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Sintering of Advanced Materials
Автор: Elsevier Science
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Sintering is a method for manufacturing components from ceramic or metal powders by heating the powder until the particles adhere to form the component required. The resulting products are characterised by an enhanced density and strength, and are used in a wide range of industries. Sintering of advanced materials: fundamentals and processes reviews important developments in this technology and its applications
Part one discusses the fundamentals of sintering with chapters on topics such as the thermodynamics of sintering, kinetics and mechanisms of densification, the kinetics of microstructural change and liquid phase sintering. Part two reviews advanced sintering processes including atmospheric sintering, vacuum sintering, microwave sintering, field/current assisted sintering and photonic sintering. Finally, Part three covers sintering of aluminium, titanium and their alloys, refractory metals, ultrahard materials, thin films, ultrafine and nanosized particles for advanced materials.
With its distinguished editor and international team of contributors, Sintering of advanced materials: fundamentals and processes reviews the latest advances in sintering and is a standard reference for researchers and engineers involved in the processing of ceramics, powder metallurgy, net-shape manufacturing and those using advanced materials in such sectors as electronics, automotive and aerospace engineering. Explores the thermodynamics of sintering including sinter bonding and densification Chapters review a variety of sintering methods including atmosphere, vacuum, liquid phase and microwave sintering Discusses sintering of a variety of materials featuring refractory metals, super hard materials and functionally graded materials
Part one discusses the fundamentals of sintering with chapters on topics such as the thermodynamics of sintering, kinetics and mechanisms of densification, the kinetics of microstructural change and liquid phase sintering. Part two reviews advanced sintering processes including atmospheric sintering, vacuum sintering, microwave sintering, field/current assisted sintering and photonic sintering. Finally, Part three covers sintering of aluminium, titanium and their alloys, refractory metals, ultrahard materials, thin films, ultrafine and nanosized particles for advanced materials.
With its distinguished editor and international team of contributors, Sintering of advanced materials: fundamentals and processes reviews the latest advances in sintering and is a standard reference for researchers and engineers involved in the processing of ceramics, powder metallurgy, net-shape manufacturing and those using advanced materials in such sectors as electronics, automotive and aerospace engineering. Explores the thermodynamics of sintering including sinter bonding and densification Chapters review a variety of sintering methods including atmosphere, vacuum, liquid phase and microwave sintering Discusses sintering of a variety of materials featuring refractory metals, super hard materials and functionally graded materials
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Sintering of Advanced Materials
Автор: Elsevier Science
Описание
Sintering is a method for manufacturing components from ceramic or metal powders by heating the powder until the particles adhere to form the component required. The resulting products are characterised by an enhanced density and strength, and are used in a wide range of industries. Sintering of advanced materials: fundamentals and processes reviews important developments in this technology and its applications
Part one discusses the fundamentals of sintering with chapters on topics such as the thermodynamics of sintering, kinetics and mechanisms of densification, the kinetics of microstructural change and liquid phase sintering. Part two reviews advanced sintering processes including atmospheric sintering, vacuum sintering, microwave sintering, field/current assisted sintering and photonic sintering. Finally, Part three covers sintering of aluminium, titanium and their alloys, refractory metals, ultrahard materials, thin films, ultrafine and nanosized particles for advanced materials.
With its distinguished editor and international team of contributors, Sintering of advanced materials: fundamentals and processes reviews the latest advances in sintering and is a standard reference for researchers and engineers involved in the processing of ceramics, powder metallurgy, net-shape manufacturing and those using advanced materials in such sectors as electronics, automotive and aerospace engineering. Explores the thermodynamics of sintering including sinter bonding and densification Chapters review a variety of sintering methods including atmosphere, vacuum, liquid phase and microwave sintering Discusses sintering of a variety of materials featuring refractory metals, super hard materials and functionally graded materials
Part one discusses the fundamentals of sintering with chapters on topics such as the thermodynamics of sintering, kinetics and mechanisms of densification, the kinetics of microstructural change and liquid phase sintering. Part two reviews advanced sintering processes including atmospheric sintering, vacuum sintering, microwave sintering, field/current assisted sintering and photonic sintering. Finally, Part three covers sintering of aluminium, titanium and their alloys, refractory metals, ultrahard materials, thin films, ultrafine and nanosized particles for advanced materials.
