RESEARCH SUMMARY _

Phase Diagrams in Liquid Phase

Sintering Treatments
__________ R.M. German
The fabrication of high performance
materials using liquid phase sintering
requires an understanding of the under-
lying equilibrium phase diagram. Al-
though sintering is not an equilibrium
process, it does represent an approach
to equilibrium; thus, phase diagrams
can aid in defining process variables.
The basic concepts are organized to in-
dicate the phase diagram features im-
portant to successful sintering in the
presence of a liquid phase. Example
phase diagrams are offered for liquid
metal infiltration of porous metal
compacts, persistent liquid phase
sintering, supersolidus sintering, tran-
sient liquid phase sintering, and reac-
tive sintering.
starting
condition
partially
infiltrated
fully
infiltrated
Figure 1. A sketch showing the sequence of
steps involved in liquid metal infiltration of a
porous solid.
Infiltration, liquid flow into solid
-low melting temperature for A
_no compounds
-low intersolubility
-liquid wets solid
Figure 2. Two example phase diagrams with
low intersolubilities that would be useful for
infiltration of a solid (porous) base using mol-
ten additive.
26
INTRODUCTION
The presence of a liquid during a sintering cycle can greatly enhance the
rate of sintering, leading to improved properties. As the focus in powder
processing shifts to higher performance applications, techniques such as
liquid phase sintering are of greater importance to materials engineers. In
this spirit, guides are needed to select alloys for high performance applica-
tions using the new processing techniques. There are recognized links
between binary phase diagrams and the processing behavior of many liq-
uid phase sintering systems. Obviously, the melting temperature guides
the selection of a sintering temperature. Additionally, binary phase dia-
grams give a visual representation of the underlying thermodynamic inter-
actions between components. This provides a useful predictive tool with
respect to some of the emerging processing techniques. This paper organ-
izes the information on phase diagram features and their use in predicting
the sintering behavior for various treatments involving a liquid phase.
Favorable attributes are indicated for hypothetical binary phase diagrams
to show their use in material and process definition.
For this presentation, the systems will be considered as binary
combinations. The major phase is termed the base and is designated as the
B component, while the minor phase is termed the additive and is designat-
ed as the A component. The overall alloy composition can represent a
pre alloyed powder or the ratio of components in mixed powders. The
sintering temperature and final composition are indicated by Tg and Xg,
respectively.
LIQUID METAL INFILTRATION
Infiltration is a two-step variant of liquid phase sintering in which a
molten metal is allowed to seep into a porous solid during sintering. It is
used to form several high density powder metallurgy systems, including
TiC-Ni, Mo-Ag, W-Cu, Co-Cu, WC-Cu, Fe-Cu and Fe-B. The elimination of
pores by infiltration improves properties such as strength, toughness, elec-
trical conductivity, wear resistance and corrosion resistance.
A presintered rigid compact formed by solid state sintering provides a
skeleton for capillary infiltration of a liquid metal such as shown in Figure
1.1,2 The pore filling relies on capillarity; thus, a liquid with the necessary
low surface energy will typically have a low melting temperature.
3
Also,
intermediate compounds are to be avoided since their formation during
infiltration would block the pores. Ideally, there should be little
intersolubility between the solid and liquid. On the one hand, if the
additive liquid is soluble in the solid base, then it will be transient and
inhibit infiltration because of diffusional solidification. Alternatively, if the
solid has a high solubility in the additive liquid, then the compact will
undergo erosion, slumping, and microstructural coarsening. Furthermore,
T - - - - - - - - - - - - - - - - - .
A B
a
T
rJ.
,
,
----- ----------- ----. ---
1
A
b
f3
B
JOURNAL OF METALS August 1986
to preserve rigidity during infiltration, the dihedral angle should be greater
than zero.
