Review: liquid phase sintering
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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.
KeywordsContact Angle Dihedral Angle Discrete Element Method Grain Shape Liquid Phase Sinter
NC cos(φ/2), dimensionless
Solid–solid contact area, m2 (convenient units: μm2)
Solid concentration in the matrix, m3/m3 or dimensionless
Grain connectivity, dimensionless
Particle size, m (convenient units: μm)
First eigenvalue of diameter of curvature, m (convenient units: μm)
Second eigenvalue of diameter of curvature, m (convenient units: μm)
Temperature-dependent solid diffusivity in the liquid, m2/s
Cumulative grain size distribution, dimensionless [0,1]
Cumulative intercept size distribution, dimensionless [0,1]
Grain size, m (convenient units: μm)
Bigger grain size, m (convenient units: μm)
Smaller grain size, m (convenient units: μm)
Median grain size, m (convenient units: μm)
Mechanism dependent parameter for neck size ratio, mm/s (convenient units: μmm/s)
Mechanism dependent parameter for sintering shrinkage, mm/s2 (convenient units: μmm/s2)
Material constant in the densification rate calculation, m3/s (convenient units: μm3/s)
Material constant in the grain growth rate calculation, typical units m2/s (convenient units: μm2/s)
Material constant relating grain size to pinned microstructure, dimensionless
Intercept size, m (convenient units: μm)
Initial length, m (convenient units: mm)
Depth of liquid penetration, m (convenient units: μm)
Median intercept size, m (convenient units: μm)
Three-dimensional grain coordination number, dimensionless
Number of grains per unit line, 1/m (convenient units: 1/μm)
Number of solid–matrix intercepts per unit length of test line, 1/m (convenient units: 1/μm)
Number of solid–solid intercepts per unit length of test line, 1/m (convenient units: 1/μm)
Gas pressure in the pores, Pa
Probability of finding n contacts, dimensionless
Universal gas constant, 8.31 J/(mol K)
First eigenvalue of radius of curvature, m (convenient units: μm)
Second eigenvalue of radius of curvature, m (convenient units: μm)
Spreading parameter, J/m2
The solubility of liquid forming additive in the base, m3/m3 or kg/m3
The solubility of solid in the additive, m3/m3 or kg/m3
Solubility ratio, dimensionless
Solid–matrix surface area per grain, m2 (convenient units: μm2)
Solid–solid surface area per grain, m2 (convenient units: μm2)
Volume fraction of liquid, dimensionless
Volume fraction of solid, dimensionless
Neck diameter or diameter of the contact, m (convenient units: μm)
Scale parameter related to the median grain size, m (convenient units: μm)
Diameter of capillary tube, m (convenient units: μm)
Pore size, m (convenient units: μm)
Geometric constant, near 192, dimensionless
Geometric constant, near 16, dimensionless
Geometric constant, near 160, dimensionless
Mechanism dependent exponent or shape parameter, dimensionless
Mechanism dependent exponent, dimensionless
Radius of curvature, m (convenient units: μm)
Liquid meniscus radius at the pore-liquid-grain contact, m (convenient units: μm)
Change in a dimension from the size L0, m (convenient units: mm)
Pressure difference across a curved liquid surface, Pa
Ratio of densification rates, dimensionless
Atomic volume, m3/mol
Angle from the grain center to the solid–liquid–vapor contact point, rad (convenient units: degree)
Pore density factor, dimensionless
Distance between contacting grain centers, m (convenient units: μm)
Liquid layer thickness between the grains, m (convenient units: μm)
Dihedral angle, rad (convenient units: degree)
Liquid–vapor surface energy, J/m2
Solid–liquid surface energy, J/m2
Solid–solid grain boundary energy, J/m2
Solid–vapor surface energy, J/m2
Liquid or solid–liquid melt viscosity, Pa s
Reaction rate constant, 1/s
Mean grain separation, m (convenient units: μm)
Contact angle, rad (convenient units: degree)
Instantaneous density, kg/m3 (convenient units: g/cm3)
Green density, kg/m3 (convenient units: g/cm3)
Sintered density, kg/m3 (convenient units: g/cm3)
Angle in capillary bonding, rad (convenient units: degree)
Packed particles heated near their melting temperature bond together by sintering. As diffusion accelerates at higher temperatures, sintering is manifested by bonding between contacting particles. Sintering occurs over a range of temperatures, but is accelerated as the particles approach their melting range. It takes place faster as the particle size decreases, since diffusion distances are shorter and curvature stresses are larger. For solid-state sintering, it is appropriate to think of sintering with respect to the melting temperature. Snow sinters to form ice at temperatures near −15 °C, while alumina requires temperatures in excess of 1000 °C.
