CHAPTER 2

REVIEW OF LITERATURE

2.1 INTRODUCTION

Electroless Ni plating was first invented by Brenner and Riddell in 1946 [15]. It was
discovered accidently, when they observed that the additive NaH 2PO2 caused apparent
cathode efficiencies of more than 100% in a nickel electroplating bath [15]. They
concluded that some chemical reduction was involved in this process and named as
electrodeless plating. Later the advances in research developed the original process and
soon the name lost ‘de’, therefore, the process is known as electroless coating, however,
‘autocatalytic’ term is also used for the process. The name electroless is somewhat
misleading as no external electrodes are present, but charge transfer (i.e., electric current)
is involved in the process. In this process, the metal is supplied by the metal salt instead
of using an anode, and replenishment is achieved by further addition of metal salt. In the
process cathode is not used for the reduction of metal, however, a reducing agent is used
to provide the electrons i.e., serving as a cathode, since no external current is used in this
process that is why it named as electroless.

2.2 ELECTROLESS COATING TECHNOLOGY

Electroless or autocatalytic plating has been employed to yield metallic coatings of Ni,
Co, Pd, Au and Ag as well as some alloys coatings containing these metals along with P
or B by a controlled chemical reduction, which is catalyzed by the metal or alloy being
deposited. In electroless (autocatalytic) plating sodium hypophosphite, hydrazine,
borohydrides, aminoborane etc., are commonly used as reducing agent to reduce metallic
ions to metal state. The reduction of metallic ions takes place only on activated surface
instead of occurring in all over bath solution (if the process is not controlled properly, the
decomposition of bath can take place i.e., the reduction process occurs in the solution,
possibly on dust particles present in the solution or on metal surface with undesirable
results). Several characteristics possess by electroless plating are not commonly found in
other techniques which result for its increasing popularity among researchers. Unlike
electroplating technique, it can be carried out without any excessive build-up on edges
and projections on a variety of substrate (metallic and non-metallic) to which the solution

9
has access (Fig. 2.1). Due to its unique property to coat all (flat as well as blind) surfaces
evenly, i.e., through this technique the intricate part geometries can be plated uniformly.
Its less porous property makes it better corrosion resistance than electroplates. It requires
very simple arrangement of apparatus (oil bath beakers pH meter and thermometer along
with mechanical stirrer) as compared to electroplating (i.e., power supplies, electrical
contacts, and other apparatus). By this technique non-conducting substances such as
glass, plastic etc., can be coated easily, which is particularly important in the PCB
(printed circuit Board). Several combinations of electroless deposits have extraordinary
or even unique magnetic properties.

Fig. 2.1: Uniform deposition of electroless coating technique.

Electroless is one of the best coating technology in which deposition is purely systematic
chemical process, in which the pretreatment procedure used prior to plating consisted of
following steps: i.e., (a) cleaning (b) surface modification (c) sensitization (d) catalyzing
and (e) activation (acceleration) where rinsing with deionised water is necessary in
between the steps. Here the term sensitization and catalyzing means the deposition of
Sn(II) and/or Sn(IV) ions from acidic SnCl 2 solution. However, in the literature [16]
AgNO3, AuCl3, and metallic Na (in the naphthalene solution) sensitizing agents have also
been reported which are oftenly used. The activation of the substrate surface is usually
carried out by PdCl2 solution, but Au, Pt, Rh, Os and Ag solutions have also been
reported in the literature [16]. It is assumed that the sensitizing ion can reduce the active
metal from the catalyst solution, see Eqn. 2.1.

Pd2+ + Sn2+Sn4+ + Pd0 2.1

10
The growth initiation of nanosized alloy or composite globules upon the catalytic sites
takes place first horizontally then vertically during the reduction process onto the
catalytic surface of the substrate [17]. Here it is important to state that the deposition rate
in the horizontal direction is faster than vertical direction, and this makes the coating
pore free (Fig. 2.2). Marton and Schlesinger [18] have demonstrated that the deposition
of, say, Ni-P on a sensitized-activated surface starts at specific activation sites on the
surface and continues on these points only. As deposition progress, the formation of
islands takes place around these nucleation sites until they unite and incessant coating
results. Both size distribution and density of metal islands are time dependent functions
during the immersion period in the plating bath solution. Reaction continues in this
process as long as the surface remains in contact with the bath solution because coating is
catalytic itself to the reduction reaction. The coating is uniform throughout the surface of
the substrate because no external electric current is used. Therefore, entire surface area of
the substrate, which is immersed uniformly in the bath has the equal probability of
getting ions deposited. As the substrate dip into the bath, deposition starts on surface of
the catalytic substrate, where reduction reaction occurs easily. The deposited metal may
also be catalytic to continue the deposition and thereby, the growth of electroless
deposition is linear with time. A mixed colloidal technology is also used by the
researchers in recent years. It is more reproducible in contrast to separate Sn-Pd
technology and in this technology only a single step is required for implementation.

Fig. 2.2: Schematic representation of nucleation and growth of electroless Ni-P

coating on the substrate [19].

11
2.2.1 Electroless Nickel Bath Description and Function of Individual
Components

Generally, acidic and alkaline baths have been used for depositing alloys. Electroless
bath solution comprises of various chemicals and each of these performs an essential role
[20] in the coating process. The electroless bath characteristics have been described
(Figs. 2.3 (a-b)) by taking nickel as metal ion source as an example given below:

 Source of nickel ions - nickel sulphate or nickel chloride.

 A reducing agent to provide electrons for the reduction of nickel
 Energy (heat)
 Complexing agents (chelates) to direct the free nickel available to the reaction

Reducing Agents

Hypophosphite, borohydride/ dialkyl amino borane and hydrazine are mainly used as
reducing agent and on the basis of the use of these reducing agents the coatings are
grouped as, Ni-P, Ni-B and pure Ni in the coating baths [21], respectively. Out of these
hypophosphite is the strongest and inexpensive reducing agent for electroless Ni-P
coating as compared to the Ni-B electroless coating [22, 23].

(a) Sodium hypophosphite baths

The main benefits of sodium hypophosphite solutions over those reduced by borohydride
or hydrazine is that it is less expensive and better ease of process control, etc. Maximum
percentage of nickel deposited on the substrate from electroless solutions is reduced by
sodium hypophosphite reducing agent. A number of mechanisms have been proposed for
the chemical reactions that occur in hypophosphite reduced electroless nickel plating
solutions. Most commonly accepted mechanisms are discussed below [24, 25].

Electrochemical mechanism, where catalytic oxidation of the hypophosphite yield

electrons at the catalytic surface, which in turn reduces nickel and hydrogen ions, is
illustrated by following Eqns:

H2PO2 + H2O  H2PO3 + 2H+ + 2e 2.2

Ni++ + 2e Ni 2.3

2H+ + 2e H2 2.4

12
H2PO2 + 2H+ + e P + 2H2O 2.5

Atomic hydrogen mechanism, where atomic hydrogen is released as the result of the
catalytic dehydrogenation of hypophosphite molecule adsorbed at the surface, is
illustrated by the following Eqns:

H2PO2+ H2O  HPO32 + H+ +2Hads 2.6

2Hads + Ni++ Ni +2H+ 2.7

H2PO2 + Hads H2O + OH+ P 2.8

The adsorbed active hydrogen, (Eqn. 2.7) then reduces nickel at the surface of the
catalyst.