There are some problems with infiltration. Craters are often seen on
surfaces exposed to the infiltrating liquid. These craters are due to erosion
(the selective dissolution of solid to attain solubility equilibrium in the
liquid during ingress of the liquid). Swelling is common, with the magni-
tude depending on the solid skeleton porosity, grain size, and dihedral
angle. Swelling originates from grain separation due to a penetrating
liquid. Typically, the best mechanical properties are observed when the
volume of infiltrant is slightly less than the pore volume. Excessive quanti-
ties of liquid will cause slumping and separation of the solid skeleton.
Alternatively, insufficient liquid results in residual pores.
Consideration of these factors leads to the ideal phase diagram shown in
Figure 2a for an infiltration system. The base, B, is the solid skeleton
while the additive, A, is the liquid infiltrant. The additive melts at a lower
temperature than the base, indicating a lower surface energy for the liquid
phase, thereby aiding capillarity. The intersolubility of the two phases
should be low to avoid diffusional solidification and surface erosion.
However, some solubility of the base in the additive is helpful to wetting;
thus, a finite solubility is shown. Alternatively, Figure 2b shows a system
which would be suitable for additive infiltration of the base, if the liquid
additive wets the solid base. An unlikely candidate for liquid metal infiltra-
tion would be a system with a high additive melting temperature and a
high intersolubility. In this case, there would be difficulty in controlling
liquid formation, wetting and surface erosion. Likewise, the formation of
an intermediate compound would be unfavorable since it would block the
infiltratibn path. An isomorphous system would also be unacceptable for
infiltration since diffusional solidification could occur at the solid-liquid
interface, leading to surface erosion, pore blockage and incomplete
infiltration.
PERSISTENT LIQUID PHASE SINTERING
Liquid phase sintering techniques are an economical route to the forma-
tion of high performance materials. The technology is currently used in the
production of such items as radiation shields, electrical contacts, cemented
carbides, ferrous structural alloys and tool steels. The fundamental stages,
densification mechanisms, kinetic events and microstructures of liquid phase
sintered systems are understood.
1
,4,5 Typically, the liquid persists through-
out the high temperature portion of the sintering cycle giving rapid
densification and grain growth. Initial rapid densification can occur by
particle rearrangement due to the capillary force exerted by a wetting
liquid on the solid particles. The amount of densification attained by
rearrangement is dependent on the amount of liquid, particle size and the
solubility of the solid in the liquid. The elimination of porosity from the
compact increases the compact viscosity; thus, the densification rate
continuously decreases. As densification by rearrangement slows, solubility
and diffusivity effects become dominant, leading to the solution-
reprecipitation stage of liquid phase sintering. Ostwald ripening and shape
accommodation, both diffusion controlled processes, contribute to
densification and microstructural coarsening during this stage. Thus, solid
solubility in the liquid is a necessary criterion for these processes to occur.
Furthermore, melting point depression provides a good indicator of the
degree of sintering enhancement due to liquid formation.
6
The success of persistent liquid phase sintering depends on satisfying
several criteria. In the classic case, mixed powders are heated to a tempera-
ture where a liquid forms, although prealloyed powders can be heated to a
supersolidus temperature to attain rapid sintering. In successful systems,
the liquid wets the solid and also has solubility for the solid. Often, low
melting temperature additives do not prove satisfactory.7 Most successful
persistent liquid phase sintering systems exhibit eutectic behavior.
8
,9
Figure 3 shows two example phase diagrams for potential systems. Fig-
ure 3a corresponds to an isomorphous system which would be a candidate
for supersolidus sintering. The concept of supersolidus sintering is to heat
a prealloyed powder to a temperature between the liquidus and solidus
temperatures. The amount of liquid formed at the sintering temperature is
determined by the lever rule. Process control is aided by a wide separation
between the liquidus and solidus curves. As illustrated in Figure 4, liquid
formation occurs within each particle during heating. This results in parti-
cle fragmentation and gives a more homogeneous distribution of liquid
than is obtained from mixed powders. Densification occurs rapidly once the
liquid has formed and increases as the amount of liquid increases. A
sintering temperature that is too high results in compact slumping and
extensive microstructural coarsening.