A widely applied variant relies on forming a liquid during the sintering cycle. Liquid phase sintering (LPS) is applied to alloys and composites that melt over a range of temperatures. In the typical situation, the solid grains are soluble in the liquid. This solubility causes the liquid to wet the solid, providing a capillary force that pulls the grains together. At the same time, the high temperature softens the solid, further assisting densification. High-diffusion rates are associated with liquids, giving fast sintering or lower sintering temperatures. Since the final product is a composite with customized properties, LPS is the dominant commercial sintering process.
Early uses of LPS involved firing ceramics with a glass bond. At high temperatures, the glass turns into a viscous liquid; early porcelain was a widely valued example. In some ceramic compositions, the liquid phase is a viscous glass, but for this treatment we refer to it as a liquid.
Important technical advances in LPS came in the 1930s with the development of several materials; cemented carbides (WC–Co), porous bronze (Cu–Sn), tungsten heavy alloys (W–Ni–Cu), copper steels (Fe–Cu–C), and cermets (TiC-Fe). Over the next 70 years, LPS processing spread to a diverse range of applications—oil well drilling tips, porcelain jacketed dental crowns, automotive valve seats, wire drawing dies, high-temperature bearings, electrical contacts, electronic capacitors, radiation shields, diesel engine turbochargers, electronic insulator substrates, golf clubs balance weights, ultrasonic transducers, electronic solders, and grinding abrasives, as examples.
The LPS mechanistic conceptualization started with the work of Price et al. . Qualitative models emerged over the next 20 years based on observations from a variety of systems [2, 3, 4, 5, 6, 7]. Cannon and Lenel  provided a qualitative conceptualization, while Kingery [9, 10] provided a quantitative treatment. A decade later Eremenko et al.  published a brief book on the subject and a more detailed treatment followed in 1985 . The publication rate accelerated as applications emerged, and today articles on LPS and liquid phase sintered products exceed 100,000 contributions.
The LPS events are ideal for densifying hard materials that cannot be fabricated using other manufacturing approaches. The WC–Co system is a prime example, where the eutectic at 1310 °C enables the bonding of micrometer size WC grains into a dense component, such as a drill or cutting insert.
Besides mixed powders, LPS is possible using alloy powders that partially melt to form a semisolid structure. This approach is used to sinter tool steels. In another variant, a transient liquid forms and dissolves into the solid over time. This is how mixed copper and tin powders are used to fabricate porous bronze bearings. Finally, there are systems where the solid and liquid are insoluble, such as W–Cu, so solid-skeleton sintering determines the densification rate. However, the common form of LPS is persistent LPS, where at the sintering temperature the solid is soluble in the liquid. On cooling, the liquid solidifies to produce a composite microstructure with tailored properties.
Microstructures and microstructure development
The study of LPS focuses on linking composition, processing, and properties, with recent attention to improved dimensional precision. The glue between these factors is in the microstructure. A homogeneous green structure greatly improves the LPS response . The amount and placement of the liquid phase have significant impact on the sintering trajectory. Most effective is placement of the liquid phase on the interface between the solid grains [19, 20, 21]. As a consequence, coated powders are an ideal starting point . Further, the identification of additives that improve wetting, accelerate diffusion, or harden the composition are linked to interfacial energy and phase relations [23, 24, 25]. Beyond additives, research also considers processing factors such as particle size, green density, heating rate, peak temperature, hold duration, and cooling rate. During heating, the mixed particle compositions interact due to diffusion driven by the chemical composition gradients between the powders. Although there is much pre-liquid densification, still rapid densification occurs when the liquid forms. If there is no solubility between the liquid and solid, then densification occurs at the rate associated with sintering the solid skeleton and the liquid is simply a pore filling agent [26, 27]. Accordingly, understanding and controlling the microstructure evolution is of great practical importance.
Contact angle and dihedral angle
The contact angle is altered by factors that change solubility or surface chemistry. For example, the addition of Mo to the TiC–Ni system decreases the contact angle from 30° to 0° . Also, surface chemistry depends on the processing atmosphere, but often this is not intentionally controlled .
Rearrangement gives the dihedral angle as a function of the ratio of the liquid interfacial energies. If the ratio of the solid–solid to solid–liquid surface energy is relatively high (>1.8), then the dihedral angle approaches 0° and liquid separates contacting grains. There is no dihedral angle if the solid is amorphous.