With its distinguished editor and international team of contributors, Sintering of advanced materials: fundamentals and processes reviews the latest advances in sintering and is a standard reference for researchers and engineers involved in the processing of ceramics, powder metallurgy, net-shape manufacturing and those using advanced materials in such sectors as electronics, automotive and aerospace engineering. Explores the thermodynamics of sintering including sinter bonding and densification Chapters review a variety of sintering methods including atmosphere, vacuum, liquid phase and microwave sintering Discusses sintering of a variety of materials featuring refractory metals, super hard materials and functionally graded materials
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Sintering of Advanced Materials
USA
Introduction
Z. Zak Fang, University of Utah
One of the first things we do when teaching sintering is to define what sintering is. Is it a process technology, a subfield of science, or a class of materials? The short answer is of course that it is primarily one category of manufacturing processes. However, those of us who study sintering will argue that the fundamentals of sintering involve all aspects of modern natural sciences, including physics, chemistry, mechanics, physical chemistry, surface science, thermodynamics, kinetics, and diffusion. On the one hand, sintering is a craft (called firing) that has been practiced since ancient civilizations for several thousand years in the form of pottery, bricks, and art. On the other hand, ever-increasing demands for near-perfect quality and high performance of modern sintered technical products place the competitive edges of a sintering practitioner squarely on his or her level of understanding of the science of sintering. Therefore, borrowing an expression from the book by Prof. Robert Cahn of Cambridge - The Coming of Materials Science - sintering is a 'craft turned into science'.
This book was initiated by Woodhead Publishing based on their marketing research that indicated needs for a book on recent advances in sintering. We were aware that there were already several excellent monographs on sintering available in libraries around the world, including most notably books by Professors R. German, M. Rahaman, and S.J. Kang. Therefore, the challenge is how a new book can serve the needs of readers by adding value to the existing books. We reckon that the unique characteristic of sintering is that it is at an 'intersection' of many sub-disciplines of materials science and engineering; hence it involves a large variety of vastly different techniques and a large family of completely different materials. It is usually difficult to find both fundamental science and sufficient specific technological information in one volume. The objective of the book was thus conceived and laid out to provide readers, in one book, not only with technical guides on advanced sintering technologies but also with the scientific fundamentals that form the common ground of all sintering techniques.
The contents are divided into three parts: fundamentals, advanced processes, and advanced materials. The fundamentals include thermodynamics, kinetics, master sintering curve theory, microstructure evolution, liquid-phase sintering theory, and modeling-simulation of sintering. The selections of topics for advanced processes and materials are more difficult. It is obvious that we cannot include all the materials that are produced in industry by sintering or all the processes that are designed to sinter metals or ceramic powders. The emphasis was thus put on relatively new and advanced processes and materials. For instance, microwave sintering and spark plasmas sintering are examples of new processes that have become popular in the past two decades. The sintering of thin films and ultra-hard materials are examples of materials that have seldom been covered in any detail in the past.
Regrettably, but inevitably, there are important processes and materials omitted from this book. For example, a large number of pressure-assisted sintering processes, including hot pressing and hot isostatic pressing (HIP), are widely practiced in industry today, but are not included. The sintering of cermet, including cemented tungsten carbide, which is perhaps the largest single family of sintered materials, is also not included. Fortunately, there are recent monographs on both topics (Hot Consolidation by A. Bose and Cemented Tungsten Carbide by G. Upadhyaya), to which readers are referred.
Finally, I wish to thank all contributors to this book for their support and hard work. The essence of this book by design, I hope, is that the unique expertise of individual contributors in individual topics makes each chapter shine in its own right. I also thank the editorial staff at Woodhead Publishing (Mr Rob Sitton, Ms Lucy Cornwell, and Ms Nell Holden) whose professionalism, kind patience and persistence made this book possible.