JOURNAL OF METALS August 1986
s
Persistent liquid Phase Sintering
wetting liquid - high solubility for B
low melting temperature A
decreasing liquidus and solidus
wide liquidus - solidus separation
T - - - - - - - - - - - - - - - - - ,
L
A
B
a
Persistent liquid Phase Sintering
.Iow A solubility i'l B
high B solubility in liquid
.Iow eutectic temperature
decreasing I iquidus and solidus
Tr------------,
A
b
Figure 3. Phase diagrams with the features
found useful for persistent liquid phase
sintering of either (a) prealloyed powders or
(b) mixed elemental powders.
Supersolidus Sintering
Figure 4. A schematic diagram showing the
particle fragmentation and rearrangement
events associated with supersolidus sintering
of prealloyed powder.
27
Transient Liquid Phase Sintering
mixed powders
low melting temperature A
high B solubility in liquid
high solubility A in B
Tr------------,
L
A
B
a
Transient Liquid Phase Sintering
mixed powders
wetting liquid
high solubility of A in B
no intermediate compounds
depressed melting temperature
Tr------------,
b
Figure 5. Two binary phase diagrams with the
solubility and melting temperature features fa-
vorable to transient liquid phase sintering.
I I
Figure 6. An optical micrograph of a quenched
Fe-S% Ti sample undergoing transient liquid
phase sintering at 1330C, showing liquid
spreading into the iron and pore generation at
the prior titanium particle site.
Figure 7. A sketch of the events expected to
occur during reactive liquid phase
28
Figure 3b is a classic eutectic system, typical to WC-Co and W-Ni-Fe
type alloys. The low additive solubility in the base, high base solubility in
the additive and liquid, low eutectic temperature, and decreasing liquidus
and solidus curves are favorable attributes. In contrast, an unfavorable
attribute would be a high additive solubility in the base which would give
swelling during heating. Also, a low base solubility in the additive would
be unfavorable. A system where the liquid forms by a peritectic reaction
gives a decreasing base solubility in the additive when the liquid forms.
Although such a system should show reasonable liquid phase sintering
behavior, there would be a sensitivity to the heating rate and other
processing factors.
TRANSIENT LIQUID PHASE SINTERING
An interesting variant to traditional liquid phase sintering involves a
transient liquid which solidifies by diffusional homogenization during
sintering.
lO
,ll The benefits of transient liquid phase sintering are easy
compaction of elemental powders (as opposed to prealloyed powders) and
excellent sintering without the coarsening difficulties associated with a
persistent liquid. However, because the liquid content depends on several
processing parameters, transient liquid phase sintering is sensitive to
processing conditions. Several applications exist for transient liquid phase
sintering. These include dental amalgams based on silver and mercury,
porous bronze bearings, structural ferrous alloys, copper alloys, magnetic
materials and alumina-based ceramics.
The requirements for transient liquid phase sintering include mutual
intersolubility between the components with the final composition
within a single phase region. Two phase diagrams of systems which could
be processed by transient liquid phase sintering are shown in Figure 5. In
Figure 5a, a low melting temperature additive, A, is used to generate the
liquid, yet the overall composition is in the single phase solid region. The
sintering temperature is between the melting temperatures of the two
components. Alterna.tively, in Figure 5b, a eutectic reaction provides the
liquid from interdiffusion of the components during sintering. The sintering
temperature is greater than the eutectic temperature and the final composi-
tion is in the single phase field. For both cases, the liquid has a high
solubility in the solid and disappears with sintering time. This characteris-
tic may induce swelling during heating to the sintering temperature. Fig-
ure 6 shows pore generation during transient liquid phase sintering of
mixed iron and titanium powders. As the eutectic liquid penetrates the
grain boundaries of the surrounding iron, it generates a pore at the prior
titanium particle site. For applications such as porous bronze bearings this
is beneficial, while for structural materials the swelling and porosity are
detrimental. The liquid must wet the solid and give a high diffusion rate
for the solid. These criteria are satisfied by the decreasing melting temper-
ature with alloying and by the intersolubility of the components. Under
these conditions, rapid sintering is anticipated when the liquid forms. The
actual steps depend on the several process variables, including particle
sizes, amount of additive, heating rate and maximum temperature. The
densification associated with transient liquid phase sintering depends on
the amount of liquid formed and the time the liquid exists.
