Sintering Theory: Brief Introduction BY Eugene A. Olevsky San Diego State University, California, Usa

SINTERING THEORY
BRIEF INTRODUCTION
BY
EUGENE A. OLEVSKY
SAN DIEGO STATE UNIVERSITY, CALIFORNIA, USA
2011 FAST
Spring School
SUMMARY
1. Science of Sintering: Fundamentals and

Historical Development
2. Classical Models of Sintering: Viscous and
Diffusion Mechanisms of Mass Transport
3. Continuum Modeling of Powder Consolidation
4. Multi-Scale Modeling of Sintering
5. Extrapolation of Sintering Concepts Towards
Constitutive Modeling of SPS
6. Sample SPS Problem Solutions
7. Further prospects of sintering modeling
SUMMARY

PHYSICAL BASIS OF SINTERING
50 years to find out!
Surface tension phenomena

PHYSICAL BASIS OF SINTERING
Surface tension phenomena

SINTERING THEORY
Frenkel approach (1945) Pines approach (1946)

coalescence of viscous particles evaporation of emptiness
driven by surface tension
pore
(vacancies)
E  2  
 s  2 2 V C  Co 1 
 r k T 
t
SUMMARY

Mass Transport in Sintering
From Swinkels and Ashby

Ashby Sintering Maps
COMPLEX SHAPE PARTS PRODUCED VIA
POWDER METALLURGY ROUTE
camshaft sprocket
auto transmission sprockets
flange pulley
metal fiber filter for

airbag inflators
palate expander parts foldable paper hole punch

Theory of Sintering: Practical Implementation
It was necessary to combine ideas of
MECHANICS
&
MATERIALS SCIENCE
The breakthrough happened in the end of 1980s

SUMMARY

The Main Constitutive Relationship
Bulk modulus: Shear modulus:
Resistance to the volume change Resistance to the shape change
Strain rate component function of porosity function of porosity
 (W )   1  
 ij   eij      e ij   PL ij
W   3  
Volume strain rate
Generalized
viscosity:
corresponds to the Effective sintering stress:
constitutive properties of function of porosity
particle material
externally applied material resistance sintering

stresses
Olevsky E.A. (1998), Theory of sintering: from discrete to continuum. Review, Mater. Sci. & Eng. R: Reports, 40-100
Continuum Theory of Sintering
Without considering sintering stress
 ( w) 1
 ij  [ ij  (   )e ij ]
w 3
 ij is the ij component of the stress tensor;  ( w) effective stress
 ( w)  20 w Linear viscous (hot deformation of

amorphous materials; free sintering)
 ( w)   y Plastic (cold pressing)
 ( w)  Awm Power-law creep (hot deformation of

crystalline materials)
 ( w) 1
 ij  [ ij  (   )e ij ]
w 3

2 (1   )3 Bulk modulus  ij Kronecker delta
3 
  (1   ) 2 Shear modulus
0 Shear viscosity of the fully-dense material

1
w  2  e2 Equivalent effective
1 strain rate
e   ii  11   22   33 volume change rate
Shape change rate
1
 (1   2 )2  ( 2   3 )2  ( 3  1 )2
3
Including sintering stress:
 ( w) 1
 ij  [ ij  (   )e ij ]  pl ij
w 3
3
pl  (1   ) 2
2 r0
pl The effective sintering stress
 Surface tension r0 Radius of the particle
 ij external stress
For free sintering, no external stress,  ij  0
Problem of free sintering of a porous body
 ( w) 1
 ij  0  [ ij  (   )e ij ]   pl ij
w 3
For linear viscous phase  ( w)  20 w
1
Projection on r direction: 20 [ r  (   )e]   pl (a)
3
1
Projection on z direction: 20 [ z  (  3  )e]   pl (b)
(a)*2+(b) 20 [ (2 r   z )  3(  1  )e]  3 pl

