over other types are,

Its resistance to a good number of organic acids like ethers,

benzene, chloroform, esters, acetone, etc.

Shows least resistance to cresol, string mineral acids and

phenol.

Excellent resistance towards alkalies.

Resistance to inorganic acids.

Very good physical properties

Very good heat resistance

Excellent chemical resistance

Excellent wear resistance

Moderate to high price

Fair to easy processing

 34

Applications of Nylon6

Electrical connectors, gear, slide, cams and bearings, cable ties

and film packaging, fluid reservoirs, fishing line, brush bristles,

automotive oil pans, fabric, carpeting, sportswear, sports and

recreational equipments.
 35

Fig. 2.3: Typical Molecular Structure of Polyamide Series. [27]

 36

2.2.4 Wollastonite / Calcium Meta Silicate

Wollastonite, an industrial mineral named after the mineralogist

Wollaston W H. It is formed when high pressure and temperature acts

an limestone in the presence of silica bearing fluids. In general

wollastonite is white in colour and consists of manganese, iron and

magnesium in small traces. The composition of wollastonite has been

high lightened in the Table 2.2. [28].

Wollastonite is also known by the names Calcium silicate /

Calcium meta silicate and is commonly used as a functional filler in

thermoplastics, particularly in polyamides and polypropylene because

of its availability in grades with very fine particle size and high aspect

ratio, containing acicular or needle-like particles [29]. Wollastonite

(CaSiO3) is an industrial mineral with calcium, silicon, and oxygen

being its main constituents. Theoretically, CaSiO3 is made up of

48.3% of calcium oxide (CaO) and 51.7% silicon dioxide (SiO2). The

specific gravity of commercial grade wollastonite is 2.90 and the

typical chemical compositions of wollastonite grades for plastics are

listed in Table 2.2.

The wollastonite mineral has many advantages and due to

which it is being used in many areas. One of the main advantages of

CaSiO3 is its low moisture absorption properties that make it possible

for being used in applications, mainly industrial, as fillers in paints,

ceramics, wear resistant materials, etc. Other characteristics of

CaSiO3 include: high brightness, low volatile content, good thermal

 37

stability, low thermal expansion coefficient, high dielectric strength,

and low loss on ignition [16, 30].

Table 2.3, based on references [31, 32] and suppliers literature,

summarizes the physical and chemical properties of wollastonite.

Table 2.2: Typical chemical analyses of wollastonite filler grades. [16]

Composition wt%a) wt%b) wt%c)

CaO 47 44 47

SiO2 49.5 50 50

MgO 0.2 1.5 0.3

Al2O3 0.6 1.8 0.3

Fe2O3 0.43 0.3 1

TiO2 Traces Not reported 0.05

MnO 0.29 <0.1 0.1

Na2O 0.02 0.2 Not reported

K2O 0.11 Not reported 0.1

a) Wolkem India Ltd (KEMOLIT grade).

b) R.T. Vanderbilt Co. Inc. (VANSIL grade).

c) NYCO Minerals Inc. (NYAD grade).

 38

Table 2.3: Typical properties of wollastonite [16]

Property

Colour White

Crystal System Triclinic

Specific gravity 2.8-2.9

Coefficient of thermal expansion 6.5 x 10-6

Specific Heat (J/Kg k) 1003

Melting point (0C) 1540

Transition temperature, 0C (to pseudo wollastonite) 1200

Hardness (Mohs) 4.5-5

Refractive index 1.63-1.67

pH (10 wt% slurry) 9.0-11

Loss on ignition, % (950 0C) 2.5

Dielectric constant (104 Hz) 6

In engineering, plastics (thermoplastics and thermoset) with the

inclusion of wollastonite, results in an overall development of the

mechanical properties, that is, enhanced flexural modulus, enhanced

tensile strength, enhanced heat deflection temperature (HDT) and

enhanced dimensional stability. It is considered that the needle-like or

acicular shape of the wollastonite is the key contributing factor for the

enhanced mechanical properties. More generally, wollastonite has

been used as a financially viable alternative / supplement to glass

fibres, either chopped or milled. Table 2.4 summarizes the economic

benefits of using wollastonite as functional filler. The surface

 39

chemistry of wollastonite provides a particular affinity for surface

treatments such as silanes, titanates, polymeric esters and other

additives. The benefits of such treatments include lower compound

viscosity for improved melt flow, easier dispersion for better property

development and improved physical properties [16].

According to Robinson et al. [33], functional fillers such as mica

and talc, having similar Youngs moduli, but platy shape of these

materials can offer enhanced overall stiffness in different directions

due to increased dissipation of stress across a wider flat plane. Impact

strength may also be improved by the use of platy minerals. However,

with proper selection of median diameter and control of top size of the

wollastonite particles, the notched impact strength performance in

certain resins can be improved over the unfilled polymer and over

other fillers.

With a thorough literature survey, and knowing the benefits of

incorporating the wollastonite, it is decided to utilize CaSiO3 as the

reinforcing filler in the present research. The following are the

improvements expected:

Table 2.4: Economic benefits of using wollastonite as functional filler. [16]

Enhanced:
Stiffness and Impact Dimensional
flexural strength resistance stability
Wear / sliding Surface Melting
resistance appearance Temperature
Electrical
properties
Features Advantages Benefits
Low cost reinforcing filler Less expensive than Better economics for
 40

milled or chopped filled plastics while

glass fibres giving strength
improvements
Binary reinforcement Cost effective Better balance of
synergy combination with stiffness, impact,
treated calcined clays and electrical
properties in
engineering resins
Moderate specific gravity Ease of volume Smoother
substitution reformulation
transition and
improved cost
Lower cost than Can replace more Maintain or improve
polymers costly resins desired properties
over unfilled systems
High melting Contributes to high Allows improvement
temperature processing of melt flow rates
temperatures and yield by
assisting lower melt
temperature
polymers to be
processed at higher
temperatures
Less costly than certain For impact Better impact at
chemical additives modification can lower cost
replace certain
chemical modifiers

2.2.5 Water Absorption Studies on Polyamide Composites

As it is already known that, PAs/nylons are high recital

engineering thermoplastics, that are semi-crystalline in nature, with

striking physical and mechanical properties that offers a broad range

of significant end-use presentations in numerous industrial

applications [34]. In general, all PAs are hygroscopic [35] i.e., they

absorb water from both air and liquids. Hygroscopic property of

polymers becomes an essential factor while selecting materials,

designing parts, mechanical performance and optimization. It is

estimated that the equilibrium moisture content of N6 is around 2.5

 41

wt% at 23C, 50% RH and 9 wt% at 23C, 100% relative humidity (RH)

[36].

