CW LPD Diode Lasers

CeFEMA
Laser surface treatment: principles and

examples of applications
R. Vilar 
CeFEMA – Center of Physics and Engineering of Advanced
Materials, Instituto Superior Técnico, Lisbon University
São Paulo School of Advanced Science on Frontiers in Lasers and their Applications
July 16 - 27, 2018, São Paulo, Brazil
Topics I
•  Introduction: Laser-assisted Surface Engineering, objectives and

methods.
•  Part I Laser processing with continuous wave (CW) and long pulse
duration lasers (PL)
–  Heat and mass transfer. Marangoni convection
–  Laser hardening
–  Laser surface melting, alloying and cladding
–  Microstructure formation in liquid-phase laser surface treatment
•  Examples of application
–  Laser surface melting of tool steels
–  Laser alloying of aluminium
–  Laser-assisted single crystal deposition
Laser-assisted Surface Engineering,
objectives and methods
The scope of surface engineering
•  Required surface properties, such as surface hardness, wear

resistance, friction coefficient, corrosion resistance, etc. are often
incompatible with a high level of bulk properties, such as strength,
formability, machinability, ductility and toughness.
•  Surface Engineering aims at creating a composite with surface and
bulk properties which cannot be achieved simultaneously, neither by
the coating material, nor by the substrate material alone.
•  Surface engineered materials can be produced by modifying the
microstructure or the microstructure and the composition of a
surface layer of material or by coating it with a layer of another
material.
•  Surface treatment processes differ in the properties and depth of the
treated layer, on the properties on the coating/substrate interface
(adhesion) and on their lateral resolution.
What is a surface in surface engineering?
Surface: physical limit of a body Two-dimensional geometric entity
Alumina (Wei, 1992)
•  Inadequate definition: the surface behaviour depends on the physical and chemical properties not only of the
surface but also of the subsurface region, to a depth depending on the properties concerned, physical and chemical
interactions with the environment, and deterioration mechanisms.
•  Optical properties depend a depth of material which is a function of the light wavelength and of the electronic
structure of the material.
•  Chemical and biochemical interactions. Wettability, etc. depend on the surface chemical composition and
microstructure up to a depth of a few nanometres.
•  The tribological behaviour depends on the shape of the surfaces in contact at all scales involved.
•  The tribological behaviour also depends on the type and extent of relative movement between bodies, forces
involved, and on the environment
Material degradation mechanisms
Degradation mechanisms
Wear
Fracture of a
dental implant Corrosion
Plastic deformation Bulk properties

Solution: correct design
Fracture
Surface properties
Corrosion Solution:
Wear Surface Treatment
Coatings
Surface properties
Surface modified region

Bulk properties
•  Mechanical strength
•  Fatigue strength BULK
•  Toughness
•  Electrical and magnetic properties ...
Surface properties
•  Resistance to corrosion
•  Wear resistance
Material selected for desired
•  Resistance to erosion bulk properties
•  Resistance to fatigue and fatigue-corrosion
•  Finishing - surface topography Surface treatment alters
•  Optical properties of metals
surface properties
•  Chemical properties
•  Electrical surface properties
•  Wettability and capillarity
•  Cell/surface interactions
•  Bacterial/surface interaction Surface treatments allow the
Industrial properties which depend on the surface compatibility of frequently
•  Surface finish antagonistic mass and surface
•  Surface roughness and texture properties
•  Catalytic properties
•  Decorative properties
•  Lubrication...
Laser surface treatment processes
•  Solid state processes (T<Tm)

–  Laser hardening (alloys that undergo diffusionless transformations)
•  Liquid phase processes (Tm<T<Tv)
–  Laser melting (alloys that do not decompose upon melting)
–  Laser alloying: surface melting with alloying elements addition
–  Laser surface melting with reinforcement particles addition
–  Laser nitriding
•  Coating processes(T≤Tm)
–  Laser cladding
–  Thin film deposition by photoablation (LPVD)
–  Thin film deposition by laser CVD
–  Laser-assisted electrodeposition
•  Ablative surface modification processes (T>Tv)
–  Surface cleaning
–  Surface texturing
–  Shock hardening
Laser processing diagrams
Laser processing with ultrafast
lasers (10 fs ~ 10 ps)
(Meijer, J. Mater Proc Tech, 149 (2004) 2-17)

Ion, Laser Processing Engineering Materials,
Butterworth, 2005
Laser surface treatment with CW lasers
Processing parameters and solidification conditions
with different lasers
Laser type Interaction time Heat affected depth Cooling rate (K/s)
Ultra-fast, solid state 10 fs - 10 ps 0.01 - 0.1 µm >109
Q-switched pulsed Nd/YAG 10 - 20 ns 0.5 - 1 µm 5*106
Q-switched Nd/YAG 250 ns 1 - 5 µm 105
Excimer laser 20 ns 0.5 - 1 µm 5*106
Pulsed Nd/YAG 5- 25 ms 100 - 250 µm 5*104
CW CO2, V= 10 mm/s 0.05 - 0.2 s 0.1 - 0.5 mm 104 - 5*103
Diode lasers 0.1 - 2 s 0.25 - 2 mm 5*103 - 2*102
Fiber lasers 10 ps - 2 s 0.1 µm - 2 mm 109 - 2*102
Energy and mass transfer in CW and LPD
laser processing
Radiation absorption and energy transfer in solids
I0 I
RI0
(1-R)I0
Tv
Tm
Tt
T
∂T
qx = k
x
(1-R)I0exp(-βx) ∂x
T0
Radiation absorption and energy transfer in solids
We are implicitly assuming that:
Due to the long interaction time the temperature of

the electronic subsystem is constantly in
equilibrium with the temperature of the lattice
subsystem.
Surface reflectivity
•  Reflectivity of metals for near infrared

(diode, fiber and Nd:YAG laser) radiation
and 10.6 mm is high: special precautions
are required to couple radiation into the
material
•  Reflectivity can be reduced by chemical

surface treatments (oxidation), surface
roughening (abrasive particles blasting,
chemical etching, etc.) or coating
(graphite)
•  The absorptivity of metals for visible and

infrared radiation is extremely high, so
Fabian et al Optical fibre cavity for ring-down experiments most radiation is absorbed in a surface
with low coupling losses, Measurement Science and layer a few nanometers thick and
Technology 21(2010):094034 thermalized: surface heat source.
Heat conduction in stationary beam laser processing 
Unidirectional models
Application conditions
o  Stationary laser beam, constant power density, radius r0.
o  Unidimensional heat conduction given by

o  Constant thermophysical properties, Lf≈0
o  Semi-infinite solid. Where:

κ: thermal conductivity, W m-1K-1
α : thermal diffusivity, m2s-1
Solutions tp: interaction time, s
I: irradiance, W m-2
t<tp A: absorption coefficient
t>tp
Influence of laser processing parameters
t2 t1 Tlim T/K
t1
(P/A)1 (P/A)2 d = 2 αt
T/K
T2
t2
T1
(P/A)1> (P/A)2
t 1 < t2
z/µm
t1 t2 t/s
Only two main independent processing parameters:

•  Power density
•  Radiation/material interaction time
Heat transfer with moving laser beam: Rosenthal
equation
•  Assumptions: point energy source of constant power q0 moving with speed ν in the
XX direction at the surface of a semi-infinite slab of material at temperature T0 (thick
plate approximation) in pseudo-steady state conditions. Interaction parameters and
material properties assumed to be time and temperature-independent.
•  The temperature is given by:
•  With
•  And the colling rate is given by:
Where
− T is temperature;
− T0 the initial temperature;
− q0 energy source power;
− v scanning speed (in the positive XX direction);
− α thermal diffusivity;
− λ thermal conductivity
− x distance to the origin in the XX axis.
Heat transfer with moving laser beam: Ashby and
Easterling model
•  Assumptions: to avoid the infinite temperature at the surface, the energy source is situated at a
distance z0 above the surface, calculated so that the correct power density is achieved at the
surface. The line source, with dimension rb and constant power density q is aligned in the YY
direction and moves with speed ν in the XX direction. Interaction parameters and material
properties assumed to be time and temperature-independent ((Ashby, M.F.; Easterling, K.E., Acta
Metallurgica 32 (1984) 1935–1948).
•  The temperature is given by:
•  With
Where
⎺  T is temperature;
•  And ⎺  T0 the initial temperature;
⎺  t time
⎺  q is the power of the linear laser source
⎺  v is the scanning speed;
•  The cooling rate is given by: ⎺  z is the depth below the surface;
⎺  A is the absorptivity of the surface;
⎺  λ is the thermal conductivity;
⎺  α is the thermal diffusivity;
⎺  rb is the laser beam radius;
⎺  e=2.718.
⎺  z0 is a length constant
⎺  t0 is a time constant
Example of application 
(M. Lima et al, Mater Res, 2007, http://dx.doi.org/10.1590/S1516-14392007000400022)
Study of the influence of the laser beam power on the phase transformations undergone by a AISI 1040 steel
treated with a fiber laser. Scanning speed 115 mm.s–1. Five levels of power : 300, 500, 700, 900 and 1100 W.
Calculations performed using Hunziker analytical model (Hunziker, PhD. Thesis n. 1687, EPFL, 1997)
1100 W
Depth and width of the martensitic region, experimental

and calculated
Example of application: optimization of laser-assisted
rapid manufacturing
Layer overlap leads to solid-state transformations in previously deposited material
Laser-assisted materials preparation  
Heat transfer model
Heat transfer by conduction
∂T
ρc p = div[k (gradT )]
∂t
Laser –beam with Gaussian distribution
2.P ⎡− 2.r 2 ⎤
Qlaser ( x, y, t ) = α exp
π .rl 2 ⎢⎣ rl ⎥⎦
Heat transfer by convection
Qconvection = h(T − T0 )
Heat transfer by radiation
Qradiation = εσ (T 4 − T04 )
Boundary conditions
!
k (∇T .n) = Qconvection + Qradiation − Qlaser
2 –Phase
AISI 420 Tool Steel
transformation during LD of AISI 420 steel
M, martensite; α, ferrite; γ, austenite; L, liquid
Finite element simulation of LFFM steel parts 
Temperature distribution
Temperature field at the end of the last deposition step.

27 ºC - blue; 2500 ºC – red
t Step = 5.5 sec., Δt = 0.5 s t Step = 37.0 sec., Δt = 5.0 s
Phase distribution
Phase distribution after the last deposition step.

100% Martensite – red; 100 % Austenite – blue
Final hardness distribution
Final hardness distribution, after cooling down to room temperature.

52 HRC – red; 50 HRC – yellow
Phase transformations during LPD of Ti6Al4V
1st Cycle 2nd Cycle
Cooling from liquid Re-heating Cooling
dT/dt ≤ 410 ºC/s

L L L
Tliq Tliq
dT/dt ≤ dT/dt >
410 ºC/s 410 ºC/s
β β
β-transus β-transus dT/dt ≤ dT/dt >
410 ºC/s 410 ºC/s β β
β β Ms Ms
β
dT/dt ≤ β
dT/dt > Mf Mf
410 ºC/s 410 ºC/s α
α’
α Troom
α Troom
α α Troom
α α α’
dT/dt > 410 ºC/s
L L
1660 ºC Tliq Tliq
β β
980 ºC β-transus β-transus
dT/dt ≤ dT/dt >
650 ºC Ms α Ms 410 ºC/s 410 ºC/s
400 ºC Mf Mf
β β Mf
α’ α’ α
Troom Troom α’ α Troom
α’
Microstructure prediction 
Deposition of a thin wall of Ti-6Al-4V
Processing parameters:
§  Vscanning= 2.5 mm/s
α §  Pbeam= 725 W
§  tiddle = 1 s
1,0
β
0,8
Volume fraction
0,6 α
β
0,4 α'
α’ 0,2
0,0
0 1 2 3 4 5
Layer number
Properties prediction 
5 s idle time Heating up of the Martensitic transformation

between tracks workpiece is not complete
500
Mf
400
Temperature (ºC)
300
200
Young’s Modulus
100
0
0 1 2 3 4 5
Layer
Non-uniform microstructure
and properties
Rockwell Hardness
Properties prediction 
Less heat accumulation Complete martensitic

Idle time = 60 s
in the part transformation in all layers
500
Mf
400
Temperature (ºC)
300
200
Young’s Modulus
100
0
1 2 3 4 5
Layer
Uniform microstructure
and properties Rockwell Hardness
Residual stresses prediction 
Idle time = 5 s Room temperature

yield stress = 790
MPa
Maximum stress in
the part ≈ 200 MPa
Idle time = 60 s
Plastic deformation at high

temperatures leads to low
residual stresses:
Cracking, distortion and
dimensional changes are
negligible
Influence of preheating on the deposition of Ti-6Al-4V
Young’s Substrate at room temperature

modulus Manufactur
of e of dental
Ti-6Al-4V crowns of Ti
parts
- αmassive
- Martensite α’
Substrate pre-heated to 500 ºC Scale in GPa
Marangoni convection in laser processing
Marangoni convection: surface-tension-
driven (also called thermocapillary)
convection
Fluid flow velocity depends on the variation of surface tension
with the radius at the surface of the meltpool
The outward shear stress at the pool surface induced by the

surface-tension gradients along the pool surface is given by:
Where γ is the surface tension, µ the viscosity, v the fluid

velocity and s and n denote the tangent and normal directions
to the surface, respectively.
The surface tension gradient is induced by the surface

temperature gradient and the variation of surface tension with
temperature. Since:
Drezet et al J. Phys. IV France 120 (2004) 299-306
Marangoni convection in laser processing
For most technological materials dγ/dT is Surface tension of metals
(Egry et al Ad Colloid Interface Sci 159 (2010)198)
negative and Marangoni flow at the
surface is centrifugal Alloy TL/K γ(TL)/Nm− 1 ∂γ/∂T/Nm− 1 K− 1
CMSX-4 1657 1.85 − 9.01 · 10− 4

IN738LC 1608 1.85 − 1.48 · 10− 3
MM247LC 1641 1.86 − 1.36 · 10− 3
C263 1641 1.74 − 6.85 · 10− 4
C-Steel 1753 1.61 − 4.47 · 10− 4
Cr-Steel 1750 1.76 − 9.04 · 10− 4
Cu-alloy 1340 1.15 − 7.28 · 10− 4
Al–75 at.%Ni 1683 1.63 − 5.88 · 10− 4
Al–65 at.%Ni 1823 1.65 − 1.01 · 10− 3
Al–31.5 at.%Ni 1523 1.16 − 1.14 · 10− 4
CuSnP 1301 1.08 − 4.77 · 10− 4

CuSn8 1305 1.05 − 3.74 · 10− 4
Rene90 1633 1.71 − 4.30 · 10− 4
ReneN5 1645 1.70 − 4.91 · 10− 4
M-SX 1648 1.58 − 4.95 · 10− 4
Millot et al The surface tension of liquid silicon at
high temperature, Materials Science and C-Steel1 1816 1.38 − 1.65 · 10− 4
Engineering A 495 8-13 2008 C-Steel2 1816 1.53 − 12.3 · 10− 4
Tool Steel 1808 1.73 − 3.38 · 10− 4
Marangoni convection in laser processing (simulation)
Longitudinal section view of velocity field,

