Professional Documents
Culture Documents
Sintering
Sintering
Sintering
SS / SV = - dASV / dASS
The sintering progress can be represented by plotting the total free surface area ASV, vs the total surface area
of the grain boundaries ASS. At the start of sintering, all surface area equals the free surface area, since no
grain boundaries exist yet, ASV = ASV0 and ASS = 0 . As sintering proceeds, ASV decreases and ASS
increases, in such a way that a monotonically decreasing curve is obtained with the slope - dASV / dASS . If, at
any point during sintering, the value of the slope reaches SS / SV , the sintering must stop due to the above
equilibrium condition. The principal objective of sintering is the elimination of porosity, i.e. a minimum ASV ,
possibly ASV =0 and ASS large, meaning little grain growth. It is thus desirable that the sintering stop condition
is reached when the slope dASV / dASS close to zero, i.e. SS << SV. Through this type of thermodynamic
considerations it is suggested that sintering can be encouraged through manipulation of the doping and/or the
environment, so the surface energy is maximised.
Note that the global decrease of system free energy is a necessary, but not sufficient, condition for sintering.
The sintering process will proceed only if driven by the local differences in chemical potential due to differences
in curvatures between the grain and the neck.
Classes (Categories) of Sintering
The majority of non-silicate ceramics are processed through high-temperature treatment and sintering of
powder compacts with little (<2 vol%) or no liquid phases. This is defined as Solid State Sintering, with
predominant mass transport (i.e. densification mechanism) through solid-state diffusion. However, most silicacontaining ceramics, including traditional porcelains as well as advanced silicon nitride, sinter in the presence
of viscous glass-type liquids, with predominant mass transport (i.e. densification mechanism) through viscous
flow. This is defined as Viscous Sintering. If the liquid component of the sintering system has low viscosity
(e.g. molten cobalt in the classical system of WC/Co) the process is defined as Liquid Sintering. In this system
the predominant densification mechanism is through rearrangement of the solid particles submerged in and
wetted by the low viscosity liquid, and through dissolution and re-precipitation of the solid.
Why Ceramics have to be Sintered?
Ceramic processing is based on the sintering of powder compacts rather than melting/solidification/cold working
(characteristic for metals), because:
as-solidified microstructures can not be modified through additional plastic deformation and recrystallisation
due to brittleness of ceramics.
low thermal conductivities of ceramics (<30-50 W/mK), in contrast to high thermal conductivity of metals (in
the range 50-300 W/mK) cause large temperature gradients, and thus thermal stress and shock in meltingsolidification of ceramics.
However, some ceramic refractories , such as Al 2O3, Al2O3/ZrO2, are manufactured through the melting /
casting / solidification process. If made properly, they are superior to the sintered versions, and the processing
costs of large, ~ 1 m tall blocks is lower.
Why do we need Sintering?
The principal goal of sintering is the reduction of compact porosity. Sometimes the initial spaces between
compacted grains of ceramics are called voids, to differentiate them from the isolated spaces = pores, which
occur in the final stages of sintering. The sintering process is usually accompanied by other changes within the
material, some desirable and some undesirable. The largest changes occur in:
- strength, elastic modulus
- hardness, fracture toughness
- electrical and thermal conductivity
- permeability to gases and liquids
- average grain number, size and shape
- distribution of grain size and shape
- average pore size and shape
- distribution of pore size and shape
- chemical composition and crystal structure
Sintering is a widely used but very complex phenomenon. The fundamental mechanisms of sintering are still a
matter of controversy. Experimental quantification of changes in pore fraction and geometry during sintering
can be attempted by several techniques, such as:
- dilatometry
- resilience
- gas absorption
- porosimetry
- indirect methods (e.g. hardness)
- quantitative microscopy
The description of the sintering process has been derived from model experiments (e.g. sintering of a few
spheres) and by observing powdered compact behaviour at elevated temperatures. The following phenomena
were observed and was modelling attempted:
- increase of interparticle contact area with time
- rounding-off of sharp angles and points of contact
- in most cases, the approach of particle centres and overall densification
- decrease in volume of interconnected pores
- continuing isolation of pores
- grain growth and decrease in volume of isolated pores
The development of microstructure and densification during sintering is a direct consequence of mass transport
through several possible paths (one of these paths is usually predominant at any given stage of sintering) :
- GAS phase (evaporation/condensation)
- LIQUID phase (solution/precipitation)
- SOLID phase (lattice diffusion)
- INTERFACES (surface diffusion, grain boundary diffusion)
- VISCOUS or PLASTIC FLOW, under capillary pressure (internal) or externally applied
pressure (pressure-sintering, hot-pressing, hot-isostatic-pressing)
Since certain mechanisms of mass transport can be dominant in some systems, two broad categories of
sintering are recognised:
1. Solid-state sintering, where all densification is achieved through changes in particle shape, without particle
rearrangement or the presence of liquid.