Generally, it is noted that the moisture content in nylon is a

prime factor affecting polymerization, compounding and moulding. It

is seen affecting the mechanical, dimensional, and surface appearance

when used in end-user products [37]. Dimensional changes of 0.7%

can result in nylon parts from the "as-moulded" state to equilibrium at

50% RH environments. This change occurs in approximately 150 days

for a 0.060 inch (1.5 mm) thick part [25]. The absorbed water in the

layers of polymer works as a plasticizer. Since Nylon being

semicrystalline material has both crystalline and amorphous phases.

The moisture actually penetrates into the amorphous region, although

small, water molecules take up space and displace the nylon

molecules. This results in the nylon molecular matrix swelling [25].

The water molecules tries to establish hydrogen-bonds with the amide

group and enhance the molecular chain mobility [37], which in turn

affects material properties such as modulus, yield stress, toughness,

etc. [34]. The water absorption by plastics also results in alterations of

dimensions and mass due to the stress and swelling that causes

serious damage to the whole structure. Being dimensionally stable is

very important for components used with narrow tolerances and

intricate shapes [38]. The moisture absorption by polyamide is a

totally reversible physical reaction. The moisture in the PAs can be

driven off by drying them in ovens. The absorption rate varies with

type of nylon as well as depends on temperature and RH.

 42

The problem of water absorption in plastics relates itself to a

number of problems, both in the use and processing of

thermoplastics. There are many ways by which water absorption in

plastics can be reduced. One of the methods is to reinforce them with

fillers. There are varieties of fillers available and some of them have

been listed in the Table 2.5. The absorption effects can also be

reduced by storing and drying them in a suitable atmosphere [38].

Knowing the concept of absorption, one should also be able to

differentiate between absorption, adsorption and hygroscopicity; as

these terms are often confusing and needs to be understood

thoroughly. Most researchers use the terms absorption and

adsorption interchangeably. Nevertheless, it should be noted that the

adsorption refers to the absorption by the material, both by gases /

vapors and liquids and absorption refers to the absorption of liquids,

whereas hydroscopicity is the propensity of a material to absorb water

[39, 40] and on the other hand, the material moisture content refers

to the percentage of water contained in it [38].

J Sukumaran et al. [41] have discussed issues related to

tribological properties of polymers subjected to water lubrication in

their review article on, A Review on Water Lubrication of Polymers.

Their observations say that water can act as a good lubricant for the

polymers, subjected to wear studies and can provide an economical

solution for lubrication related issues. They further report that,

polymers subjected to water lubrication have shown positive frictional

character in comparison with polymers subjected to oil and air

 43

lubrication, wherein wear behaviour was uncertain. Therefore,

understanding the Tribo-mechanical characteristic in wet state abets

to select suitable material for water lubricated applications. Some of

the regularly used engineering plastics such as Polyamide 6 (PA6),

Polyoxymethylene (POM) and Polytetrafluoroethylene (PTFE) have been

tested for their tribological performance under water lubrication. The

outcome of the tests indicates that the PTFE has better frictional traits

on comparing with POM and Ultra High Molecular Polyethylene (UHM-

PE) [42].

Water absorption can be a major problem and a key parameter

for polymeric materials like coatings and electrical insulations, which

are immersed in water for shorter or longer durations at some stage in

the application. Water absorption by polymeric materials actually

increases dielectric constant and on the other hand decreases volume

resistivity [43].

Pawlikowski and Gregory [44], in their work on Effects of

Polymer Material Variations on High Frequency Dielectric Properties,

have discussed issues related to PAs and say that Water can set

plasticization in the PAs, and due to which PAs exhibit variations in

the dielectric properties.

 44

2.2.6 Mechanical, Electrical and Tribological Properties of

Polyamide-6 Composite Materials

PAs are one of the most frequently used polymers used in many

engineering applications, but inherently PAs have certain

disadvantages like high water absorption, low impact strength, certain

fragility, etc. and therefore additional functional materials are added

to PAs to improve the mechanical properties in a cost effective manner

such that they can be suited for end-use applications. But, on the

other hand, PAs are characterized by their possessing of high tensile

strength, elasticity, tenacity and resistance to abrasion. These

properties of PAs make it usable for short term applications [45-47].

Over the years, several types of fillers have been in use with

PAs. Biobased fibres such as coconut fibre, wood flour, sisal, wheat

straw, kenaf, jute and minerals such as carbon fibres, mica, talc,

calcium carbonate, glass fibres and wollastonite have been favourably

used with PA either as fillers or as reinforcements to provide better

strength and modulus to the composite, and sometimes PAs are also

mixed with other polymers to bring in changes with respect to the

mechanical, electrical and thermal properties [46, 47]. Compounding

or blending of polymers with fillers is fairly an easy way to create new

polymeric materials with preferred properties. These functional

materials are classified into different groups, namely: modifiers,

property extenders and processing aids. Antioxidants, light stabilizers,

UV absorbers, peroxide decomposers, nucleating agents, flame

retardants, colourants, lubricants, and blowing agents come under a

 45

class of additives which are dispersed in the PA resin during several

stages of processing to provide resistance and also to stabilize the

base material. They also contribute by improving the mechanical,

thermal and electrical properties to a certain extent that simple

polymers do not [32, 48-51].