3
e  2 r   z  20 3 e  3 pl  pl  20 e

Continuity equation e
1
3 2 
 (1   )
 pl  2 r0
e   
20 1   2 (1   ) 3
20
3 
9  9 9
     ln     dt
80 r0  80 r0 80 r0
 :Specific time of sintering
s
9
  dt    1 exp( )
s 80 r0 s
Pressing in rigid die and free sintering of a powder cylinder
E. Olevsky, G. Timmermans, M. Shtern, L. Froyen, and L. Delaey, The permeable element method for
modeling of deformation processes in porous and powder materials: Theoretical basis and checking by
experiments, Powd. Technol. - 93/2, 123-141 (1997)
Gravity Influence: Grain Segregation Effect
E.A. Olevsky and R.M. German, Effect of gravity on dimensional change during sintering, II. Shape distortion,
Acta Mater., 48, 1167-1180 (2000)
SUMMARY

MULTI-SCALE MODELING OF SINTERING
Idealized unit-cell used for the
determination
of the effective constitutive parameters
Sintering theory was traditionally

developed either as the
application of complex diffusion
or viscous flow mechanisms to a
simple geometry or as complex
evolution of microstructure with
simple diffusion mechanisms. For
example, the bulk modulus  can
be obtained from the solution of
the problem of hydrostatic
loading of the chosen
representative unit cell. The
disadvantage of this model basis hydrostatic stress
is the high degree of the ~
volume strain
idealization of the grain-pore
structure.
CONSTITUTIVE PARAMETERS OF MODELS FOR POROUS
MATERIAL DENSIFICATION
Normalized shear modulus  Normalized bulk modulus 
Kuhn & Downey 2 2

3(2  (1 )2 )(1 ) 9( 2   )(1  )
(1   1/ 3 )2 8 (1 1/ 3 ) 2 ln
2
for Green 2
3 (3  21/ 4 )(1  ) 9 (3  2 1/ 4 )(1  )
plastic Shima & Oyane 2 4 2 (1 )9
(1  )
9 3 2.49  0 .5 14
flow Doraivelu et al. 2(2(1 )2  1) 2(2(1 )2  1)
3(2  (1 )2 )(1  ) 9( 2  )(1   )
Skorohod (1  )2 2 (1 )3
3 
Gurson (Doraivelu et al. 2 1  3 2 1  3 1
approximation) 9 1  2 9 1  2  2
for Ponte Castaneda (1  )2 / ( m 1 ) 27(1  )2 ( m 1 )
1  2 3 8
power-law Cocks (1  )2 / ( m 1 ) (m  1)(1  )(1  ) 2 ( m 1 )
1  2 3 3
creep Duva & Crow (1  )2 / ( m 1 ) 2 
1   
m 2 (m  1)
1  2 3 3  m m 
(m is the 2 (m1) 2 (m  1)
McMeeking & Sofronis 1    2 
1   
m
creep
exponent) 1    3  m m 
Monte Carlo Model was used to simulate grain growth,
vacancy diffusion and vacancy annihilation
We use a digitized microstructure
Energy E   1   qi , q j 
1 N 8
2 i 1 j 1
grain growth pore migration vacancy annihilation

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E. Olevsky, V. Tikare, and T. Garino, Multi-scale modeling of sintering – A Review, J. Amer. Ceram. Soc., 89 (6),
1914-1922 (2006)
Mesoscale Simulation Using the Potts Model
 E. Olevsky, V. Tikare, and T. Garino, Multi-scale

modeling of sintering – A Review, J. Amer.
Ceram. Soc., 89 (6), 1914-1922 (2006)
 E. A. Olevsky, B. Kushnarev, A. Maximenko, V.
Tikare, and M. Braginsky, Modeling anisotropic
sintering in nanocrystalline ceramics, Phil.
Mag., 85, 2123-2146 (2005)
 V. Tikare, M. Braginsky, E. Olevsky, and D. L.
Johnson, Numerical simulation of anisotropic
shrinkage in a 2D compact of elongated
particles, J. Amer. Ceram. Soc., 88, 1, 59-65
(2005)
 M. Braginsky, V. Tikare, and E. Olevsky,
Numerical simulation of solid state sintering,
Int. J. Solids and Structures, 42, 621-636 (2005)
 E. Olevsky, B. Kushnarev, A. Maximenko, and
V. Tikare, Modeling of sintering at multiple
length scales: anisotropy phenomena, TMS First publication:
Letters, 3, 55-56 (2004) V. Tikare, E.A. Olevsky, and M.V. Braginsky,
 V. Tikare, M. Braginsky, and E.A. Olevsky, Combined macro-meso scale modeling of
Numerical simulation of solid-state sintering: I, sintering, in: Recent Developments in Computer
Sintering of three particles, J. Amer. Ceram. Modeling of Powder Metallurgy Processes, ed. A.
Soc., 86, 49-53 (2003) Zavaliangos and A. Laptev, IOS Press, 85-104
(2001)
Results: Simulation of Microstructural Evolution during
Sintering
Time, t = 0 MCS t = 2,000 MCS t = 50,000 MCS

