Mechanical and Tribological

harecterisation Of electroless
ckel coating
Project
Project done
done under
under the
the guidance
guidance of
of :-
:-

Prof.
Prof. Gautam
Gautam Majumdar
Majumdar ,, Jadavpur
Jadavpur University
University

Associated
Associated students
students :-
:-

Amritansh
Amritansh kashyap
kashyap ,B.M.E-3
,B.M.E-3rd ,, Jadavpur
rd
Jadavpur university
university

Niraj
Niraj kr.
kr. Mishra
Mishra ,, B.M.E.-3
B.M.E.-3rd ,, Jadavpur
rd
Jadavpur University
University
Jahangir
Jahangir Khan,
Khan, B.M.E-3
B.M.E-3rd ,, Jadavpur
rd
Jadavpur University
University
What is electro less plating ?
Electro less plating uses a redox reaction to deposit
metal on an object without the passage of an electric
current.
Because it allows a constant metal ion concentration
to bathe
all parts of the object, it deposits metal evenly along
edges, inside holes, and over irregularly shaped
objects which are difficult to plate evenly with
electroplating. Electro less plating is also used to
deposit a conductive surface on a nonconductive
object to allow it to be electroplated.
Electro less technologies have been used for many
decades.
They involve reduction of a complex metal using a
mild reducing agent, typically formaldehyde. For
example,
mirrors can be manufactured using this reaction:
R-CHO + 2 [Ag(NH3)2]OH 2 Ag(s) + RCOONH4+
H2O + 3 NH3
where R is an organic group or hydrogen.
The reaction deposits a shiny coat of elemental silver
on the walls of the container
 ELECTROLESS NICKLE
PLATING

ctro less nickel (EN) plating is a chemical reduction process

ch depends upon the catalytic reduction process of nickel ions
n aqueous solution (containing a chemical reducing agent) and
subsequent deposition of nickel metal without the use of electrical energ
techniques can also be used to manufacture composite coatings by
pending powder in the bath. Electro less nickel plating has several
antages versus electroplating. Free from flux-density and power supply
ues, it provides an even deposit regardless of work piece geometry,
with the proper pre-plate catalyst, can deposit on non-conductive surfac
What are the major steps involved
The plating procedure?
The charecterisation of electroless
coating can be studied under two broad
heads
Mechanical properties
 Melting
point

ctro less nickel deposits do not have a precise melting point but rather have
eltingrange.

is an alloy and as the phosphorus content is increased within the film, the depos
ins to soften at lower temperatures and continues to soften until it eventually m

melting range decreases linearly as the phosphorus levels increase.

eutectic or lowest melting point for NiP alloys is 880C (1620F) and
urs at a deposit phosphorus content of 11% b.w.

e highest melting point is for low Phosphorus deposits (less than 3%) that claim
have melting points at 1,200C (2,200F).
 Magnetic
properties

Electroless nickel coating remain non-magnetic even after one-hour bake cycles
of 250-300C.Due to this the single largest application for electro less nickel
is as a sub layer for computer memory discs.

In recent years, the data storage industry has pushed the high side of this
temperature range even higher. This can be achieved only with
high phosphorus alloys (> 10.5% P) and/or with specific additives.

Reducing the onset and the rate of crystallization, minimizing the volume fractio
of microcrystallinity and maintaining a homogeneous grain structure at higher
bake temperatures are key requirements for optimization of the films
thermomagnetic performance.
 Ductility

lthough electroless nickel is widely considered an engineering coating it does no

ompare well to other coatings in terms of certain mechanical properties.

uctilityis one of these. Electroless nickel is considered a very strong

et brittle material.

he relatively low ductility is due to the various microcrystalline and amorphous

ructures that limitplastic deformation,i.e. the ability to stretch without fractur

t is not uncommon for heavy build deposits (in excess of 25m) to crack when
xposed to severe loads. This is especially evident in lower phosphorus films or
hose plated from older baths (in excess of 150g/l of orthophosphate)
th high tensile stress
 Internal stress

Internal stressplays a role in adhesion, wear and corrosion resistance and

therefore must be regulated or at a minimum, taken notice of.

Internal stress can be developed both extrinsically and intrinsically.

Extrinsic stress is the least insidious and is brought on by differences in

thermal coefficient of expansion between the deposit and the substrate.

When plated on substrates that have a higher COTE than EN (brass and
aluminum for example) the EN deposit will develop tensile stress.

