1

DIFFERENT
CHARACHTERISATION
TECHNIQUES OF
ELECTROLESS NICKEL
COATING.
Class : B.M.E.-III
Section : A-1
Under The Guidance of : Professor Rajat
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GROUP MEMBERS:

NAME
ROLL NUMBER

SAYAN DASGUPTA
001411201008
AISHIK ROYCHOUDHURY
001411201009
PARAMESH DAS
001411201010
SHUBHANKAR BANERJEE
001411201011
SOURADIP DAS
001411201012
PRADIP KUMAR HEMBROM
001411201013
 3

What is electroless coating ?

Electroless Metal Deposition is a

chemical reduction process
which involves the auto-catalytic
reduction of metal ions in an
aqueous solution, containing a
chemical reducing agent, and
the subsequent deposition of
metal onto a substrate without
the use of electrical energy.
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Why go for electroless coating ?

Do not require electrical power.
Uniform coating on parts surface
can be achieved.
No sophisticated jigs or fixture is
required.
There is flexibility in plating volume
and thickness.
Excellent corrosion resistance.
Wear and abrasion resistance.
High hardness.
Deeply recessed areas (eg. through
holes)
which are difficult to plate through
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CORROSION RESISTANCE

EN coating is known to offer

superb protection against
corrosion and it is nobler than
steel and aluminium.

In neutral or acidic environment,

alloys
containing high P are more
resistant to
corrosion attack than those with
lower
phosphorus contents .
 6

Applications of electroless nickel

coating

Rail car components such as safety The excessive wear of this aluminum
vents, valve assemblies and cover pelletizer for
plates are plated with electroless polyethylene was overcome by
nickel. electroless nickel
plating.
 7

Wear on meat grinding Electroless nickel

equipment is greatly reduced plated body for
by electroless nickel. large ball valve.

Typical butterfly
valve plated to
provide
corrosion
resistance,
hardness and
lubricity.

Corrosion and wear of down hole drill Electroless nickel plated mud pump
motor rotors are resolved by bodies.
electroless nickel plus chromium
 8

Memory discs present a Electroless nickel

huge and demanding provides a hard,
market for electroless durablecoating with
nickel. good solderability on
heat sinks.

Electroless
The plated TO- 3 power nickel/immersion gold
transistor device is still in deposits now being
large demand by the used on printed circuit
 Experimental
Steps
The entire process can be divided into namely 3
sections:
Synthesis-where we prepare the electroless
coating.
Characterization- where we test the different
properties of the prepared electroless coating.
Computation- where we apply different
optimization techniques to obtain the best
combination of the input parameters.
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Optical
Microscope
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LIMITATIONS OF OPTICAL
MICROSCOPE

Any object thats less than half the wavelength of the

microscopes illumination source is not visible under that
microscope. Light microscopes use visible light, with a
minimum wavelength of 400 nm. This means that we will
never be able to see any object smaller than
approximately 200 nm (about the width of an average-
sized bacterium) using a light microscope.
Also, in practice, many light microscopes cant get close to
this resolution because of lens quality.
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INTRODUCTION OF ELECTRON
MICROSCOPES
A beam of electrons is used to illuminate specimens
and magnetic lenses to magnify images.
As the wavelength of an electron can be up to
100,000 times shorter than that of visible light
photons, electron microscopes have a higher
resolving power than light microscopes.
magnifications of up to about 10,000,000X.
 13

Mainly there are two types of electron

microscopes :

SEM : It detects the electrons which are reflected from

the surface and shows the surface of the
sample.

TEM : It detects the electrons passed through of the

sample and thus shows the interior of the sample.
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Difference between SEM

and TEM
 15

SEM
 Characteristic Information :
SEM
TOPOGRAPHY:
The surface features of an object: Texture; direct relation between
these features and material properties

MORPHOLOGY
The shape and size of the particles making up the object: direct
relation between structure and material properties

COMPOSITION
The elements and compounds of the objects and their relative
amounts: direct relation between composition and material
properties

CRYSTALLOGRAPHIC INFORMATION
Atomic arrangement of the object: direct relation between atomic
arrangements and material properties
Instrument: Actual picture with
block diagram
Electron beam-Sample Interactions

