Chapter-2

Coating and Thin Film Processing Technologies

Surface Engineering by Changing Surface Metallurgy

Outline:
Flame surface hardening
Induction hardening
High energy beam surface hardening
Laser beam hardening
Shot peening
Plasma surface modification
 Fe-C equilibrium diagram
(Steel part)

A
3
 Austenite

Cooling rate
Martensite

Time
Bainite

Pearlite
Effect of carbon on hardness of martensite structures
Flame surface hardening:
Heat the surface of a steel part rapidly to a temperature above the
critical point of the steel form austenitic grain structure
(austenitized) quickly quench (water or force air) to transform
austenite to martensite form a hard case (the core of the part in its
original state: ferrite and pearlite);
Requirements: hardenable carbon steels (wrought or cast, 0.37-
0.55%C) and cast irons (0.35-0.80%C), martensitic stainless steels, tool
steels, steels with adequate carbon and other alloy element addition.

Relationship of carbon content to minimum

surface hardness attainable by flame heating
and water quenching
Spot (stationary) and progressive methods of
flame hardening. (a) Spot (stationary) method
of flame hardening a rocker arm and the
internal lobes of a cam; quench not shown. (b)
Progressive hardening method
(ASM Handbooks Online)
Spinning methods of flame
hardening. In methods shown at left
and at center, the part rotates. In
method at right, the flame head
rotates.

Combination progressive-spinning
flame hardening.

(ASM Handbooks Online)

Principal operating variables:
Distance from inner cone of oxy-fuel gas flames or from air-fuel
gas burner to work surface;
Flame velocities and oxygen-to-fuel ratios;
Rate of travel of flame head or work;
Type, volume, and angle of quench.

Advantages:
Parts that are so large that conventional furnace treatments are
impractical or uneconomical;
Prevention of detrimental treatment of the entire component when
only small segments of the part require heat treatment;
Use of less costly material to obtain the desired surface properties
where alloyed steels would be normally applied.
 Surface conditions detrimental to flame hardening of steel parts
Defect or Probable origin of Detrimental effects to be expected on flame-hardened
condition condition areas
Laps, seams, Localized overheating (or, at worst, surface melting), with
Rolling mill or forging
folds, fins consequent grain growth, brittleness, and greater hazard of
operations
(wrought parts) cracking
Insulating action against heating, with resulting underheated
Rolling or forging; prior heat areas and soft spots
Scale (adherent)
treatment; flame cutting
Localized retardation of quench, causing soft spots
Similar to scale condition as noted above left
Storage and handling of
Rust, dirt Severe rusting may result in surface pitting that will remain
material or parts
after hardening.
Present in as-received steel
In severely decarburized work, no hardening response will
bar stock; heating for
Decarburization be found when parts are tested by file or other superficial
forging or prior heat
means
treatment of parts or stock
Pinholes, Localized overheating (or, at worst, surface melting), with
shrinkage Casting defects consequent grain growth, brittleness, and greater hazard of
(castings) cracking
Coarse-grain Casting gates located in
Increased cracking hazard during quenching, compared with
gate areas areas to flame hardened
nongated areas; shrinkage defects also likely in these areas
(castings) (avoid, if possible)
Parts welded with an alloy Weld zone reaction dissimilar to base-metal reaction. Weld
Improper welds
dissimilar to base metal may separate, requiring rewelding or scrapping of the part
(a) Hardness and temperature profiles with the distance from the surface Z for
the specimen flame-treated at 1050oC followed by air cooling and (b) the
positional difference of microstructure.
After: M.K. Lee, G.H. Kim, K.H. Kim, W.W. Kim, Surface and Coatings Technology,
184, 2004, p239.
Induction hardening:
An induction coil with varying current magnetic field eddy
currents generated in a electrically conductive material to be treated
dissipate energy and produce heat;

d
e = N
Induced voltage
dt
Number of
turns in coil
Time rate of change
of magnetic field ()
Pattern of currents and the magnetic field in a
solenoid coil (a); In (b), note that the induced
eddy current in the specimen is opposite to
that in the coil.
 Set-up for induction hardening of gear