In some situations, the solid–solid contacts form low energy grain boundaries, resulting in large dihedral angles. These grain contacts rotate to give grain growth by coalescence. More typically, the grain boundary energy varies with crystallographic misorientation and chemical segregation. Although the dihedral angle tends to be reported as a single value, it is not single valued. Further, because of the distribution in contact situations, disagreement exists as to the presence of liquid on the grain boundaries after sintering. What is observed in transmission electron microscopy depends on several factors, such as impurities, grain misorientation, and cooling rate after sintering—factors often not properly controlled.
Low dihedral angles and contact angles promote densification in LPS. Accordingly, solid solubility in the liquid is critical to LPS. In a wetting situation, a high-liquid content ensures rapid densification. However, if there is too much liquid, then distortion occurs. Densification is also influenced by the scale of the microstructure (measured by the grain size) and the relative quantity of liquid phase.
In persistent LPS, the solid and liquid contents converge to constant values while the pores are annihilated, giving densification, but this is not always the case. In some LPS systems, the sintered density peaks and then decreases as evaporation or reaction occurs . A key indication of an unstable situation is a progressive mass loss. On the other hand, time-dependent volume fraction changes occur in reactive systems; often these prove difficult to control.
In LPS systems characterized by multiple solid phases, the grains often exhibit core-rim gradients . This is because the two solids have differing solubility–temperature relations that result in preferential dissolution of one solid during heating. Subsequent solvation of the second solid at a higher temperature reduces the solubility of the first solid in the liquid. Accordingly, the stepwise solvation and precipitation events influence grain growth and densification. As a consequence, grain growth inhibitors exhibit temperature ranges where they are most effective . From a practical standpoint, control of these events allows manipulation of the sintered microstructure for property optimization [55, 56, 57].
Porosity, pore size, and pore location
Pores are initially present as interparticle voids, but might also arise from inhomogeneous particle packing (for example large liquid forming particles in a matrix of small solid particles), or volatile phases (such as polymers) in the green body. In sintered bronze bearings, the creation of pores for oil storage is achieved by intentional selection of the tin and copper particles sizes.
Pores larger than the grain size prove difficult to eliminate. Compact swelling due to pore formation at prior particle sites is observed if the liquid forming particles have substantial solubility in the solid during heating [63, 64]. Swelling is reduced by use of small melt-forming particles, sized to be similar to the interparticle voids. Coated powders work best since they avoid pore formation [21, 22, 65, 66, 67]. Unfortunately, pore coarsening works against densification, especially in cases where a gas exists in the pores [68, 69, 70], since the pores will coarsen and enlarge.
In some cases, the collapse of gas-filled pores requires an external pressure, such as by hot isostatic pressing . Pore growth occurs in LPS, in part due to annihilation of the smaller pores, but also due to vapor production during sintering. In the extreme, enormous pores or blisters form as the gas accumulates inside the component to form a single large pore.
At high-solid contents, the grains take on a shape that helps eliminate pores . For isotropic solid–liquid surface energy and liquid contents over about 30 vol.%, the grains are spherical except for the contact faces. At lower liquid contents, the grains are prismatic and the liquid conforms to the spaces between the grains. With lower liquid levels, there is insufficient liquid to fill all pores, so densification requires the grains to undergo shape accommodation. Because of coarsening, the particle shape prior to LPS has no significant effect on the sintered grain shape.
Grain size distribution
Comparison of model assumptions and actual LPS microstructures for grain size distribution
Reality in LPS
Rounded or prismatic
Grain separation, population, and surface area
Thus, when measured versus sintering time, the grain separation scales with the grain size. Usually, grain size increases with the cube-root of sintering time, so the grain separation increases with the cube-root of LPS time.
Similarly, the number of grains decreases over time. The number density of grains (grains per unit volume) times the grain volume gives the solid content per unit volume. If the solid volume remains constant, then as the grain size increases the number density of grains must decrease. For most LPS materials, the grain size increases with the cube-root of time, so the number of grains per unit volume declines with inverse time . The solid–liquid interface area per unit volume is inversely proportion to the grain size. Grain coarsening causes the grain-liquid interface area to decrease with the inverse cube-root of time.
Neck size and shape
Since the terminal neck size depends on the grain size, X/G remains constant. Thus, late-stage LPS exhibits neck growth proportional to grain growth. Typically the mean grain size increase with the cube-root of time, so the neck size shows a similar dependence (X ~ t1/3), which is the same as seen for early stage neck growth .