On substrates that have a lower COTE than EN the deposit will be in a

compressive state. This of course, assumes no loss of adhesion or serious
cracking as the component seeks to adjust to the shrinkage.
nsic stress is brought on by the plating process itself.
er phosphorus EN processes operated under good practice will produce deposits
neutral or compressive stress. Lower phosphorus deposits (less than 4%) will als
bit lower tensile stress. This can attributed to the presence of homogenous struct
es .
Tribological
properties
 Friction
hey are similar to those of chromium.

ardchrome is well known as possessing a self healing lubricating film.

hereas EN does not exhibit this feature, it still offers
xcellentlubricity because of presence of phosphorus.

aries with phosphorus/boron contents and with heat treatment

he phosphorus content provides natural lubricity, and minimizes heat buildup

hich can be very useful for applications such as plastic molding.

he coefficient of friction for electroless nickel/boron versus steel is 0.12 to 0.13

or lubricated conditions and 0.43 to 0.44 for un-lubricated conditions

he frictional properties of these coatings vary little with either phosphorus conte
with heat treatment .
Coefficients of friction of chromium coating, electroless nickel(EN) in
the as-deposited condition and after heat treating at 400C (EN400)
and at 600C (EN600) are listed in the below Table

EN coating have higher coefficient of friction then chromium

coating.
 Lubricity
Lubricity plays an important role in optimizing wear resistance.
In electroless Ni-P deposit, the natural lubricity of phosphorus provides a
good lubrication property .
Lubricity can by improved by codeposition of fluorinated carbon (CFX)
or polytetrafluoroethylene (PTFE) particles.

Friction Coefficients of Several Mating Surfaces

Mating Surface Coefficient of Friction

Unlubricated Lubricated

Electroless nickel vs Steel 0.38 0.20

Electroless nickel vs Chrome 0.43 0.30

Deposit hardness
Deposit hardness is one of the key tribological properties of ENP
coating technology.

Factors that affect hardness are the film composition (%P), the heat
treatment
temperature and the heat treatment time.

Typical microhardness values for the as plated ENP deposits range

from
500 to 720 VHN This is in contrast to electrolytically deposited nickel,
which have typical values of 150-400VHN.[

Heat treatment of ENP deposit will significantly increase the

microhardness

The increase in microhardness for ENP films is attributed to the phase

transformations that take place during the heat cycle to form nickel
metal and
nickel phosphide. Some volume shrinkage and cracking of the film will
occur and
must be taken into account if the application requires corrosion
Wear resistance
Electroless Nickel Phosphorus coatings are specified for a wide variety of
engineered
applications related to wear resistance.

This is mainly attributed to the fact that the coatings not only have high
hardness
and intrinsic lubricity but also afford excellent corrosion resistance and
deposit
uniformity.

The wear properties of ENP films can also be enhanced through the
codeposition
of inert particles such as PTFE(polytetrafluoroethene), Silicon Carbide or
Boron Nitride forming a composite coating.

Adhesive wear is defined as the removal of material between mating

surfaces and
measures the films ability to resist galling, welding or seizing.

The adhesive wear resistance of ENP films improves with increasing

phosphorus content.
Table representing wear resistance

The as plated low phosphorus deposits tend to withstand

abrasive wear better than the high phosphorus coatings, largely
attributed to the higher hardness values. However, after heat
treatment the trends remain the same even though the deposit
hardness is similar suggesting that other factors, such as deposit
composition, play a role in abrasive wear resistance.
CORROSION

. Electroless nickel coating is noble than steel and aluminum.

It protects the substrate by providing a pore free barrier coating.

This is in direct contrast to sacrificial films such aszincorzinc
alloythat protect the base material by sacrificing itself.

Due to its amorphous nature in high phosphorus and passivity,

the corrosion resistance of the coating is excellent and in many
environments,
superior than pure nickel or chromium alloys.

Amorphous alloys have better corrosion resistance to attack than

corresponding polycrystalline materials because of their
freedom from grain or phase boundaries, and because of the
glassy films which form on and passivate their surfaces.

Alloys containing high P are more resistant to attack than those

with lower phosphorus contents in neutral or acidic
environments.
Corrosion

Electroless coating has many pin-holes due to hydrogen bubble

evolution during electroless deposition. These pin-holes reduce
the corrosion
protection ability of the coating.

Sol-gel ceramic coating on electroless nickel deposit reduces the

pin-holes
on the surface . Single layer of different inorganic and hybrid
ceramic sols has
been coated on electroless Ni-P coated mild steel followed by
heat treatment
at 400C for 1 h.

Hybrid/inorganic silica, alumina and yttria stabilized zirconia sols

were used to
enhance the corrosion resistance of electroless coating without
modifying its
other properties . Addition of inorganic molybdenum salt or
loys containing low phosphorus (3-4%) are more resistant to strong alkaline
vironments than high phosphorus deposits.

eat treatment on electroless nickel starts forming nickel phosphide

ound 250C, reducing the phosphorus content of the remaining material.
duces the corrosion resistance of the coatings.

he Ni-B alloy coatings are less corrosion resistant than that of high phosphorus
Ni-P alloys.

addition to the results given in the table, tests show nil corrosion rate of both
oatings in benzene, brine (3.5% salt, H2S saturated, 95C), carbon tetrachloride,
otassium hydroxide (50%), sodium hydroxide (45%),water (distilled, N 2 deaerate
00C), water (distilled, O2 saturated, 95C), and water (sea, 3.5% salt, 95C), all
t 20C unless specified otherwise.
Some other physical properties
 Thermal Properties
The coefficient of thermal expansion of electroless nickel coatings varies from
22.3 m/m/C at 3% phosphorus to 11.1 at 11% phosphorus.
For comparison, the value for high purity electrodeposited nickel is in the
range 14 to 17 pm/m/C