Problems can arise in transient liquid phase sintering if an intermediate
compound forms between the additive and base. A system with an interme-
diate compound would be expected to give swelling. A high melting tempera-
ture compound will inhibit interdiffusion and the formation of the eutectic
melt between the compound and the base. Consequently, use of pure A as
the additive is counterproductive in this case. Better transient liquid phase
sintering occurs from use of the intermediate compound as the starting
additive component.
reactive sintering A + B - AB _ increasing temperature--
initial state
mixed powder
solid-state
diffusional
reaction
solid -liquid
rapid react ion
final state
densified
compound
JOURNAL OF METALS August 1986
REACTIVE SINTERING
Reactive sintering is similar to transient liquid phase sintering. A sche-
matic diagram of the reactive sintering process is shown in Figure 7. The
mixed powders are heated to a temperature where a liquid forms by
interdiffusion; however, the liquid is transient and the final product is an
intermediate compound. Reactions between the constituent powders are
often characterized by a large heat liberation. Rapid sintering results from
the formation of a liquid (possibly due to reactive self-heating from an
exothermic reaction) between the mixed powders. Two phase diagrams
showing possible reactive sintering variants are given in Figure 8. The
initial compact is composed of mixed powders which diffusionally interact
during heating to form a compound. Swelling during heating is common,
especially if the diffusion rates are different or the enthalpy of compound
formation is large.
7
When a liquid forms in the compact, rapid compound
formation begins with liquid flow into the pores. The final product is
typically a single phase compound which may densify during the simultane-
ous sintering and reaction; however, pore generation is more typicaI.12,13 In
Figure 8a, the components are mixed and reacted to form the intermediate
compound. The reaction temperature must exceed the eutectic tempera-
tures to aid liquid spreading and the production of a homogeneous sintered
product. If the starting base is an off-stoichiometric compound, such as
shown in Figure 8b, then reactive sintering can be used to form the
stoichiometric compound using a transient supersolidus liquid phase.
Reactive sintering is still in the developmental stage although it has
been applied to forming intermetallics, ceramics and various compounds.
Studies to date have identified several processing sensitivities and problems.
Swelling due to the rapid reaction is a common problem. The exothermic
reaction must be controlled to maintain dimensions and avoid microstruc-
ture damage. Because of the limited knowledge on process control, reactive
sintering is being applied to forming compounds for subsequent
consolidation. However, the potential exists for direct consolidation of materi-
als by reactive sintering, especially when combined with an external
pressure. 14
MECHANICAL PROPERTIES
In several cases, the effect of specific phase diagram features has been
noted with respect to ease of sintering and potential problems with the
properties of the sintered product. Strengthening is possible from the
additive, in a traditional alloying sense as well as from improvements in
sintering. Other benefits include microstructure control, such as from a
smoother pore structure. However, additives can degrade sintered proper-
ties by initiating rapid grain growth, contributing to swelling, or embrittling
the material. Also, because of possible liquid reformation, high tempera-
ture use may be limited.
Besides these concerns, it is often found that intermediate compound
formation during sintering or during cooling results in degraded properties.
15
Intermediate compounds often nucleate at heterogeneous sites such as
grain boundaries or interphase boundaries. As a consequence, they contrib-
ute to reduced mechanical properties. For this reason, the most successful
phase diagrams found for the various liquid phase sintering treatments do
not have intermediate compounds.