Al-Si-Mg alloy, 2.5 kW, 2 m.min−1
Top view of velocity field of weld pool

surface, Al-Si-Mg alloy, 2.5 kW, 2 m.min−1
Pang et al Journal of Physics D Applied Physics 44(2010):025301
Laser transformation hardening
Laser transformation hardening
Aim
•  To
increase the surface hardness, wear resistance and fatigue resistance of ferrous and, less-
frequently, Ti alloys that may undergo a martensitic transformation.
Alternatives
•  Thermal
processes (heating of the surface layer to austenitise the steel, followed by quenching
to produce a martensitic transformation): flame, induction and laser hardening;
•  Thermochemical processes (modification of chemical composition by diffusion at high

temperature): carburising, carbonitriding, nitriding.
Advantages of laser hardening

•  no external quenchant is required;
•  very little or no distortion;
•  no contact and no tooling is required; fixturing is kept to a minimum;
•  high production rates;
•  easy automation;
•  both selective area treatment and large area coverage are possible;
•  complex shape components can be treated;
•  residual compressive stresses are induced at the surface.
Laser hardening: principles
Heating
Cooling
Laser transformation hardening diagram
Melting threshold
(Adapted from J. Ion)
Laser processing diagram: laser transformation
hardening
(Source: J. Ion, Surf. Engn. 18(2002)14)

Laser hardening optics 
(Klocke et al Coatings 2017, 7(6), 77)
Conventional optics: defocalised beam,

flat top beam, scanners Galvanometric mirrors scanner Corresponding intensity and temperature
distributions
Corresponding temperature distributions
Optimised focusing mirror
Cross sections of the hardened zone
Applications
Laser hardening gives thin, wear resistant layers • Improving wear resistance
on steel and cast iron surfaces. Controlled - rocker-arm shafts
application of concentrated energy allows - couplings
hardened layers to be produced without serious - pump shafts
distortion or other heat damage to the bulk of the
part. - gears
- track pins
- crankshaft bearings
High power CO2, fiber and diode lasers can be - bearing races
used to produce transformation hardened
components. The system choice depends upon - camshafts
the specific application. Diode laser have the - etc.
advantage of a large spot size giving high rates • Improving fatigue resistance
of surface coverage without requiring special
- truck, tractor and automobile
optics, but they are not flexible.
axle shafts,
-  hydraulic piston rods
- steering knuckles
-  flanged axle shafts
-  etc.
Laser alloying/cladding
Laser treatments in the liquid phase
Laser melting Laser alloying by powder injection
Laser alloying by remelting a precoated substrate Laser cladding by lateral powder injection
Laser processing diagram: laser alloying and cladding
(Source: J. Ion, Surf. Engn. 18(2002)14)

Laser cladding as a coating process
Blown powder/wire laser cladding Blown powder laser cladding system
with lateral nozzle
Coating created by overlapping of laser

cladding tracks
Axisymmetric laser powder deposition for rapid
manufacturing
Optomec LENSTM Process
VarioCladTM Process
Laser/powder/surface interactions
•  The laser radiation interacts with the powder
•  The powder absorbs radiation and heats up to a
temperature that depends on the radiation
intensity distribution, powder velocity,
interaction time and materials properties
•  The powder scatters radiation, which may be
reabsorbed or not, and casts a shadow on the
surface. It also absorbs and scatters the
radiation reflected at the surface.
•  The heat stored in the powder is transferred to
the meltpool when the powder is absorbed by
the liquid.The energy distribution at the surface
is modified and, since the system is not
axisymmetric, distorted.
•  Energy is lost when powder is lost by
ricocheting or rebounding on the solid surface:
a large powder catchment efficiency is critical
for good powder and energy use efficiency:
good alignment is critical!
Heat balance in laser powder deposition
⎡ Tm Tmax
⎤
α P = κ∇T + h (T − T0 ) + εσ A (T − T0 ) + η m ⎢ ∫ c p (T ) dt + Lm + ∫ c p (T ) dt ⎥
4 4 s l
+
⎢⎣ T0 Tm ⎥⎦ powder
⎡T ´m s Tmax
⎤
+Ac D ρ subs ⎢ ∫ c p (T ) dt + Lm + ∫ c p (T ) dt ⎥
l
⎢⎣ T0 T ´m ⎥⎦ substrate
Where:
-  T is temperature; -  Lm is the latent heat of melting of the addition or
substrate materials;
-  α is the average material absorptivity;
-  ρ is the substrate material density;
-  P is the incident laser beam power;
-  Ac is the clad cross-sectional area;
-  κ is the thermal conductivity;
-  D is dilution.
-  h is the convection heat transfer coefficient;
-  T0 is the ambient temperature;
-  ε is the surface emissivity;
-  σ is the Stefan-Boltzmann constant;
-  A is the effective clad surface area;
-  η is powder catchment efficiency;
  𝑚  is the powder feed rate;
  𝑐↓𝑝↑𝑠  is the temperature dependent specific heat of the
solid material;
  𝑐↓𝑝↑𝑙  is the temperature dependent specific heat of the
liquid material;
-  Tm is the melting temperature of the addition material;
-  T´m is the melting temperature of the substrate material;
-  t is time:
Geometry of the clad tracks and dilution
Profiles of the cross section of laser cladding Cross section of a laser clad layer. Surface
tracks (after Weerasinghe and Steen) coverage by overlapping single tracks.
Asubs
Dilution: D =
Asubs + Aadd
•  The difference between laser alloying and cladding lays on the dilution that is
achieved in the process.
•  In laser alloying D~100%.
•  In laser cladding, in order to optimise the materials properties and the surface
coverage efficiency and minimize the coating defects:
•  5<D<15% and
•  45<α<80°
Laser beam/powder interaction 
(Liu, Lin Opt Laser Tech 35(2003)81)
•  Interactions between particles in the powder stream are neglected,

reducing the model to the analysis of individual particles
•  Spherical powder particles with constant absorptivity
•  Diverging (defocused) laser beam with flat top energy distribution
•  Constant shielding gas velocity
•  No interaction between shielding gas and laser beam.
Energy balance for a single particle
•  V and S particle volume and surface area

•  Ρ, c material density and specific heat
•  T particle temperature
•  t time
•  I laser radiation intensity
•  Kab average particle absorptivity
•  h convective heat transfer coefficient
•  T∞ temperature of the shielding gas
•  ε particle surface emissivity
•  σ Stefan–Boltzmann constant
•  Lf and Le latent heats of melting and
evaporation
Powder temperature 
Effect of particle velocity, 1000W,

45 µm and 500 W, 75 µm
Effect of the laser power,

particles 45 and 75 µm
Vaporisation!
Melting and
solidification
Powder vaporisation 
•  Due to the high temperatures reached particles may vaporise at a

rate given by
•  The powder temperature depends on factors such as the beam intensity, beam
divergence angle, powder absorption coefficient, powder diameter, powder
velocity and shielding gas velocity.
•  The variations in powder temperature infuence powder mass loss in laser
cladding and powder/liquid reactions, producing significant uncertainties in clad
quality.
•  Laser heating increases powder temperature. Finer powders lead to higher
temperature resulting in larger mass loss over shorter in-flight distances.
•  The velocity of the powder is significantly affected by mass losses through
evaporation, shielding gas drag force, and initial powder velocity.
•  Proper powder size and radiation intensity must be selected to prevent
overheating of powder during coaxial laser cladding.
Energy distribution in laser cladding 
(Picasso et al, Metall Mat Trans B 25(1994)281)
•  laser beam attenuation by the powder − Pl laser beam power

jet − Pat attenuated power
− rl laser beam radius
− θjet angle of the powder jet in relation to the horizontal;
− rjet radius of the powder jet at the substrate surface;
− rp radius of the powder particles; 
− vp powder particles speed;
− 𝑚* mass powder feed rate;
− Pabs laser beam power absorbed by the workpiece;
− βw absorption coefficient of the workpiece;
− βp gas/powder jet absorptivity;
− ηp powder catchment efficiency;
•  Power absorbed by the surface
Direct beam Heat transferred from the particles
•  Due to the higher reflectivity of the substrate as compared to the powder a considerable proportion of the laser beam
energy is absorbed by the powder before reaching the substrate. This proportion increases with increasing powder
feed rate (typically 20% as compared to 8 or 9%).
•  The powder jet enhances the global energy use efficiency, a clear advantage of laser powder deposition as
compared to wire feeding methods.
•  The beam polarization affects the process efficiency due to the influence of the incidence angle on reflectivity
Temperature distribution in the powder jet 
O Diniz Neto, Vilar Journal of Laser Applications 14, 46 (2002); https://doi.org/10.2351/1.1436485)
Assumptions
•  Powder jet: point source of particles with Powder
constant powder feed rate (Q) and particles Laser y feeding
tube
velocity (ν0), corresponding to a constant beam α y´
x
mass flow rate z
´
•  Gaussian laser beam with power P0 and z
constant radius ω0 Powder

jet
•  Energy loss to the atmosphere by
convection and irradiation Substrate
•  Influence of reflected and scattered
radiation and particles collisions neglected
Temperature of the particles given by:
Laser/powder/surface interactions
Laser energy distribution and temperature distribution of stellite particles at the instant they reach the
substrate surface, absorptance and specific heat varying with temperature
Laser beam Laser beam
Powder Powder
•  Stellite powder 50 mm diameter

