Liquid phase sintering (LPS) is a process for forming high performance, multiple-phase components from powders. It involves sintering under conditions where solid grains coexist with a wetting liquid. Many variants of LPS are applied to a wide range of engineering materials. Example applications for this technology are found in automobile engine connecting rods and high-speed metal cutting inserts. Scientific advances in understanding LPS began in the 1950s. The resulting quantitative process models are now embedded in computer simulations to enable predictions of the sintered component dimensions, microstructure, and properties. However, there are remaining areas in need of research attention. This LPS review, based on over 2,500 publications, outlines what happens when mixed powders are heated to the LPS temperature, with a focus on the densification and microstructure evolution events.

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Review: liquid phase sintering

Cemented carbides are, from a technical point of view, one of the most successful composite materials. The physical and chemical aspects of the components (transition-metal carbides and iron-group metals) and of their interaction in hardmetals are reviewed with emphasis on the materials science point of view focusing on those compositions which have gained technical interest. Crystal structures and phase relationships are discussed in detail. The interaction of components (wetting, residual stresses) and some microstructural aspects (size, contiguity, and shape) are treated also. These fundamentals are the basis of understanding the production processes and the properties of cemented carbides.

Physical and chemical nature of cemented carbides

If the grains dispersed in a liquid matrix are spherical, their surface atomic structure is expected to be rough (diffuse), and their coarsening has been observed to be controlled by diffusion in the matrix. They do not, furthermore, undergo abnormal growth. On the other hand, in some compound material systems, the grains in liquid matrices are faceted and often show abnormal coarsening behavior. Their faceted surface planes are expected to be singular (atomically flat) and therefore grow by a defect-assisted process and two-dimensional (2-D) nucleation. Contrary to the usual coarsening the-ories, their growth velocity is not linearly dependent on the driving force arising from the grain size difference. If the growth of the faceted grains occurs by 2-D nucleation, the rate is expected to increase abruptly at a critical supersaturation, as has been observed in crystal growth in melts and solutions. It is proposed that this growth mechanism leads to the abnormal grain coarsening. The 2-D nucleation theory predicts that there is a threshold initial grain size for the abnormal grain growth (AGG), and the propensity for AGG will increase with the heat-treatment temperature. The AGG behavior will also vary with the defects in the grains. These predictions are qualitatively confirmed in the sintered WC-Co alloy prepared from fine (0.85-Μm) and coarse (5.48-Μm) WC powders and their mixtures. The observed dependence of the AGG behavior on the sintering temperature and the milling of the WC powder is also qualitatively consistent with the predicted behavior.

Abnormal growth of faceted (WC) grains in a (Co) liquid matrix

Sintering occurs when packed particles are heated to a temperature where there is sufficient atomic motion to grow bonds between the particles The conditions that induce sintering depend on the material, its melting temperature, particle size, and a host of processing variables It is common for sintering to produce a dimensional change, typically shrinkage, where the powder compact densifies, leading to significant strengthening Microstructure coarsening is inherent to sintering, most evident as grain growth, but it is common for pore growth to occur as density increases During coarsening, the grain structure converges to a self-similar character seen in both the grain shape distribution and grain size distribution Coarsening behavior during sintering conforms to classic grain growth kinetics, modified to reflect the evolving microstructure These modifications involve the grain boundary coverage due to pores, liquid films, or second phases and the altered grain boundary mobility due to these phases

Coarsening in Sintering: Grain Shape Distribution, Grain Size Distribution, and Grain Growth Kinetics in Solid-Pore Systems