2. Liquid-phase sintering, where some liquid that is present at sintering temperatures aids compaction. Grain
rearrangement occurs in the initial stage followed by a solution-reprecipitation stage. Usually, the liquid amount
is not sufficient to fill the green-state porosity in normal liquid-assisted sintering of ceramics. In many
instances, supposedly Solid State Sintering proceeds in the presence of previously undetected (or transient)
small amounts of liquid (perhaps introduced as impurities during the powder preparation stage, such as silicates
in oxide ceramics Al2O3 , ZrO2).
Simple model experiments with spheres or rods illustrate sintering phenomena, classified into three stages of
sintering, as discussed below.
The very same driving force which propels sintering (i.e. elimination of excessive surface energy) also leads to
grain growth during sintering. In this process larger particles grow at the cost of smaller particles, according to
the general formula:
rn - r0n = k SV t
where: r = average particle size after time t , r0 = initial average particle size at t = 0 , SV = surface energy, k,n
= constants, n = 3 to 4 . The growth of large grains at the expense of small grains is defined as Ostwald
ripening, with the grain size t1/3.
3. Final stage of sintering, involving:
3A. Isolation of pores, i.e. relative density exceeding ~93%
3B. Elimination of porosity
3C. Grain growth
The final sintering stage begins at about 93-95% of theoretical density, when porosity is already isolated.
Ideally, at the end of this stage all porosity is eliminated. The complete elimination of porosity in the final stage
of sintering can only happen when all pores are connected to fast, short diffusion paths along grain boundaries
(or, equivalently, if the grain boundaries remain attached to the pores).
This favourable situation happens only if the pores follow the movement of the grain boundaries and are not
trapped within grains. This means that discontinuous grain growth (i.e. few grains growing at a very large rate
at the expense of all other grains, trapping porosity on its path) is suppressed through grain growth limiting
additives, such as secondary phase particles at grain boundaries, and/or appropriate time and temperature
control of the sintering process
In the final stage of sintering small pores attached to grain boundaries move quickly to collapse together and
thus reduce surface energy. Along with pores, grain boundary movement is accelerated, leading eventually to
discontinuous grain growth, when pores do not pin any more the grain boundaries. This leads to rapidly moving
grain boundaries that consume small grains.
Thus, some grains appear with many highly curved sides and therefore grain boundary motion further
accelerates, leaving behind closed porosity that is trapped within large grains. Closed porosity is difficult to
eliminate, because it involves relatively slow diffusion through lattice of the gas trapped in the pore. The critical
grain size rc at which discontinuous grain growth starts can be expressed as rc = rp/f , where rp and f are the
average pore radius and pore volume fraction respectively.
Pores trapped within large grains are much more difficult to eliminate in the final sintering stage, because
diffusion paths are long and slow, because lattice diffusion is the controlling step. Moreover, trapped gas resists
densification. The closed porosity at the final sintering stage allows external gas pressure to be applied
isostatically in order to accelerate the final densification. This approach is commercially known as Gas
Pressure Sintering (GPS)
The principal variables that control shrinkage at all stages of sintering are: temperature; time; particle size;
chemical composition of ceramic; and chemical composition and pressure of the gas phase
different sintering stages (neck formation, neck growth, rearrangement, grain growth with or without
shrinkage, closed porosity sintering) are controlled by different mechanisms which interact and overlap in a
complex way
5.1.2. Mechanisms of Mass Transport and Neck Growth in Solid State Sintering
A macroscopically measured quantity (for example by dilatometry) indicative of densification during sintering is
the compact shrinkage L/L. For the idealised model of a dense uniform arrangement of spherical particles of
radius r, the relative centres approach by h/r, which is equal to the overall shrinkage of the compact L / L. In
real systems, these quantities are generally not equal, because of particle shift and rearrangement, formation
and break-up of contacts, and interactions with porosity.