1
Thermodynamics of sintering
R.M. German, San Diego State University, USA
Abstract:
Particles bond together when heated by a sintering process that is a combination of several atomic level events that include diffusion, creep, viscous flow, plastic flow and evaporation. Significant strengthening occurs in powder compacts due to sintering. Sintering consumes surface energy to build bonds between those particles. Small particles have more surface energy and sinter faster than large particles. Since atomic motion increases with temperature, sintering is accelerated by high temperatures. The thermodynamic driving force for sintering then is found in the surface area, interfacial energies and curvature gradients in the particle system. Actual atomic motion is by several transport mechanisms with concomitant microstructure changes.
Key words
surface energy
surface area
diffusion
creep
viscous flow
plastic flow
particle size
interfacial energy
dihedral angle
contact angle
wetting
curvature
1.1 Introduction
Sintering acts to bond particles together into strong, useful shapes. It is used to fire ceramic pots and in the fabrication of complex, high-performance shapes, such as medical implants. Sintering is irreversible since the particles give up surface energy associated with small particles to build bonds between those particles. Prior to sintering the particles flow easily while after sintering the particles are bonded into a solid body. From a thermodynamic standpoint sinter bonding is driven by the surface energy reduction. Small particles have more surface energy and sinter faster than large particles. Since atomic motion increases with temperature, sintering is accelerated by high temperatures.
The driving force for sintering comes from the high surface energy and curved surface inherent to a powder. The initial stage of sintering corresponds to neck growth between contacting particles where curvature gradients normally dictate the sintering behavior. The intermediate stage corresponds to pore rounding and the onset of grain growth. During the intermediate stage the pores remain interconnected, so the component is not hermetic. Final stage sintering occurs when the pores collapse into closed spheres, giving a reduced impediment to grain growth. Usually the final stage of sintering starts when the component is more than 92% dense. During all three stages, atoms move by several transport mechanisms to create the microstructure changes, including surface diffusion and grain boundary diffusion.
Sintering models include parameters such as particle size and surface area, temperature, time, green density, pressure and atmosphere. Further, the addition of a wetting liquid induces faster sintering. Accordingly, most sintering is performed with a liquid phase present during the heating cycle. These basic thermodynamic attributes are treated in this first chapter.
1.2 The sintering process
Sintering is fundamentally a one-way event. Once sintering starts, surface energy is consumed through particle bonding, resulting in increased compact strength and often a dimensional change. Accordingly, the definition of sintering is as follows:¹
Sintering is a thermal treatment for bonding particles into a coherent, predominantly solid structure via mass transport events that often occur on the atomic scale. The bonding leads to improved strength and lower system energy.
The bonding between particles is evident in the scanning electron microscope in terms of the newly formed solid necks between contacting particles. Figure 1.1 illustrates spherical bronze particles after sintering at 800 °C. Necks grow between the contacting spheres, providing strength and rigidity. Longer sintering gives a larger neck and usually more strength. The emergence of the necks between is driven by the system thermodynamics, while the rate of sintering depends mostly on the temperature. At room temperature, the atoms in a material such as bronze are not noticeably mobile, so the particles do not sinter. However, when heated to a temperature near the melting range, the atoms are very mobile. Atomic motion increases with temperature and eventually this motion induces bonding that reduces the overall system energy.
1.1 Scanning electron micrograph of the sintering neck formed between 26 μm bronze particles after sintering at 800 °C.
The energy changes in sintering are usually small, so the rate of change during sintering is slow. In the case of the 26 μm bronze powder shown in Fig. 1.1, which has a solid–vapor surface energy of 1.7 J/m², the energy per unit mass stored as excess surface area is about 50 J/kg. But not all of this energy can be consumed during sintering, since the structure usually fails to sinter to full density and other interfaces emerge, such as grain boundaries, which add energy into the system. The total surface energy increases as the particle size decreases, so with nanoscale powders smaller than 0.1 μm there is a large driving force for sintering, meaning faster sintering or a lower sintering temperature.
Early models for sintering realized that a sphere affixed to a flat plate presented a large energy difference, since the sphere has much more surface area and by implication more surface energy. Accordingly, early sintering studies measured the neck size between spheres and plates, and subsequently between contacting spheres. The two-sphere model considers two equal-sized spheres in point contact that subsequently fuse to form a single larger sphere with a diameter 1.26 times the starting sphere diameter, as sketched in Fig. 1.2.