Most of the fillers are polar in nature, so there arises a problem

of reduced adhesion between the non polar matrix and the polar filler

which can affect the final properties of the composite. As a solution,

several types of coupling agents or compatibilizers were developed

with the aim of improving the bonding. Literature studies have shown

that wollastonite reinforced polymer composites have been used in

most of the end user applications [52-54].

N6 and High Density Polyethylene (HDPE) materials have been

used in a large number of industrial applications and many a times,

they have also been used in combination for specific applications [55,

56].

A large variety of filled PA composites are found in the vehicles

interior, exterior and under-the-bonnet applications. Long glass fibre

reinforced PA have found its use as bumper beams. Talc filled impact

copolymer composites are used in door and instrument panels [57].

Low cost, ease of processing and recyclability of PP composites are

paving way to the rapid market growth in the automotive sector.

Huseyin Unal et al. [58], have made a study on the mechanical,

tribological and electrical properties of N6 composites by using

graphite as filler. According to them, composites by IM method

 46

showed enhanced properties when the percentage of graphite varied

from 5 to 15 wt%. They have identified that the youngs modulus,

dielectric losses, dielectric permittivity increases when the graphite

content increases.

Ozcan Koysuren et al. [59] have discussed about Nylon

6/carbon black conductive composites. They have made an in-depth

study on the distribution of agglomerates of carbon black in the

matrix of N6 and in turn, its effect on the electrical and mechanical

properties. The electrical resistivity, impact strength, and elongation

at fracture of the prepared composites decreases and on the contrary

tensile modulus increases with the increase in carbon black content

in the composites.

Abdul Razak Rahmat et al. [27] and Akay et al. [60] have

reported that fibre reinforced thermoplastic compounds, produced by

IM method, offered an improvement in mechanical properties over

unreinforced ones. The composites so prepared have the ability to be

used in a variety of engineering applications because of their ease in

fabrication of materials. According to them, thermoplastic composites

containing short fibres have been used in many applications, due to

their ability to reduce the tribulations relating to defects like cracks

and voids in the materials that may be formed in the matrix or in the

fibre or at the matrix / fibre interface.

 47

Amintowlieh [61] has discussed the use of wheat straw as a

reinforcing fibre for N6. He reports that wheat straw reinforcement

increased modulus by 26.9 % and decreased the strength by 9.9 %.

Patricia Alvarez de Arcaya et al. [62] have discussed the use of

high performance thermoplastic matrices such as PAs instead of the

commonly used polyolens to develop natural fibre composites for

substituting glassbres without renouncing to their mechanical

properties. For this purpose, they have used different natural fibres

such as ax, jute, pure cellulose, and wood pulps with PAs to analyse

the effect of fibre content on mechanical properties.

P.A.Mahanwar and Suryasarathi Bose [24] have discussed the

effects of fillers on the Properties of N6. They report that composites

showed improved mechanical, thermal, as well electrical properties on

addition of fillers. According to them, the size of filler has a greater

influence on the electrical properties of the composites. They also

stated that the dielectric strength increases with the increase in filler

concentration.

Junlong and Huo [63] have used Kevlar fibre as a reinforcement

material, embedded into the matrix of PA6. The resulting product was

a composite of PA6/kevlar. The composites, so produced, were

subjected to study the effects of Kevlar fibre content and wear

condition on the tribological properties of the composites. The worn

surface was investigated under a scanning electronic microscope. It

was found that Kevlar fibre had improved the wear resistance of PA6.
 48

The observed values indicated that wear of PA6/Kevlar fibre composite

was lower than that of the PA6 and increased slowly, while its friction

coefficient decreased gradually with load.

Iztok S et al. [48] have discussed the effects of incorporating

wollastonite into the matrix of Isotactic polypropylene (iPP), and

according to them, wollastonite improves some of the mechanical

properties such as stiffness, hardness and strength of the ipp, but at

the same time reduces toughness.

Jin Tong et al. [64] have discussed the effects of the wollastonite

incorporation on the sliding wear behaviour of the Ultra-high

molecular weight polyethylene (UHMWPE) composites. They report

that with the incorporation of wollastonite, improved wear resistance,

tensile strength and the impact resistance of the UHMWPE composites

were observed.
 49

Table 2.5: Effect of filler type on properties [6, 65]

Synthetic fibres

Metallic oxides
spheres

Carbon black
Wollastonite

Sand/quartz
Carbon fibre
Glass Fibre

carbonate
Whiskers

Cellulose
Asbestos

Graphite

Calcium
powder

Kaolin
Silica
Mica

Talc

Glass
Tensile strength
Compressive
Modulus of
strength
Impact strength - - - - - - - - -
elasticity
Reduced
Better thermal
shrinkage
Electrical
conductivity
Electrical
conductivity
Chemical
resistance
Better abrasion
resistance
behaviour

Large Influence, influence, no influence, - negative influence

 50

2.3 METALLIZATION OF PLASTICS

2.3.1 Overview

Metallization of polymer substrates is an important practice in the

electronics and automotive industries. It is used for various purposes,

such as EMI / RFI applications, reduction in weight, better impact

strength, and corrosion resistance. The techniques available for the

metallization of polymer substrates include chemical [66] and physical

vapor deposition [67], metal-powder coating [68] and electroless plating.

Metallization of plastics has gained much importance these days

due to its increasing use in EMI shielding applications [69]. Also,

metalized plastic parts can be used for decorative or functional purposes

[70]. Previously, POP / metallization of plastics were done to provide

decorative and aesthetic views to the plastics. In the early days of the

1960s, plating began on a commercial level and this was possible only

with the improvement in chemical processing techniques. Industries that

exploited this technique of plating apart from automotive and electronics

were plumbing and appliance related industries. The reasons of this

exploitation were mainly due to the reduced weight, lower cost, design

freedom, and no secondary operations with plated parts. Reduction in

weight of the parts came in handy when the gasoline crisis occurred in

the early 1970s. Polypropylene was one of the earliest plastics to be

plated and today there are many plastics that can be plated, viz, ABS,

Polysulfone, Polyethersulfone, Polyetherimide, Teflon, Polyarylether,

 51

Polycarbonate, Polyphenylene oxide (modified), Polyacetal, Urea

formaldehyde, Diallyl phthalate, Mineral-reinforced nylon (MRN) and

Phenolic [71].