Grain coordination, contiguity, and connectivity
The subscript SS denotes the solid–solid intercepts and SL denotes the solid–matrix (solidified liquid) intercepts. The factor 2 is necessary since the solid–solid grain boundaries are only counted once by this technique, but are shared by two grains.
For example, a typical 3D grain coordination number is 6 for a solid content near 60 vol.% with a dihedral angle of 60°, giving two contacts per grain in 2D, in agreement with experiment.
The formation of solid–solid necks leads to generation of a rigid solid skeleton. At a low solid fraction, grain settling induces contacts, but Brownian motion also induces contacts [85, 95]. Percolation refers to the formation of a continuous chain of solid–solid bonds in the microstructure. At the percolation limit, the grain connectivity is 1.5, while sufficient rigidity to resist distortion during LPS occurs near three contacts per grain .
Microstructure studies describe the amount of each phase, its distribution, and its composition. This requires descriptors of size (grain size, pore size, surface area, and grain separation), shape (grain shape, pore shape, and liquid shape), and relations between the phases (contiguity, coordination number, and grain orientation). In turn, microstructure governs properties.
Example mean microstructure parameters measured after LPS
1480 °C, 2 h
1400 °C, 1 h
1200 °C, 1 h
1540 °C, 1 h
1400 °C, 1 h
Grain size (μm)
Dihedral angle (°)
Interfacial energies control much of the microstructure evolution during LPS. The interfacial energies change when the first liquid forms and are sensitive to segregation and temperature. Further, interfacial energies change due to reactions, diffusion, or solvation. Anisotropic surface energies change with minor chemical changes . Thus, LPS microstructure parameters are distributed, time-dependent, temperature-dependent, impurity-dependent, and even change with location in the sintered body, facts that are often forgotten. Although initial microstructure transients have been emphasized here, cooling also changes the microstructure. Care is needed to properly freeze the microstructure from the sintering temperature since temperature-dependent solubility changes alter the microstructure during slow cooling. For this reason, reports on the LPS microstructure are only valid with respect to the “sintered” condition and are not relevant to the conditions existing during “sintering.” This is seen in disagreements on the grain boundary condition, such as for WC–Co . Slow cooling induces segregation and precipitation, so experiments can be constructed to show either grain boundaries free of Co or grain boundaries with a Co segregated layer.
The evolution of the LPS microstructure takes place in several steps, starting from the consolidated powders and finishing with the cooling cycle. Here we take up the key steps associated with heating to the sintering temperature, initial liquid formation, and then the progressive coarsening and densification stages.
Microstructure evolution prior to liquid formation is equivalent to solid-state sintering of mixed powders. Factors favorable for densification in heating prior to liquid formation are also favorable for densification during LPS. Despite the prevalence of practical systems based on mixed powder sintering, only a few quantitative models predict densification and microstructure changes [104, 105, 106]. The parameters that influence densification include particle size and green density as found in solid-state sintering. However, added complications include temperature-dependent diffusivity and solubility characteristics, as well as concentration and spatial distribution effects associated with the powders. Savitskii  points out the important chemical gradients associated with mixed powders to show how they can dominate early sintering.
Microstructure evolution during heating is often ignored in LPS, since only a few applications exist for systems sintered to the pre-liquid state. None-the-less, this stage is important in understanding subsequent densification.
Systems such as W–Cu with low mutual solubility (typically <10−3 at.%) are termed noninteracting. In such systems, particle size is a dominant factor with respect to densification. Chemical gradients play an important role in systems where the solubility exceeds about 0.1 at.%. On the other hand, systems with high solubility (>5 at.%) of solid in the additive phase, but little reverse solubility, are ideal for LPS. This is the most common situation, since substantial densification occurs, often prior to liquid formation, such as in the WC–Co system. On the other hand, a high solubility of the liquid forming additive in the solid leads to swelling during heating, and without LPS the resulting product is friable, as is the case for Cu–Sn.
Often small particles prove difficult to handle in automated compaction equipment, so it is common to agglomerate the particles into clusters prior to compaction. However, if there is a bimodal pore size after compaction (small pores in the agglomerates and large pores between the agglomerates), then these treatments work against sintering densification. Depending on the packing characteristics, differential shrinkage between the agglomerates and inside the agglomerates leads to defects . Once the liquid forms, LPS tends to homogenize the microstructure, eventually removing the inhomogeneities.