1.2 Two-sphere sintering model, where the two spheres grow a neck during sintering that grows to the point where the spheres fuse into a single sphere that is 1.26 times the diameter of the starting spheres.
The rate of particle bonding during sintering depends on temperature, materials, particle size and several processing factors.² Small particles are more energetic, so they sinter faster. Thus, the thermodynamics of sintering show the importance of smaller powders, while the kinetics of sintering emphasizes the importance of temperature.
Sintering occurs in stages, as illustrated in Fig. 1.3. Without compaction a model powder system starts at a packing density of 64%, the dense random packing. In the initial sintering stage, the interparticle neck grows to the point where the neck size is less than one-third of the particle size. Often there is little dimensional change so at the most 3% linear shrinkage is seen in the initial stage. For loose spheres this generally corresponds to a density below 70% of theoretical. Intermediate stage sintering implies the necks are larger than one-third the particle size, but less than half the particle size. For a system that densifies, this corresponds to a density range from 70% to 92% for spheres. During the intermediate stage the pores are tubular in character and connected (open) to the external surface. The sintering body is not hermetic so gas can pass in or out during firing. Final stage sintering corresponds to the elimination of the last 8% porosity, where the pores are no longer open to the external surface. Isolated pores, associated with final stage sintering, are filled with the process atmosphere.
1.3 Illustration of the sintering stages with a focus on the changes in pore structure during sintering.
1.3 Surface energy
Surface energy is the thermodynamic cause of sintering. A model of a surface is generated by starting with an ideal crystal, such as shown in Fig. 1.4, where each atomic species occupies specific, repeating sites. Between atoms are bonds, represented by lines. If scissors were used to snip these atomic bonds, then the resulting surface would consist of broken bonds. These bonds provide the atomic interaction responsible for the surface energy. Figure 1.5 illustrates this concept, where the free surface is covered with broken bonds. Surface energy relates to the density of broken bonds (bonds per unit area), so it varies with crystal orientation. Also, since stronger bonding is associated with a higher melting temperature, surface energy is higher for high melting temperature materials.
1.4 An illustration of a perfect crystal where each atom is in a repeating position and atomic bonds are linking the atoms.
1.5 An illustration of how a free surface for a crystalline material results in disrupted atomic bonding; it is the dangling atomic bonds that give surface energy.
An atomic model for the grain boundary would be similar, where broken atomic bonds from the two crystal lattices only partly match. As illustrated in Fig. 1.6, some misorientations lead to more disrupted bonding and high grain boundary energies, while other misorientations lead to less disruption and lower grain boundary energy. Thus, depending on the misorientation between the two crystals, the grain boundary energy might be high (much disrupted bonding) or low (good bond matching).
1.6 Grain boundary misorientation and the relative energy from the misorientation, such that during sintering the random particle to particle contacts result in a wide array of microstructure relations.
Some grain orientations are higher energy than others, so touching grains rotate or rearrange during sintering to reduce their grain boundary energy. In a sintering structure consisting of solid particles and pores, a variety of grain boundary configurations are possible between the randomly assembled particles. Further, a range of solid–vapor surface energies come from the range of crystal surface orientations. With a liquid, the inventory of surface energies increases to include grain boundary, solid–vapor, liquid–vapor, and solid–liquid combinations. All of these are distributed properties and not single-valued. Rather than dealing with this level of detail, sintering models rely on average values that reflect the millions of different combinations.
For many engineering materials, the average solid–vapor surface energy is in the 1 to 2 J/m² range, while grain boundary energies are even lower. For a single-phase solid, sintering is slow since the energy release on sintering is low. Similar to other chemical reactions, as the surface energy is consumed, then the driving force for continued sintering is diminished and the process continually slows.