Plastics, being nonconductors, were difficult to plate materials and

thus various methods of metalizing plastics were explored like vacuum

metallization, plating, flame or arc spraying and painting, apart from the

ones discussed above. But, of all the processes, plating was the most

economical methods discovered till date. Plating of plastics includes

electroless and electroplating procedures, that gives the plastic parts a

glossy appearance, enhanced reflectivity, improved abrasion resistance,

high electrical conductivity, and / or to provide electromagnetic shielding

[70]. More about the plating has been discussed in the ensuing

paragraphs.

One important observation that is made during this literature

survey was that, the majority of the work on plating was done

considering the aesthetic and decorative applications only. Very few

literatures address the application of plating from the strength

enhancement point of view. Therefore the present work will be to discuss

the application of plating procedure from strength enhancement point of

view.
 52

2.3.2 Plating of Plastics

2.3.2.1. Electroless Plating

Electroless (without the use of electricity) plating refers to the

deposition of metal layers over a suitably treated / activated surface in a

controlled manner so as to prepare the material / substrate for further

electroplating process [72].

Plating using electroless technique is more frequently used in POPs

due to its advantages like giving an unbroken uniform coating on

materials with greater complexity, its easiness in transforming

nonconductors into conductors, its inexpensiveness, etc., makes it an

affordable and reliable technique for POPs [73-74].

The reducing agent actually converts the metal ions (Mn+) to the

metal (M) which gets plated over a catalytic surface as shown in Eqn. 2.1.

+ + + 2.1

The driving force in electroless plating is an autocatalytic redox

reaction on a pretreated active surface. An important aspect of

electroless plating is the preparation of the surface of the object such

that an active surface is obtained [72] and for that, the electroless plating

process involves degreasing, etching, surface seeding with a catalyst,

electroless plating and electroplating. [75]

(a) The degreasing process is usually a cleaning process that uses

alkaline or acid solutions containing surfactants to remove oils and

 53

other organic chemicals and make the surface of the polymer dirt

free.

(b) Chromic acid and/or sulfuric acid are some of the strong oxidative

acids used for chemical etching [76, 77] or hydrogen peroxide, to

roughen the sample surface for adhesion enhancement [78, 79].

The roughening actually creates a bonding site for further plating

of samples.

(c) Surface seeding with a catalyst involves treating the surface of

polymers with stannous chloride and a palladium chloride solution

alternatively [72].

(d) In the electroless plating, the catalyst imbued polymer substrate is

dipped in a solution containing a metal salt, a reducer, a stabilizer

and a buffer system.

(e) Electroplating involves the deposition of a metal over the

electroless plated substrate, by electrolysis. This process actually

produces a dense, uniform and adherent coating, which may later

be used for decorative and/or protective purposes or for enhancing

the specific properties of the surface.

2.3.2.1.1 Composition of Electroless Plating Bath

A typical electroless plating bath consists of:

(a) A soluble electroactive metal salt (chloride or sulphate).

 54

(b) Reducing agents like hypophosphites, formaldehyde, sodium

borohydride, hydrazine are added to improve the overall plating

process.

(c) To improve the plating quality, complexing agents like tartrate and

citrate are added into the plating bath.

(d) Exaltants like succinate / fluoride are added to the plating bath to

boost the plating rate.

(e) Stabilizers (prevents the instability of the bath) e.g. lead, calcium,

thallium ions, thiourea.

(f) Buffer is added to control the pH.

2.3.2.1.2 Advantages of Electroless Plating

Electroless plating has the following advantages over electroplating:

1. No usage of electrical power

2. Can be used for POPs and semiconductors

3. Due to the better throwing power of electroless baths, complex

shaped articles can be plated with ease.

4. Hydrogen gas liberated is not trapped in blind holes.

5. Coatings that are produced by electroless plating are harder.

6. Levelers are not required in electroless plating.

7. Deposits produced in electroless plating have exclusive

properties (magnetic, electrical, and mechanical).

 55

2.3.2.1.3 Applications of Electroless Plating

Electroless baths have better throwing power. Therefore,

electroless plating is practiced on objects which have complex shapes.

The deposits are pore-free and have better corrosion resistance than

electroplated ones. They give rise to harder surfaces and as a result the

wear resistance also increases. Electroless Ni-P coatings are used in

electronic applications. Polymers such as ABS plastics, coated with

electroless Ni have decorative and functional applications. Thus, knobs

on hi-fi equipments, tops on perfume bottles, costume jewellery and car

trim make use of electroless plating. Plastic cabinets coated with

electroless Cu and Ni are used in digital and electronic instruments for

EMI shielding. The electroless technique is used where plating-through-

holes is required.

2.3.2.1.4 Electroless Plating of Copper

In case of metals, copper from its solution gets attracted towards

metals like gold, silver, platinum, palladium, rhodium, iron, cobalt and

nickel, and the deposition starts impulsively when it comes across these

reducing agents as discussed above, but in insulators like glass and

plastics, the substrates need to be activated before they are subjected to

electroless treatment (plating). A best example for electroless plating is in

case of PCBs, in PCBs the base object is a plastic material and upon

which a layer of Cu is deposited. The reactions occurring in the

electroless plating is as shown in the Eqns. 2.2-2.4

 56

Pretreatment and Activation of the surface

The plastic substrate is first degreased, and then subjected to

etching treatment. The etched samples needs to be activated and this is

done by dipping the etched substrate in a solution made of stannous

chloride and HCl, the solution bath is maintained at room temperature,

say 250C followed by palladium chloride treatment.