•  CW gaussian CO2 laser beam
•  Po = 1.5 kW
•  ω0 (laser beam radius) = 1 mm
•  powder jet divergence = 5°
•  particles velocity = 2.5 m/s
•  α = 45
Microstructure formation in laser alloying
and laser cladding
Meltpool dynamics and solidification
•  Heat (and the powder chemical elements) are redistributed in the

meltpool due to Marangoni convection.
Since•  the large cooling
Solidification rates
starts when achieved
the laser goes awayinfrom
laser alloying
a particular
andpoint. The temperature field evolution defines the solidification front
cladding do not allow diffusional solid state
position and the solidification parameters and kinetics (constrained
reactions to develop
solidification) to any
and hence significant
the final extent,
solidification the final
microstructure
structureandandthe materials
properties properties.
of laser alloyed and laser clad
materials depends only on the solidification path and,
consequently, on the solidification parameters and
their spatial and temporal evolution, which depend on
the energy and mass transfer during the process
Solidification on a solid substrate
In laser processing solidification

starts by growth of the solid on a
substrate. This substrate may be
of the same material (laser
melting), of a similar material
(laser alloying) or of a different
material (laser cladding). The
applicable nucleation model is
heterogeneous nucleation.
V= Vt. cosΘ Vt
Liquid
V Liquid
σNL
h
Nucleus
θ
R σIL Vt
σIN
a
Substrate
Inclusion r
t2
θ Solid
t1
Becker and Doring heterogeneous nucleation model
Free energy change
Using σ IL − σ IN = σ NL cosθ
Nucleation versus epitaxial growth
Nucleation on a Homogeneous
substrate nucleation
(heterogeneous
nucleation)
Hete Hete Homo

Nucl 1 Nucl 1 Nucl
ΔG *hete = ΔG *hom o * f(θ)
2 − 3cosθ + cos3 θ
f(θ) =
4
Chemical segregation: Scheil equation
Solidification in interface equilibrium conditions
•  Solidification with equilibrium at the solid/liquid interface
–  The composition and temperature of the solid and the liquid at the
interface are given by the equilibrium phase diagram
–  Phases are not homogeneous
•  Assumptions
–  Transport in the liquid state by diffusion and convection
–  No solid-state diffusion
–  Concentrations expressed in atomic fractions
•  Three case studies
–  Homogeneous liquid (intense convection): Scheil equation
–  Stationary liquid (no convection): solidification is mostly partitionless
–  Intermediate situations: Partition is characterized by the effective
partition coefficient
Unidirectional solidification model
T
C0
TL
C0/K0 dTl
m=
dC
Cross section: 1 unit area
TS
€
x
L
C x
fs =
Solidus and liquidus lines are assumed to be linear L
€
Important relations and definitions
x
fs = T - Cooling rate
L G - temperature gradient at the interface
R - solidification rate (velocity of S/L interface)
T˙ = G * R
€
T
" CS %
€ K0 = $ '
# C L & T,eq.
TL
dT ΔT0
m= L TS
€ dC
ΔC 0
C0 C 0 (1 − K 0 )
ΔC 0 = C L − C s = − C0 = €
K0 K0
ΔT0 = TS − TL = −mΔC 0 €
C0*K0 C0 C0/K0
C
€
Homogeneous liquid: evolution of chemical
composition
CSi/K0
CSi/K0
C0
CSi
K0C0 CSi
D. A. Porter, K. E. Easterling, M. Sherif, Phase Transformations

in Metals and Alloys, 3.rd Ed CRC Press
Evolution of chemical composition, stirred liquid
During the time interval dt the solid liquid interface
advances of df. The hatched areas in the figure
represent the amount of solute that must be
transferred from the liquid to the solid. Considering
that the total amount of solute in the system must be
conserved, a mass balance can be established as
follows :
Since the concentration of solute in the solid and the

liquid at the interface is given by the (equilibrium)
partition coefficient
And
Evolution of chemical composition, stirred liquid
The mass balance may be rewritten as
Using the boundary condition
The following integration may be performed:
Leading to Scheil equations for the liquid and the solid
Scheil equation:
Evolution of chemical composition, stagnant liquid
CSi/K0=C0/K0
CSi=C0
C0
K0C0
Initial Stationary regime Final

transient transient
Solute transport in the liquid
x = 0 ⇒ CL = C0 K
0
x = ∞ ⇒ CL = C0
% dC (
R(C Li − C Si ) = J L (0) = −D' L *
& dx ) x =0 CSi/K0=C0/K0
Solute flux due to the migration of the S/L interface at speed R:

€
J1 = RC ( x + dx) − RC ( x) = RdC
Solute flux due to liquid phase diffusion:

C
# dC ( x) dC ( x + dx)& dC
0 x
J 2 = [ J ( x) − J ( x + dx)] = −%D −D ( = Dd( )
$ dx dx ' dx
The sum of the two fluxes is equal to the variation of solute content in the volume
element:
dC # R &
J1 + J 2 = dx 1− K0
dt C L ( x) = C 0 + C 0 exp%− x(
dC d 2 C dC K0 $ D '
R +D 2 =
dx dx dt # R &
2
d C
⇒D 2 +R
dC
=0
= C 0 + ΔC 0 exp%− x(
dx dx in stationary regime. $ D '
€ São Paulo School of Advanced Science on Frontiers in Lasers and their Applications
€
Evolution of chemical composition, intermediate
conditions
$ R '
C L ( x) = C 0 + ΔC 0 exp&− x)
% D (
& R )
€ C L = C L (∞) = C L (δ ) = C 0 + ΔC 0 exp(− δ +
' D *
ΔC 0
€ If δ > thickness of the
boundary layer (~ 2D/R)
δ CL~C0
€C0
x
Evolution of chemical composition, intermediate
conditions: effective partition coefficient
C S int
K eff =
CL
K 0 C L int K 0 C0 K
K eff = = 0
C L (∞) C L (δ )
1− K0 % R (
C L (δ ) = C 0 + C 0 exp'− δ *
K0 & D )
1
K eff =
1− K0 % R ( Effective partition coefficient
1+ exp'− δ *
K0 & D )
€
Solidification in eutectic phase diagrams
Solidification ends in the
eutectic reaction
Ceut
C0
C0 C’
T 0 K0C0
Stationary regime Final

transient
Solidification
ΔC0 ends in the
Tinterf.
eutectic
Stationary
reaction
regime ΔC’
0
Ceut
C
Interface morphology and solidification
microstructures in pure substances
t t+dt
Interface stability analysis:
•  Solidification kinetics controlled by heat transfer
•  Equilibrium conditions at the interface
•  Heat balance: S
−k L (G L ) 0 + L v R = −k S (GS ) 0
Heat flux reaching Latent heat of Heat flux away