The mass transport from surfaces: evaporation-condensation
The mass transport can proceed through a gas phase, driven by a differential in vapour pressure. Evaporation
- condensation takes place because the vapour pressure p1 on a curved surface of radius r1 is different from
that on a flat surface (p0 , r0 = ) or any other surface at r2 . This is expressed by the Kelvin equation:
so
Accordingly, convex surfaces show overpressure (r1 > 0, p > 0), whereas concave surfaces show
underpressure (r1 < 0, p < 0). The pressure gradient results in faster evaporation from convex surfaces (i.e.
from grains, especially small grains), transport under the pressure gradient, and condensation within concave
surfaces (i.e. within necks). Quantitatively, the effect is not large. For example p/p0 = 1.02 for SiO 2 of r1 = 10-7
m (0.1 m) at 1700C.
The most important case of evaporation-condensation mass transport is from the surface of convex (spherical)
particles (r > 0) to the surface of concave necks (rn < 0) where |rn| << |r| at the contact region. No shrinkage
occurs in this process and y3 is a linear function of time:
For diffusion-controlled mechanisms, i and i are proportional to the diffusion coefficient D = D0exp(-H/RT),
where H is the activation energy for diffusion. For viscous flow sintering i and I are inversely proportional to
the viscosity coefficient , where = 0exp(Q/RT) and Q is the activation energy for viscous flow. NOTE, that
temperature has an exponential effect on the two above modes of sintering.
Conversely, for evaporation-condensation, is proportional to vapour pressure and therefore is linear with
temperature (pV=RT). It is therefore frequently found, that the detrimental evaporation-condensation
mechanisms are predominant at lower temperatures, whereas viscous flow and/or diffusional sintering take
over at higher temperatures. If it is desired to avoid substantial particles growth through evaporationcondensation before densification (i.e. in most cases of sintering), fast heating rate is recommended.
Sintering kinetics is accelerated for 1. fine grained materials; 2. elevated temperatures 3. high surface energy
The powder composition and sintering atmosphere intervene in the densification through modification of the
diffusion coefficient D. However, increasing the temperature far beyond T = 0.5Tm does not guarantee an
increased sintering rate and full densification. This is due to the coarsening of grains (as explained above,
through evaporation/condensation and surface diffusion) that can effectively stop densification (compaction
through volume diffusion and grain boundary diffusion).
chemical doping,
atmospheric control
Sintering of MgO
For example, MgO sintering proceeds through lattice diffusion. Diffusion of magnesium is faster than oxygen ,
DMg > DO. The sintering rate is increased if the diffusivity of oxygen is increased through the creation of
additional oxygen vacancies through doping with M 2O (for example Na2O).
Sintering of Al2O3
Another example of solid state sintering is the sintering of Al 2O3. Initially, it was observed, that small additives
of MgO (0.25 wt%) in Al 2O3 allow the achievement of fine-grained material at full density (which is the
ceramists dream). Additional microstructural observations revealed that MgO eliminates the discontinuous
grain growth of Al2O3 . It was found that grain boundaries do not break away from the pores, which prevents the
inclusion of pores trapped inside new large grains, with slow/long diffusion paths for densification. The
mechanism by which MgO slows down grain boundary movement in alumina could be as follows:
- The majority of MgO doped into Al 2O3 resides at the grain boundaries, because the dissolution of MgO
in Al2O3 is small, ~300 ppm. This is due to the relatively large difference in ionic radius: 0.72A for Mg 2+ and
0.53A for Al3+ .
- Any fast migration of the grain boundary would have to incorporate Mg 2+ ions into the Al 2O3 lattice,
with the resulting increase in internal energy, unless a NEW compound, spinel, forms.
In Al2O3, oxygen diffusion along grain boundaries is faster than diffusion of aluminium on the surface or within
the lattice. Therefore, the diffusion of aluminium, the slowest moving ion along the grain boundary, its fastest
diffusion path, is the limiting factor in the densification of Al 2O3. The solid solubility of MgO in Al 2O3, although
small (300-1400 ppm between 1600 and 1800C), creates interstitial Al i and thus increases the diffusivity of
aluminium, increasing rate of densification relative to the rate of grain growth. Arguments on the role of MgO in
Al2O3 sintering continue to the present time.