Schematic diagram of equipment used for in-line induction through

hardening and tempering of pipe-mill products
Applicable materials:
Medium-carbon steels (1030 and 1045);
High-carbon steels (1070);
Some alloy steels.
Applicable fields:
Transportation field: crankshafts, camshafts, axle shafts, transmission
shafts, splined shafts, universal joints, gears, valve seats, wheel spindles,
and ball studs;
Machine-tool field: lathe beds, transmission gears, and shafts;
Metalworking and hand-tool fields: rolling-mill rolls, pliers, hammers.
Advantages:
Ease of automation and control;
Reduced floor space requirements;
Quiet and clean working conditions;
Suitability for integration in a production line or general work area;
Self-monitoring capability.
 Microhardness distribution for
induction hardening treatment

After: Y. Totik, R. Sadeler,

H. Altun, and M. Gavgali,
Materials and Design, 24,
2003, p25.

Wear traces of AISI4140 steel (a-b) normalised;

(c-d) induction hardened for 27s
 Comparison of flame- and induction-hardening processes
Characteristics Flame Induction
Oxyfuel torch, special head quench Power supply, inductor,
Equipment
system quench system
Ferrous alloys, carbon steels, alloy steels,
Applicable material Same
cast irons
Speed of heating Few seconds to few minutes 1-10s
Depth of hardening 1.2-6.2mm 0.4-1.5mm; 0.1mm for impulse
Processing One part at a time Same
Part size No limit Must fit in coil
Tempering Required Same
Can be automated? Yes Yes
Operator skills Significant skill required Little skill required after setup
Control of process Attention required Very precise
Operator comfort Hot, eye protection required Can be done in suit
Cost
Equipment Low High
Per piece Best for large work Best for small work
Electron-beam hardening:
Heat the surface of a hardenable alloy above its transformation
temperature by direct bombardment or impingement of an accelerated
stream of electrons: electron/atom interaction ~75% of the power
generated by an electron beam converted to heat

U 2

S ( m) = 2.1 10
8 B


UB: acceleration voltage of
electron beam in volts
: density of material in
g/cm3
Electron beam generating system and gun
(ASM Handbook Online)
Workpiece configurations and heating patterns for electron-beam
heat treating (ASM Handbooks Online)
Application criteria:
Must contain adequate carbon to produce satisfactory case hardness;
Mass of the part must be sufficient to self-quench the heat treated
area;
Stream of electrons must have line-of-sight access to the area
requiring heat treatment and a beam-impingement angle of at least
25;
Component being heat treated may be processed in a vacuum
envelope or chamber, or at pressures up to 1atm in air or inert gas;
Surface to be heat treated should be machined or ground to final
dimensions;
Component being heat treated must be demagnetized prior to
hardening.
Advantages:
Precise control and reproducibility of energy input with respect to
location and time;
Constant hardening depth for both areal and laterally patterned
hardening up to a track width of 50-100 mm;
Low thermal stress imposed on the workpiece;
No scaling or oxidation of component surfaces;
No component-dependent means of energy transfer;
No preparation of surfaces to be hardened or of regions that have to be
left untreated;
CAD/CAM compatible and easy to integrate into mechanical flow
lines;
Plant operation requires only electric power and low quantities of
cooling water;
High energy efficiency;
High process productivity;
No waste products generated.
 Optical micrographs of the : (a) ion nitrided layer; (b) electron beam
hardened zone
After D. Dimitrov, M. Aprakova, S. Valkanov, and P. Petrov, Vacuum, 49, 1998,
p239
Distribution of the microhardness within Abrasive wear resistance: Curve-1:
the depth: Curve-1: ion nitriding layer; ion nitriding layer; Curve-2: after
Curve-2: after electron beam hardening electron beam hardening
Laser-beam hardening:
Energy of a laser beam absorbed by workpiece surface heat the
surface layer to austenitization temperatures quenching the material
from the austenite region to form hard and very fine martensite
increase hardness;