H2PO2+ H2O H+ + HPO32 + H2 2.9

Through this reaction mechanism, it has been inferred that at the catalytic surface small
amount of the hypophosphite has been reduced by absorbed hydrogen to form hydroxyl
ion and phosphorus (Eqn. 2.8). This mechanism is also able to explain the continuous
deposition of Ni-P instead of Ni-alloy coating due the presence of hypophosphite, which
is catalytic in nature and get oxidized to orthophosphate and gaseous hydrogen (Eqn. 2.9)
which suppresses the deposition of Ni-alloy coating. It has been reported [26, 27] that for
the average efficiency of 37%, to reduce ~1 kg of nickel around 5 kg of sodium
hypophosphite is required. It has also been noticed that the nature of buffer additive can
vary the coefficient of utilization of hypophosphite e.g., for the solution containing
sodium acetate and sodium citrate have the highest and lowest degree of utilization of the
hypophosphite, respectively. While during the progress of the process a change in the
composition of the bath solution occurs e.g., a decrease in the concentration of nickel salt
and hypophosphite, however, an increase in the concentration of acid occurs [26].

13
 Electr
oless
Temp 90 ⁰C (EL)
pH 9
Washe bath
d with Washed with H2O
H2O

Pretreatment Sensitization Washing with

with SnCl2 with PdCl2 water

(a)

(b)

Fig. 2.3: Schematic representation (a) to carry electroless coating on substrate

surface and (b) electroless bath.

14
(b) Amineborane baths: For deposition of Ni-B composite coating only two compounds
viz., n-dimethylamine borane (DMAB: (CH3)2NHBH3) and diethylamine borane (DEAB:
(C2H5)2NHBH3) have been reported [27-29] to be used as reducing agents. DMAB and
DEAB is used primarily in European and USA establishments, respectively. DMAB has
good solubility in aqueous solutions as compared to DEAB, which needs to be dissolved
in organic solvents such as ethanol, before mixing into plating bath. Over a wide range of
pH, DMAB and DEAB are effective reducing agents but due to extensive evolution of
hydrogen an optimum range of pH has been chosen for the deposition process e.g., the
amineborane baths have been used in the pH range of 6 to 9 [28]. The operating pH value
of the bath can also affect the percentage of Ni in the deposit, i.e., % of Ni in the deposit
increases as pH of the bath increases. These baths are generally operated in the
temperature range from 50-80 °C, however that can be used at temperature as low as 30
°C. For plating at non-catalytic surfaces including plastics and non-metals these
aminoborane baths are very useful. The depositions rate (7 to 12 m/h) of the coatings is
a function of pH and temperature and varies on changing either of the parameters [30].

(c) Sodium borohydride baths: For metallic electroless nickel plating borohydride ions,
the most powerful reducing agents are used. Generally, sodium borohydride is preferred
[26] over others due to its high water solubility. As mentioned in the previous paragraph
that in the presence of aminoboranes Ni-B coating occurs, therefore, in case of sodium
borohydride possibility for the formation of Ni-B coating can not be ruled out. It has also
been reported that in the acid or neutral pH range a fast hydrolysis of borohydride ions
occur which in the presence of nickel ions form nickel boride. To prevent the formation
of nickel boride, the pH of the solutions is maintained between 12 and 14, at which the
reaction product is principally elemental nickel. A continuous addition of an alkali
hydroxide is required to maintain the pH of the reaction during the course of reaction.
Sometimes this high operating temperature limits the use of this bath for aluminium
substrates. The reaction between sodium borohydride and nickel ions is in 1:1 molar ratio
i.e., to reduce 1 kg of nickel, 0.6 kg of sodium borohydride is required. To operate the
bath between 12 to 14 pH range, a problem of hydrolysis of nickel ions is very common
and to prevent that ethylenediamine is added to the bath solution as a complexing agents,
which is very effective for this operating pH range and prevent precipitation of nickel
hydroxide. Since the presence of such complexing agents reduces the rate of reaction by

15
masking the free nickel ions and thereby reduces the rate of deposition. It has been
reported [30] that at 90 °C of bath operating temperature the rate of deposition lies ~ 25
to 30 m/h.

(d) Hydrazine baths: Hydrazine baths can also be used to deposit electroless nickel
deposits [31,32]. The operating conditions of these baths are: 90-95 °C temperature range
and 10-11 pH range, but hydrazine baths are very unstable at high temperature and
thereby difficult to control under these operating conditions. The deposition rate of
coatings from hydrazine bath is around 12 m/h and contains high amounts of nickel.
Despite having high % of nickel, these coatings do not look metallic. Apart from this, the
coatings are brittle and highly stressed for practical applications.

(e) Energy: For electroless coating the energy is not important but the operating
temperature of the bath is an important parameter and can affect the rate of deposition. At
operating temperatures below 65 °C, the rate of deposition is low which increases with
increase in temperature and this is true for almost all the systems. The bath is generally,
operated about 90 °C, above which the aqueous solution starts evaporating and the bath
tends to become unstable [33].

(f) Complexing agents: In the electroless coating technique complexing agents also play
an important role to maintain the bath composition or in other words to prevent the
decomposition of bath. As the reaction progress, the concentration of nickel ions
decreases continuously in the solution as a result the rate of reduction of nickel ions
decreases. The solution cannot be replenished due to the excessive precipitation of nickel
phosphate, and the solution tends to decompose. Once the nickel phosphite is
precipitated in the bath, a rough and dark coating results with deteriorated surface
quality. The complexing agents thus form complexes with nickel ions and prevent the
uncontrolled reduction of nickel ions in the solution to some extent. In the literature a
number of complexing agents have been reported [34, 35], e.g.,
glycolic/succinic/malonic acids, sodium citrate, ethylenediammine, etc. It has been
reported [34] that for sodium citrate best results occur at the concentration 30g/l which
effectively reduces the formation of nickel phosphite and helps to check the coating to
become dull and porous.

16
(g) Stabilizers: The addition of Bi, Pb, Cd, Te, thiourea and cyanides in concentrations
of a few ppm (parts per million) can help in stabilizing the electroless bath [30].

(h) Accelerator: On adding complexing agents to the bath the rate of deposition
decreases, therefore, to accelerate the rate of deposition some salts e.g., carbonic acids or
soluble fluorides etc., can also be added to the bath to increase the rate of deposition,
moreover it is also economical. The main function of the accelerator is to break H-P bond
of hypophosphite molecule, allowing phosphorous to be more easily removed and
adsorbed onto the catalytic surface. Succinic acid is the most frequently used accelerator
in hypophosphite reduced solutions.

2.2.2 Factors Affecting the Coating Process

Electroless coating technique is a prominent area of ongoing research for last three
decades and surplus of research papers are available in the literature. The research papers
specially review articles which specifically highlights the factors influencing the coating
process, and characteristics [17,20,30,33,37-40]. The important parameters which chiefly
influence the coating process and characteristics are discussed below and summarized in
Table 2.1.

(a) Concentration of Ni2+ ions in the electroless bath, nickel sulphate (NiSO4) and
nickelchloride (NiCl2) are mainly used as source of Ni 2+ ions for depositing amorphous
alloys. It has been reported [38-39] that the variation of concentration of Ni 2+ ions in the
bath solution has very little influence on the reduction rate of nickel ions. However, high
concentrations of Ni2+ ions can cause the formation of rough deposits and thus
deteriorates the quality of coatings. However, sulphate and chloride salts of nickel result
a systematic and arbitrary [37] deposition, respectively.