Incipient liquid formation
Densification by grain rearrangement depends on the liquid content and the particle characteristics. More liquid means less grain shape accommodation is required to reach full density. Usually about 30 vol.% liquid is sufficient to give complete densification by rearrangement. Otherwise, grain shape accommodation and solid-state sintering are required for complete densification.
Nonspherical particles provide an additional inducement to rearrangement, since a wetting liquid generates a rearrangement torque to bring flat surface into contact . This torque increases with the relative liquid content, resulting in more rearrangement as the particle shape departs from spherical. Note spherical and irregular particles have different sensitivities to the liquid quantity; irregular particles undergo less rearrangement at low liquid contents .
After liquid formation, a cascade of rearrangement and solution-reprecipitation events densify the compact. Rearrangement forces the solid grains pack to a higher coordination. Continued densification comes from solution-reprecipitation and solid skeleton sintering that work to eliminate residual pores while the solid grains change size and shape.
solid dissolution into the liquid, preferentially from higher energy regions, including asperities, convex points in the microstructure, areas under compression, and small grains,
diffusion of the dissolved solid in the liquid, and
precipitation of the dissolved solid onto concave regions or larger grains in areas not under compression.
In most cases, the controlling solution-reprecipitation step is diffusion through the liquid, although interfacial reaction control is observed in some systems. Rounded grains are characteristic of diffusion control. A curved surface has a high density of atomic scale surface ledges that provide surface dissolution and precipitation sites. Flat-faced, prismatic grains indicate reaction control. The low population of defects on planar crystallographic faces slows the solution-reprecipitation rate. Most LPS microstructures evidence rounded grains, indicative of densification by diffusion-controlled solution-reprecipitation.
Grain shape accommodation
For an isotropic surface energy, the excess energy associated with a nonspherical grain shape is termed the sphering force . At full density, a low liquid content causes more grain shape accommodation, giving a larger sphering force. A dense compact with shape accommodation is not at the lowest energy condition. This is demonstrated by immersing a full density compact with grain shape accommodation into a liquid reservoir. Additional liquid wicks into the compact, allowing the solid–liquid interface to relax toward a lower energy spherical grain shape.
Usually pores remain in the compact after rearrangement, especially since the typical liquid content is below the 30 vol.% needed to fill all voids on liquid formation. Solution-reprecipitation is the most important means to reach full density during LPS. Three mechanisms are envisioned as means to densify the structure.
The second densification mechanism involves dissolution of small grains with reprecipitation on large grains. Small grains disappear while large grains grow and undergo shape accommodation. Diffusion in the liquid is the controlling transport mechanism, as sketched in Fig. 39b. This mechanism does not involve shrinkage, so it is not an explanation for densification, except that grain shape accommodation enables better packing of the solid.
The third mechanism involves growth of the intergrain contact by diffusion along the liquid wetted grain boundary, as indicated in Fig. 39c [127, 128]. The contact zone enlarges to change the grain shape with simultaneous shrinkage of the grains. This does not involve grain coarsening, but it does require a cooperative redistribution process of the mass deposited where the grain boundary intersects the liquid .
These three mechanisms differ in the source of the solid and in the detailed transport path, but together they explain grain shape accommodation, grain growth, and densification. Grain growth occurs with densification. Indeed, grain size and density tend to follow a common trajectory for most LPS systems, showing more rapid grain growth as pores are eliminated. Although neck growth is initially active, it is not sufficient to explain all microstructure changes. On the other hand, contact flattening and small grain dissolution couple to fully explain the microstructure and density progression typical to LPS.
If transport is controlled by interfacial events, then it is reaction controlled. Reaction control is observed in mixed phase systems, such as complex cemented carbides from WC, VC, TiC, or TaC with a cobalt-based liquid [130, 131, 132]. Grain growth inhibitors slow interfacial reaction events. The most effective inhibitors reduce the number of reaction sites, leading to the emergence of flat-faced grains or core-rim grains, where the chemistry changes from the outside to the inside [133, 134, 135, 136]. In diffusion-controlled growth, the grains remain rounded with an abundance of atomic steps, so there is no limitation from the population of interfacial sites available for dissolution or precipitation [9, 131, 137].
Solid-state diffusion by grain boundary diffusion in the grain contact is another densification mechanism. The predicted neck growth rate is the same as given by solid-state grain boundary diffusion models. Since solid-state diffusivities are low when compared to liquid diffusivities, solid-state sintering is only significant in those cases where there is no solid solubility in the liquid; for example, systems used in electrical contacts and electronic heat sinks (Mo-Ag, Mo-Cu, W–Cu, SiC-Al, and WC-Ag).
green density determines the initial number of neighboring grains for bonding,
temperature controls solubility, wetting, and diffusivity,
particle and grain size control the curvature, surface area, and diffusion distance, and
time determines the cumulative changes.