Plating Bath Solution

Solution of copper sulphate (12 g/L), reducing agent

formaldehyde (8 g/L) buffer, EDTA complexing agent and exaltant (20

g/L), sodium hydroxide (15 g/L) and Rochelle salt (14 g/L), pH 11

Reactions

Cathode 2+ + 2 2.2

Anode 2 + 4 2 + 22 + 2 + 2 2.3

Overall reaction 2+ + 2 + 4 + 2 + 22 +

2 2.4

Plating Process

The plating is carried out at room temperature by dipping the

activated plastic surface in the bath solution. The temperature is

maintained at about 25 oC. The process is continued till a layer of 5 to

100 m thickness is obtained. The rate of plating is maintained at 1 to 5

m h-1.
 57

2.3.2.1.5 Electroless Nickel Plating

Electroless plating of Ni on aluminium, iron, copper and brass can

be carried out directly in the presence of reducing agents without

activation. The stainless steel surface has to be activated by dipping in a

hot solution of 1:1 sulphuric acid. Magnesium alloys are given a thin

layer of zinc and copper. Insulators such as plastics are subjected to

electroless Ni plating by dipping them in solutions as depicted in Table

2.6. The chemical reactions in electroless Ni process are as shown in

Eqns. 2.5 - 2.7.

Reactions

Cathode 2+ + 2 2.5

Anode 2 2 + 2 2 3 + 2 + + 2 2.6

Overall reaction 2+ + 2 2 + 2 + 2 3 + 2 + 2.7

 58

Table 2.6: Electroless plating (Nickel) procedure. [75]

Sl No. Process Chemicals Concentration

Sodium carbonate (Na2CO3) 50 g/L

Sodium dodecylbenzene
Cleaning / 35 g/L
1 sulfonate (C18H29NaO3S)
degreasing
Disodium metasilicate
3 g/L
(Na2SiO3)

Chromic acid (CrO3) 400 g/L

2 Etching Sodium bisulte (NaHSO3) ---

Sulfuric acid (H2SO4) 400 g/L

Nickel(II) acetate
---
Surface ((CH3CO2)2Ni.4H2O)

3 activation and Cobalt chloride (CoCl2) ---

reduction. Sodium borohydride (NaBH4) ---

Stannous chloride (SnCl2) ---

Nickel sulphate (NiSO4.7H2O) 26 g/L

sodium acetate (CH3CO2Na) 16 g/L

Electroless sodium hypophosphite

38 g/L
4 Nickel plating (H2PO2Na)

bath sodium citrate (C6H5O7Na3) 46 g/L

ammonium hydroxide
To adjust pH = 9
(NH4OH)
 59

Plating process

The plastic substrate is first cleaned with solvents as indicated in

Table 2.6. The cleaned surfaces are given acid treatment, followed by

dipping of acid treated substrates in the electroless Ni plating bath. The

pH is maintained at around 9 and the plating is carried at 930C at a rate

of 20 m per hour. During the reaction, H+ ions are released and this

reaction changes the value of the pH of the solution. This mostly affects

the quality and the rate of plating. The buffer controls the pH during the

plating. The Plating will start only when the temperature of the bath

reaches 700C. It is also observed that at 930C maximum rate of

deposition is achieved, say about; 20 m h-1. A further rise in

temperature leads to the decomposition of the electroplating bath

solution.

2.3.2.2 Electroplating

Electroplating or electrodeposition is the process of deposition of a

layer of metal, over the surface of a substrate by electrolysis. The

substrate may be a conductor like metals, or nonconductors like

polymers, and composites [72]. Electrodeposition can be made on:

(i) Single metals like tin, copper, nickel, chromium, zinc,

cadmium, lead, silver, gold and platinum.

(ii) Alloys like Copper-Zinc, Copper-Tin, Lead-Tin, etc.

(iii) Composites
 60

2.3.2.2.1 Principles of Electrodeposition

The process of electrodeposition is initiated by passing the current

through the suitable electrolyte placed in the tank. The tank composes of

cathode and anode. The cathode is the substrate and the anode is the

metal to be deposited on the cathode. With the passage of electricity, the

metal ions due to the anode in the bath get transferred onto the

substrate. The reactions in the plating bath of the electrolyte MA is

given by:

The ionization of electrolyte in aqueous solution

+
( ) ( ) + ( ) 2.8

Anode dissolves in the electrolyte to give metal ions

+
( )+ 2.9

Cathode takes the reduced metal ions from the electrolyte

+ + 2.10

To maintain the concentration of M+ in the electrolyte of the tank, the

current efficiencies of reactions (2.9) and (2.10) are maintained equal. If

it is not maintained, then there are chances of oxygen evolution from the

anode as seen from the reaction 2.11.

1
2 2 +2 + + 2 2.11
2
 61

Under acid conditions a side reaction involving release of H 2 may take

place as seen from reaction 2.12

1
+ + 2 2 2.12

Also, it becomes necessary to have a solution with high

conductivity and optimum current density to get a good deposit.

2.3.2.2.2 Mechanism of Electrodeposition

Deposition of metal and the crystal growth are fairly similar. The

deposition of metal on the substrate, usually happens in two stages:

(i) Nuclei formation takes place on the substrate. This growth of

nuclei is for a few atomic layers.

(ii) There will be further growth of these atomic layers, which may

grow up to 60 m thick.

It is interesting to note that, for the nuclei formation it is always

necessary to have a higher overvoltage initially. As the formation begins,

they grow more swiftly at a lower overvoltage. The atoms so formed will

promptly occupy a place that helps in further development of atoms into

layers. These places / sites which the atoms occupy are called as kink

sites and here the atoms network themselves with the three

neighbouring atoms as shown in the fig. 2.4. There are also some places

like edge sites where the atoms reside, here it is believed that atoms

interact with two neighbouring atoms or sometimes even remain as

 62

single atoms called adatoms which interact with only one neighbouring

atom. It has been identified by researchers that the phase growth

happens in successive stages, viz.

(1) Atoms start to deposit on the surface of the electrode due to the

mass transport of ions in the solution.