(b) Concentration of reducing Agents in the electroless bath reducing agents are the
source of electrons and thus reduce the Ni2+ ions in the bath on the substrate surface.
Therefore, the variation of concentration of reducing the agent can affect the coating
process considerably. The increased concentrations of reducing agents can improve the
rate of reduction of nickel ions, but excessive amounts of reducing agents can not be
used because it may cause reduction to take place in the bulk of the solution. The
optimum concentration of reducing agent can be optimized qualitatively by observing the

17
evolution of hydrogen gas during the course of reaction i.e., the evolution of low and
high amount of hydrogen gas is an indication of a low and high concentration of reducing
agent, respectively. Phosphorus deposited in the process may present as phosphide or as
solid solution.

(c) Properties of sbstrate surface also affect the deposition process e.g., higher
magnetization of deposits has been exhibited on aluminium substrates than on a brass
substrate.

(d) pH of the bath need to be adjusted properly because it is an important parameter and
can affect phosphorus content (Fig. 2.4) in the deposite e.g., if the alkalinity of the
solution increases, phosphorus content of the deposite decreases. One can have low,
medium and high phosphorus content in the deposite by adjusting the pH of the bath (this
is discussed in the next section 2.3). For acidic bath a very bright and smooth surface of
nickel deposits obtained. However, coatings obtained from alkaline bath have a bright
surface.

(e) Temperature of the bath has a considerable influence on the rate of deposition (Fig.
2.4). The rate of the process increases with increase in temperature and attains a
maximum at about 92 °C. Beyond this temperature, the quality of the coating deteriorates
as it is difficult to maintain the pH of the solution. The bath loading factor has also
affected the rate of deposition e.g., as the bath loading factor increases the rate of
deposition increases. There is a critical bath loading factor above which the bath
decomposes totally [38-40].

(f) Effect of heat treatment: Heat treatment is an important and essential part for the
electroless coating process as it can improve the adhesion of the deposite to the substrate
by diffusion and also improves the mechanical properties of the coatings e.g., hardness,
structure and morphology of deposit [41-46] and transformation of deposites from
amorphous to crystalline phase. Agarwala et al., [46] studied the hardness of electroless
Ni-P deposit as a function of annealing temperature (Fig. 2.5) and the group concluded
that the optimum heat treatment temperature for Ni-P deposites is around 400 C/ h as it
results in maximum hardness of electroless nickel coatings (Fig. 2.5). At this temperature

18
 (a) (b)
Fig. 2.4: Effect of solution pH and bath temperature on the plating rate of
electroless nickel deposites [36].

Table 2.1: Components of electroless bath and their functions [22].

Components Function Example

Metal ion Source of metal NiCl2, NiSO4 and (CH3COO)2Ni
Hypophosphite Reducing agent Sodium hypophosphite
ions
Complexing Form nickel complexes, prevent Mono carboxylic acids,
Agent excess free Ni ion concentration dicarboxylic acids,
so stabilizing and preventing Ni Hydroxycarboxylic acids,
phosphate precipitation; also act ammonia and alkanolamines, etc.
as pH buffers
Accelerators Active reducing agent and Anions of some mono- and di-
accelerate deposition; mode of carboxylic acids, fluorides borates
action opposes stabilizers and
complexing agents
Stabilizer Prevent solution breakdown by Pb, Sn, As, Mo, Cd or Th ions and
(inhibitors) shielding catalytically active thiourea, etc.
nuclei
Buffers For long term pH control Sodium salt of certain complexing
agent, choice depends on pH
range used
pH regulators For subsequent pH adjustment Sulfuri acid, hydrochloric acids,
soda, caustic soda and ammonia
solution
Wetting agents Increase wettability of surfaces Ionic and non-ionic surfactants
to be coated

19
the deposites get crystallized as fine particles of Ni 3P, which is evidenced by the powder
XRD and attributed to the increased hardness of the deposites. Heat treatment at higher
temperature for longer duration can cause growth of nickel grains and phosphides
coarsening, which leads to a decrease in progressive hardness. Apart from heat treatment
temperature, the degree of hardening also depends upon time of heat treatment and
percentage of phosphorous content in the deposite. For example, to harden, low
phosphorous (~ 3%) and high phosphorus (10.5-12 %) deposites the recommended
temperature for heat treatment is ~ 350 C and 400 C [40], respectively. Similarly for
electroless Ni-B coatings, heat treatment temperature is reported as 350 °C and 450 C
for 1h, which transforms the amorphous phase of deposite to crystalline Ni 3B and Ni2B
phases. Beyond 450 C the growth of crystalline nickel and conversion of Ni 2B phase to
a more stable Ni3B phase [43] occur.

This improved adherence and strength of the coatings after heat treatment is believed to
come from the chemical surface modification by diffusion bonding between substrate
metal e.g., Al, Cu, Steel, etc., and the alloy coating (Fig. 2.6 a). This can be explained
that during the heat treatment, the diffusion of atoms at the interface of the two layers
(metallic and coated layer) takes place, to form Ni xMy, an intermetallic layers due to the
diffusion bonding (Fig. 2.6 b). This diffusion mechanism is not applicable for ceramics,
glass substates.

Corrosion resistance properties of electroless nickel coatings have also been affected by
heat treatment. It has been found that as-deposited coatings exhibit the best corrosion
resistant properties as compared to heat treated coatings due to the amorphous structure
of as-deposited coatings. As discussed in the previous paragraphs, on heat treatment the
crystallinity of the coatings increases, which results in increased grain boundaries that
serve as active sites for corrosion attack [44]. In a recent report [43] a new kind of
thermochemical treatment has been proposed, which is found to produce better corrosion
resistance in electroless Ni-B coatings compared to normal heat treatment.

20
Fig. 2.5: Effect of heat treatment temperature on the hardness of nickel-
phosphorous coatings [46].

Fig. 2.6 Schematic representation of diffusion bonding mechanism showing, (a)

interface of as-coated electroless Ni-P coating and (b) diffusion layer of Ni xMy at the
interface after heat treatment [47].

2.3 CLASSIFICATION OF ELECTROLESS COATINGS

Electroless coatings may be grouped into three major types, as follows:

1. Metallic coatings (i.e., Pure nickel and copper coatings),

2. Electroless nickel alloy coatings (e.g., Ni-P and Ni-B alloys deposits).
 Polly alloys Ni-P-B and Ni-W-P [41].
3. Electroless composite/ nanocoatings coatings

2.3.1 Electroless Metallic Coating

21
Pure electroless nickel is of great use mainly for semiconductor applications. This is
produced by using hydrazine as a reducing agent for nickel ions present in the bath. But
industrial interest of the coating is restricted due to their high cost and hazardous nature.
However, electroless copper precoating is being used for electroplating on plastics,
ceramics, polymers and non-conducting materials [48,49]. In shielding electronic
devices, electroless copper coating is also utilized. The thickness of these coatings varies
from 0.12 to 3 µm. The typical nickel plating bath composition is as follow: nickel
acetate (60 g/l), glycolic acid (60 g/l), EDTA (ethylene diamine tetra sodium salt, 25 g/l),
hydrazine (100 g/l), sodium hydroxide (30 g/l), pH 10.5-11, and temperature 85-90 C
[50].

