SURFACE MODIFICATION

Surface Modification- Why ?

•To increase the wear resistance

•To modify the frictional behavior

Related Factors
Adhesion
Hardness
Brittleness
Strength
Impact Strength
 WEAR PROTECTION/TRIBOLOGY

Real tribological problems are extremely complex!

- Interdisciplinary
- Contact mechanics, adhesion, elasticity,
plasticity, fracture
- Chemical interaction
- Environment (temperature, humidity)
 SURFACE TOPOGRAPHY

Adsorption layer
• gases, ...
• few Å
Oxide layer
• 1 - 10 nm
Beilby-Layer
• extremely deformed until
amorphous
• 0,1 - 1 µm
Plastically deformed zone
• deformation possible
• 5 - 10 µm
Elastically deformed zone
Surface of the solid in contact
Base material
with the environment
SURFACE ENGINEERING

Objective : -
Optimization of the functioning of a component by
varying the surface features
How ?
o Surface modification.
o Characterization of layers on the surface.
(Microstructure, chemical composition, properties)
o Understanding the correlation between formation-
production - process, microstructure and properties.
Surface Engineering: Example
Turbine Blades

Service Conditions:
• High Temperature (Until 1400°C)
• Oxidative Atmosphere
• High Mechanical Load
Material Requirements
- Thermal Stability
- Oxidation-/Corrosion -Resistance
- Mechanical Stability At High Temp.
(Creep Resistance, Fatigue Strength)
Surface Engineering: Example
Turbine Blades
Co/Ni-Basis-Super alloy
• Ts = 1230 …1315 °C
ZrO2 – Heat insulation
coating
• Phase transformation:
→ Y2O3 - Stabilization
• Oxidation diffusion:
→ Oxidation protective
layer
MCrAlY
• M = Co or Ni
respectively
 Surface Engineering

Surface Treatments Surface Coatings

1. Micro structural Treatments 1. Hard Facing

2.Thermo chemical Treatments 2.Vapor Deposition

3.Miscellaneous
Deposition
Techniques
 Micro structural Treatments
• Induction Hardening

• Flame Hardening

• Laser Hardening

• Electron Beam Hardening

• Chill Casting

• Work Hardening

• Cold Working
Induction Hardening

• High frequency A.C induces eddy currents

• Normally employed for medium carbon steels

• Thickness of hardened surface depends on time of

application, frequency of A.C and power density of A.C

• Water Quenching

• Process takes 30 s – 60 s

Flame Hardening
• Exposure to high temperature flame or hot gases

• Quenching
Laser Beam Hardening
• Laser beam(1-15 kW Carbon Dioxide laser) hits the
surface for a short period and melts a thin layer
(1-100 micrometer) adjacent to the surface.
• Bulk material acts as a heat sink.

Electron Beam Hardening

• Heating is done by direct bombardment of accelerated
stream of electrons.
• Self quenching is achieved by stopping the electron flow
• Size of components is a limitation
Chill Casting
• Chills are used to cool the casting rapidly.
• In cast iron the precipitation of graphite is prevented
• Used to harden critical surfaces of cast iron parts

Work Hardening
• Plastic deformation of the surface of materials
• Shot peening and metal working can impart hardness
• A residual stress is developed due to interaction of
dislocations
• Grain size reduces
Applications of Micro structural
Treatments
Various surfaces of
 Cam shafts
 Crank shafts
 Gears and Sprockets
 Bearing surfaces
 Shear blades
Thermo chemical Treatments
• Carburizing
• Nitriding
• Carbonitriding
• Nitro carburizing
• Boriding
• Chromizing
• Aluminizing
• Siliconizing
• Sheardizing
• Ion Implantation
Carburizing
• To increase the carbon content in
low/medium carbon steels
• Heating to 9250C and holding in a carbon rich
medium
• Can produce very thick case of high hardness
Nitriding
• Introduce nascent nitrogen into the ferritic phase
• Heating to 500- 5900C and holding in a nitrogen
containing plasma.
• Takes a longer time than other processes.
• Employed for alloy steels with Cr, Al, Mo, V and W.
Carbonitriding
• Carbon and Nitrogen are simultaneously
introduced in low/medium carbon steels.
• Heating to 800-870 0C and holding in a such a
medium and then quenched.
• Diffused amount of carbon is more than Nitrogen

Nitrocarburizing
• Diffused amount of Nitrogen is more than Carbon
• Gives exceptional wear and fatigue resistance
Boriding
• Carried out between 900 0C and 1100 0C
• Forms borides of Iron, Molybdenum, Chromium
• Applied for plain and low carbon alloy steels.
• Borided steels have extremely high hardness