Vacancy anihilation: “jump” and “shift” algorithms
Digitized images can be mined for many types of data
Schematics of Multi-Scale Modeling
Diffusion mass
Potts Model
transport
Meso-Scale FEM Vacancy anihilation
Macroscopic shape distortions

Density distribution
Macro-Scale FEM Macroscopic damage
Macroscopic stress-strain state
Two possible approaches:

 Direct determination of the macroscopic constitutive
parameters based on the mesoscale simulations.
 The macroscopic level envelopes the mesoscopic
simulators.
CONSTITUTIVE PARAMETERS
sintering stress bulk and shear moduli grain growth kinetics
DETERMINATION
Theoretical: Experimental:
Mesoscale Simulation Sinter-forging and free
sintering experiments
Sintering Stress and Bulk Modulus Approximations
Based on Mesoscale Simulations
2
1.8
1.6
PL  a (1  ) b
1.4
Sintering Stress
1.2
1
0.8
0.6
0.4 PL  1.7(1  ) 0.26
0.2
0
0.7 0.75 0.8 0.85 0.9 0.95
Relative Density
Potts Model Approximation Skorohod Model
120
2 (1  ) c

100
Bulk Modulus
80
3 d
60
40
20
0
2 (1  ) 2.23
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35

Porosity 3 1.12
Normalized Bulk Modulus (Potts) Normalized Bulk Modulus (Skorohod)
Normalized Bulk Modulus (approx)
E. Olevsky, V. Tikare, and T. Garino, Multi-scale modeling of sintering – A Review, J. Amer. Ceram. Soc., 89 (6),
1914-1922 (2006)
Multi-Scale Virtual Reality of Powder Processing
each element
initial state current state
at each time step

Boundary conditions
Sample problem solution: sintering with inclusion
SUMMARY

MODELING OF SPS
Overwhelming majority of publications on SPS describe

empiric trial-and-error attempts to consolidate various
powder material systems.
The conducted theoretical studies are mostly reduced
to the modeling of temperature and electric current
density distributions. In practically all of the
publications the role of electrical field is narrowed down
to the generation of Joule heat, which thereby reduces
the theoretical framework, required for the description
of shrinkage and grain growth, to the existing
constitutive models of powder consolidation.
Generic physically-based modeling concepts are
currently in strong demand to enable the understanding
and control of the thermal and “field effects” – a
distinguishing set of factors rendering different spark-
plasma vs. conventional hot pressing and sintering
results.
Comparative study of SPS – HP of hypereutectic Al-Si-Fe-X powder
Heating rate 20°C/min

100
FAST 450°C-80 MPa
95
Relative density (%) FAST 400°C-149 MPa
90 FAST 350°C- 229 MPa
HP 450°C-80 MPa
85 HP 400°C-275 MPa
HP 350°C -460 MPa
80
75
70
65
60
0 50 100 150 200 250 300 350 400 450
Temperature (°C)
Courtesy S. Kandukuri & L. Froyen

SPS: ENHANCEMENT OF MASS TRANSPORT
Thermal Effects in SPS Field Effects in SPS

 high heating rates  electromigration
 high local non- (diffusion enhancement)
uniformities of  electroplasticity
temperature distribution (electron wind,
(local melting and magnetic depinning of
sublimation) dislocations)
 macroscopic  dielectric breakdown of
temperature gradients oxide films at grain
 thermal diffusion boundaries
 thermal stresses  ponderomotive forces
 “pinch effect”
 surface plasmons
SPS: ENHANCEMENT OF MASS TRANSPORT
Thermal Effects in SPS Field Effects in SPS