Eventually, the neck size reaches a stable size dictated by the dihedral angle. For grains of size G with a bond of size X, the equilibrium neck size depends on the dihedral angle φ as given in Eq. 16. Once formed, the distributions in grain sizes, contact misorientation angles, and surface energy give a distribution to the neck sizes.
In a LPS material with a dihedral angle of 60° the neck size ratio grows to a limiting value of X/G = 0.5, corresponding to a peak shrinkage of 6.25%. But at a dihedral angle of 23°, the corresponding shrinkage is just 1%. After the stable neck size ratio is formed, as dictated by the dihedral angle, X/G remains constant and further neck growth depends on grain growth. Since the number of necks per grain remains fairly constant, there is a decrease in the number of necks per unit volume as grains grow.
Large–small grain combinations naturally favor coalescence. Also, chemical gradients, where the solid grains have differing compositions, accelerate boundary motion and coalescence .
The grain growth rate constant is sensitive to temperature, since solubility, diffusivity, surface energy, solid–liquid ratio, and other parameters change with temperature. These changes are lumped into a single Arrhenius temperature dependence leading to an apparent activation energy. Various efforts have added the solid volume fraction to the rate constant. Ardell  added a diffusion geometry assumption that predicted a broad grain size distribution, but showed a greater sensitivity to volume fraction than seen experimentally. Davies et al.  included coalescence events, resulting in a broad grain size distribution. Other treatments have assumed separated spheres and ignored coalescence, leading to an abundance of models not relevant to LPS. However, DeHoff  developed a model that included interactions between neighboring grains while Takajo et al.  assumed all coarsening was by coalescence, resulting in a broad grain size distribution. German and Olevsky [91, 166] showed how contiguity alters the relative solid-state and liquid-phase contributions to coarsening and their model was later extended to include pores in LPS .
The atmosphere or vacuum level used during LPS provides an opportunity to alter the material chemistry and sintering. Usually, oxide-based ceramics are sintered in air, nitride-based ceramics in nitrogen, and carbide-based ceramics, cemented carbides and tool steels in a carbon-controlled atmosphere. Highly reactive metals are sintered in vacuum. Ferrous systems are sintered in hydrogen or hydrogen–nitrogen atmospheres. In several cases, small changes in the atmosphere composition, such as partial pressure of oxygen or water, produce a measurable change in sintered properties. A completely inert atmosphere, such as argon, inhibits full densification since the trapped argon stabilizes closed pores.
The initial atmosphere tasks are to provide heat transfer and sweep away polymer decomposition products from binders and lubricants. Differential thermal analysis, thermogravimetric analysis, differential scanning calorimetry, and in-line mass spectroscopy help identify the atmosphere reactions. For example, these tools are used to identify polymers that do not burnout properly and become sources of residual carbon.
Delayed reactions between impurities and the sintering atmosphere are problems in LPS. During solution-reprecipitation, solid is dissolved into the liquid with the release of dissolved impurities. Effectively each grain undergoes zone refining. Reactions between the impurities and sintering atmosphere might generate insoluble reaction products, leading to stable pores. Examples are the reaction of carbon and oxygen to form CO or CO2 in alumina  or the reaction of hydrogen and oxygen to form water vapor in tungsten heavy alloys , cemented carbides , and alloy steels . The internal pressure in the pore increases with temperature, leading to compact swelling. Additives are known that can inhibit some of these reactions ; for example, strong oxide formers such as aluminum are effective in copper alloys.
Heating and cooling rates
Chemical reactions, diffusional homogenization, and solid-state sintering occur during the heating cycle. Slow heating is more costly, but leads to more impurity removal, but a coarser microstructure. In transient LPS there is a strong sensitivity to heating rates [181, 182]. Slow heating favors pore formation for reactive and transient liquid systems. In other forms of LPS, there is little importance to the heating rate since most densification and microstructure development occur after liquid phase formation.
Densification is not sensitive to cooling rate. However, the liquid contracts on cooling in the same manner as castings contract; thus, shrinkage pores form in the liquid with rapid cooling. Also, solid precipitates out of solution during cooling. The precipitate size is sensitive to the cooling rate, so properties are sensitive to cooling rate. Impurity segregation occurs during cooling and this can be detrimental to properties. Optimized cooling rates offer a possibility of controlling the extent of hardening while suppressing impurity segregation [183, 184].