The incident electron beam is scattered in the sample, both

elastically inelastically, which gives rise to various signals that we
can detect.
Interaction volume increases with increasing acceleration voltage
and decreases with increasing atomic number
Essential components of SEM 19
 What comes from specimen?

high energy
Backscattered electrons
compositional contrast
Brightness of regions in
Secondary electrons image increases as atomic
number increases

Fluorescent X-rays

low energy
topographic contrast

composition - EDS
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Overview of SEM characterization

Penetration depths can go deeply below the surfaces

Method Principle Depth Spatial Analytical

analyzed resolution sensitivity

Secondary
electron
SEM emission 5x10^-8 40x10^-8 High, but
induced by m m, typically not
a focused quantitative
electron
beam
spatially
imaged
 Electroless Coating 22

Characterization using SEM

Aluminium plates (7 x 1 x 0.1 cm) were used as the substrate
for Ni-P electroless plating

The substrates were degreased with acetone, alkaline

cleaned with 5% (w/v) sodium hydroxide, acid cleaning with
20% (v/v) HNO3 and zincated before electroless plating

The nanocrystalline Ni-P coatings on aluminium were

analyzed by scanning electron microscope, SEM and the
elemental compositions of the deposits were determined with
an energy dispersive X-ray analysis
 23

The surface structure of as-deposited Ni-P deposit produced

at 30 s shows homogeneous structure as shown in Fig below.
Nickel deposition starts to develop by nucleation after
dissolution of the zincated aluminium substrate

SEM images on two magnifications X3000 & X40000,

plating time 30s
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SEM images in Fig below after 600 s of electroless
deposition show a significant change on the Al surface.
Ni-P deposits formed at 600 s of the as-deposited plate
have tiny spherical nodular structure and formation of
more uniform crystal structure as shown in.

SEM images on two magnifications X3000 & X40000,

plating time 600s
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The surface morphology of Ni-P deposits produced at 1800 s

has smaller crystals with increased dimension and the larger
number of nodular grains, fully covered on the surface of
aluminium without any pores as shown in Fig below.

SEM images on two magnification X3000 & X40000,

plating time 1800s
 26

TEM
Transmission Electron Microscope
The electron beam is produced by an
electron gun

The electron beam is accelerated by an

anode typically at +100 keV (40 to 400
keV) with respect to the cathode.

The electron beam is focused by

electrostatic and electromagnetic lenses,
and transmitted through the specimen
that is in part transparent to electrons
and in part scatters them out of the
beam.

When it emerges from the specimen, the

electron beam carries information about
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Transmission electron microscopy (TEM) is a

microscopy technique in which a beam of
electrons is transmitted through an ultra-thin
specimen, interacting with the specimen as it
passes through it.
An image is formed from the interaction of
the electrons transmitted through the
specimen.
The image is magnified and focused onto an
imaging device, such as a fluorescent screen,
on a layer of photographic film, or to be
detected by a sensor such as a charge-
coupled device
 30

Electron
Gun
The electron gun is formed of the following components
:

the filament
a biasing circuit
a Wehnelt cap
an extraction anode
 31
By connecting the filament to the
negative component power supply,
electrons can be "pumped" from
the electron gun to the anode
plate, and TEM column, thus
completing the circuit.
The gun is designed to create a
beam of electrons exiting from the
assembly at some given angle,
known as the gun divergence
semi-angle, .
By constructing the Wehnelt
cylinder such that it has a higher
negative charge than the filament
itself, electrons that exit the
filament in a diverging manner
are, under proper operation, forced
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Electron Lens

Designed to work similar to optical

lenses.
Focuses parallel electrons at some
constant focal distance.
The majority of electron lenses for
TEM use electromagnetic coils to
generate a convex lens.
Electron lenses are manufactured
from iron, iron-cobalt or nickel cobalt
alloys.
 33

Aperture
s
Apertures are annular metallic plates, through which electrons
that are further than a fixed distance from the optic axis may be
excluded.
Itconsist of a small metallic disc that is sufficiently thick to
prevent electrons from passing through the disc, whilst
Requirement
permitting axial of
electrons.
Aperture
apertures decrease the beam intensity as electrons are filtered
from the beam, which may be desired in the case of beam
sensitive samples.
this filtering removes electrons that are scattered to high
angles, which may be due to unwanted processes such as
spherical or chromatic aberration, or due to diffraction from
interaction within the sample.
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Imaging Methods