 high heating rates  electromigration
 high local non- (diffusion enhancement)
uniformities of  electroplasticity
temperature distribution (electron wind,
(local melting and magnetic depinning of
sublimation) dislocations)
 macroscopic  dielectric breakdown of
temperature gradients oxide films at grain
 thermal diffusion boundaries
 thermal stresses  ponderomotive forces
 “pinch effect”
 surface plasmons
E. Olevsky and L. Froyen, Constitutive modeling of spark-plasma sintering of conductive
materials, Scripta Mater., 55, 1175-1178 (2006)
E. Olevsky, S. Kandukuri, and L. Froyen, Consolidation enhancement in spark-plasma sintering:
Impact of high heating rates, J. App. Phys., 102, 114913-114924 (2007)
E. Olevsky and L. Froyen, Influence of thermal diffusion on spark-plasma sintering, J. Amer.
Ceram. Soc., 92, S122-132 (2009)
Micromechanical Model
E. A. Olevsky, B. Kushnarev, A.
2 2
c a Maximenko, V. Tikare and M.
ra  rc 
p p
ap cp Braginsky, Modelling of
anisotropic sintering in crystalline
ceramics, Philosophical Magazine,
 x  b1x  y 2  b2 x  y  b3 x 85, (19), 2123-2146 (2005)
 y  b1 y  x2  b2 y  x  b3 y J ygb is the flux of matter in the direction of the

axis y caused by the grain boundary diffusion,
a
  c  cp  Dgb is the coefficient of the grain boundary
  dx   sin 2   
0
x x
c 
c diffusion,  gb is the grain boundary thickness,
k – Boltzman constant; T – absolute
 temperature.
 x (c )  ;
rc
 gb Dgb   x  J ygb (c) 
 x J gb
  y   gbx  
 x  0    y  0  0 2  a  ap  c  cp 
y
kT  
y
where  is the surface tension,  is the dihedral angle, a and c

are the grain semi-axes;  x - effective (far-field) external stress in
the x-direction (compressive x is negative). Parameter
c  cp c  cp  gb Dgb   3
 1 1  c  cp 

x  gbx      sin    x 
c
is a local stress on the grain boundary (
stress concentration factor).

c
is the
kT  a  a  c  c 
p p  c
  rc c 2 c2  

 3 1 1  3 
 2  3  1 1 3
x   2   sin   3
 x  c  c 
p  y    

sin     x c  cp 

 2c  c
r c 2  2c 
  2 c 2 2 rc  2c
Influence of High Heating Rates
 Experimentally, it has been shown in a number of investigations that
an increase in heating rate considerably increases the consolidation
rate of conductive and non-conductive powders during SPS.
 For example, it was shown for an alumina powder (Zhou et al.) that
the increase of heating rate from 50 to 300C/min with the same
maximum temperature and the corresponding six time decrease of
sintering time allowed obtaining the same final density. Physically,
this was attempted to be explained as a result of the existence of
additional defects in the material directly related to high heating rates
and short time of the process. They could be initial “biographic”
defects resulting from processes of powder synthesis (Ivensen or
defects in grain-boundaries between particles (Dabhade et al.).
 Gillia and Bouvard have conducted a series of fundamental
comparative experiments on sintering of WC-Co powder system with
different heating cycles. They employed cycles with the same average
heating rate but with various temperature histories (by employing
sequences of steady ramps and isothermal periods). Their results
indicate the dependence of the densification rate on the average
heating rate but no dependence on the temperature history.
E. Olevsky, S. Kandukuri, and L. Froyen, Consolidation
enhancement in spark-plasma sintering: Impact of high
heating rates, J. App. Phys. 102, 114913-114924 (2007)
 x   gbx   crx  f  ,  , G 
4
3 D    
  s s 4 2 1   2   1       1    
2
Du and Cocks 8kTG    

G is the porous material’s grain growth rate, G0fd
G 
3
G  G0fd  0   1.34
is the grain growth rate of the fully-dense material θ
G with the grain size G0 , G0 is the initial grain size of = e = εx
the porous (powder) material 1- θ
Beck et al.
G fd is the current grain size of the fully-dense  4  1 
3
235 K / s  G0  1.34
4
T 3.55101 6.67 10 
G  ln G0    , if T  533 K
G fd  G0fd t 6.6710 material; G0fd is the initial grain size of the fully-  K  G
dense material; t is time, s; and T is temperature, K  0, if T  533 K