the interface from solidification from the interface •  Superheated liquid: flat
the liquid into the solid
(plane) interface
€
•  Undercooled liquid:
dendritic interface
Interface morphology in the solidification of pure
substances
In a pure substance:
•  the S/L interface is plane when the liquid is superheated Tliq>Ti-Δtinterf
(Gs/l>0)
•  The S/L interface evolves towards a cellular or dendritic morphology
when the liquid is undercooled Tliq<Ti-Δtinterf (Gs/l<0)
W. Kurz, D. J. Fisher, Fundamentals of Solidification 4th Edition, CRC Press
Interface morphology during alloy solidification:
constitutional undercooling
C, T T
eq
T(x)
TL ( x)
C0/K0
TL C0
€
TS C0/K0
C0 C0
x
C
C0*K0 C0 C0/K0
$ R '
C L ( x) = C 0 + ΔC 0 exp&− x) D. A. Porter, K. E. Easterling, M. Sherif, Phase Transformations
% D ( in Metals and Alloys, 3.rd Ed CRC Press
€
C, T T(x)
2. dT/dx > 0, dT/dx < dTL/dx
3
TL ( x) 2 No thermal undercooling,
C0/K0
1. dT/dx > 0, dTL/dx > dT/dx
ΔTconst
€ Thermal + constitutional
undercooling
C0 C L ( x) 3. dT/dx > dTL/dx

€
x Superheated liquid
€ 1
D. A. Porter, K. E. Easterling, M. Sherif, Phase Transformations

in Metals and Alloys, 3.rd Ed CRC Press
constitutional undercooling criterium
Taking into consideration that T(x)
C, T TL ( x)
# dC &
−D% ( = R (C L,i − CS,i ) C0/K0
$ dx ' 0
# dC & R
% ( = − C L,i (1 − K )
€
$ dx ' 0 D
And
dTL dC C0 x
TL = Tm + mC ⇒ =m L
dx dx
To avoid constitutional undercooling
# dT & # dC & Constitutional undercooling criterion

G ≥ % L ( ⇒ G TL ≥ m% L (
T
L
$ dx ' 0 $ dx ' 0
# dC & G −mCS.i (1 − K ) G L −mC 0 (1 − K 0 )
T
G ≥ m% L ( ⇔ L ≥
L
$ dx ' 0 R D
≥
R DK 0
In stationary regime, with stagnant liquid G L −mΔC 0
≥
G L −mC 0 (1 − K 0 ) −mΔC 0 R D
CS.i = C 0 ⇒ ≥ =
R DK 0 D
€ €
Constitutional undercooling and interface morphology
Conditions for cellular solidification:
δ ∼ rnuc_hom
•  Small undercooled region
Conditions for dendritic solidification
δ >> rnuc_hom
Dendritic
solidification •  Large undercolled region
Cellular
solidification
Interface morphology during alloy solidification
Steady-state patterns formed at the crystal–melt interface of a binary alloy of
succinonitrile and coumarin 152 during directional solidification
Plane front solidification
Conditions for plane front solidification: no thermal
undercooling in pure metals or no thermal or
constitutional undercooling in alloys
Cellular solidification
Conditions for cellular or dendritic solidification_

thermal undercooling ahead of the S/L interface in
pure metals or constitutional undercooling in alloys
Cellular solidification
Small undercooled region: cellular solidification

Large undercooled region: dendritic solidification
Undercooled bulk liquid: equiaxed solidification
Dendritic solidification
Losert W et al. PNAS 1998;95:431-438

©1998 by The National Academy of Sciences
Plasne interface stability: Mullins and Sekerka analysis
(Mullins and Sekerka, J. Appl. Phys., 35 (1964) 444)
Stability conditions for plane S/L interface
Absolute stability criterion
ΔT 0D
V≥
kΓ
Constitutional undercooling criterion
mVΔC 0
G>
D
Phases in dendrite growth: coalescence
Dendrite tip
Secondary arm growing region
Tertiary arm growing region
Coalescence region
Preferential growth directions in dendrites
Secondary dendrite arm spacing
λ2 depends on the local solidification time ts

Following Katamis and Flemings, 1965
1
λ 2 ∝ (Mt S ) 3
% C ml (
ΓDln' C *
& 0)
M= ≈ 1 −10
m(1 − k )(C 0 − C l )
m
Where Clm is the composition of the residual liquid

Since
€ ΔTr ΔT
tS ≈ = r
$ dT ' GR
& )
% dt (
n
λ 2 ∝ (GR )
By measuring the secondary dendrite arm spacing

the cooling rate can be estimated
W. Kurz, D. J. Fisher, Fundamentals of Solidification 4th Edition, CRC Press €

Formation of the microstructure in laser surface
treatment: melt pool shape and solidification parameters
Vt
V= Vt. cosΘ
Influence of processing conditions on solidification
parameters
Influence of processing conditions on
solidification parameters
Microstructural transitions in solid

solution solidification
Stability of a plane solid-liquid interface:

(Constitutional undercooling criterion)
mV ΔC 0
G>
D
Microstructural transitions in a laser clad
Co-1.1C-28Cr-4.5W-3Ni-3Fe alloy (Stellite 6) coating
Dendritic
structure
Cellular
structure
Plane front
solidification
structure
Columnar and equiaxed solidification in laser surface
treatment
Al7Cr Al11Cr
Al7Cr
Al4Cr
α Al
Equiaxed solidification with

heterogeneous nucleation
Transition between columnar and equiaxed solidification 
Hunt’s model
Assumptions:
•  Dendritic interface undercooling given by Burden and Hunt model
# C 0VS & C0 = concentration
12
ΔTden = % ( Vs = solidification rate

$ A ' A = constant
•  heterogeneous nucleation of the equiaxed structure

N0 = heterogeneous nuclei concentration
€ $ ΔG c ' N = equiaxed dendrites concentration
I = (N 0 − N )I 0 exp&− )
% kT ( ΔG c = critical nuclei free energia
I0 = pre-exponential factor
•  Solidification is equiaxed if fraction of equiaxed grains exceeds 50%

€ €
$ ΔT 3 ' ΔTc ,ΔTn = columnar interface and

13 N
Equiaxed growth: G < 0,617N 0 &1− 3)
ΔTc heterogeneous nucleation
% ΔTc ( undercoolings
13
$ ΔT€ 3'
N
Columnar growth: G > 0,617(100N 0 ) &1− 3)
ΔTc
€ % ΔTc (
€
Equiaxed dendrites grow from a floating nuclei
(a)
(b)
(c)
The development of equiaxed dendrites: (a)

a spherical nucleus; (b) the interface
becomes unstable; (c) primary arms develop
in crystallographic directions (<100> in cubic
crystals); (d) secondary and tertiary arms
develop (after R.E. Reed-Hill, Physical
Metallurgy Principles, Van Nostrand, New
York) (d)
Non-equilibrium solute partition (Aziz model) 
(Aziz J Appl Phys 53(1982)1158)
•  Binary ideal (dilute) solution
•  with
Where Partition coefficient K as a function of

interface velocity for Si-As alloys. Dashed
curve Aziz model, solid Sobolev model)
kv velocity dependent partition coefficient
f geometrical factor
υ vibration frequency
δ interactomic distance
R gas constant
QD energy barrier for interdiddusion
Influence of SDAS on properties
The secondary dendrite arm spacing

controls the materials strength
The dependence is similar to the Hall-
Petch relation
Since the arm spacing is proportional to
cooling rate, this becomes an important
parameter.
Hall-Petch equation:
k
σy = σ0 +
d
Effect of the secondary dendrite arm
spacing on the properties of an aluminum
casting alloy
€
Laser surface melting of tool steels
Laser surface melting of martensitic stainless tool
steels
Fe - 13%Cr - 0.5% C AISI 420 tool steel
P = 1250 W/mm2
γ(220)
γ(220)
15%γ γ(220)
Μ/α(211)
75%γ 100%γ
Μ/α(200)
γ(311)
γ(311) γ(311)
Μ/α(211)
Μ/α(200) Μ/α(200) Μ/α(211)
30 32 34 36 38 40 42 44 46 30 32 34 36 38 40 42 44 46
30 32 34 36 38 40 42 44 46 θ θ
θ
Scanning
1 Speed (mm/s) 10 20
Primary solidification phase in Fe-Cr-C tool steels
440
420
In constrained growth conditions the phase that grows with lower