Imaging methods in TEM utilize the information contained in the

electron waves exiting from the sample to form an image. The
projector lenses allow for the correct positioning of this electron
wave distribution onto the viewing system. The observed
intensity, I, of the image, assuming sufficiently high quality of
imaging device, can be approximated as proportional to the time-
averaged amplitude of the electron wavefunctions, where the
wave that forms the exit beam is denoted by .
 35

High Resolution images 1,000,000 X

Sub-micron level diffraction
Defect imaging dislocations, twins,
stacking faults, point defects,
antiphase boundaries
Simultaneous imaging, structural and
compositional analysis
Orientation studies possible
Identifying the phases and crystal
structures
Site occupancy of atoms/ions
 36

Sample Preparation

TEM specimens are required to be at most hundreds of nanometers

thick, as unlike neutron or X-Ray radiation the electron beam
interacts readily with the sample, an effect that increases roughly
with atomic number squared (z2). Therefore sample preparation in
TEM can be a complex procedure. Preparation of TEM specimens is
specific to the material under analysis and the desired information
to obtain from the specimen. As such, many generic techniques
have been used for the preparation of the required thin sections.
Some of them are:
Mechanical milling
Chemical etching
Ion etching
Replication
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TEM Diffraction- What can

we infer?
Phases and crystal structure types
Crystal symmetry and space group
Orientation relationships between
phases
Determining growth directions,
interface coherency
Identifying defects , i.e. twinning,
SFs, Dislocations
Ordering behavior of crystal
structures and the site occupancy
preferences
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XRD
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What are X-rays?

When highly energized
electrons are made to
strike metal target ,
electromagnetic radiations
come out. A large part of
this radiation has
wavelength of the order of
0.1 nm or 1A.
 40

If the X-rays coming from a X-ray tube

is examined for all the wavelengths
present, before a minimum value of
wavelength(cut-off wavelength ) no X-
ray is emitted .

At certain sharply defined

wavelengths the K and K This
happens when a the high velocity
electron knocks out another electron
of the target metal from K shell.
Another electron from higher state
(e.g. L or M shell) may make a
transition to the vacancy.

This energy of e is converted to that
S
X-ray Spectrum from an Iron target of a photon responsible for K and K .
W
(suffix for transitions from L and M
 41

History of X-Ray Diffraction

1895 X-rays discovered by
Roentgen
1914 First diffraction pattern of a
crystal made by Knipping and
von Laue
1915 Theory to determine crystal
structure from diffraction
pattern developed by Bragg.
1953 DNA structure solved by
Watson and Crick
Now Diffraction improved by
computer technology; methods
used to determine atomic The first X-ray
 42

From wavelength of K we can find which material it is using Moseleys Law.

MOSELEYS LAW: C (Z )

DIFFRACTION:
Diffraction of a beam may be defined as bending of a beam around
some obstacle.

Scattering
Interaction with a single particle

Diffraction
Interaction with a crystal
 43
How Diffraction Works: Braggs Law
X-rays of
wavelength l

nl=2dsin(Q)

Similar principle to multiple slit experiments

Constructive and destructive interference patterns depend on lattice
spacing (d) and wavelength of radiation (l)
By varying wavelength and observing diffraction patterns, information
about lattice spacing is obtained
 44

2d hkl sin

dhkl dhkl
For parallel planes of atoms, with a space dhkl between the planes, constructive
interference only occurs when Braggs law is satisfied.
In our diffractometers, the X-ray wavelength l is fixed.
Consequently, a family of planes produces a diffraction peak only at a specific
angle q.
Additionally, the plane normal must be parallel to the diffraction vector
Plane normal: the direction perpendicular to a plane of atoms
Diffraction vector: the vector that bisects the angle between the incident and
diffracted beam .
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How Diffraction Works: Schematic
46
 47