For an aluminum alloy 
dT
= const is the heating rate, K/s
powder dt
0.35
200C/min
0.30 100C/min
50C/min
0.25
25C/min
Porosity
0.20 10C/min
0.15
0.10
0.05
0 1000 2000 3000
Time, s
For aluminum powder

150 250 350 450 550
-5.E-04
Shrinkage Rate, 1/s
-2.E-03
200C/min
-3.E-03 100C/min
50C/min
25C/min
10C/min
-4.E-03
150 250 350 450 550
Temperature, C
-1.E-03
Shrinkage Rate, 1/s

Model -3.E-03
200 C/min
100 C/min
Experiment -5.E-03
50 C/min
-7.E-03
For aluminum powder Temperature, C
Influence of Thermal Diffusion
 Q T 
*
J   D  Cv  Cv 
 kT T 
J is the vacancy flux, D is the coefficient of
diffusion, Cv is the vacancy concentration,
Cv is the vacancy concentration gradient,
Q* is the heat of vacancy transport, T is the
temperature gradient.
 Ludwig-Soret effect of thermal diffusion causes concentration gradients in
initially homogeneous two-component systems subjected to a temperature
gradient.
J. Chipman, The Soret effect, Journal of the American Chemical Society, 48, 2577-2589 (1926)
 For the case of atomic and vacancy diffusion in crystalline solids, this effect
was studied by a number of authors including it’s theoretical interpretation by
Shewmon and Schottky.
P. Shewmon, Thermal diffusion of vacancies in zinc, Journal of Chemical Physics, 29, (5), 1032-1036 (1958)
G. Schottky, A theory of thermal diffusion based on lattice dynamics of a linear chain, Physica Status Solidi, 8, (1),
357 (1965)
 For the electric-current assisted sintering, the effect of thermal diffusion was
analyzed by Kornyushin and co-workers. Later, for rapid densification, the role
of temperature gradients was studied by Searcy and by Young and McPherson.
Y. V. Kornyushin, Influence of external magnetic and electric-fields on sintering, structure and properties, Journal of
Materials Science, 15, (3), 799-801 (1980)
A. W. Searcy, Theory for sintering in temperature-gradients - role of long-range mass-transport, Journal of the
American Ceramic Society, 70, (3), C61-C62 (1987)
R. M. Young and R. McPherson, Temperature-gradient-driven diffusion in rapid-rate sintering, Journal of the
American Ceramic Society, 72, (6), 1080 (1989)
 Johnson argued against thermal diffusion significance in microwave sintering
D. L. Johnson, Microwave-heating of grain-boundaries in ceramics, Journal of the American Ceramic Society, 74, (4),
849-850 (1991)
 We demonstrate a possible significance of thermal diffusion for SPS
E. Olevsky and L. Froyen, Influence of thermal diffusion on spark-plasma sintering, J. Amer. Ceram. Soc. 92, S122-
132 (2009)
J is the vacancy flux, D is the coefficient of
 Q T  *
diffusion, Cv is the vacancy concentration,
Schottky: J   D  Cv  Cv  Cv is the vacancy concentration gradient,
 kT T  Q* is the heat of vacancy transport, T is the
temperature gradient.
Young & Cv H f
McPherson: C  2
T H m is the enthalpy of vacancy migration;
kT H f is the enthalpy of vacancy formation
T
J 
DCv
 H f  Q* 
kT T DCv T
Q*  H m  H f
J  Hm
Wirtz: kT T
Cv  H m  H f ; T  T is the thermal diffusion ratio ( T is

Kornyushin: T  J  D T
k T T the spatial average of temperature)
Heat transfer equation:
did not include the term Cv ! Otherwise: T T is the thermal conductivity; C is
T T  C q heat capacity; t is time; and q is the
dt heat production per unit volume of the
material and per unit time, which in the
case of SPS can be represented as
Cv H m
We re-define: T  q  e E 2 , where e is the specific
k T electric conductivity, and E is the
T
 T 2 electric field intensity
divJ   D C  
T T  t 
E
The driving force for  e