References
1. R.M. German, Liquid Phase Sintering, (New York, NY: Plenum Press, 1985).
2. E.R. Lumpkins, "A Theoretical Review of the Copper Infiltration of PM Components," Powder Met.
Inter., 17 (1985), pp. 120-123.
3. P. Schwarzkopf, "The Mechanism of Infiltration," Symposium on Powder Metallurgy, Special Report
58, (London, UK: The Iron and Steel Institute, 1956), pp. 55-58.
4. F.V. Lenel, Powder Metallurgy Principles and Applications,(Princeton, NJ: Metal Powder Industries
Federation, 1980), pp. 285-307.
5. V.N. Eremenko, Y.V. Naidich and l.A. Lavrinenko, Liquid Phase Sintering, (New York, NY: Consult-
ants Bureau, 1970).
6. C.J. Li and R.M. German, "Enhanced Sintering of Tungsten-Phase Equilibria Effects on Properties,"
Inter. J. Powder Met. Powder Tech., 20 (1984), pp. 149-162.
7. A.P. Savitskii and L.S. Martsunova, "Effect of Solid-State Solubility on the Volume Change Experi-
enced by Aluminum During Liquid Phase Sintering," Soviet Powder Met. Metal Ceram., 16 (1977), pp.
333-337.
8. R.M. German and K.A. D'Angelo, "Enhanced Sintering Treatments for Ferrous Powders," Inter.
Metals Rev., 29 (1984), pp. 249-272.
9. W.J. Huppmann, "The Elementary Mechanisms of Liquid Phase Sintering II. Solution-Reprecipitation,"
Z. Metallkde., 70 (1979), pp. 792-797.
10. W.H. Baek and R.M. German, "Transient Liquid Phase Sintering of Iron-Titanium," Powder Met.
Inter., 17 (1985), pp. 273-279.
11. J. Puckert, W.A. Kaysser and G. Petzow, "Dimensional Changes During Transient Liquid Phase
Sintering of Fe-Ni," Inter. J. Powder Met. Powder Tech., 20 (1984), pp. 301-310.
12. S. Yangyun and R.J. Brook, "Preparation of Zirconia-Toughened Ceramics by Reaction Sintering,"
Sci. Sintering, 17 (1985), pp. 35-47.
13. A.P. Savitskii, "Some Characteristic Features of the Sintering of Binary Systems," Society Powder
Met. Metal Ceram., 19 (1980),pp. 488-493.
14. Y. Miyamoto, M. Koizumi and O. Yamada, "High Pressure Self Combustion Sintering for Ceramics,"
J. Amer. Ceramic Soc., 67 (1984), C224-C225.
15. R.M. German, "The Identification of Enhanced Sintering Systems Through Phase Diagrams,"
Modern Developments in Powder Metallurgy, Vol. 15, ed. E.N. Aqua and C.l. Whitman, (Princeton, NJ:
Metal Powder Industries Federation, 1985), pp. 253-273.
JOURNAL OF METALS August 1986
Reactive Sintering
- mixed A and B powders
- A + B - AB + heat
_ stable intermediate compound
- eutectic liquids
T
L
A
X:
inal B
a
Reactive Sintering
-mix off-stoichiometric powders
-AB
1
-
X
+ xB - AB
-broad and stable compound
-transient liquid phase
T
A
I
I
L
: AB
final
tart- - --- ---- - ----
b
Figure 8. Two eXl;lmples of reactive sintering
where either (a) elemental powders or (b) off-
stoichiometric powders are used to form an
intermediate compound.
ACKNOWLEDGEMENTS
This study was performed at Renssel-
aer Polytechnic Institute under the
sponsorship of the U.S. Department of
Energy.
ABOUT THE AUTHOR _____ _
R.M. German received his Ph.D. from the
University of California at Davis. He is
currently professor in the Materials Engineer-
ing Department at Rensselaer Polytechnic
Institute.
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