1.4 Sintering stress
The capillary stress arising from the surface energy acts to move surfaces during sintering. The neck between contacting particles is associated with a large change in curvature over distance. For example in Fig. 1.1, the base of the neck is concave. A concave surface acts to pull itself into a flat surface. On the sphere surface away from the neck, the curvature is convex with an opposite curvature. The Laplace equation gives the stress s associated with a curved surface as,
[1.1]
where γ is the energy associated with the curved surface (for example solid–liquid, solid–vapor, or liquid–vapor surface energy), and R1. and R2 are the radii of curvature for the surface. For a sphere, both radii are the same and equal to the radius of the sphere so the stress is uniform, but during sintering the two radii vary with position in the microstructure and often are opposite in sign. This is evident with the saddle surface seen in the sintering neck. The sintering microstructure consists of a mixture of convex and concave surfaces, and the shift from tension to compression occurs over distances smaller than the particle size. The natural tendency is to remove the gradients during sintering.
Because the stress in the neck region is different from the neighboring region, the curvature gradient gives a thermodynamic gradient that drives mass flow during sintering. Atomic motion takes place to remove the gradient. When heated to where atomic motion occurs, the atoms naturally flow from the convex to concave surfaces. Atom motion is faster at higher temperatures and small particles have large gradients. Accordingly, particles sinter faster when they are small and heated to high temperatures.
As sketched in Fig. 1.7, a concave solid surface tends to fill and a convex surface tends to flatten. In a powder compact consisting of a mixture of pores and particles, sintering acts to remove the curvature gradients – namely to smooth the pores. The convex particles represent mass sources and pores represent mass sinks that fill using mass from the convex regions. From the instantaneous pore-grain geometry it is possible to quantify these parameters and assess the sintering stress and its dissipation over time. As with many reactions, sintering goes more slowly as it progresses, simply because the action of sintering is to remove the gradients.
1.7 The action of sintering is to remove concave and convex surfaces and to move toward flat surfaces, as schematically illustrated here. The mass from the convex transports to fill in the convex surface.
In the initial stage of sintering, the saddle surface formed between particles has a sharp curvature at the root. Assuming isotropic surface energy and spherical particles, then for a small neck size a substitution into Equation 1.1 gives the sintering stress σ as follows:
[1.2]
where X is the neck diameter, D is the particle (sphere) diameter, and γsv is the solid–vapor surface energy. This relation is valid in the initial stage of sintering when X/D < 0.3. This stress induces particle bonding as a natural part of sintering. Although surface energy is consumed as the neck grows, not all surface energy is available for sintering. For a crystalline solid, nearly every particle contact forms a grain boundary. The grain boundaries are defective regions with high atomic mobility. For most inorganic powders, diffusion along the grain boundary proves to be a dominant sintering mechanism. As the neck grows to remove surface energy the grain boundary grows and adds interfacial energy, so sintering only continues as long as the rate of surface energy annihilation exceeds the rate of grain boundary annihilation.
Heat stimulates the atomic motion that allows sintering to proceed. Most sintering processes are thermally activated, meaning that input energy is necessary for mass flow. For example, sintering by diffusion depends on the energy to create a vacancy and the energy to move an atom into that vacancy. The population of vacant atomic sites and the number of atoms with sufficient energy to move into those sites both vary with an Arrhenius temperature relation. The Arrhenius relation determines the probability that an atom has enough energy to move, as determined by the activation energy Q. For example, the volume diffusion coefficient Dv is determined from the atomic vibrational frequency D0, absolute temperature T, universal gas constant R, and the activation energy Q, which corresponds to the energy required to induce atomic diffusion via vacancy exchange,
[1.3]
Sintering is faster at higher temperatures, because of the increased number of active atoms and available sites. Thus, temperature is a dominant parameter in defining a sintering cycle. Other important factors include the particle size, applied pressure, formation of a liquid phase, sintering time, heating rate, and process atmosphere.
Another important source of sintering stress comes from wetting liquids. About 80% of all sintering occurs with a liquid or glassy phase. The liquid causes the powder to agglomerate since significant capillary stress is generated by a wetting liquid. Wetting refers to a liquid that spreads over a surface. We rely mostly on the contact angle to measure wetting. Also known as the wetting angle, the contact angle is formed at the intersection of liquid, solid, and vapor phases. When gravity is ignored, the contact angle θ is defined by the horizontal equilibrium of surface energies, as illustrated in Fig. 1.8. The general consensus is to measure the contact angle on a surface perpendicular to the gravity vector. Then ignoring gravity the horizontal solution is known as Young’s equation,
1.8 Contact or wetting angle definition based on a droplet sitting flat on a surface so the vertical forces are balanced.