interface undercooling (higher interface temperature) is kinetically
favoured.
Influence of the processing parameters on the
microstructure of AISI 420 tool steel
Fe - 13%Cr - 0.5% C tool steel
4000
3500
Μ+γ
Power Density (W/mm2)
3000 ≈50% γ
2500
≈ 100% γ
2000
1500
1000
γ
500
0
0 20 40 60 80 100
Scanning Speed (mm/s)
Solidification microstructure selection criterion
!T 2 !T1
Selection criterion (Tammann and Botschwar, 1926) T liquidus
In constrained growth conditions, the prevailing phase

and morphology are those that grow with higher solid-
liquid interface temperature
Ti = Tliquidus + ΔTtherm + ΔTkin + ΔTcomp + ΔTcurv
given by the required for Influence of influence

equilibrium latent heat required for segregation in of curvature in
diagram evacuation atom transfer equilibrium equilibrium
(equiaxial across the interface interface
solidification) interface temperature temperature
Response function of a dendritic interface
•  No thermal undercooling: growth columnar
•  Curvature of dendrite tip given by Ivantsov model
•  Non-equilibrium partition coefficient given by Aziz model (1982)
•  Non-equilibrium liquidus given by Boettinger and Coriell model (1986)
Response function: * k V ΔT 0 Iv ( P e ) 2Γ
T i = T f + m' C L + -
1 - ( 1 - k V ) Iv ( P e ) R
T liquidus ΔTsc ΔTcurv
With:
∞ exp ( - z )
Solute transport described by Ivantsov equation (1947): Ω = Iv ( P e ) = P e exp ( P e ) ∫ dz
z
P
e
C* - C
Supersaturation given by: Ω = L 0
*
C - C * k + (δ V D )
L S i i
Partition coefficient: kV =
1 + δ V D )
(
VR i i
Peclet number: Pe =
2D
L
⎧⎪ k - k [ 1 - ln ( k k ) ] ⎫⎪
σ V V
Γ= Liquidus slope: m ' L = m L ⎨1 + ⎬
Gibbs Thomson coefficient: ⎪⎩ 1 - k ⎪⎭
ΔS
Phase selection during solidification of Fe-Cr-C steels
Comparison of dendrite tip temperature for austenite and ferrite using KGT model
1500
AISI 440C - Fe-18Cr-1C
AISI 420 AISI 420
1480 Tl Austenite
Fe-13Cr-0,4C
1460
T* (ºC)
1440 γ
1420 Austenite
Ferrite
1400
0 0,05 0,1 0,15 0,2
R (m/s)
1430
AISI 440C
Fe-18Cr-1C 1420
γ
Tl Austenite
1410
T*(ºC)
1400 Austenite
Ferrite
1390
1380 δ
1370
0 0.005 0.01 0.015 0.02 0.025 0.03 0.035 0.04
V solidification (m/s)
Examples of laser surface alloying of
aluminium
Al-TM surface alloys by injection of TM powder
particles
Incomplete homogenisation of
the melt pool
Al-Nb alloy
Alloy formation
•  Homogenisation of the melt pool can be attained by:
–  Convection
–  Diffusion
–  Diffusion mass transport usually negligible within the meltpool lifetime
–  Homogenisation by Marangoni convection can be characterised by the
surface tension number
-  (dσ/dT) temperature derivative of the surface
tension
-  q net laser heat flow
-  d laser beam diameter
-  μ viscosity
-  v0 laser scanning speed
-  k thermal conductivity
S > 45000 => intense convection SAl ≈ 42000

S < 45000 => weak convection
Chande and Mazumder, Metall. Trans. B 14, 1983, 181

Convection is weak
Particles/melt reactions Al-Cr and Al-Mo
Al-Cr Al-Mo Al-Nb
Dissolution kinetics of Nb particles in molten Al
(Costa and Vilar, J. Appl. Phys. 80(1996)4350
Influence of local meltpool temperature of TM mixing
Complete dissolution of Nb particles in the

(Thermal model: Ashby and Easterling,
Acta Metall. 32, 1984, 1935-1948) liquid may occur in a layer of about 360 µm
below the surface
Microstructure of Al-Nb Alloys
Alloy homogenisation by laser remelting
•  Melting of Al-TM alloys
ü  defects are eliminated
–  P = 2000 W
ü  alloy is homogenized
–  Beam diam. = 2 mm ü  microstructure is refined
–  Vb = 5, 10, 20 and 40 mm/s
Al-Cr alloy
Microstructure of Al-Cr surface alloys
Equiaxed region (E)

5 mm/s 10 mm/s
20 mm/s 40 mm/s
As-alloyed (A)
and remelted
columnar regions
(C)
Microstructure formation in Al-Cr alloys
VS=Vbcosθ
Columnar to equiaxed transition

estimated using Hunt’s model (Mater.
Sci. Engn. 65, 1984, 75)
Wear resistant Al-based MMCs for rapid tooling and
aerospace rapid manufacturing
Chopper rotor head
Al-based composites
Properties
•  High strength-to-weight ratio

•  Good ductility
•  Good electrical and thermal conductivities
•  High wear and corrosion resistance
Aircraft engine manifold
Applications
•  Rapid tooling
•  Plastic mould industry
•  Aerospace and automotive industries
Microstructure of Al-12Si-SiC Coatings
Processing parameters
•  Power density: 330 MW/m2
•  Interaction time: 0.08 s
•  Specific energy: 26 MJ/m2
Vol. proportion of SiC: 32±2 %

Microstructure of Al-12Si-SiC Coatings
Microstructure
Only few SiC particles remain at

the bottom of the deposit
Reactions between liquid Al and SiC
4Al(l) + 3SiC(s) → Al4C3(s) + 3Si 940 < T < 1620 K
4Al(l) + 4SiC(s) → Al4SiC4(s) + 3Si 1670 < T < 2200 K

€
8Al(l) + 7SiC(s) → Al8SiC7(s) + 6Si T > 2200 K

€
€ The reaction products depend on the temperature
Source: J.C. Viala, P. Fortier, J. Bouix, J. Mater. Sci., 25 (1990) 1842.
Spatial temperature distribution of powder particles at
different injection velocities
SiC Al-8Si
•  Due to the material higher reflectivity Al-7Si particles do not warm up excessively,
but SiC particles temperature may reach 3000°C for low injection velocities ->
high particle/melt reactivity
•  The best methods to achieve composites with adequate microstructure is to
increase the particle injection velocity or to use particles with low reactivity
towards molten aluminium and low solubility product
Control of particles/melt reactions
v = 1 m/s v = 5 m/s
At v = 1 m/s
•  Low SiC fraction

•  Plate-like Al4SiC4 and
equiaxed Si particles
At v = 5 m/s
•  high SiC fraction

•  No Al4SiC4 and Si
Larger proportions of Al4SiC4

and Si near the surface of the
deposit → reaction rate
depends on local temperature.
Microstructure of Al-12Si-TiC coatings
Deposition parameters: power density = 224 MW/m2 , interaction time = 0.27 s
Coating: thickness = 1mm, free of pores and other defects, volume proportion
of TiC: 34±2 %
•  TiC and a small volume fraction of Ti3SiC2 particles dispersed in a matrix

containing α-Al dendrites (A) and α-Al+Si eutectic (B).
Microstructure of Al-12Si-TiB2 coatings
Deposition parameters: power density = 224 MW/m2 , interaction time = 0.27 s
Coating: thickness = 1mm, < 1% porosity, volume proportion of TiB2: 34±3 %
•  TiB2 particles dispersed in a matrix containing α-Al dendrites (A) and α-