2.3.2 Electroless Nickel Alloy Coatings

Apart from plating by reduction reaction, two other methods have also been reported
which include (i) immersion plating on steel from solutions of nickel chloride and boric
acid [51], and (ii) decomposition of nickel carbonyl vapour on steel substrate [52].
However, the later is hazardous, and the first one has a poor adherent and non-protective.
Several binary (e.g., Ni-P and Ni-B) and ternary alloys (Ni-P-B and Ni-W-P, etc.) have
been deposited and reported in the related context. Nickel is the single widely coated
element along with phosphorous and boron. These coatings possess paramagnetic
properties and, therefore, show many industrial applications such as excellent resistance
to wear and corrosion and high hardness. For the deposition of Ni-P and Ni-B alloy
coatings two type of baths are used, i.e., acidic and basic bath.

(a) Acidic bath for Ni-P: A typical bath composition for Ni-P acidic bath is as follow:
nickel sulphate (33 g/l), sodium hypophosphite (20 g/l), lactic acid (28 g/l), sodium
succinate (16 g/l), lead (0.003 g/l) at pH 5-6 (maintained using ammonium hydroxide)
and temperature 85-90 C. Hot acid bath have several advantages over alkaline baths
including high thickness of better quality deposits onto metal surface and relatively high
stability of bath solution during plating. Apart from this, phosphorus content can also be
controlled easily as compared to alkaline baths as given below:

 In acidic and alkaline bath Ni-P and Ni-B alloys deposits [38-39,53]:

Alkaline Bath Acidic Bath

22
 Ni-P alloy Ni-B alloy Coating Properties
(% P) (% B)
3-5 (L) 0.1-2 (L) Excellent wear resistant and corrosion
resistance in concentrated caustic soda.
Ni-P Ni-B
alloy alloy 6-9 (M) 2-5 (M) Shows corrosion protection and abrasion
resistance. The plating bath works
economically.
10-14 (H) 5-10 (H) Very ductile and corrosion resistant against
chlorides solutions.
L = Low; M = Medium; H = High.
The coatings with different phosphorus content posses different properties a few of them
are summarized in Table 2.2.

(b) Acidic bath for Ni-B: The acidic bath composition for electroless nickel-boron
coatings is: nickel chloride (30 g/l), diethylamine borane (3 g/l), methanol (40 g/l),
dimethylamine borane (DMAB, 4 g/l), sodium acetate (20 g/l), sodium succinate (20 g/l)
and sodium cetrate (10 g/l) and the operating conditions are pH 5-6, temperature 50-60
°C. In acidic bath, DMAB is used as a reducing agent for electroless nickel-boron
coatings where boron content varies from 0.1 to 4% [52, 53]. Ni-B coatings have higher
hardness as compared to Ni-P coatings and, therefore, used very oftenly for industrial
wear applications. For coatings having boron more than 1%, possess good ultrasonic
bonding, brazing and soldering characteristics.

(c) Alkaline bath for Ni-P: Nickel–phosphorus deposits are mainly reduced by sodium
hypophosphite and the composition of hot alkaline nickel-phosphorus bath is 30 g/l
nickel chloride, 10 g/l sodium hypophosphite, 65 g/l ammonium citrate, and 50 g/l
ammonium chloride. To produce 10 µm/h rates for deposition, the bath is operated at pH
8-10 and temperature at around 80-90 C. above 90 C, bath pH suddenly decreases due
to loss of ammonia and causes high instability of the bath which is the main disadvantage
of alkaline bath. However, low temperature alkaline bath is used to deposit nickel on
plastics. The deposits from low temperature alkaline solution provide good solderability
for the electronic industry. However, lower adhesion to steel, poor corrosion resistance
and difficulty in processing aluminum at high pH, are the limitations. The thickness of
deposition is very much temperature dependent and so the alkaline bath

Table 2.2: Properties of Ni-P electroless coatings having different phosphorus

concentration.
23
 Property Low-Phosphorus Mid-Phosphorus High-Phosphorus
3 to 4% P, balance 6 to 9% P, balance 11 to 12% P,
Composition
Ni Ni balance Ni
Mixed crystalline
Structure Micro- crystalline Amorphous
and amorphous
Internal Stress -10 MPa +40 MPa -20 MPa
Final Melting Point 1275 ºC 1000 ºC 880 ºC
Density 8.6 g/cm3 8.1 g/cm3 7.8 g/cm3
Coefficient of
12.4 m m/m- ºC 13 m m/m- ºC 12.0 m m/m- ºC
Thermal Expansion
Electrical
30 mW – cm 75 mW –cm 100 mW – cm
Resistivity
Thermal
0.6 W/cm.K 0.05 W/cm.K 0.08 W/cm.K
Conductivity
Specific Heat 1,000 J/kg-K ND 460 J/kg-K
Magnetic Coercivity 10,000 A/m 110 A/m 0
Tensile Strength 300 MPa 900 MPa 800 MPa
Ductility 0.70% 0.70% 1.50%
Modulus of
130 GPa 100-120 GPa 170 GPa
Elasticity
Hardness, as
700 HV100 600 HV100 530 HV100
deposited
Hardness, heat
960 HV100 1000 HV100 1050 HV100
treated
Coefficient of
ND 0.38 0.45
Friction
Taber Wear Index,
11 mg/1,000 cycles 16 mg/1,000 cycles 19 mg/1,000 cycles
as deposited
Taber Wear Index,
9 mg/1,000 cycles 12 mg/1,000 cycles 12 mg/1,000 cycles
heat treated
Corrosion
Protection, salt fog 24 hours 96 hours 1,000 hours
resistance
(Data reproduced with kind permission of Dr. Paul Szymanowski;
[email protected])

found little industrial use. To plate steel and other metals, hot acid hypophosphite-
reduced baths are frequently used. Whereas, for plating plastics and non-metals [27]

24
warm alkaline hypophosphite baths are used. There are several other factors that can
affect the bath life such as surfactants, stabilizers, bath temperature, etc. Surface coating
characteristics such as high hardness, high corrosion and wear resistance, etc. are also
[38-40] improved.

(d) Alkaline bath for Ni-B: For Ni-B, alkaline bath is of two types: hot and cold, the
bath composition for hot condition is as follow:

Hot alkaline bath: For hot alkaline bath the composition is 30 g/l nickel chloride, 60 g/l
ethylenediamine, 1.2 g/l sodium borohydride, 0.07 g/l thallium nitrate, and 40 g/l sodium
hydroxide and the operating pH is 14 and temperature is 90 °C giving a deposition rate of
20-25 µm/h.

Cold alkaline bath: The composition of cold alkaline bath is 30 g/l nickel sulfate, 3 g/l
dimethyl amine borane (DMAB), 15 g/l ammonium citrate, 15 g/l ammonium chloride,
and 0.0002 g/l 2-metcaptobenzo-thiazole and deposition rate is 7-12 µm/h at pH ~ 7.5
and temperature 25-35 °C.

To control nickel hydroxide precipitation, ethylenediamine is used as complexing agent

[39]. A vacuum heating technique is proposed by Dervos et al. [54] which yield a higher
surface hardness in less than 30 minutes as compare to those heating in an inert
atmosphere for several months.

2.3.3 Electroless nickel composite/nanocomposite coatings

Composite coatings are represented by dispersed second phase particulate material into a
metal matrix. Since the co-deposition of second phase particulate material including
(i) hard (diamond, SiC and Al2O3, etc.) and (ii) lubricating (PTFE, Mo 2S, graphite and
BN, etc.) particles can further enhance hardness, anti-sticking, lubricity and anti-wear
properties [38-40]. According to the requirement, soft and hard particles are added as
second phase particles e.g., for wear resistant applications hard particle are added to the
containing coatings, whereas to reduce the friction coefficient (i.e., energy conversion
factor) solid lubricating particles are added [38,39]. Such type of composite coatings
show a wide spectrum of applications e.g., claddings and anti-reflection films, etc., [55]
and in mechanical and electronic industry.