Aluminizing
• Aluminum is diffused into steel at 750 – 1000 0C.
• Aluminizing imparts resistance to corrosion and
oxidation
Siliconizing
• Silicon (powder form) is diffused into steel or
malleable cast iron
• High resistance to wear, scaling and corrosion
• Carried out at 950 – 1200 0C

Sheardizing
• Zinc is diffused into steel at 350 – 450 0C.
• Imparts corrosion protection to the surface.
Ion Implantation
• Atomic species injected on to the surface by ion
beam of high energy
• The penetration is of the order of few nanometers
• Carried out at low temperatures
• Mainly employed for delicate and finished
substrates.
• Used to change the physical, chemical, or electrical
properties of the solid. Ion implantation is used in
semiconductor device fabrication and in metal
finishing, as well as various applications in materials
science. Si, N etc. are implanted.
Applications of Thermo Chemical
Treatments
Various surfaces of
 Cam shafts
 Crank shafts
 Gears and Sprockets
 Bearing surfaces
 Shear blades
 Milling cutters
 Casting dies
 Various IC Engine parts
 Press tools, Moulds, Dies etc.
 Surface Coatings
• Generally applied from micrometers to millimeters
• Soft coatings
• Coatings with low to moderate friction
• Coatings with high wear resistance and moderate friction
• Cr, Ni, Co, Ni based alloys, Stellites* (High cobalt, Fe, Al, Ni),
Triballoys* (Fe, Co, Ni), Haynes alloys (Co, Mo and Wb for
High temp.)
• Oxides, Carbides, Nitrides, Borides, Silicides of the
refractory materials.
• PTFE bonded polymers are used for solid lubrication
• Source : http://www.stellite.com
• http://nt-systemloesungen.de/
Welding
Coating material is melted and fused onto the substrate
Features :-
•As the metal gets melted it affects the microstructure
and composition of the parent metal
•Good mechanical properties and wear resistance

Cladding
Metallic plates of thickness up to 1 mm are metallurgically
bonded onto the surface.
Features:-
Thickness achieved is more
True metallurgical bond is achieved
 PHYSICAL VAPOUR DEPOSITION
TECHNIQUES
Physical Vapor Deposition (PVD) is a process by which a
thin film of material is deposited on a substrate according to
the following sequence of steps:
1) the material to be deposited is converted into vapor by
physical means;
2) the vapor is transported across a region of low pressure
from its source to the substrate.
3) the vapor undergoes condensation on the substrate to
form the thin film.

In VLSI fabrication, the most widely-used method of

accomplishing PVD of thin films is by sputtering.
PHYSICAL VAPOUR DEPOSITION
TECHNIQUES
PHYSICAL VAPOUR DEPOSITION
TECHNIQUES
 PHYSICAL VAPOUR DEPOSITION
TECHNIQUES
Sputtering is a mechanism by which atoms are dislodged from the
surface of a material as a result of collision with high-energy particles.
PVD by Sputtering is a term used to refer to a physical vapor
deposition (PVD) technique wherein atoms or molecules are ejected
from a target material by high-energy particle bombardment so that the
ejected atoms or molecules can condense on a substrate as a thin
film.
Sputtering has become one of the most widely used techniques for
depositing various metallic films on wafers, including aluminum,
aluminum alloys, platinum, gold, titanium and tungsten.
 PHYSICAL VAPOUR DEPOSITION
TECHNIQUES
Advantages
Sputtering can be achieved from large-size targets, simplifying the
deposition of thin films with uniform thickness over large wafers.
Film thickness is easily controlled by fixing the operating
parameters and simply adjusting the deposition time.
Control of the alloy composition and grain structure, is more easily
accomplished than by deposition through evaporation.
Sputter-cleaning of the substrate in vacuum prior to film deposition
can be done.
Device damage from X-rays generated by electron beam
evaporation is avoided.
 PHYSICAL VAPOUR DEPOSITION
TECHNIQUES

Disadvantages:
1) High capital expenses are required;

2) The rates of deposition of some materials (such as SiO2) are

relatively low.

3) Some materials such as organic solids are easily degraded by

ionic bombardment.

4) Sputtering has a greater tendency to introduce impurities in the

substrate than deposition by evaporation because the former

operates under a lesser vacuum range than the latter.

 PHYSICAL VAPOUR DEPOSITION
TECHNIQUES

A complete theory on how sputtering occurs has not yet been

established due to the complexity of interactions involved, but

experts in the field state that sputtering is comparable to billiard

ball kinetics in three dimensions.

Sputtering yield primarily depends on three major factors: 1) target

material; 2) mass of the bombarding particles; and 3) energy of

bombarding particles.

In the energy range where sputtering occurs (10 to 5000 eV), the

sputtering yield increases with particle mass and energy.