Al+Si eutectic (B).
Superalloy Single Crystal Laser-assisted
Deposition
Typical turbine aircraft engine
(Source: http://powertodayindia.com/turbine.html)
Manufacturing of single crystal turbine blades
<100>
Investment casting mold
Evolution of Ni-superalloy
turbine blades:
polycrystalline, unidirectional
and single crystalline Simulation of crystal
selection in single crystal
turbine blade solidification
Microstructure of a Ni-based superalloy
•  Matrix (continuous phase): FCC Ni-base solid-solution with high percentage of elements such as Co, Cr, Mo, and W (γ
phase)
•  Cuboid precipitates of the FCC ordered (L12) phase Ni3(Al,Ti) (γ'): The precipitates are coherent with the matrix. This
requires identity of crystal lattice and similarity of lattice parameters
•  Minor phases: carbides (e.g., TiC, TaC, or HfC) and Topologically Close-Packed Phases (TCPs), with complex
crystallographic structure.
From: http://www.tms.org/meetings/specialty/superalloys2000/superalloyshistory.html
Motivations
Motivation
Why of the work at IST:
single crystals?
• improving thermalthe
To optimise fatigue resistance
microstructure and properties of single
improving creep resistance
crystalline depositions of Ni-based superalloys on single
increasing service temperature and lifetime
crystal superalloy components
What microstructure and how is it obtained?
γ/γ’ coherent precipitation microstructure is obtained by a complex
ageing heat treatment
This microstructure is essential to reach the required properties
and long-term behaviour
Single crystalline turbine blade repairing
SEM image EBSD image
?
<100> Deposited
material
Substrate
8 layers
0° 54
°
Multilayer single crystalline coatings produced by

<100>
controlled solidification laser deposition, with the
same crystallographic structure and orientation of
the substrate
Single crystalline turbine blade repair
Ideal case
Columnar
dendrites
Epitaxial
growth
[001]
Equiaxed
grains
To avoid
Non-epitaxial
columnar grains
[001]
Conditions for single crystalline growth if an overlay layer
•  Nucleation
–  No nucleation from the melt. Free nucleation originates stray
crystals.
–  Epitaxial growth on the substrate preserves the single
crystalline nature of the part to be repaired and the orientation of
the crystal
•  Growth
–  Misoriented grains must be eliminated by the competitive
columnar dendritic growth process.
–  No equiaxed grains should be allowed to form èNo columnar
to equiaxed solidification transition.
Nucleation versus epitaxial growth
ΔG*hete = ΔG *hom o * f(θ)

Epitaxial growth = correct
orientation relationship
f(θ) = between
2 − 3cosθ + cos θ
4
3
the substrate and the deposition

€ Epitaxy
θ
è same crystalline structure,
Heterogeneous Homogeneous or
similar lattice parameters

nucleation on a
substrate
heterogeneous
nucleation in the
liquid
Condition for dendritic growth
(Mullins and Sekerka, J. Appl. Phys., 35 (1964) 444)
Stability conditions for plane S/L interface
Absolute stability criterion
ΔT0 D
Vab ≥
k0 Γ sl
Constitutional undercooling criterion
mVΔC0
G>
D
Microstructural selection criteria
!T 2 !T1
T liquidus
Selection criterion (Tammann and Botschwar, 1926)
In constrained growth conditions, the prevailing phase
and morphology are those that grow with higher solid-
liquid interface temperature
Competition between dendrites in columnar
growth
Tint = Tliquidus + ΔTtherm + ΔTkin + ΔTcomp + ΔTcurv
Given by the Required for Influence

equilibrium latent heat Required for of curvature in
Influence of
diagram evacuation atom transfer equilibrium
segregation in
(equiaxial across the interface
equilibrium
solidification) interface temperature
interface
temperature
Response function of a dendritic interface
•  KGT Model
•  no thermal undercooling: growth columnar
•  curvature of dendrite tip given by Ivantsov model
•  non-equilibrium partition coefficient given by Aziz model (1982)
•  non-equilibrium liquidus given by Boettinger and Coriell model (1986)
Response function:
k Δ T Iv ( P ) 2Γ
*
T i = T f + m' CL + V 0 e -
1 - ( 1 - k ) Iv ( P ) R
V e With:
T liquidus ΔTsc ΔTcurv
∞exp ( - z)
Solute transport described by Ivantsov equation (1947): Ω = Iv ( P e) = P eexp (P e) ∫ dz
z
Pe
C*L - C0
Supersaturation given by: Ω=
C*L - CS
* k + (δ iV D i)
Partition coefficient: kV =
VR 1 + ( δ iV D i )
Peclet number: Pe =
2DL
σ ⎪⎧ k - kV[ 1- ln (k kV )] ⎫⎪
Gibbs Thomson coefficient: Γ= Liquidus slope: m'L = mL ⎨1 + ⎬
ΔS ⎪⎩ 1- k ⎪⎭
Calculation of the solidification rate for dendritic growth
Columnar
dendrites
Vt
Scanning direction
V = Vt cosθ
Conclusion:
dendrites with a <100> direction
parallel to the gradient of
cosθ
V = Vt temperature prevail over dendrites
cosφ with other orientations
Microstructural transitions in laser solidification
Stability of a plane solid-liquid interface:
(Constitutional undercooling criterion)
mRΔC0
G≥
D
S/L morphology transitions in a laser clad

NiCrAlY-type alloy coating
Dendritic
structure
Cellular
structure
Plane front
solidification
structure
Columnar dendritic to equiaxed dendritic solidification 
Hunt’s model
Assumptions:
•  Dendritic interface undercooling given by Burden and Hunt model
12 C0 = concentration
# C 0VS &
To avoid equiaxed ΔTden = %
$ A '
( Vs = solidification rate
A = constant
solidification heterogeneous
€
•  heterogeneous nucleation of the equiaxed structure
$ ΔG c '
N0 = heterogeneous nuclei concentration
N = equiaxed dendrites concentration
I = (N 0 − N )I 0 exp&− )
nucleation in the liquid must % kT ( ΔG c = critical nuclei free energia

I0 = pre-exponential factor
•  Solidification is equiaxed if fraction of equiaxed grains exceeds 50%
be avoided and the liquid

€
$ ΔT 3 '
€
ΔTc ,ΔTn = columnar interface and

13
must be superheated
Equiaxed growth: G < 0,617N 0 &1− N3 )ΔTc
% ΔTc (
heterogeneous nucleation
undercoolings
13
€ 3'
$ ΔT
Columnar growth: G > 0,617(100N 0 ) &1− N3 ) ΔTc
€ % ΔTc (
Single crystal coatings: starting materials
•  Coating: NiCrAlY
–  Composition (wt.%): 68,8 Ni – 24,63 Cr – 5,72 Al – 0,41 Y
•  Substrate: SRR 99 superalloy
–  Composition (wt.%):
67.235Ni-9.5W-8.5Cr-5.3Al-4.8Co-2.65Ta-2.05Ti-0.5Mo-0.015C
FCC γ - phase γ’ precipitates

in a γ- phase matrix
Microstructure of the laser deposited material:
interface structure
Epitaxial interface
Plane front
solidification region
Dendritic solidification region
Cellular solid- liquid

interface region
Microstructure of the laser deposited material
Interface between
successive layers
Misoriented dendrites,
heterogeneously nucleated at
the liquid surface
Microstructure of the deposited material
Dendritic
solidification
region
γ/γ’ eutectic cell

near the melt front
(100
γ (100)
Nominal (100) direction of

the substrate
Study of mosaicity by X-ray diffraction
Electron backscattered images of the same area of the coating with the surface of the
sample perpendicular to the electron beam, and after tilting 5 degrees
twist 3
tilt 2
substrate
1
Mosaicity in NiCrAlY coatings
Measurement point Mosaicity (°)

location
Y-scanning X-scanning
Substrate 0.67 1.11
Interface 1.73 3.48
Coating, half-height 1.51 5.56
Coating, top 1.20 6.06
Single crystal remanufacturing: materials
Substrate
Wt.% Ni Cr Co Mo W Al Ti Ta Hf Re
CMSX-2 66.6 8 4.6 0.6 7.9 5.6 0.9 5.8 n.a. n.a.
CMSX-4 61.8 6.5 9 0.6 6 5.6 1 6.5 0.1 3