divJ   D T T
the vacancy migration: T
T
 T  T  T 
divJ   D C  e E 2  J tdgb  2  divJ  G  2 gb Dgb C  e E 2  G
T T  t  T T  t 
T is the thermal conductivity; C is
heat capacity; t is time; and q is the
heat production per unit volume of the
material and per unit time, which in the J tdgb   gb DgbT   T 2 G
 td
  C  
T T  t 
case of SPS can be represented as E
2  G  rp    G  rp 
gbx 2 e 2
q  e E 2 , where e is the specific
electric conductivity, and E is the
electric field intensity
 x   curvature driven   th _ diffusion driven   crx  f  , G 

gbx gbx
θ  is porosity; G is the average grain size

= e = εx
1- θ
3
G 
G  1.5 10 10
m / s   0   1.34
G
E. Olevsky and L. Froyen, Influence of thermal diffusion on spark-plasma sintering, J. Amer. Ceram. Soc. 92, S122-132 (2009)
Influence of Thermal Diffusion 1
  m
m 1
   xG   3  3  xG  
  2      
2
  
2
 2 
2
   1  
 9 gb Dgb     Gref 3  2   
  gbx      3      

 2 
 
1 4 kTG 4 1 9 1     
m 3
 2    A0 exp  Qcr  4
2
 G  
1  
2

    RT  
   
 
2
 gb Dgb Cv H m  T 2
3  2  
 C   E 
t  2 G 1   
e
T k T 
2
curvature-driven grain boundary diffusion thermal diffusion power-law creep

625 0.35 1300 0.45
0.40
0.30 1118
525 Temperature
Porosity - Model 0.35
Temperature 0.25 936 Porosity - Experiment
Temperature, C
Temperature, C
425 Porosity - Model 0.30
Porosity
Porosity
Porosity - Experiment 0.20 753 0.25
325
0.15 571 0.20
225 0.15
0.10 389
0.10
125
0.05 207
0.05
25 0.00 25 0.00
0 200 400 600 800 1000 0 70 141 211 281 352 422
Time, s Time, s
Porosity kinetics during SPS of aluminum Porosity kinetics during SPS of alumina powder.
powder. Comparison of the developed model Comparison of the developed model taking into
taking into account the impact of thermal account the impact of thermal diffusion with
diffusion with experimental data of Xie et al., experimental data of Shen et al., Spark plasma
Effect of interface behavior between particles on sintering of alumina, J. Amer. Ceram. Soc., 85, (8),
properties of pure al powder compacts by spark 1921 (2002)
plasma sintering, Materials Transactions, 42, (9),
1846-1849 (2001)
T
J  D T  The intensity of thermal diffusion increases for
T
higher pulse frequencies.
 The thermal diffusion promotes components’
(atoms and vacancies) separation. At early stages
of sintering, this should lead to the growth of
inter-particle necks, which corresponds to the
enhancement of sintering. At the final stages of
sintering, however, the pores may serve as
vacancy sinks under thermal diffusion
conditions, which impedes sintering.
 It is possible that the increased pulse frequencies
enhance sintering at the early stages of SPS and
hinder sintering at the late stages of SPS
process.
 In some experimental studies the pulse frequency
was found to have a limited impact on SPS
results - its contributions at early and late stages
of SPS could offset each other.
E. Olevsky and L. Froyen, Influence of thermal diffusion on spark-plasma sintering, J. Amer. Ceram. Soc. 92, S122-132 (2009)
Major Components of Densification-Contributing Mass
Transfer During SPS (model including electromigration):
grain-boundary diffusion power-law creep
driving sources
externally applied load

sintering stress electromigration
Nernst-Einstein equation
J  CE E  C 
Blech’s formula
 gb Dgb *  gb Dgb
CE  Z eq C 
kT kT
where  is the atomic volume, Z * is the valence of a migrating ion, and eq is
• M. Scherge, C.L. Bauer, and W.W. Mullins, the electron charge (the product Z *eq is called “the effective charge”).
Acta Met. Mater., 43 (9), 3525-3538 (1995):
electromigration stress of 23MPa along grain
 gb Dgb  1 U  x  J ygb (c) 
boundaries under an electric field of 500 V/m (in a 1- gb
  *  gbx 
y 
thick film) and up to GPa range stresses for grain J y Z eq 2  a  ap  c
structures with closed surface junctions kT  l
• M.R. Gungor and D. Maroudas, Int. J. Fracture,
109 (1), 47-68 (2001): electromigration stress of
U and l are the electric potential and the characteristic length along the
140MPa in a 1 -thick film under the field of about 425 electric field.
•
V/m
 gb Dgb  
 Z eq U 3  1
*
1  G  rp 