[1.4]
where γSV is the solid–vapor surface energy, γSL is the solid–liquid energy, and γLV is the liquid–vapor surface energy. Wetting liquids are associated with contact angles near zero and nonwetting liquids are associated with contact angles over 90°. During spreading or retraction of a liquid over a solid surface, the contact is not in equilibrium. Further, various corrections exist for the effect of surface roughness, since finely textured solid surfaces will induce wetting even though the contact angle predicts nonwetting.
Finally, the dihedral angle describes the grain boundary structure. The angle formed by a grain boundary where it intersects with another solid, pore, or liquid during sintering is described by a thermodynamic balance termed the dihedral angle. As illustrated in Fig. 1.9, it is determined by a vertical surface energy balance. For the case of a grain boundary in contact with a liquid during liquid phase sintering the vector balance gives,
1.9 The dihedral angle is defined based on a solid–solid grain boundary energy intersecting a liquid or vapor phase.
[1.5]
where γss is the solid–solid interfacial energy (grain-boundary energy) and γSL is the solid–liquid interfacial energy. Alternatively,
[1.6]
In the case of a grain boundary in contact with the free surface, a thermal groove forms and the dihedral angle is determined by the solid–vapor surface energy γSV. In materials held at high temperature for a prolonged time the dihedral angle is evident at all surfaces and exposed grain boundaries. Grain boundary grooving on a free surface is a reflection of the dihedral angle. Since segregation changes grain boundary and surface energies, the dihedral angle exhibits a time dependence related to the diffusion of species to or from grain boundaries and free surfaces.
1.5 Atomistic changes in sintering
The surface stress associated with a curved surface gives a nonequilibrium vacancy concentration. A flat surface free of stress is at equilibrium. In sintering, microstructure curvature drives mass flow by taking both the concave and convex surfaces toward a flat state. Mass from the convex surface moves to fill in the concavity. The vacancy concentration C under a curved surface depends on the local curvature,
[1.7]
where C
is the atomic volume, k is Boltzmann’s constant, and T is the absolute temperature. The equilibrium concentration increases on heating. As shown in Fig. 1.10, two perpendicular arcs pass through at any point on the surface. These arcs have radii of curvature designated as R1 and R2. The more highly curved the surface, the smaller R1 and R2 and the departure from equilibrium. For a concave surface, the vacancy concentration is higher than equilibrium; for a convex surface it is lower; thus, atomic flow is from regions of vacancy deficiency – convex – to regions of vacancy excess – concave. When a radius of curvature is located inside the solid it is deemed negative while a radius located outside the solid is positive. A concave surface is a source of vacancies that works with a counter flow of atoms to fill the concavity.
1.10 The definition of surface curvature in terms of the radii of the two perpendicular arcs passing through a point on a curved surface.
Atomic motion (volume diffusion) depends on atomic exchange with neighboring vacancies. For diffusion to occur, an atom must have sufficient energy QB to break existing bonds with neighboring atoms and then additional energy to exchange its position with a neighboring vacant site. The probability of a neighboring atomic site being vacant depends on the vacancy formation energy QN. In other words, volume diffusion requires both the formation of a vacancy and the provision of sufficient energy to break an atom free so that it can jump into the vacant site. As an approximation to the rate of atomic diffusion, the Arrhenius equation gives the relative number of active atoms NA compared with the total number of atoms N0 as follows:
[1.8]
where R is the gas constant and T is the absolute temperature. Most typically, the rate of atomic diffusion is termed the diffusivity, which depends on several parameters including the frequency of atomic vibration, crystal class, lattice parameter and similar factors. The resulting form for the diffusion coefficient is an Arrhenius equation given earlier as Equation 1.3. The activation energy Q is the sum QN + QB. In turn, for a given crystal structure both activation energies can be rationalized to the number of atomic bonds that must be broken to form a vacancy and the number of atomic bonds that must be broken to move an atom. Many handbooks compile data diffusion data as D0 and Q, which allows calculation of D at any temperature.