(2) Adatom formation.

(3) Movement of adatoms into the kink sites.

It is to be noted that the steps (2) and (3) play an important role in

the identification of plating deposits. High quality plating is always

exemplified by certain identification and remarkable qualities like (a)

adhesion (b) fine and equally grained structure (c) uniform thickness (d)

throwing power (e) covering power (f) brightness.

Fig. 2.4: Kink sites, edge sites and adatoms on electrodeposited

surface.
 63

2.3.2.3 Effects of Plating Variables

The nature of electrodeposit is affected by several factors. The

important ones are discussed below.

(a) Current Density

The current density (c.d.) is the current per unit area normally

expressed in (mA / cm2) of the electrode surface. At low current densities,

diffusion of ions on the surface is fast compared to the electron transfer

and the adatoms move towards Kink sites that later result in excellent

deposition. Further, with the increase in the current density, the

diffusion of ions slows down and the adatoms may not be able to reach

the most favourable positions. But there will be an increase in nuclei

formation that causes disordered plating, also when the current densities

are higher; there are chances of hydrogen evolution along with the loose

bonding of particles / atoms to the surface of the material to be

electroplated. The hydrogen evolution results in formation of oxides and

hydroxides. Therefore, it becomes important to identify and use the best

possible current density for electroplating purpose.

(b) Plating Bath

The plating bath contains a solution of the metal salt and also in-

order to improve the plating process, the plating bath is added with

additives (organic), buffers, electrolytes, and complexing agents.

 64

(i) Metal-ions: the optimum metal ion (either a simple ion or a

complex ion) concentration is normally 1-3 mol dm-3. Higher

concentrations increase the mass transfer leading to poor

deposit.

(ii) Other electrolytes: Other electrolytes are added to increase the

conductivity of the electroplating bath. These do not help the

plating bath in any having any reactions. These only help in

increasing the conductivity of the plating bath and also to

control the change in pH.

(iii) Complexing agents: These are added to enhance the adhesion

between the electroplated layers and the surface. These also

help in forming fine-grained layers. More often in electroplating

the Complex ions are used:

When the plating ion is known to react with the cathode

metal.

When plating is required at a lower potential.

To improve current efficiency.

To improve the throwing power of the electroplating bath.

Examples of complexing agents are cyanides, hydroxides and

sulphamates. Copper, silver, gold, zinc and cadmium are plated as

smooth deposits in the presence of cyanide ions.

 65

(iv) Organic additives: Organic additives like levellers and

brighteners, wetting agents and structure modifiers are used to

alter the properties of electroplating tank and hence the plating

on surfaces.

Brighteners: These are basically used to give a lustrous

finish for the plated surfaces. These when added into the

tank gives fine deposits. Aromatic sulphones and molecules

containing , = = , = groups (e.g. thiourea and

coumarin) are used as brighteners.

Levellers: Plating happens swiftly in the regions of cracks or

dislocations. These are the areas that attract the ions and

results in producing non-uniform coating thickness on the

surface. Therefore, in-order to tackle with such issues,

levellers are added into the plating bath. Levellers get into

the regions that are prone to faster deposition, thereby,

reduce the electron transfer rate.

Structure modifiers: Commonly known as stress relievers

and have the capacity to change the properties of

electrodeposits. Saccharin is the most commonly used stress

reliever. Many a times electrodeposits may result in the

formation of residual stresses and due to which may result

in microcracking of the deposits

 66

Wetting agents: During electroplating hydrogen is evolved

at the cathode and in-order to liberate hydrogen from getting

entrapped in the surface of the cathode, wetting agents are

added. These agents help the plating baths to acquire

properties such as reduced brittleness of the deposits, for

providing uniform levelling and homogenous plating,

Sodium lauryl sulphate are used as a wetting agent.

(v) pH: From the previous paragraph, it is understood that

hydrogen gas is released at the cathode and the reason for this

is due to the low pH that results in burnt deposits. If the pH of

the plating bath increases, then the possibilities of electrode

getting coated with insoluble hydroxides is more. For that

reason pH in the range of 4 8 is desirable. Buffers are added

during the plating process to control the pH of the plating

solution. Buffers like borate and citrate are used in nickel and

gold plating respectively.

(vi) Temperature: One of the other reasons for hydrogen liberation

at the cathode is the high temperature. The temperature rise of

the bath can lead to the corrosion of the plating tank. It has

also been observed that due to the high temperature the organic

additives have sometimes undergone decomposition. For good

deposits, it becomes important to have reasonable temperature

that enhances surface diffusion and reduce hydrogen evolution.

 67

The optimum temperature for good deposits can be in the range

of 35 and 60 oC.

(vii) Throwing Power: Knowing the throwing power of the plating

bath / tank is particularly essential while plating substrates of

intricate shapes. The ability to completely plate the surface of

the object under consideration is called the throwing power of

the plating bath. Haring Blum cell (fig. 2.5) is mainly used to

find out the throwing power of the plating tank. If uniform

distribution is observed on the substrate then it is said that the

throwing power is good.

The Haring-Blum cell is made up of (i) the electrolyte, (ii)

an anode, positioned at the exact centre of the plating tank, and

(iii) cathodes (two nos.). The cathodes are so positioned that

their distances measured from the anode are C1 and C2, where

C1 > C2 as shown in the fig. 2.5. Once the initial setup is

established, electroplating is performed on both the cathodes.

Later, the amount of metal deposited on both the cathodes is

recorded as w1 and w2 (which represent the masses). It will be

noticed that C1 will have a lesser deposit in comparison to C2.

This is due to the lower over-potential at C1 in comparison to

C2.

Equation 2.14 is used to calculate the throwing power of

the plating bath.

 68

100 ()
% = 2.14
(+2)

Where X = c1/c2 (when c1 > c2) and Y= w2/w1

If the masses w1 and w2 are equal, irrespective of the

distances C1 and C2 of the electrodes, the throwing power is

then to be 100%. It should be remembered that throwing power

cannot be used as a tool to measure the type and character of

the plating. Factors like conductivity, anodes, complexing

agents, and hydrogen evolution are often expressed in terms of

throwing power.