Electrical Properties

The resistivity of high purity nickel is 7.8 x 10-6 ohmcm, but that of
electroless nickel can be as much as ten times greater. This results
from the disruption of the regular lattice structure of high purity
nickel by the codeposition of phosphorus and consequently
resistivity of electroless nickel increases with increasing phosphorous
content. Typically, values are in the range of 30 to 100 x 10-6
ohmcm, as shown for low, medium and high phosphorus deposits in
Fig
Thickness Uniformity

A feature of great importance in all applications for electroless

nickel is the ability to produce deposits with a very high degree of
thickness uniformity. It is obviously beneficial when coating
complex parts with critical dimensions, such as ball valves or
threaded components. This huge advantage over
electrodeposited nickel is due to the fact that no current is
involved and the associated problems of current distribution do
not exist
A Glimpse of NANO METROLOGY
NANOMETROLOGY
INTRODUCTION
Metrology is the science of measurement and hence

Nanometrology is the science of measurement at

nanoscale level.
Nanometrology has a crucial role in order to produce

nanomaterials and devices with a high degree of

accuracy and reliability innonmanufacturing.
NANOSTRUCTURE:- A nanostructure IS therefore be

characterised by surfaces, interfaces, grain boundaries,

precipitates, thin layers, particles as small as even a
few atoms, or as large as 100 nm. e.g., peptides,
viruses,etc.
WHY IS NANOMETROLOGY AT ALL IMPORTANT

IMPORTANCE OF NANOMETROLOGY:-
1. Nanotechnology is already a large sector of industry, and is
expected to continue to grow at very fast rate.
2. Precise control of dimensions of objects is the key issue of
nanotechnology and the science of nano-objects. The dimensions
of these objects are below 100 nm and this requires new methods
of measurement to be developed.
3. The measurement techniques developed for conventional
materials could lead to severe mistakes in evaluating results.
4. Standards have to be developed to match technology advances
and support the increasing applications of nanostructures.
Hence, the nanometrology field is a vivid and exciting research
and development area combining chances for discoveries in basic
science and offering commercialisation opportunities.
INDUSTRIAL NANOMETROLOGY AND RESEARCH
NANOMETROLOGY

Research-oriented nanometrology is well established in research

institutes and in industry. However, implementation of industrial
nanometrology is still facing a variety of problems. The main
differences between those two nanometrology streams can be
identified in the area of precision, cost/efficiency and parameter types
and of course conditions in which measurement takes place.
CLASSIFICATION OF NANOMATERIALS ACCORDING TO
DIMENSIONALITY

According to Royal Academy of Engineering,

nanomaterials are classified into 3 groups:-
1. Nanoscale in one dimension: thin films layers
and surfaces.
2. Nanoscale in two dimensions: carbon
nanotubes, inorganic nanotubes, nanowires,
biopolymers .
3. Nanoscale in three dimensions:
nanoparticles, fullerenes, dendrimers,
quantum dots.
NANOMETROLOGY STANDARDISATION INITIATIVES

Nanotechnology is a global enterprise and hence any standards

related to it must be developed with global acceptance.
The most important entity towards this standardisation is the ISO TC

229 technical committee on nanotechnologies, which aims to

develop internationally agreed definitions, standards and metrology
techniques related to nanotechnology.
Other nanoforum partners are:-

1. BSI (British Standards Institution) initiatives.

2. European Committee for Standardization, (CEN) .

3. ISO International Standards Organisation .

4. ANSI (American National Standards Institute) Nanotechnology

Standards Panel .
5. Euspen - European Society for Precision Engineering and
Nanotechnology.
NANOMETROLOGY TECHNIQUES
Important characterisation techniques used in nanometrology are:-
1. Atomic Force Microscopy (AFM) or Scanning Force Microscopy (SFM).
RANGE-depth: 0,5nm-5nm lateral resolution: 0,2-130nm.
2. Electron Diffraction.
RANGE nanometric scale.
3. Scanning Tunneling Microscopy (STM).
RANGE- depth: 1- 5nm lateral resolution: 2-10nm .
4. Transmission Electron Microscopy (TEM)
RANGE - depth: 200nm lateral resolution: 2- 20nm
5. Scanning Transmission Electron Microscopy (STEM) .
RANGE - depth: 200nm lateral resolution: 2- 20nm
6. Energy Dispersive XRay spectroscopy (EDX or EDS or XEDS)
RANGE - 0.1m for heavier atoms and 1m for ligther elements
7. Neutron Diffraction
RANGE Nanometric scale.
8. Auger Electron Spectroscopy (AES)
RANGE - depth: 0,3- 3nm lateral resolution30 nm
REFRENCES
Wikipedia.org
Properties and applicationsof electroless nickel
(Nickel Development Institute ) by Ron Parkinson.
THE ENGINEERING PROPERTIES OF ELECTROLESS NICKEL
COATINGS.
ELECTROLESS NICKEL, ALLOY, COMPOSITE AND NANO
COATINGS - A CRITICAL REVIEW . (Jothi Sudagar Department of
Metallurgical and Materials Engineering, Indian Institute of Technology-Madras
(IIT-M), Chennai - 600 036, India)
Thank you