Similar to vacancy creation and annihilation at free surfaces, the grain boundaries are important to sintering. Diffusion on a grain boundary undergoes a rapid increase with a modest temperature increase. Further, impurities preferentially segregate to grain boundaries, so often the fast diffusion observed along the grain boundaries is a reflection of the segregated impurities. At very high temperatures the impurities are more soluble in the materials being sintered, so there is less effect. But at intermediate temperatures, segregation is more severe and leads to significant changes in sintering rates. This is true in systems such as tungsten doped with nickel, where low concentrations of nickel doped into the tungsten greatly lower the sintering temperature.³
1.6 Sintering changes prior to interfacial energy equilibrium
During sintering, shrinkage causes grains to come into contact with each other and form new sinter bonds, at times much delayed from the initial bonding. Grain rearrangement is observed due to the grain boundary torque.⁴ The motion of grains or particles into new and higher density packing positions is frequent in liquid phase sintering. During heating, the liquid spreads to wet the solid grains as soon as it forms, dissolving existing solid–solid necks. The resulting loose grain structure with a wetting liquid produces a capillary force that acts to pull the separated grains together. The individual rearrangement events happen very quickly when the liquid forms, so the grains literally jump into new positions. However, the formation of liquid requires heat transport through the porous compact, which tends to be a slow step.⁵ For this reason most powder compacts show a slow rearrangement step that is controlled by heat transport. Each individual bond undergoes rearrangement in a split second, but the thermal wave needed to form the liquid propagates through the compact over a few minutes.
An especially important nonequilibrium transient occurs in liquid phase sintering. Newly formed liquid spreads, and if it has solubility for the solid, then it penetrates the solid–solid interfaces on liquid formation. This results in a dimensional change, usually swelling, where the amount of swelling varies with the liquid flow into the surrounding pores. The liquid flow is estimated as a function of hold time as follows:
[1.9]
where x is the depth of liquid penetration, dp is the pore size, γLV is the liquid- vapor surface energy, θ is the contact angle, t is the hold time, and η is the liquid viscosity. Several aspects of sintering are explained by this transient liquid penetration of grain boundaries. The solid skeleton formed during heating dissolves, reducing compact rigidity, and in turn this allows for distortion. A second is that liquid can be stranded on grain boundaries, leading to what is termed a necklace microstructure. Finally, the dihedral angle and other equilibrium thermodynamic properties vary during sintering.
1.7 Microstructure gradients
A natural affinity exists between the pores and grain boundaries. Because of the solid–vapor surface energy, a pore contributes surface energy. At the same time a grain boundary has grain boundary energy. If the pore sits on the grain boundary, then the configurational energy is lower; effectively the pore-boundary combination is pinned. Thus, there is a high probability for a pore to attach to a grain boundary, even during grain growth. However, sintering works to minimize energy and this usually means a reduction in grain boundary energy through an increase in grain size. Thus, a dynamic exists where pores are attached to grain boundaries while at the same time grains are growing to reduce grain boundary area. Mobile pores remain with the moving grain boundaries and sintering progresses to full density. On the other hand, if the pores and grain boundaries separate, then a porous sintered body results. It is effectively impossible to shrink a pore that is removed from a grain boundary.
At high sintered densities the pores are mostly associated with the largest grains. In final stage sintering the relation between grain size G, pore diameter dP, and fractional porosity ε is given as:
[1.10]
where R expresses the ratio of attached pores to randomly placed pores, and K is a geometric constant. Values of R range from 1.7 to 5.7 for various sintering materials.⁶ The degree of boundary-pore contact remains essentially constant during most of the sintering cycle.