Q.F. Duan and Y.L. Shen, J. Appl. Phys. 87 (8),
 gbx         x 2 
G  r    l G  rp 2G 
4039-4041 (2000): electromigration stress of 2
450MPa along fast-diffusion length of 15 under 650
kT
p  G  
V/m
• Z. Suo, Q. Ma, and W.K. Meyer, MRS  is the surface tension,  x - effective (far-field) external stress in the x-
Symposium Proceedings, 6p. (2000): direction
electromigration stress in 0.5 -thick Al film under 300
V/m field should reach the level of 1.5GPa G  a  c is the grain size, rp  a p  c p is the pore radius.
Constitutive Model of Spark-Plasma Sintering
shrinkage due to grain-boundary diffusion

shrinkage due to dislocation creep
G  rp   3   3 
3
 Z *eq U 3  1
m
 gb Dgb 1 
5
  
  A 1   
2 2
 x   gbx   crx     x  
2
         1   
G  r    l G 2   2   2G 
2 x
kT G  rp 2G  
p 
G is the grain size; rp is the pore radius; A and m are power-law creep frequency
factor and power-law creep exponent, respectively; Dgb is the coefficient of the
grain boundary diffusion,  gb is the grain boundary thickness, k is the Boltzman’s
constant, T is the absolute temperature;  is the atomic volume, Z * is the
valence of a migrating ion, and eq is the electron charge (the product Z *eq is
called “the effective charge”); U and l are the electric potential and the
characteristic length along the electric field;  is the surface tension;  x -
effective (far-field) external stress in the x-direction;  is porosity.
E. Olevsky and L. Froyen, Constitutive modeling of spark-plasma sintering of conductive materials, Scripta Mater. 55, 1175-1178 (2006)
Contribution of different factors to shrinkage under SPS
0.35
Grain Size: 40

1
100nm 0.3
0.25
1.E+08
Porosity
0.2
1.E+05
external load
0.15
Shrinkage Rate, 1/s
1.E+02
0.1
1.E-01 surface tension
0.05
1.E-04 electromigration
0
1.E-07 1.E-08 1.E-07 1.E-06 1.E-05 1.E-04
Grain Size, m
1.E-10
0.00 0.10 0.20 0.30 0.40
0.40 0.50
0.50 0.60
0.60
Densification map for aluminum powder,
Porosity
T=673K, =28.3MPa
shrinkage rate due to electromigration
electromigration (electric
(electric current)
current)
shrinkage rate due to sintering stress
stress (surface
(surface tension)
tension)
shrinkage rate due to power-law creep
creep (punch
(punch load)
load) E. Olevsky and L. Froyen, Constitutive modeling of spark-
plasma sintering of conductive materials, Scripta
Mater. 55, 1175-1178 (2006)
Contribution of different factors to shrinkage rate of aluminum powder under SPS
U V
 417 , T=6730K,  x =28.3MPa
l m
Shrinkage kinetics during SPS of aluminum powder:
comparison with experiments
Pressure 10 MPa
Field 250 V/m
10 MPa
250 V/m
The average particle size is 55m. The applied field is accepted to be of

V
500 (Joule heat generation balance –based estimation), the pressure is
m
constant and equal to 23.5 MPa.
E. Olevsky and L. Froyen, Constitutive modeling of spark-plasma sintering of conductive materials, Scripta Mater. 55, 1175-1178 (2006)
SUMMARY

Coupled electro-thermo-mechanical FEM calculations
  ( el V )  0 Conductive DC
T 2
 Cp    (kT T)   el V
Heat Transfer
by Conduction
t
 (W )  .  1 . 
 ij  ij     e ij  PLij Stress-Strain
W   3   Analysis
.
 .
e Densification
1 
TEMPERATURE DISTRIBUTION DURING SPS
prismatic die
temperature temperature gradient

cylindrical die
temperature temperature gradient

SPS SCALABILITY (SIZE DEPENDENCE)
Alumina Disk-Shape Specimens (Same Aspect Ratio):
Size 1 Size 2 Size 3 Size 4