25
Odekerken in 1966 [56], was studied the co-deposition of particulate matter with
electroless nickel coatings, he used an intermediate layer of Al 2O3 and PVC particles
distributed within a metallic matrix. Metzger et al., [57] and S. B. Sharma [38] have
developed electroless nickel coatings containing alumina (Al 2O3) particles of micron
size. The first commercial application of electroless Ni-P-SiC coatings was on the
Wankel (rotary) internal combustion engine [56]. The methodology pursued for
producing the composite coatings was similar to those prevailing in conventional
electroplating. The initial attempts to produce such deposits were not successful because
the dispersion of finely divided second phase particles into the electroless plating bath
increases substantially (i.e., upto 800 times) the surface area of loading. That is not
normally acceptable for conventional electroless plating and ultimately leads to
homogenous decomposition of the bath [58]. Later the coating procedure was improved
by using proper mixing method, by adding surface active substance to the bath or
preparing second phase particles within the electroless bath by using an innovative
process such as sol-gel [59]. The surfactants are used in the colloidal solution to maintain
the uniformity of the solution and stability of the bath and to enhance the adsorption
capacity. The mechanism of particle incorporation in electroless Ni-P matrix has received
very little attention and two methods have been reported to add second phase particles
into Ni-P matrix:

Conventional (or Ex-situ): In this method second phase particles are synthesized outside
and then added to the electroless bath during deposition process so that X is co-deposited
along with Ni-P.

Non-Conventional (or In-situ): In this method second phase particles are synthesized
inside the bath by adding suitable precursors to the bath so that the formation as well as
dispersion of X into Ni-P matrix takes place, simultaneously.

In both the cases i.e., conventional and non-conventional, the reduction reaction process
is followed along with suspensions of particles to produce electroless composite coating.
Several second phase particles such as Al2O3, BN, SiC, TiO2, B4C, MoS2,
C (graphite/diamond), PTFE and Si3N4, etc., [38-40] of micronsize have been
co-deposited successfully into electroless Ni-P matrix. The successful co-deposition of
second phase particles into Ni-P matrix depends on various factors summarized below:

26
(a) Factors Influencing Particle Incorporation: Incorporation of second phase
particles in electroless Ni-P matrix is influenced by several factors including particle
shape, size, relative density and charge on particle, catalytic or inert nature of particles,
and concentration of particles in the plating bath. Apart from this, electroless bath
composition; method and degree of agitation, compatibility of the particle with the
matrix, and the orientation of the particle being plated have also affected the process of
deposition and coating properties. During the deposition process the convection forces
also play an important role, which move the particles straight to the substrate surface
before being definitely incorporated to the growing coating. The size of the particles has
a definite impact on their incorporation in the electroless Ni-P matrix. In general, it is
recommended that particles size should be selected according to the thickness of the
electroless nickel deposit. Particle shape also plays a vital role in determining their
incorporation level. From the previous studies, it has been concluded that angular
particles have a greater tendency to incorporate into metal matrix than round ones.
However, better results have also been obtained with spherical particles of alumina. The
difference in particle shape also affects the finishing of the deposit. Very smooth and very
rough surfaces were obtained from small rounded particles and large angular particles,
respectively [38, 40]. The possibility of second phase particles to get agglomerate can not
be ruled out beyond a critical concentration. Because at high concentration the mean
distance between the particles decreases which, resulting a decrease in the level of
incorporation settlement of the particles. Therefore, concentration of second phase
particles within the bath is very important in the distribution of particles in the deposit
[60]. Surfactants have also played an important role in the incorporation of second phase
particles especially for soft and lubricating particles, e.g., polytetrafluoroethylene
(PTFE), graphite and molybdenum disulfide [61-64].

(b) Inclusion of Second Phase (X) Particles into Ni-P Matrix: Extensive research
has been carried out to control these parameters to co-deposit second phase nano-
particles in the electroless Ni-P matrix and led this old electroless coating technology to a
newer step, i.e., electroless nanocomposite coatings. Several particles have been
incorporated in the nickel matrix and the choice of the co-deposition of second phase (X)
elements depends upon the application. For example, when high wear resistance
properties are the main requirement then hard particle, viz., SiC, WC, Al2O3 and Si3N4,
etc., are preferred for codeposition [38,39,65-67]. Out of Ni-P-X (where X= hard

27
particles), Ni-P-SiC coatings show high hardness and wear resistance to replacing
existing ‘‘hard chromium” plating in the aerospace industry [65-67]. Among others, this
combination (Ni-P-SiC coatings) has proved a cost-effective and best-performing
combination applied in industry.

Dong et al. [68] reported that incorporation of SiO 2 nanoparticles in electroless Ni-P
coating significantly improve the microhardness (on heat treatment at ~ 400 C) and wear
resistance [68] of the coatings. The corrosion resistance property of electroless Ni-P-SiO 2
coatings against salty solutions has significantly improved, where SiO 2 is (2 wt. %; size
~20 nm) [68-69]. To develop Ni-P-TiO2 composite coating a novel technique, i.e.,
addition of transparent TiO2 sol into the conventional electroless plating solution has
been developed by [59]. Microhardness test results show a significant improvement from
~710 HV0.2 to 1025 HV0.2 then conventional Ni-P-TiO2 coating [59].

Furthermore, soft particles such as PTFE, hexagonal boron nitride (BN (h)),
molybdenum disulfide (MoS2), inorganic fullerene-tungsten disulphide (WS2), carbon
nanotubes and graphite (C) provide good lubrication, and are capable of providing a low
lav when incorporated in the electroless Ni-P matrix [61-64,70-76]. These soft/lubricating
particles have ability to prevent the adhesion between the two mating surfaces under
unlubricated conditions. Ebdon [63] has reported that the low coefficient of friction of
Ni-P-PTFE is due to the transfer of PTFE to the counter face material as compared to
plain Ni-P [77], in both as-plated and heat treated (400 C/ h) conditions. Ni-P-inorganic
fullurene-WS2 (nanoparticles) deposit shows increased wear resistance property under oil
lubricated conditions as compared to Ni-P and Ni–P-graphite deposits [70]. This is due to
their ability to work as spacers between the asperities of two metal surfaces [63, 70] in
contact.

For abrasive wear resistance properties, Ni-P-SiC coating has proved to be the most cost
effective and best-performing combination [65-67]. As the incorporation level of SiC
increases wear resistance properties also increase. As-plated Ni-P-BN(h) (where BN(h) =
hexagonal boron nitride) shows higher wear resistance than heat treated (at 400 C for 1
h) Ni-P coating [71]. However, wear resistance properties nearly doubles when the Ni-P
matrix is incorporated with 33 vol. % BN(h) particles [71].