The pursuit of a comprehensive theory for the origin and evolution of granitoids is hindered by our incomplete understanding of the nature of the source and the mechanisms by which the magma is segregated and transported. This paper is a collection of three largely independent and necessarily incomplete perspectives on these outstanding issues. Lower to mid-crustal regions, which contain the principal source material for granitoid magmas, are highly heterogeneous. Consideration of available transfer mechanisms suggests that (1) this heteroge­ neity survives all foreseeable lower crustal processes; (2) closure is on very different scales for different chemical systems (e.g. Pb, Nd, Sr and 0 isotopes); in almost all cases, however, closure scale is much smaller than the scale of magma extraction zones for plutons; and (3) pluton-wide homogenisation of magmas by diffusion is precluded by low diffusivities in felsic melts. Thus, granitoid magmas begin life as aggregates of small, isolated chemical domains; homogenisation occurs only through (and on the scale of) effective stirring by convection. Because of variability in local conditions as well as in bulk composition, crustal regions undergoing anatexis must be patchworks with variable melt fractions and melt compositions. The way in which magma is extracted from and coalesces with this patchwork exerts a critical influence on the nature of granitoid magmas. Decoupling and unusual coupling of compositional parameters and isotopic heterogeneity within plutons are to be expected in crust-derived granitoids and do not require contamination. Granites image their sources, but these sources <),re ill-defined and do not correspond to simple, easily-recognised materials. Extent and patterns of heterogeneity remaining in crystallised plutons may be effective indicators of the ascent process. The efforts of materials scientists in characterising the nature and evolution of solid-phase interconnectivity in partially-molten materials may offer some insights into crustal magmatic processes. In particular, the rheological properties of partially-molten crustal rocks are probably strongly affected by the contiguity of the solid grains in the system (i.e. the fraction of their surface area that is shared with other grains). Theory and experimental data for simple alloy systems reveal that contiguity depends principally upon melt fraction and upon the characteristic wetting angle ( 8) of the system. Measured B's in granitoids ( ~50° on average) imply contiguities as high as ~0·2 for melt fractions of 0·5 or greater. This value in turn suggests that, at least under static conditions, a continuous skeleton of solid grains is maintained to quite high degrees of melting in the crust. Consequently, regions consisting of 50% or more of melt can, in principle, maintain not only high yield strength, but also high viscosity (provided the strain rate is sufficiently low to avoid disrupting contiguity). Despite the fact that on some time scale the continuous solid skeleton of a partially-molten region resists deformation, it is itself subject to textural evolution that could lead to the upward migration of melt. Occasional detachment of grains from the skeleton and subsequent "microsettling" within the partially-molten column may lead eventually to compaction of the solid (without plastic deformation) and net upward displacement of melt. Proposed granite transport mechanisms are discussed, although several are viewed as having historical interest only. In the absence of tectonic transport, diapirism appears to be the most compelling of these processes. However, considerable diversity exists in the literature regarding a pivotal requirement for this mechanisrv. Structural studies have tended to conclude that the granite diapir must be highly crystallised in order to ascend, whereas results of physical modelling yield contradictory results. For ascent to occur in these models, the magmas must be sufficiently fluid to allow convective circulation. Indeed, heat loss associated with diapirism is so efficient as to be a significant restriction on overall ascent. The resolution of these contrasting views appears to be that they reflect different phases of the ascent/emplacement continuum. Understanding the emplacement history of a southeastern Australian pluton allows assessment, via the diapir model, of the flow properties of the rock within the deformation aureole. Results suggest rock viscosities about an order of magnitude lower than those predicted by laboratory experiments, perhaps reflecting difficulties in reproducing natural conditions in the laboratory.

Perspectives on the source, segregation and transport of granitoid magmas

Measurements have been made of the contiguity, the dihedral angle, and the continuity of the carbide phase in alloys of a number of transition-metal carbides with cobalt, which were prepared by liquid-phase sintering. During sintering, the carbide contiguity in a given alloy develops towards an equilibrium value, which is directly related to the dihedral angle between carbide grains and therefore to the relative values of the interfacial energy and the contiguous boundary energy. A direct relationship between the contiguity and the angle of contact of the liquid on the carbide, however, does not exist. The contiguity at the start of sintering depends to some extent on the history of the specimen before liquid-phase sintering and in most cases is higher than the equilibrium value. Observations were made which indicate that the carbide grains in the majority of cemented carbides exist as a continuous skeleton. Arguments are presented to show that neither the presence of such a skeleton nor the prese...

R. Warren

Papers

Microstructural development during the liquid-phase sintering of cemented carbides