Note that other grain-growth inhibitors can be added to Al 2O3. For example, submicron ZrO 2 particles (10-20
vol%) residing at the triple points of grain boundaries of alumina effectively inhibit grain growth according to the
equation: r4 - r04 = a t, where: r = the average particle size after time t, r0 = the average initial particle size,
t=0, and a = constant.
Sintering of SiC
As an another example consider sintering of silicon carbide. Pressureless sintered SiC requires B and C as
additives, which affect the relative diffusion coefficients. Presence of silica impurities in SiC can enhance
evaporation - condensation mechanisms through a volatilisation reaction:
SiO2 (solid) + SiC (solid) SiO(gas) +CO (gas)
Carbon removes SiO 2 and Si from the surface of SiC according to the carbothermal reduction reaction:
SiO 2 + 3C SiC + 2CO ; C+Si SiC
Thus, fewer defects are present at the surface and diffusion along the surface decreases. This slows down the
coarsening mechanisms. Simultaneously, boron has been found to selectively segregate toward grain
boundary regions, where its role is unclear, i.e. it is suspected that:
- it lowers the grain boundary surface energy ss and thus increases the macroscopic driving force sv - ss
- it introduces additional defects (silicon vacancies) and enhances grain boundary diffusion
In general, the following characteristics determine sinterability of ceramic compacts:
Powder:
fine; equiaxed; non-aggregated; narrow size distribution powder compact
high green density; no gross defects
Powder compact:
high green density; no gross defects
Kinetics after compact formed and heated:
microstructure controlled by relative rates of coarsening and densification and by pore-grain boundary
interactions
Pores: size; size distribution; location relative to grain boundary
Second phases: size; size distribution; location relative to grain boundary
Dopants/impurities: in solution; in second phases
Non-stoichiometry
by ~ two orders of magnitude in hot isostatic pressing (HIP) at 200 - 300 MPa pressure
The pressure applied to the external surface of a green compact is transmitted to the components interior
through what is initially the much smaller effective surface of the contacting particles. The local contact
pressure, or "effective pressure", drives localised particle deformation by yield and creep, and causes
progressive densification. However, as densification proceeds, the contact area increases and the additional
driving force for densification rapidly decreases. This results in apparent "geometrical hardening" of the hotpressed powdered compacts.
Therefore, removal of the last few % of porosity in pressure assisted sintering is not much faster than in
pressureless sintering. Furthermore, non-densifying mechanisms such as surface diffusion or vapour transport
are NOT enhanced in pressure-sintering. The excess of driving force for sintering due to externally applied
pressure is frequently used to decrease the processing temperature (usually by 100 to 500C) rather than to
achieve rapid densification rates. Thus, fine-grained microstructures are obtained. Alternatively, materials
which are difficult to sinter, such as composites or covalent solids, can be densified by pressure assisted
techniques.
New sintering mechanisms are added to solid-state sintering when pressure is applied. These are :
- agglomerate fragmentation
- particle rearrangement
- plastic flow
- diffusional creep
The additional sinterability allows the compact to reach high density and to narrow the distribution of the
residual flaw size (porosity). This usually translates to less scatter in component strength and a higher Weibull
Modulus.
1. Hot Pressing
This is the older technology of the two. In essence, it consists of a heated uniaxial press. It involves simple
instrumentation AND poor shape capability. The pressure capability is limited by mould strength (20-40 MPa.
2. Hot Isostatic Pressing
Here, GAS is the pressing medium, with pressure capabilities ~ 200 to 300 MPa. The pressure can only be
transmitted to the interior of the component if the surface is SEALED using metal or glass cans, or predensification until closed (>92%TD) porosity is produced.
In HIP-ping driving force is the same as in hot pressing , however additional diffusivity is provided from
increase in stress at contact area. Sample must be jacketed , otherwise open pores will not be removed. The
jacket materials include metal can (Pt. Ni, Fe, Ti, W ) or glass , must be viscous and non-penetrating the
component.
By HIP-ping we can densify many hard to densify materials. Jacketless variant is possible, where must sinter
sample to the closed pore stage without pressure, and then apply pressure to fully densify the component.
Location of pores after sintering is important: pores inside grains will remain, whereas pores on grain
boundaries will be removed.
dD/dt = Ki fi(D)
Ki and f i (D) vary, depending on the particular densification mechanism "i". For example, for densification by
lattice diffusion at low densities (D<90%),
Ki = 5.6DvMP/(RTr2)
and
fi(D) = (D - D0)-1