In-situ co-precipitation of X particles in Ni-P-X (X=ZrO 2-Al2O3-Al3Zr) deposit has been

carried out by Sharma et al., [78, 79] using alkaline bath. The coating has been developed
28
on three different substrate materials like low carbon steel, commercial aluminum, and
carbon fabric and studied their tribological behaviour. The wettability of Ni-P coated
fabric in the liquid aluminum alloy matrix has also been studied [78, 79]. Alumina
powder (Al2O3 of size 50, 300 and 1000 nm) has been co-deposited into Ni-P matrix and
studied [79] to see the influence of particle size on the hardness, microstructure and
corrosion resistance properties. As barium hexaferrite (BaZn 2-yCoyFe16O27) is an
important magnetic material and widely used as magnetic recording media, permanent
magnet and microwave absorbers [80]. Therefore, attempts to incorporate nano barium
hexaferrite into electroless Ni-P matrix have also been made [80] and reported to show
microwave absorption properties [80]. Increased wear resistance [81-83] property has
been observed for Ni-P-X particles (X= Cr3C2 (27 vol. %), teflon, diamond). Winowlin
Jappes et al., [83] has studied corrosion resistance of Ni-P-diamond composite coatings
against 3.5 wt. % NaCl solution, which, show a marginal increase incorrosion resistance
compared to plain Ni-P deposit. In few research papers [84-86], corrosion resistance of
composite coatings Ni-P-CeO2 [85] and Ni-P-TiO2 [86] determined by electrochemical
impedance spectroscopy, that show better corrosion resistance than the plain Ni-P
deposits. Due to smaller tendency of CeO 2 containing coating to undergoing local cell
corrosion, it shows better corrosion resistance than plain in 3.5 wt. % NaCl solution [85]
at room temperature, Ni-P-Fe3O4 composite coatings exhibit better corrosion resistance
than plain Ni-P coatings [87]. Shibli et al. [11, 12] reported improved corrosion
resistance on incorporation of ZnO nanoparticles in the Ni-P matrix. On TiO 2 powders of
~ 10 nm size have also been coated with Ni-P [86].

Corrosion and tarnish resistance properties of Ni-P-X (where nanosized X = SiO 2, CeO2
[68,69,85], Zn3(PO4)2, ZnSnO3, and ZnSiO3 [88] particles) have also been discussed. The
mechanism for codeposition of nanometer diamond particle along with Ni-P has been
explained [89] and studied for their anti-fretting and anti-wear properties. It has been
observed that it shows excellent anti-fretting and wear properties for high load at room
temperature than nano-diamond composite coating prepared by electro-brush plating
[90]. Higher micro-hardness, of these coatings especially, at relatively high temperature
is observed as compared to conventional Ni-P coating. Reddy et al. [91] reported the
wear resistance of Ni-P-diamond, for different size diamond particles (range: 3-40 µm).
The inference made from the study is that the coatings with finer C particles (3-6 µm) are
more wear resistant as compared to particles of bigger size (20-40 µm). Since at given

29
thickness more number of fine particles with small size can be incorporated. A recent
study also reports that the coatings with diamond particles of size (~ 4-8 µm) exhibit
better wear resistance when compared to coating dispersed with larger diamond particles
[92]. Xiang et al. [93] reported that the nanosized diamond particles (0.52-2.21 wt. %) in
Ni-P matrix changed the surface properties from smooth and bright to rough and foggy,
with nodular surface. Increased oxidation resistance for Ni-P-X (where X = Si 3N4 (8.01
wt. %), CeO2 (7.44 wt. %) or TiO2 (5.42 wt. %)) has been reported [38]. Ni-P-Fe3O4
composite coatings show better resistance to cyclic oxidation test at 800 C in air.

Bozzini et al., [94] reported the magnetic dependency of Ni-P-B 4C in as-deposited and
heat treated condition. In as-deposited form, the coating exhibits a strong dependence of
magnetic susceptibility in applied magnetic field because of larger structural
heterogeneity as compared to plain Ni-P deposit. Further on heat treatment, composite
coatings preserved field dependence and exhibit typical super paramagnetic nature,
whereas plain Ni-P deposits became homogeneous and attained ferromagnetic nature.
The difference in magnetic behavior of these coatings is due to the concentration of B 4C
(25 vol. %) which acts as main reason for the nickel phase precipitation.

Recently carbon nanotubes (CNT) are co-deposited in Ni-P matrix and their tribological
properties are evaluated [72-76]. Carbon nanotubes are the most typical one dimensional
nanomaterial (in order of micrometers in length and nanometers in diameter), which
possess unique topological hollow tubular structure. CNT has many potential and
practical applications due to their outstanding electrical and physical properties. The Ni-
P-CNT composite coatings are successfully fabricated by suspension of CNT in an
electroless bath [76]. Ni-P-CNT (CNT = 12 vol. %) and exhibit better wear resistance
than that of Ni-P-SiC and Ni-P-graphite, in both as-plated and heat-treated conditions
[72]. Ni-P-CNT provides a low coefficient of friction [72-73] with significantly
improved electrochemical characteristics. CNTs can be impregnated into very small
pores in the porous Ni-matrix to make the passive film more stable and compact because
of that, it shows excellent corrosion resistance and high microhardness. Ni-P-CNT
composite coatings have wide applications in modern electronic industry.

By chemical vapour deposition in a microwave heating system at 650 C in methane gas,

carbon nanofibers (CNFs) were fabricated along with Ni-P alloy on a Si substrate [95].
The catalytic Ni-P alloy film, without any pre-treatment, provides nucleation sites for

30
CNFs to grow. The CNFs grown on the Ni-P alloy catalytic surface showed random
orientation, composed of parallel graphite planes with defects tilted from their axis. It has
been reported [95] that Ni-P catalyzed CNFs exhibited excellent field emission
properties.

2.4 PROPERTIES OF ELECTROLESS COATINGS

Some of the chemical, physical, electrical and mechanical properties of varying

concentration of phosphorous (low, medium and high) content are summarized in Table
2.2 in previous section. However, features and benefits of the coatings are summarized in
Table 2.3. Therefore, it is relevant to describe briefly other important properties of
electroless coatings such as hardness, wear resistant and corrosion resistant properties of
the coatings.

2.4.1 Hardness

For many successful applications hardness of electroless nickel deposits is a very

important parameter. It is strongly influenced by the phosphorus content in as-deposited
condition. Heat treatment of electroless nickel results in a dramatic increase in hardness.
The optimum temperature range for heat treatment of electroless nickel is described
between 345 to 400 °C. Hardness for low phosphorus deposits in as-deposited condition
is good. Hardness of all types of deposites increases dramatically in the range of ~ 850 to
950 HK100. However, all deposits have greater hardness values than electrodeposited
nickel.

2.4.2 Ductility

For phosphorus content within the normal operating range [17,20,38,39] electroless
nickel deposits possess a low ductility. The coatings are hard and brittle, and elongation
to fracture is typically 1 to 2.5 %. On heat treatment, hardness of electroless nickel
increases ductility reduces.

Table 2.3: Properties of electroless nickel coatings (Source: www.macdermid.com).

Feature Benefit
Excellent corrosion resistant Good coating durability
High hardness Low wear characteristics
Low friction co-deposits available Self-lubricating coating

31
Deposit uniformity Eliminates post plate finish
Good brightness Attractive finish
Fast plating rate High production output
Good chemical resistance Acts as protective coating
Solderability/weldability/brazeability Functional in many applications
Non-magnetic/magnetic Magnetic property selectivity

2.4.3 Wear Resistance

Because of high hardness and good natural lubricity, electroless nickel coatings exhibit
good wear resistance. Wear resistance of deposits can be enhanced by heat treatment and
codeposition of particulate matter (e.g., silicon carbide, diamond, alumina, fluorinated
carbon and polytetrafluoroethylene). In the as-plated condition electroless nickel coatings
have good resistance to erosion and abrasion. However, heat treatment of deposit can
significantly improve hardness and wear resistance. Therefore, hardness of electroless
nickel deposits depends mainly on heat treatment and phosphorus content that can be
advantageous to prevent galling. Low phosphorus deposits provide better wear properties
[17,20,38,39] in the as-deposited condition, and this would naturally be attributed to
greater hardness.