Conductance of the solution: This is an important

factor to be considered for having a uniform rate of deposition

on any intricate substrates. If the plating bath has high

conductance, then the distribution of the current would be

uniform everywhere in the plating bath.

Anodes: Uniform deposition can be attained with the

identification of suitable and most favourable positions for the

anodes in the plating tank.

Complexing agents: addition of levellers and brighteners

into the plating bath improves the throwing power.

Hydrogen evolution: As already discussed hydrogen

evolution poses a major problem such as hydrogen

embrittlement in the cathodes.

 69

Fig. 2.5: The Haring-Blum cell

2.3.2.4 Components of Electroplating

Commercial electroplating depends on the type of metal to be

electroplated, the size and type of substrate material and its number, the

objective of plating and the economics. Depending on the size and the

number of articles to be plated, plating tanks of various sizes and

fixtures are used. Some of the fixtures used are jig or rack mounting for

large scale routine jobs; barrel plating for routine processing of large

batches of small objects; individual mounting for large and single

specialized work pieces (e.g. motor car parts and computer frames) and

wire mounting. A description of a rectangular tank (vat) plating process

is as shown in the fig. 2.6.

 70

Fig. 2.6: Electroplating process

(a) Electroplating tank: Electroplating is generally carried in a steel

tank (vat) lined with polymeric materials on the inner side of the

tank to provide thermal insulation.

(b) Heating Process: The electroplating bath is heated by either

heating coils or hot gases. To maintain uniform temperature of the

electrolyte air is passed through a low pressure compressor that

helps in setting a convection cycle in the plating bath.

(c) Electroplating bath: For electroplating the solution used should

be conducting. Sometimes electrolytes are mixed with certain

chemicals that ultimately increase the conductivity of the solution

and hence the throwing power. For maintaining pH the electrolytes

are added with buffers. Also to improve the deposition process

additives are added. It should also be ensured that tank has

 71

sufficient electrolyte to see that the cathode and anode are

completely immersed in the tank.

(d) Electrical equipment: A DC voltage of 8 to 12 Volts is generally

used in the electroplating process. Also a current density of 1 and

200 mA / cm2 is desirable. This is achieved by using either a motor

generator or DC rectifier units.

(e) Filters used in electroplating tanks: Utmost care has to be

taken with respect to plating bath, as there are chances of metal

particles or sludge from the anode getting mixed with the

electrolyte and disturbing smooth deposition process. These

particles of the anode can be retained by covering it with cotton

bags.

(f) Electrodes - Anode and Cathode: The power (DC) to the

electroplating bath is supplied via bus bars or cables (brass,

aluminium or copper). The cathode and the anode are attached to

these cables and then dipped in the tank. Anodes are those

materials that form a deposit on the cathode. Anodes may be in the

form of plates / rods.

2.3.2.5 Plating Process

The plating process is carried out by pretreating the object followed

by electrolysis.
 72

Pretreatment

The substrate surface should be free from impurities. These are

removed by pretreating the substrate as follows.

(i) Removal of organic impurities (greases): Organic solvents

remove organic impurities like greases from the surface. An

effective method is the vapour phase degreasing, wherein the

vapours of the solvent are allowed to condense on the substrate

surface. Trichloroethylene was previously used for removing

varnish or paint films and resins; perchloroethylene for removing

high melt waxes and 1,1,1-trichloroethane for cleaning PCBs and

other electronic components. These are banned and in their place

non-hazardous substances such as isopropyl alcohol are

recommended. The treatment (alkaline) given to the surface

transforms the surface into a cathode with the removal of

impurities and the treatment is carried in between 60 and 800C.

The current required for this treatment will be in the range of 30 to

80 mA/cm2. This procedure ensures that the impurities are

removed with liberation of hydrogen at the cathode.

(iii)Pickling: removal of oxide scale: after the removal of organic

impurities, the substrate is immersed in 10% sulphuric acid, to

remove the scales formed due to oxidation.

 73

(iv) Polishing: electroplated substrates are further treated by either

chemical or mechanical means to get a polished surface.

(v) Rinsing and drying: The substrate is finally rinsed with hot

deionized water and dried.

Electrolysis

For the electrolysis process, the electricity is passed through the

electrodes that are dipped in the electrolyte. One of the electrodes will be

the substrate (cathode) on which the plating is to be carried out and the

other called anode dissolves in the electrolyte and helps in the deposition

on a substrate under study. The cathode is dipped in the electrolyte only

after it undergoes necessary pretreatment procedures. The plating bath

is maintained at the required temperature. The plating time depends on

the complexity of the substrate to be plated. Sometimes the plating time

varies from a few seconds to several minutes. The plating thickness can

vary from a few microns to 100 microns. There are various plating

processes known and practiced these days and few of them have been

discussed in the ensuing sections.

 74

2.3.2.6 Electroplating of Chromium

Plating bath Chromic acid bath; chromic acid (CrO3) and H2SO4
in 100:1 proportion

Operating 45 - 60 0C
temperature

Current density 100 200 mA / cm2

Current efficiency 8 12%

Anode Insoluble anodes Pb Sb or Pb Sn coated with

PbO2 or stainless steel.

Cathode Objected to be plated; pretreatment

Application Decorative and corrosion resistant finish.

The plating bath contains CrO3 in which Cr is in +6 oxidation

state. This is reduced to +3 oxidation state by a series of complex

reactions in the presence of SO2

4 furnished by H2SO4. Cr3+ ions are

reduced to elemental Cr which gets deposited on the substrate. The

reactions taking place during Cr plating are given below,

3 + 2 2 4 42 + 2 + 2.15

22 4 2 2 7 + 2 2.16

2 2 7 2 72 + 2 + 2.17
 75

.(42 )
2 72 + 14+ + 6 2 3+ + 72 2.18

3+ + 3 2.19

2
2 3+ + 32 23 + 6 2.20

In order to get good deposits it becomes essential to restrict the

quantity of 3+ ions. To control the 3+ ions, anodes that are insoluble

are covered with lead oxide layer. This oxidizes 3+ to 6+ oxidation

state. Usually, anodes made of Cr are not employed in Cr plating and

this is due to the formation of black deposit of Cr obtained in the

presence of large concentration of 3+ ions.