Solid phase sintering
The final stage of LPS corresponds to a microstructure of connected solid grains with liquid occupying the space between the grains. This system is rigid. Grain growth continues while the solid skeleton sinters to full density, or to where gas trapped in the pores halts densification. For low-solubility systems, such as W–Cu, densification is paced by the solid phase sintering rate, while for systems with solid solubility in the liquid the solution-reprecipitation events control final densification.
For most of its history, LPS science has been empirically based, due both to the emphasis on applications and the relative complexity of the field. Further, the large variety of materials processed by LPS requires broad generalizations. However, now it is possible to predict the properties of liquid phase sintered components in silico. This has been facilitated by the astounding growth of computing power in conjunction with refinements to the simulation algorithms. Computer simulations critically test our understanding of the complexity associated with LPS, and in doing so provide new insights. We can now anticipate the point where computer simulations will guide future practice and the discovery of new LPS materials.
As a manufacturing process, LPS bridges between topics from solid-state physics, chemistry, solid mechanics, rheology, and engineering. Many of the LPS computer simulations borrow knowledge from these fields, as well as metal forming and polymer processing. This section is organized around the simulation length scale, ranging from simulations at the grain scale up to the component scale.
Matsubara and Brook [185, 186, 187, 188] simulated microstructure developments with multiple mechanisms of mass transfer in a MC simulation of sintering densification and grain growth for micrometer-sized grains. The MC simulations were performed using an array of 2D triangular lattices to handle the multiple phase systems.
Ryoo et al.  used a pseudo-MC simulation based on atomic adsorption and coalescence to model the process of triangular prism formation and abnormal grain growth of WC-25Co during LPS.
Liu et al. [190, 191, 192] used the MC method based on a 3D multiple grain arrangement model to simulate the 3D coordination number, contiguity, and grain growth in the LPS of W–Ni–Fe alloys. Liu  used the same MC method to simulate the effect of the wetting angle on a dihedral angle distribution and on the degree of the grain boundary penetration by the liquid phase during LPS.
- Aldazabal et al.  and Luque et al.  used MC methods to simulate precipitation during LPS. The introduction of appropriate phase diagrams and diffusion algorithms are essential to the final results since the diffusion rate has a large influence on the final microstructures. The main variables are the concentration of solute in the matrix, the diffusion of this solute, and interfacial energy. The algorithm works on microstructures discretized using homogeneous cubic elements called voxels. The microstructure scale was refined to show thin layers of matrix between solid grains. Figure 55 shows the simulation results of a microstructure evolution during isothermal LPS .
Potts Monte-Carlo method
Tikare et al. [198, 199] modified the PMC model for solution-reprecipitation by allowing neighboring sites to exchange places by the classical Metropolis algorithm for isotropic grain growth by Ostwald ripening during LPS. The representation of the two phases, solid grains in a liquid matrix, was achieved by populating the lattice with a two-component, canonical ensemble.
Zhang et al.  used a modified PMC computer simulation for grain growth during intermediate and final stages of LPS as applied to grain growth of a BaTiO3-based ceramic. The presence of a liquid phase blocked grain boundary motion and restricted grain growth, a factor that seems at odds with practice.
Itahara et al.  developed a PMC model on a 2D triangular lattice to design grain-oriented microstructures of ceramics processed by plate-like templated anisotropic grain growth for functional materials due to anisotropy in interfacial energies during LPS.
- Lee et al.  used the MC route with a three-dimensional Pott model with voxel element reflecting LPS in a system. They allowed full solid wetting to investigate the coarsening kinetics and microstructures and to obtain the properties of solid grains, including the volume of critical nuclei and the distribution of grain sizes as a function of time, as shown in Fig. 56.
The PMC method does not rely on explicit input of thermodynamic and kinetic characteristics. The powder is represented on a square or triangular lattice as an agglomerate of grains with different interface energies, and statistical sampling is performed to find configurations of increasingly lower energy. Methods have been developed for treating sintering mechanism and grain growth during LPS. The limitation of this method is in deciding on the range and relative size of the interface energies. This may be overcome by using a multiscale modeling approach.
Discrete element method
Wonisch et al.  used DEM to investigate anisotropic grain arrangement and show how this leads to an isotropic strain rate in macroscale during the LPS process.