Hardness profile of laser surface

hardened cast iron
 (ASM Handbooks Online)

Overlap zones between parallel laser tracks

General guidelines for choice of processing conditions:
Usable power density: 500-5000W/cm2; dwell time: 0.1-10s. For carbon
steels, the power density is usually from 1000 to 1500W/cm2 and the dwell
time 1-2s;
Materials with high hardenability can be processed at low power density and
low speed, materials with low hardenability should be processed at high power
density and high speed;
Rectangular, square, or round laser spots with uniform power density are
suitable in obtaining uniform hardened case;
High power density and high speed give shallow case, but high cooling rates;
Maximum surface temperature is approximately proportional to the square
root of the processing speed. Hence, a doubling of the power density requires a
quadrupling of the speed to obtain equivalent maximum surface temperatures;
Increasing power density results in lower total energy input for the same
maximum surface temperature;
Steel with normalized, annealed, or spheroidized structures; steel with
proeutectoid cementite; cast irons and steels with stable alloy carbides require
long dwell time;
Small workpieces require higher power densities and higher speed than large
pieces, unless external quenching media are used.
Advantages:
Close control of the power input with metal-working lasers;
Provide high power density in selected areas, which in turn
minimizes the total energy input, and thereby, dimensional distortion;
Able to reach normally inaccessible areas on the workpiece surface;
No vacuum or protective atmosphere enclosure is needed, and the
distance from the workpiece to the last optical element of the laser
system can be quite long, it is possible to process very large or
irregular-shaped workpieces;
Laser beam can be optically shaped or split to accommodate different
geometries.

Disadvantages:
Depth of case obtainable is limited to about 2.5mm;
Capital cost of the equipment may be high.
 Taper-section of a sandblasted Transition area (top half, refined
specimen showing a lath mar- microstructure ) and base metal
tensitic microstructure in the surface (bottom half )
layer

Microhardness profile of a laser-treated

specimen
After: A.I. Katsamas, G.N. Haidemenopoulos,
Surface and Coatings Technology, 115, 1999,
p249
Shot peening:
Generation of compressive stresses in the exposed surface layers of
metallic parts by the impingement of a stream of shot, directed at the
metal surface at high velocity under controlled conditions;
Purpose: increase fatigue strength; relieve tensile stresses that
contribute to stress-corrosion cracking; form and straighten of metal
parts, test adhesion of silver-plate on steel.

Effects of shot peening on stress-corrosion life of alloys

Time to failure
Material Solution to which exposed
Unpeened Peened

Magnesium, AZ31B-H Potassium chromate and sodium chromate 110s >10days

Magnesium, AZ61A-H Potassium chromate and sodium chloride 9.25min 430h

Brass cups, cold drawn Ammonia 2.5h 19 and 47h

Stainless steel, type 309 Hydrated magnesium chloride 270h >3000h

Control of process variables:
Size of shot: shot size peening intensity & depth of
compressed layer but coverage ;
Hardness of shot: Variations in the hardness of shot do not affect
peening intensity, provided the shot is harder than the workpiece;
Velocity of shot: Peening intensity increases with shot velocity;
Angle of impingement: As this angle is decreased from 90,
peening intensity is reduced;
Breakdown of shot: The percentage of full-size and rounded shot
in the system should never fall below 85%.
Automatic machine for wet peening with glass beads
Fatigue curves for peened and unpeened steel spring wires
(ASM Handbooks Online)
 Influence of shot peening on fatigue behavior
of a TiAl alloy

After: J. Lindemann, C. Buque, F. Appel, Acta Materialia, 54, 2006, p1155.