Setup

Detector
X-ray Gun

Sample Holder

User can choose to move the sample and detector

(fixed source) or detector and source (sample stage
fixed) at the same time
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XRD patterns of as-deposited electroless nickel coatings (a) Ni-P; (b)

Ni-P-Si3N4
 49

XRD is used to determine

Phase Composition of a Sample
Quantitative Phase Analysis: determine the relative amounts of phases in a mixture by
referencing the relative peak intensities
Unit cell lattice parameters and Bravais lattice symmetry
Index peak positions
Lattice parameters can vary as a function of, and therefore give you information about,
alloying, doping, solid solutions, strains, etc.
Residual Strain (macrostrain)
Crystal Structure
By Rietveld refinement of the entire diffraction pattern
Epitaxy/Texture/Orientation
Crystallite Size and Microstrain
Indicated by peak broadening
Other defects (stacking faults, etc.) can be measured by analysis of peak shapes and
peak width
 50

AFM
51
 52

History
The Scanning Tunneling Microscope (STM) was invented
by G. Binnig and H. Rohrer, for which they were
awarded the Nobel Prize in 1984
A few years later, the first Atomic Force Microscope
(AFM) was developed by G. Binnig, Ch. Gerber, and C.
Quate at Stanford University by gluing a tiny shard of
diamond onto one end of a tiny strip of gold foil
Currently AFM is the most common form of scanning
probe microscopy
How the AFM Works
The AFM brings a probe in close
proximity to the surface
The force is detected by the
deflection of a spring, usually a
cantilever (diving board)
van der Waals force
Forces between the probe tip curve
and the sample are sensed to
control the distance between
the tip and the sample.

53
Non-Contact Mode
Uses attractive forces to
interact surface with tip
Operates within the van der
Waal radii of the atoms
Oscillates cantilever near its
resonant frequency (~ 200
kHz) to improve sensitivity
Advantages over contact: no
lateral forces, non-
destructive/no contamination to
sample, etc.
van der Waals force
curve

54
Contact Mode
Contact mode operates in the
repulsive regime of the van der
Waals curve
Tip attached to cantilever with
low spring constant (lower than
effective spring constant
binding the atoms of the sample
together).
In ambient conditions there is
also a capillary force exerted by
the thin water layer present
(2-50 nm thick).
van der Waals force
curve

55
Force Measurement
The cantilever is designed
with a very low spring
constant (easy to bend) so it
is very sensitive to force.
The laser is focused to reflect
off the cantilever and onto
the sensor
The position of the beam in
the sensor measures the
deflection of the cantilever
and in turn the force between
the tip and the sample.

56
 57

EDAX
 58

EDX Analysis

Energy dispersive X-ray analysis is an analytical

technique used for the elemental analysis or chemical
characterization of a sample.
It relies on an interaction of some source of X-ray
excitation and a sample.
Its characterization capabilities are due in large part to
the fundamental principle that each element has a
unique atomic structure allowing a unique set of peaks
on its electromagnetic emission spectrum (which is the
main principle of spectroscopy).
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Principle of EDX analysis

 60

Equipment required for EDX

analysis
Four primary components of the EDS setup are

the excitation source (electron beam or x-ray beam)

the X-ray detector
the pulse processor
the analyzer.
Electron beam excitation is used in electron microscopes, scanning
electron microscopes (SEM) and scanning transmission electron
microscopes (STEM). X-ray beam excitation is used in X-ray
fluorescence (XRF) spectrometers. A detector is used to convert X-
ray energy into voltage signals; this information is sent to a pulse
processor, which measures the signals and passes them onto an
 61

EDX Spectra of electroless Ni-P-Si3N4

 62

Accuracy of EDAX analysis

Accuracy of EDAX can be affected by various
factors:

Many elements will have overlapping peaks

(e.g., Ti Kand V K, Mn Kand Fe K).
X-rays can be generated by any atom in the
sample that is sufficiently excited by the
incoming beam. These X-rays are emitted in
any direction, and so they may not all escape
the sample. The likelihood of an X-ray escaping
the specimen, and thus being available to
detect and measure, depends on the energy of
the X-ray and the amount and density of
 63

REFERENC
ES:
http://www.electrolessplating.org
Electroless diposition of Nickel by Mordechay Schlesinger.