CMSX-10* 69.6 2 3 0.4 5 5.7 0.2 8 0.03 6
Powder
Wt.% Ni Cr Co Mo W Al Ti Ta Hf Nb Fe C V Zr
Rene 80* 59.87 14 9.5 4 4 3 4.8 n.a 0.75 n.a n.a 0.16 n.a. 0.3
Rene N 63.35 9.25 7.5 1.5 6.0 3.7 4.2 4.0 n.a. 0.5 n.a. n.a. n.a. n.a.
Rene N4* 61.5 9.8 7.6 1.6 6.1 4.4 3.4 4.9 0.17 0.5 0.08 0.06 0.04 0.01
*wt% Boron from 0.0015% to 0.005%
Microstructure of the CMSX-4 substrate
Vane seal segment
γ’-Ni3Al
γ-Ni
Chemical segregation in the dendritic

structure
Microstructure of a single clad track
P = 500W
v = 4 mm/s
f = 1 g/min
d = 1 mm
[001] substrate 100
001
X [100] direction
MC carbides, M=Ta, Ti, Nb, …
G mΔC 0 ΔT0
PFS >− =
R D D
€
Microstructure of a single clad track: stray grain
formation
Stray grain formation at the top of the Stray grain formation from coarse
ten-layer deposit γ’-Ni3Al of the substrate
Mosaicity analysis: single track
S CSR ESR
Electron Backscattered Diffraction
Orientation Mapping
Microstructure and mosaicity in multilayer deposits
X [100]
P = 500W, v = 4 mm/s P = 800W, v = 8 mm/s
Powder flow rate = 1 g/min, laser beam diameter = 1 mm
Microstructure before and after after heat
treatment
Before heat
treatment
Substrate Laser deposited material
Coating,
after heat
treatment
Coating after heat treatment 1 Coating after heat treatment 2

A1: 1050° C, 6 h / A2: 870°C, 24h A1: 1050° C, 24 h / A2: 870°C, 24h
Origin on non-cuboid shape precipitation
k ef −1
CS = k ef C 0 (1− fs )
k0
12 kef = Cr
⎛ Vδ ⎞
k0 + (1− k0 ) exp ⎜ −
10 ⎝ DL ⎟⎠
Ta
8
Cs, wt%
Chemical segregation
6 in the dendritic Al
structure
4 Ti
W
2
Mo
0
0 0.2 0.4 0.6 0.8 1
fs
Idealised model for segregation
Heat treatment
Homogenization: 1265 ˚C/2h+1275 ˚C/2h+1285 ˚C/1.5h
Precipitation: 1050 ˚C/3h
Clad
Substrate
(a) (b)
Interface substrate/clad after homogenization (a) and homogenization

and precipitation (b) heat treatments
Contactos
Rui Vilar
Departamento de Engenharia Químca.
Instituto Superior Técnico, Lisboa
Email: rui.vilar@ist.utl.pt

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Laser surface treatment: principles and

• Introduction: Laser-assisted Surface Engineering, objectives and

• Required surface properties, such as surface hardness, wear

Alumina (Wei, 1992)

Plastic deformation Bulk properties

Surface modified region

• Solid state processes (T<Tm)

(Meijer, J. Mater Proc Tech, 149 (2004) 2-17)

Laser surface treatment with CW lasers

Ultra-fast, solid state 10 fs - 10 ps 0.01 - 0.1 µm >109

Q-switched pulsed Nd/YAG 10 - 20 ns 0.5 - 1 µm 5*106

Q-switched Nd/YAG 250 ns 1 - 5 µm 105

Excimer laser 20 ns 0.5 - 1 µm 5*106

Pulsed Nd/YAG 5- 25 ms 100 - 250 µm 5*104

CW CO2, V= 10 mm/s 0.05 - 0.2 s 0.1 - 0.5 mm 104 - 5*103

Diode lasers 0.1 - 2 s 0.25 - 2 mm 5*103 - 2*102

Fiber lasers 10 ps - 2 s 0.1 µm - 2 mm 109 - 2*102

We are implicitly assuming that:

Due to the long interaction time the temperature of

• Reflectivity of metals for near infrared

• Reflectivity can be reduced by chemical

• The absorptivity of metals for visible and

o Unidimensional heat conduction given by

o Semi-infinite solid. Where:

Only two main independent processing parameters:

• The temperature is given by:

• And the colling rate is given by:

Depth and width of the martensitic region, experimental

Layer overlap leads to solid-state transformations in previously deposited material

Heat transfer by convection

Heat transfer by radiation

M, martensite; α, ferrite; γ, austenite; L, liquid

Temperature field at the end of the last deposition step.

t Step = 5.5 sec., Δt = 0.5 s t Step = 37.0 sec., Δt = 5.0 s

Phase distribution after the last deposition step.

t Step = 5.5 sec., Δt = 0.5 s t Step = 37.0 sec., Δt = 5.0 s

Final hardness distribution, after cooling down to room temperature.

t Step = 16.0 sec., Δt = 0.5 s t Step = 52.0 sec., Δt = 5.0 s

dT/dt ≤ 410 ºC/s

5 s idle time Heating up of the Martensitic transformation

Less heat accumulation Complete martensitic

Idle time = 5 s Room temperature

Plastic deformation at high

Young’s Substrate at room temperature

The outward shear stress at the pool surface induced by the

Where γ is the surface tension, µ the viscosity, v the fluid

The surface tension gradient is induced by the surface

Drezet et al J. Phys. IV France 120 (2004) 299-306

CMSX-4 1657 1.85 − 9.01 · 10− 4

Al–31.5 at.%Ni 1523 1.16 − 1.14 · 10− 4

CuSnP 1301 1.08 − 4.77 · 10− 4

Longitudinal section view of velocity field,

Top view of velocity field of weld pool

Pang et al Journal of Physics D Applied Physics 44(2010):025301

• Thermochemical processes (modification of chemical composition by diffusion at high

Advantages of laser hardening

(Adapted from J. Ion)

(Source: J. Ion, Surf. Engn. 18(2002)14)

Conventional optics: defocalised beam,

Corresponding temperature distributions

Optimised focusing mirror

Cross sections of the hardened zone

Laser melting Laser alloying by powder injection

•  Introduction: Laser-assisted Surface Engineering, objectives and

•  Required surface properties, such as surface hardness, wear

•  Solid state processes (T<Tm)

Diode lasers 0.1 - 2 s 0.25 - 2 mm 5103 - 2102

•  Reflectivity of metals for near infrared

•  Reflectivity can be reduced by chemical

•  The absorptivity of metals for visible and

o  Unidimensional heat conduction given by

o  Semi-infinite solid. Where:

•  The temperature is given by:

•  And the colling rate is given by:

•  Thermochemical processes (modification of chemical composition by diffusion at high

•  Interactions between particles in the powder stream are neglected,

•  V and S particle volume and surface area

•  Due to the high temperatures reached particles may vaporise at a

•  laser beam attenuation by the powder − Pl laser beam power

•  Power absorbed by the surface

•  Stellite powder 50 mm diameter

•  Heat (and the powder chemical elements) are redistributed in the

•  heterogeneous nucleation of the equiaxed structure

•  Solidification is equiaxed if fraction of equiaxed grains exceeds 50%

•  Binary ideal (dilute) solution