2.4.4 Corrosion Resistance

The major reason for wide spread use of electroless nickel is due to its high corrosion
resistance, which enables it to use as a protective coating. All electroless nickel deposits
do not perform in the same way. Depending on the specific exposure conditions the
coatings must be selected to meet the requirements e.g., high phosphorus deposits are (i)
good performer at elevated temperature than low phosphorus deposits, and (ii) superior
in neutral or acidic media than strongly alkaline media. Electroless nickel deposits have
very low porosity and uniform thickness. As the thickness of coating increases porosity
decreases and for deposits phosphorus (containing ~ 10% P) [17, 39] tendency to form
porous coatings is greatly reduced. However, on heat treatment an increase in porosity of
the coating generally occurs, which decreases corrosion resistance. This is probably due
to the formation of micro cracks [17, 39] and is of most concern with high phosphorus
deposits.

32
2.5 Applications of Electroless Ni-P Coatings

Electroless nickel coatings are mainly used for wear resistance, corrosion resistance,
lubricity, buildup of worn over machined surfaces and solderability. By all segments of
the industry in varying degrees, these properties are utilized either separately or in
combination; some of them are summarized in Table 2.4. In engineering coating
applications, where high hardness, wear resistance and corrosion protection are required
these coatings are commonly used. Applications include oil field valves, drive shafts,
rotors, paper handling equipment, fuel rails, door knobs, kitchen utensils, and optical
surfaces for diamond turning, bathroom fixtures, electrical/mechanical tools and office
equipment, etc. It is also commonly used as a coating in electronics printed circuit
board and hard disk drives manufacturing. The coating can be used to salvage worn parts
due to its high hardness. Its use in the automotive industry for wear resistance has
increased significantly.

Several industries in which electroless nickel has been used successfully are summarized
earlier by our group, i.e., Agarwala et al., [30] and are shown in Table 2.4. It does not
assume that this table covers all the section of industries in which electroless nickel is
being used. The important properties of electroless nickel deposits in various industries

Table 2.4: Application of electroless Ni-P coatings.

Application Components Coating
avenue thickness
(µm)
Automotive Heat sinks, carburettor components, fuel injection, ball 2–38
studs, differential pinion ball shafts, disk brake pistons and
pad holders, transmission thrust washers, synchromesh
gears, knuckle pins, exhaust manifolds and pipes, mufflers,
33
 shock absorbers, lock components, hose couplings, gear
and gear assemblies. Fuel pump motors, aluminium
wheels, water pump components, steering column wheel
components, air bag hardware, air conditioning compressor
components, decorative plastics and slip yokes
Air craft/ Bearing journals, servo valves, compressor blades, hot 10–50
zone hardware,pistons heads, engine main shafts and
Aerospace
propellers, hydraulic actuator splines, seal snaps and
spacers, landing gear components, pilot tables, gyro parts,
engine mounts, oil nozzle components, turbine front
bearing cases, engine mount insulator housing, flanges, sun
gears, breech caps, shear bolts, engine oil feed tubes,
flexible bearing supports, break attach bolts, antirotational
plates, wing flap universal joints and titanium thruster
tracks
Chemical & Pressure vessels, reactors, mixer shafts, pumps and 25–125
impellers, heat exchangers, filters and components, turbine
petroleum
blades and rotor assembles, compressor blades and
impellers, spray nozzles, valves: ball, gate, plug, check and
butterfly, stainless steel valves, chokes and control valves,
oil field tools, oil well packers and equipment, oil well
turbine and pumps, drilling mud pumps, hydraulic systems
actuators and blowout preventors
Electrical Motor shafts, rotor blades of stator rings 12–25
Motor
Electronics Head sinks, computer drive mechanisms, chassis memory 12–25
drums and discs, terminals of lead wires, connectors, diode
and transistor cans, interlocks, junction fittings and PCB
Food Pneumatic canning machinery, baking pans, moulds, grills 12–25
and freezers, mixing louts, bun warmers, feed screw and
extruders
Marine Marine hardware, pumps and equipment 25–50
Material Hydraulic cylinders, shafts, extruders, link drive belts, 12–75
gearsand clutches
Handling
Medical & Disposable surgical instruments and equipment, sizering 12–25
screens, pill sorters, feed screws and extruders
Pharmaceutica
l
Military Fuse assemblies, tank tarred bearings, radarwave guides, 8–75
mirrors,motors, detonators and firearms

Mining Hydraulic systems, jetting pump heads, mine engine 30–60

components,piping connections, framing hardware

Moulds & dies Zinc dies, cast dies, glass moulds, plastic injection moulds 15–50

34
 ofplastic and extrusion dies
Printing Printing rolls and press beds ~38
Rail road Tank cars, diesel engine shafts and car hardware 20–90
Textiles Feeds and guides, fabric knives, spinnerets, loom ratchets 12–50
andknitting needles

Wood & paper Knife holder corer plates, abrading plates and machine ~30
parts.
Miscellaneous Chain saw engine ~25
Drills and taps ~12
Precision tools ~12
Shower blades and heads ~8
Pen tips ~5

are shown in Fig. 2.7 and a few examples on which electroless Ni coating was
successfully done and use in various sectors are shown in Fig. 2.8.

However, the Table 2.4 includes applications in many major industries. In relations to
specific properties, successful performance of the coating has also been described. It is
anticipated through presentation of this information, that new opportunities for the use of
electroless nickel coatings will become apparent to those not already familiar with their
broad range of properties. This information will help future researcher to find new ways
for promoting growth of these in the industry, for new applications.

35
 Fig. 2.7: Primary uses for electroless nickel deposits (source: www.pfonline.com).

Fig.2.8: A variety of pins, washers and equipments plated with electroless nickel
alloy coating use in different industries (source:
http://en.wikipedia.org/wiki/Electroless_nickel ).

36
2.6 ZINC OXIDE (ZnO)

For the desired corrosion resistance along with antibacterial property of electroless
composite nanocoating of Ni-P, the inorganic antibacterial agents play the key role.
Different applications and classification in terms of chemical composition of antibacterial
nanoparticles are shown in Fig. 2.9 (a)-(b) [96]. Among inorganic materials, metal oxides
such as TiO2, ZnO, MgO and CaO are of great interest as they are stable under harsh
process conditions [97, 98]. As well as these materials are regarded as safe materials for
human beings and animals [97, 98].

Among these metal oxides, ZnO and ZnO-based materials demonstrate significant
antimicrobial activity as they are non-irritating, and absorb moisture and odours.
Moreover, due to its non-toxic nature and compatible with skin, it is used as an additive
for textile and surfaces of common use [99-101]. Due to attenuation properties it is also
used as an effective additive to packaging plastics and to protect from UV damages [100,
102]. Thermal stability of zinc oxide based materials enables it to be incorporated into
plastics and also shows activity in the condition that experience extreme processing or
harsh application environments. Nanoscale zinc oxide offers greater surface area than
their bulk counter-parts, which improves product performances in several ways:

1. Easy incorporation into surface coatings (paints), plastics and textiles.

2. Increased surface area of nanosized ZnO increases its interaction with bacteria.
This makes use of a small amount of ZnO for the same or improved biostatic
behavior.
3. After being exposed to direct sunlight it prevents paint from peeling, plastics and
resins from cracking.