Height
Sample [mm] 4 8 12 16
Radius
[mm] 7.5 15 22.5 30
Height
Die [mm] 30 60 90 120
Radius
[mm] 15 30 45 60
Height
Punch [mm] 20 40 60 80
Height
Ram [mm] 40 80 120 160
Radius
[mm] 40 80 120 160
experimental verification
(size 2):
temperature evolution porosity evolution

Porosity Gradient
0.40
0.219
(Porosity (Center) – Porosity (Surface))/ Sample Radius
0.20
0.216
0.00
0.015 0.030 0.045 0.060
-0.20
0.195 0.140
-0.40
0.106
0.187
-0.60
0.175
-0.80
0.153
-1.00
Die Radius [m]
SPS SCALABILITY (SIZE DEPENDENCE): GRAIN GROWTH
3.5E-08
(Grain Size (Center)– Grain Size

(Surface))/ Sample Radius
Ram 3.0E-08
2.5E-08
2.0E-08
Die
1.5E-08
Punch
Plane used for 1.0E-08
displaying results
5.0E-09
0.0E+00
0.015 0.030 0.045 0.060
Ram Die Radius [m]
SPS Setup Geometry Grain Size Gradient
Grain Size Evolution at Sample Center Grain Size Evolution at Sample Surface
SUMMARY

Further prospects
 Development of on-line sintering damage

criteria
 Modeling of nano-powder sintering
 Modeling of sintering with phase
transformations or chemical reactions
 Modeling of field-assisted sintering
 Development of sintering optimization
approaches
 Multi-scale modeling of sintering

Sintering Theory: Brief Introduction BY Eugene A. Olevsky San Diego State University, California, Usa

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SINTERING THEORY

1. Science of Sintering: Fundamentals and

1. Science of Sintering: Fundamentals and

50 years to find out!

Surface tension phenomena

Surface tension phenomena

Frenkel approach (1945) Pines approach (1946)

1. Science of Sintering: Fundamentals and

From Swinkels and Ashby

auto transmission sprockets

metal fiber filter for

palate expander parts foldable paper hole punch

It was necessary to combine ideas of

The breakthrough happened in the end of 1980s

1. Science of Sintering: Fundamentals and

externally applied material resistance sintering

 ( w)  20 w Linear viscous (hot deformation of

 ( w)   y Plastic (cold pressing)

 ( w)  Awm Power-law creep (hot deformation of

0 Shear viscosity of the fully-dense material

(a)*2+(b) 20 [ (2 r   z )  3(  1  )e]  3 pl

1. Science of Sintering: Fundamentals and

Sintering theory was traditionally

Kuhn & Downey 2 2

grain growth pore migration vacancy annihilation

 E. Olevsky, V. Tikare, and T. Garino, Multi-scale

Time, t = 0 MCS t = 2,000 MCS t = 50,000 MCS

Meso-Scale FEM Vacancy anihilation

Macroscopic shape distortions

Two possible approaches:

sintering stress bulk and shear moduli grain growth kinetics

Potts Model Approximation Skorohod Model

at each time step

1. Science of Sintering: Fundamentals and

Overwhelming majority of publications on SPS describe

Heating rate 20°C/min

Courtesy S. Kandukuri & L. Froyen

Thermal Effects in SPS Field Effects in SPS

Thermal Effects in SPS Field Effects in SPS

 y  b1 y  x2  b2 y  x  b3 y J ygb is the flux of matter in the direction of the

where  is the surface tension,  is the dihedral angle, a and c

stress concentration factor).

Du and Cocks 8kTG    

For aluminum powder

Shrinkage Rate, 1/s

Cv  H m  H f ; T  T is the thermal diffusion ratio ( T is

 x   curvature driven   th _ diffusion driven   crx  f  , G 

θ  is porosity; G is the average grain size

curvature-driven grain boundary diffusion thermal diffusion power-law creep

externally applied load

shrinkage due to grain-boundary diffusion

Grain Size: 40

Field 250 V/m

The average particle size is 55m. The applied field is accepted to be of

1. Science of Sintering: Fundamentals and

temperature temperature gradient

temperature temperature gradient

Size 1 Size 2 Size 3 Size 4

temperature evolution porosity evolution

(Grain Size (Center)– Grain Size

SPS Setup Geometry Grain Size Gradient

1. Science of Sintering: Fundamentals and

 Development of on-line sintering damage