 TEM dark-field image of microstructure in
surface of shot peened sample (left); at the
distance of about 10 m from the surface of
shot peened sample (right)

Potentiodynamic polarization
curves of shot-peened and as-
received samples of 1Cr18Ni9Ti
After: T.S. Wang, J.K. Yu, B.F. Dong, Surface and stainless steel obtained in 3.5%
Coatings Technology, 200, 2006, p4777. NaCl solution
Laser shot peening (Laser shock processing)/LSP:

The plasma burst induces a pressure wave into the surface of the component
inducing residual compressive stress
After: G. Hammersley, L.A. Hackel, F. Harris, Optics and Lasers in Engineering, 34,
2000, p327.
Residual stress profile in INCO 718 alloy
 AFM images of Inconel 600 alloy surface (a) after LSP treatment and (b)
original surface
After: A.A. Bugayev, M.C. Gupta, R. Payne, Optics and Lasers in Engineering,
44, 2006, p102.
 Comparison of initiation (fatigue crack development to a
specified size, and usually the detectable limit) and later
cracking stages at max = 260 MPa for crack detection tests on
7075-T7351 aluminum alloy
After: C.S. Montross, T. Wei, L. Ye, G. Clark, Y.W. Mai, International Journal of
Fatigue, 24, 2002, p1021.
Plasma surface modification:
Plasma: the fourth state of matter and is composed of highly excited
atomic, molecular, ionic, and radical species; obtained when gases are
excited into energetic states by radio frequency, microwave, or
electrons from a hot filament discharge; highly unusual and reactive
chemical environment in which many plasma-surface reactions occur;
high-density of ionized and excited species in it can change the surface
properties (chemical, tribological, electrical, optical, biological, and
mechanical) of normally inert materials;

Sources:
Atmospheric arc plasma source;
Electron cyclotron resonance plasma source;
Corona discharge plasma source;
Laser plasma source;
Radio frequency glow discharge plasma source;
Vacuum arc plasma source.
Plasma sputtering and etching:

A negative voltage is applied to the substrate and an argon plasma

is generated by RF-GD or ECR;
Ions are accelerated towards the substrate by the applied electric
field, but cannot go very deeply into the substrate;
Energy is transferred to the surface atoms via elastic and inelastic
collisions with the materials;
Some surface atoms will acquire enough energy and escape from
the substrate into the vacuum chamber.

Plasma polymerization:
Low-molecular-weight molecules (monomers) were transformed
into high-molecular-weight molecules (polymers) with the assistance
of energetic plasma species such as electrons, ions, and radicals
Plasma-grafting co-polymerization:
Polymers are first exposed to the plasma to create radicals on the
surface where inelastic collisions between the electrons in the
plasma and polymer surface produce radicals in the polymer chains;
Polymers are then exposed to a vapor of the monomer or an
aqueous or organic solution of the monomer;
Plasma-grafting co-polymerization is often employed to alter the
surface hydrophilicity of polymers.
SEM micrograph of silicone rubber modified using electroformed screen
mesh mask of square (left) and round meshes (right). The Ar+ energy is 1
keV.

After: F.Z. Cui, Z.S. Luo, Surface and Coatings Technology, 112, 1999, p278.
 AFM images of PTFE pre- and post-DBD plasma treatment (a) before
treatment and (b) after DBD plasma treatment
(Improving surface wettability of the polymer surfaces through changes in
both surface chemistry and microstructure)
After: C.Z. Liu, N.Y. Cui, N.M.D. Brown, B.J. Meenana, Surface and Coatings
Technology, 185, 2004, p311.
XRD pattern obtained from 304 stainless
steel, untreated and samples treated at
different C2H2/N2 gas pressure ratios

After: A.M. Abd El-Rahman, F.M. El-Hossary,
T. Fitz, N.Z. Negm, F. Prokert, M.T. Pham, E.
Richter, W. Moller, Surface and Coatings
Technology, 183, 2004, p268
Relative microhardness for 304
ASS samples treated at different
C2H2/N2 gas pressure ratios
 XPS spectra of N-depth profiles

Anatase structure TiO2 thin films were

surface-treated by N2-H2 mixed gases
plasma and its optical reactivity was
significantly improved
Tauc plots of (h)1/2 as a
After: L. Miao, S. Tanemura, H. Watanabe, Y. function of photon energy
Mori, K. Kaneko, S. Toh, Journal of Crystal
Growth, 260, 2004, p118.