4. ZnO is biosafe and biocompatible and can be used for biomedical applications
[103].

Apart from this, ZnO is a transparent conductive oxide (TCO), i.e., electrically
conducting and transparent in the visible region [104]. Due to a direct wide band gap
(3.37 eV) and large exciton binding energy (60 MeV) it is an attractive material for blue
light-emitting devices (LEDs) and ultraviolet light-emitting devices. Several studies
[105-108] have been carried out as its application for photo transistors [105],
photovoltaic solar cells [107-108], gas sensors [106] and other optoelectronic devices.

37
Low cost of ZnO compared with other materials makes it a good candidate for industrial
applications.

To develop Ni-P-ZnO composite coatings by conventional or nonconventional method,

the ZnO nanoparticles are either produced out-side the bath or inside the bath. There are
several investigations are available in the literature [108-115], on the synthesis of ZnO
nanoparticles by different routes. ZnO is a versatile compound which can be produced in
different morphologies by changing composition of reaction mixture or reaction
operation conditions. The synthesis of ZnO particles can be carried out by different
methods viz., hydrolysis of zinc precursor [109], hydrothermal methods [112] and
electrochemical routes [114], etc. Out of these, the hydrolysis route is very attractive as it
is relatively easy to perform and allows us to tailor the morphology of ZnO particles.
Morphology of the particles can be controlled by controlling the rate of hydrolysis and
condensation reactions [112,115].

ZnO particles are also developed having different morphologies e.g., nanobelts of ZnO of
length 700 mm have been obtained by Hossain et al. [116], using refluxing technique. To
obtain nanoparticles of size less than 5nm, it is necessary to prevent particle
agglomeration [114,115], for which different capping agent such as polyvinyl pyridine
(PVP), polyethylene glycol (PEG), etc. have been used. Hydrothermal method is
commonly used for more than 50 years [108,112,117], to synthesize ZnO nanoparticles
with different morphologies at lower temperatures (80 °C to 200 °C). In the present study
sol-gel, mechanical milling and autocombustion methods are used to synthesize ZnO
nanoparticles. As these metods present an easy way to prepare ZnO nanoparticles. Apart
from this, these are simple and offer the possibility of excellent compositional control,
lower crystallization temperature, homogeneity, and low production costs. Several
investigations have also been carried out on antibacterial activity and toxicity of ZnO
nanoparticles [118-125]. The methods used for the present study are summarized here in
detail.

38
 (a)

( b)

Fig. 2.9: (a) The scope of antibacterial nanoparticles practical applications (b) The
classification of antibacterial nanoparticles in terms of chemical composition [96].
39
2.6.1 Sol-gel Method of Synthesis

In this work ZnO powder was synthesized using sol–gel route [126-128]. Sol-gel
materials encompass a wide range of inorganic and organic/ inorganic composite
materials which share a common preparation strategy. They are prepared via sol-gel
processing involving the generation of colloidal suspensions (“sols”) which are
subsequently converted to viscous gels and then to solid materials. A sol is a dispersion
of colloidal particles suspended in Brownian motion within a fluid matrix. Colloids are
suspensions of particles of linear dimensions between 1nm (10Å) and 1µm (104Å).

2.6.2 Mechanochemical Synthesis

Milling of precursor powders leads to the formation of a nanoscale composite structure

of the starting materials that react during milling or subsequent heat treatment to form a
mixture of separated nanocrystals of the desired phase within a soluble salt matrix
[129,130]. The separation of the nanoparticles will occur due to existence of NaCl that
prevents the subsequent agglomeration ZnO nanoparticles during calcination. Removal
of the salt matrix is usually carried out through simple washing. For example, ultrafine
ZnO powder was synthesized by the milling and subsequent heat treatment of a ZnCl 2,
NaCl and Na2CO3 powder mixture. Removal of the NaCl with a simple washing process
resulted in separated ZnO particles [129-130].

2.6.3 Autocombustion Method

Auto combustion method is also known as self-propagating high temperature synthesis

(SHS) is widely used for the synthesis of a variety of oxides as it presents some
advantages over other methods including requirement of simple reagents, dopants can be
easily introduced into the final product, and agglomeration of powders remains limited
[131]. The method uses the energy produced by the exothermic decomposition of a redox
mixture of metal nitrates with an organic compound. In the combustion mixture, nitrates
and organic compounds behave like conventional oxidants and fuels. The reaction is
carried out by dissolving metal nitrates and fuels in a minimum amount of water in a
pyrex dish and heating the mixture in order to evaporate water in excess. The resulting
viscous liquid foams, ignites, and undergoes self-sustained combustion, producing ashes
containing the oxide product. During the combustion, exothermic redox reactions
associated with nitrate decomposition and fuel oxidation take place. Gases such as N 2,
40
H2O, and CO2 evolve, favouring the formation of fine particle ashes after only a few
minutes. The properties of the final product (particle size, surface area and porosity)
depend on the method of combustion. The departure of gases favours the desegregation
of the products (increases the porosity) and heat dissipation (inhibits the sintering of the
products). Exothermicity of combustion is controlled by the nature of the fuel and the
ratio of oxidizer to fuel. The combustion synthesis is also advantageous over the solid
state synthesis in terms of better compositional homogeneity and purity of the final
product. However, only a few efforts have been made to correlate the effect of synthesis
parameters like pH, fuel-to-oxidant ratio and effect of different fuels with powder
characteristics. In this study ZnO is prepared by autocombustion method.

2.7 RESEARCH GAPS

41
The review of literature outlines the different aspects of electroless nickel coatings. In
particular, it reviews the methods of formation of electroless nickel–phosphorus/boron,
polyalloys, composite/nano-composite coatings with different particulate material and
their effect on coating characteristics, applications and their recent developments. It also
includes applications in many major industries and the successful performance of the
coating has been described in relationship to specific properties. The review of literature
also outlines the properties and different synthetic methods of zinc oxide nanoparticles.
Through the extensive survey of literature the following gaps have been identified:

1. A few reports have been found in the literature on nano composite Ni-P-ZnO coatings
[11-13], to the best of author’s knowledge. Thus work in the area of synthesis of nano
composite Ni-P-ZnO coatings using electroless coating technique on different
substrates and testing them for corrosion protection and for providing microbial
resistance is more desirable.

2. The wear resistant and anti-corrosion properties of the Ni-P-X coatings have been
reported for a wide variety of hard (X= SiC, Al2O3, B4C, WC and diamond etc.,) and
soft particles (X= Graphite, WS2, MoS2 and PTFE, etc.) [59-76], but a limited studies
have been reported in literature on Ni-P-ZnO [11-13]. Therefore, it is desirable to
study anticorrosion properties of Ni-P-ZnO composite coatings.

3. Attention towards antibacterial property of Ni-P-X composite/nanocomposite coatings

has not been paid, only one research paper has been published recently on Ni-P-TiO 2
[59], therefore, it is worth mentioning to study their antibacterial activity.

Therefore, in the present thesis, it is proposed to develop some new class of electroless
composite coating of Ni-P by incorporating synthesised nanosized ZnO particles. It is
proposed that the coating developed will possess antibacterial activity and could prevent
the transmission of bacterial infection along with improved hardness and corrosion
resistance.

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