Finite difference method
Fan et al.  developed the ‘‘grid-tracking’’ numerical technique based the FDM with an explicit two-step of predictor–corrector to simulate liquid phase migration (LPM) due to an interfacial-energy-driven flow during the LPS of functionally graded WC–Co.
Finite element method
McHugh and Riedel [217, 218] used FEM to simulate the LPS of tungsten carbide and silicon nitride materials. The focus was on shape distortions based on grain rearrangement, contact flattening by the solution-precipitation, grain coarsening, and bulk viscosity. They developed density dependent functions to enable the predictions, but several approximations were required to implement the approach.
Ganesan et al.  used FEM for an assumed viscous flow of a semisolid LPS structure driven by curvature and gravity. They relied on Stokes equations with consideration of solid volume fraction to estimate the effective viscosity of the solid–liquid mixture. From this, they simulated component distortion during LPS for tungsten alloys in microgravity and ground-based sintering conditions.
Olevsky et al.  also used FEM with a continuum theory of sintering to predict shape distortion caused by gravity in LPS of a W–Ni–Fe powder system.
Kraft  used an optimization algorithm for compaction and LPS to predict and minimize the distortion as a result of inhomogeneous density distributions in the green body.
Binet et al.  used the a fluid flow model to simulate transient distortion under gravity as calculated under changes in surface tension, density, and viscosity for LPS of W–Ni–Fe.
Maximenko et al.  used FEM to predict liquid flow with coupled deformation of the refractory skeleton during LPS of cemented carbides.
Blaine et al.  used FEM to predict distortion with experimentally determined constitutive parameters for LPS of a stainless steel doped with boron.
Villanueva et al.  used the parallel adaptive FEM of Cahn–Hilliard/Navier–Stokes system to numerically investigate wetting phenomena in capillary-driven flow during LPS. The model captured qualitatively the important phenomenon in LPS, such as wetting and microstructure behavior, including deformation, coalescence, pore migration, and pore elimination.
FEM proves most useful. The approach relies on a database of measured material properties for input. Simulation of the final component size and shape, properties, and defects are fast using personal computer resources. The reduction of the time and cost needed to obtain material properties to feed the FEM simulations is an area of current research, since experimental testing for each system is quite expensive. The hope is that such synthesis of material properties might be possible based on material informatics using existing databases or new techniques such as data mining and computer thinking algorithms.
Boundary element method
Voorhees et al.  used the 2D BEM for intergrain diffusional interactions to adjust interfacial concentrations during simulation of the morphology evolution of grains during diffusion-controlled Ostwald coarsening.
Multiscale modeling is now applied to solid-state sintering. The extension to LPS is still pending. Two cases have been reported; one goes from DEM for mesoscale to macroscale continuum mechanics  and the other goes from MC simulation for microscale to FEM for macroscale . Successful development of these methods will undoubtedly require large research investments. However, much benefit might be possible if more efficient processes can be developed, with better optimization and time reduction routines applicable to LPS.
Liquid phase sintering emerged from an empirical origin that started in the 1930s. Since the 1950s, there has been progress in the quantitative treatment of LPS to the point of effective computer simulations that predict microstructure, component size, and component shape. The scientific principles have advanced to include many processing factors and provide a platform for the identification of new systems.
There is much about LPS that is in need of research attention. From an industrial view, the most pressing needs relate to dimensional control. Because of tight industrial tolerances, many LPS materials are machined or ground after sintering. These post-sintering dimensional adjustments are costly. How can LPS be used to give the final size and shape? What factors, beside green density gradients, contribute to distortion during LPS? How might nonuniform sintering shrinkage be minimized? Can changes in the starting microstructure (for example, via particle size, mixing technology, or compaction conditions) be used to minimize distortion? Efforts focused on these areas show LPS systems often distort shortly after the liquid forms and continue to distort with a viscous flow or creep behavior. Is it possible to separate densification events from distortion to improve sintered tolerances? Possibly there are gains from idealized cycles, such as by slow heating.
Modeling efforts in LPS have included most of the key concepts. The initial chemical gradients associated with coated or mixed powder are important to the initial sintering trajectory, as is the green body density homogeneity. Recent efforts have made good progress using integral work concepts to explain LPS densification, distortion, and coarsening [139, 224, 230]. Next will be integration of these ideas to include particle size and solubility effects so the models can be generated with minimum experimentation. In turn, constitutive equations derived from simple relations will enable accurate computer simulations of the size, shape, density, microstructure, properties, and performance.
The authors are most thankful to Wei Li for his great care in reviewing the manuscript.
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