CHEMICAL VAPOUR DEPOSITION
TECHNIQUES
CHEMICAL VAPOUR DEPOSITION
TECHNIQUES
 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

Background

Chemical vapour deposition or CVD is a generic name for a

group of processes that involve depositing a solid material

from a gaseous phase.

Similar in some respects to physical vapour deposition

(PVD).PVD differs in that the precursors are solid, with the

material to be deposited being vaporised from a solid target

and deposited onto the substrate.

 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES
Types of CVD Processes

CVD covers processes such as:

Atmospheric Pressure Chemical Vapour Deposition (APCVD)·

Low Pressure Chemical Vapour Deposition (LPCVD)

Metal-Organic Chemical Vapour Deposition (MOCVD)

Plasma Assisted Chemical Vapour Deposition (PACVD) or Plasma Enhanced

Chemical Vapour Deposition (PECVD)·

Laser Chemical Vapour Deposition (LCVD)

Photochemical Vapour Deposition (PCVD)

Chemical Vapour Infiltration (CVI)

Chemical Beam Epitaxy (CBE)

 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

How Does CVD Work?

Precursor gases (often diluted in carrier gases) are delivered
into the reaction chamber.
As they pass over or come into contact with a heated
substrate, they react or decompose forming a solid phase
which and are deposited onto the substrate.
The substrate temperature is critical and can influence what
reactions will take place.
 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

Coating Characteristics
 CVD coatings are typically Fine grained Impervious, High
purity, Harder than similar materials produced using
conventional ceramic fabrication processes

 CVD coatings are usually only a few microns thick and are

generally deposited at fairly slow rates, usually of the order of

a few hundred microns per hour.

 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

CVD Apparatus

A CVD apparatus will consist of several basic components

-Gas delivery system For the supply of precursors to the reactor chamber

-Reaction chamber – Chamber within which deposition takes place

-Substrate loading mechanism – A system for introducing and removing

substrates, mandrels etc.

-Energy source – Provide the energy/heat that is required to get the precursors

to react/decompose.

-Vacuum system – A system for removal of all other gaseous species other than

those required for the reaction/deposition

 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

-Exhaust system – For removal of volatile by-products from the reaction chamber

-Exhaust treatment systems – In some instances, exhaust gases may not be

suitable for release into the atmosphere and may require treatment or conversion

to safe/harmless compounds

-Process control equipment – Gauges, controls etc to monitor process

parameters such as pressure, temperature and time. Alarms and safety devices

would also be included in this category.

 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES
Energy Sources
There are several suitable sources of heat for CVD processes. These include
Resistive Heating e.g. tube furnaces
Radiant Heating e.g. halogen lamps
Induction heating
Lasers - Other energy sources may include UV-visible light or lasers as a source
of photo energy.
Precursors
Materials are deposited from the gaseous state during CVD. Thus precursors for
CVD processes must be volatile, but at the same time stable enough to be able to
be delivered to the reactor.
Generally precursor compounds will only provide a single element to the
deposited material,
 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

Typical Precursor Materials

CVD precursor materials fall into a number of categories such as Halides -
TiCl4, TaCl5, WF6, etc. Hydrides, SiH4, GeH4, AlH3(NMe3)2, NH3, etc., Metal
Organic Compounds, Metal Alkyls, AlMe3, Ti(CH2tBu)4, etc., Metal Alkoxides,
Ti(OiPr)4, etc. Metal Dialylamides, Ti(NMe2)4, etc., Metal Diketonates.,
Cu(acac)2, etc. Metal Carbonyls - Ni(CO)4, etc., Others – include a range of
other metal organic compounds, complexes and ligands.
.
 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

Materials That Can be Produced by CVD Processes

CVD is an extremely versatile process that can be used to process almost any
metallic or ceramic compound.
Some of these include Elements, Metals and Alloys, Carbides, Nitrides, Borides,
Oxides, Inter-metallic compounds

CVD Gas Products

An often neglected by-product of the CVD process are volatile gases. However,
these gases may be toxic, flammable or corrosive so must be treated
appropriately.
 CHEMICAL VAPOUR DEPOSITION
TECHNIQUES

Applications
CVD has applications across a wide range of industries such as:·

Coatings
Coatings for a variety of applications such as wear resistance, corrosion
resistance, high temperature protection, erosion protection and combinations
thereof.

Semiconductors and related devices – Integrated circuits, sensors and

optoelectronic devices

Composites – Preforms can be infiltrated using CVD techniques to produce

ceramic matrix composites such as carbon-carbon, carbon-silicon carbide and
silicon carbide-silicon carbide composites.
Thermal Spraying
Features :
• Materials that can be melted without decomposition
• No deformation of the parent metal
Thermal spraying – Plasma