 76

2.3.2.7 Electroplating of Copper and Nickel

Electroplating of Copper
Sulphate bath Cyanide bath
Plating bath 200 - 250 g of CuSO4, 50 - 75 g H2SO4 per L of 40 - 50 g of CuCN, 20 - 30 g of KCN,
bath solution 10 g K2CO3 per L
Operating 20 - 400C 40 - 700C
temperature
Current density 20 50 mA / cm2 10 40 mA / cm2
Addition agents Gelatin, dextrin, sulphur containing brighteners, Sodium thiosulphate
sulphonic acids
Current efficiency (%) 95 99 60 - 90
Anode Phosphorous containing rolled Cu O2 free high conductivity Cu
Cathode Object to be coated pretreated Object to be coated pretreated
Applications In printed circuit boards, low throwing power As an undercoat for Cr plating, in
(not suitable for iron and iron alloy plating) printed circuit boards, good throwing
power
(suitable for iron and iron alloy
plating)
 77

Electroplating of Nickel
Sulphate bath Cyanide bath

Plating bath 250 g of NiSO4, 45 g of NiCl2, 30 g of boric acid 600 g of Ni sulphamate, 5 g of NiCl 2,
40 g of boric acid per L, pH 4

Operating 40 - 700C 50 - 600C

temperature

Current density 20 50 mA / cm2 50 400 mA / cm2

Addition agents Coumarin, Saccharin, benzene sulphonamide Napthalene 1,3, trisulphonic acid

Current efficiency (%) 95 98

Anode Ni pellets or pieces Ni pellets or pieces

Cathode Object to be coated pretreated Object to be coated pretreated

Applications As an undercoat for Cr plating medium throwing Decorative to be coated pretreated,

power Decorative, mirror finish at 400 mA /
cm2
 78

2.3.2.8 Distinction between Electroplating and Electroless Plating

Electroplating Electroless

Driving force Current Autocatalytic redox

reaction

Anode Separate anode Catalytic surface of

substrate

Cathode Object to be plated (treated Object to be plated

to remove surface (treated to make
impurities) surface catalytically
active)

Reducing Electrons Chemical reagents

agent

Applicability Only to conductors Conductors and non

conductors

Nature of Not satisfactory for intricate Satisfactory for all

deposit parts parts.

2.3.2.9 Conductive Paints

Conductive Paints (CPs) have usually been employed to paint

plastics and to realize EMI shielding. This method / technique

requires the inclusion of a conductive filler(s) and pigment(s) into a

binder usually made of resin. Generally, present day CPs are based on

nickel, copper, graphite, or silver. The binders used for manufacturing

of CPs comprises of epoxies, vinyls, polyurethanes, and acrylics [69].

A large variety of Conductive Inks- Paste/ Paints are available in

the market. Some of them are air-drying/curing type, firing type,

 79

thermally conducting and electrically insulating compounds and

grease, some used in PCB repair kits, etc. Conductive Inks- Paste/

Paints are prepared by using conductive metal powder(s) that includes

silver, gold, platinum, palladium, graphite and carbon. The particle

size of the metal powders range from 2 to 25 microns and will be 99.9

percent pure [80].

Conductive painting method offers a radically unusual method

of networking with electronics and its applications. The CPs can today

be used on textiles. These paints can be used as a substitute for acid

etching used in electroless procedure. Most of the CPs developed are

nontoxic and water-soluble, which can be used without gloves and

mask. These paints dry very rapidly / quickly at room temperature

[81].

In the present day, the CP technology that is used commercially

is based on copper and silver. But one disadvantage associated with

copper plating is that, it is prone to oxidation and hence needs a

protective coating upon Cu plating such as Ni coating. The benefits of

using Ni paints when compared with silver and copper CPs is the

permanence of Ni paints, but due to the problem with its conductivity

the use of Ni paints has been restricted from its use in many of the

present day electronic products. Among all the types of coats / paints,

a silver-based CP presents excellent conductivity. Conversely, the

inflated material costs linked with silver paint tend to confine its use

[69].
 80

The Cu and silver paints are being used in EMI/RFI

applications [69] also coatings are used to give decorative surfaces

and also to impart other desirable characteristics such as abrasion

and corrosion resistance, thermal and impact resistance, electrical

and thermal conduction and thermal and optical reflectively [72].

CPs are applied by some usual techniques like High-volume,

low-pressure (HVLP) equipment. The HVLP equipment and robots are

employed for high-volume production; these are used to enhance the

constancy and homogeneity of the CPs during their applications [69].

Before selecting or choosing CPs, the relative cost associated

with it has to be inspected from the process point of view. Differences

in cost of CPs are based on applications, for instance, use of CPs for

certain applications may find it very useful and for some it may be

little more expensive and hence it becomes very important to identify

the variables / elements of the process cost that can play a significant

role in influencing the overall cost. In some cases, the cost associated

with the use of CP and electroless plating are comparable, for

example, applications that require Double-sided plating will involve

less cost in plating, but at the same time requires exterior painting for

the product. Therefore, in such cases CPs can be used to avoid the

plating procedure. Therefore, one has to be careful while choosing

CPs. Sometimes certain factors like fabrication losses, disposal of

waste, etc. needs to be considered [69].

To summarize, CP technology unrelentingly evolved itself with

the product design changes and the convolution of the present day
 81

electronics. The evaluation of CP should be based on the ability of the

process to handle all the important variables / elements of product

design. In addition to that, cost is also an essential consideration that

one has to make in the selection process.