Consequently, grain size tracks with porosity during sintering; grain size increases, porosity decreases, and pore size initially decreases, but late in sintering might increase. In the initial stage of sintering the pores pin the grain boundaries to retard grain growth. If a grain boundary were to move then it must drag the pore and that is a slow event. In the intermediate stage of sintering the pores are smaller yet located on the grain edges. The pore surface area declines while the grain size enlarges, effectively making the pore diameter smaller and the pore length longer. Accordingly, a fundamental relation is observed where the grain size and solid–vapor surface area per unit volume SV tracks with the square of the porosity e, and the grain size G tracks with the inverse of the remaining surface area [7,8]:
[1.11]
Of course this predicts an infinite grain size at full density. The terminal condition in sintering is a single crystal, or one grain, so this is not overly incorrect. As porosity declines the pore surface area that retards grain growth decreases, so grain growth occurs with decreasing impediment. Thus, grain size increases rapidly as full density is approached [1,9]. As plotted in Fig. 1.11, the declining surface energy associated with pores diminishes grain boundary pinning, so there is little resistance to a rapid rise in grain size as full-density is approached.
1.11 Grain size plotted as a function of porosity during the sintering of 8 μm copper powder to illustrate how rapid grain growth occurs as pores are removed with a reduction in the grain boundary pinning effect that retards grain growth at higher porosities.
Typically the assumed grain geometry during late stage sintering is the tetrakaidecahedron, a 14-sided polyhedron consisting of squares and hexagons. Figure 1.12 shows a sketch of this grain shape. In intermediate stage sintering the pores exist as tubes on the grain edges and in the final stage of sintering the pores are spheres located at the grain corners.
1.12 The tetrakaidecahedron is a 14-sided polygon with 35 edges and 24 corners that packs to full density. It consists of six squares and eight hexagons, and pores then occupy the edges during intermediate stage sintering or the corners during final stage sintering.
During intermediate stage sintering the pores form a tubular network that is attached to the grain boundaries. As densification occurs the pores shrink while simultaneous grain growth stretches the pores. As this continues, eventually the elongated and thinning pores pinch off into closed spherical pores, a process termed pore closure. Based on energy reduction, a calculation of the instability of a cylindrical pore of length l and diameter dP gives the critical condition for closure into separate pores as follows:
[1.12]
For a cylindrical pore occupying the edges of tetrakaidecahedron grains this instability occurs at a porosity of approximately 8%. In reality, due to distributions in initial particle sizes, the instability that induces pore closure occurs over a broad range of densities from 85 to 95% and final stage sintering occurs with rapid grain growth and slow densification from that point.
1.8 Chemical and strain gradients
Sintering is a process where energy is consumed and the material is relaxed. If the powder is milled and has stored strain energy, then the release of that strain during sintering increases the sintering rate. Indeed, thermal stresses from rapid heating will improve the sintering rate, but often damage the component. Phase transformations are another means of including strains to alter the sintering rate. Adding energy to the material increases the sintering rate, so radiation and electromagnetic fields have beneficial effects.
Chemical gradients are important to mixed powder sintering. For example, mixed powders are compacted and heated to form an alloy such as bronze or stainless steel. Most common is the formation of steel using mixed iron and graphite powder. During the sintering cycle the carbon goes into solution. Other examples include mixed copper and tin powders used to form bronze, and mixed silica and alumina used to form mullite. The number of combinations is large.
Mixed powder sintering is biased by the phase diagram thermodynamics. If an intermetallic is produced, typically it involves an exothermic reaction, such as NiTi, MoSi2, or Ni3Al. Some reactions are so strong that the system self-heats once initiated. Phase diagrams are equilibrium depictions of the phases that form versus temperature and composition, but mixed powders are not necessarily at equilibrium during heating. The tendency to react, swell, densify, or otherwise change traces to the phase diagram. For example, the iron-aluminum system shows solubility of aluminum in iron, but not the reverse solubility. Thus, during heating the aluminum melts and diffuses into the iron, leaving a pore behind at the prior aluminum particle sizes. Figure 1.13 is the Fe-Al phase diagram and the resulting microstructures below the phase diagram show images taken during heating as the core aluminum particle first melts, reacts, and then diffuses out to create a pore, giving compact swelling.
1.13 The pore evolution in sintering mixed iron and aluminum, showing the reaction around the aluminum particle to form an intermediate compound. The phase diagram shows that the intermetallic phases are very stable, thus the chemical reaction dominated sintering
Other features of great importance to sintering can be identified from phase diagrams. These include solubility, dissolution, and liquid phase formation. Several of the important reactions are categorized elsewhere [1,3,10,11]. One of the more difficult sintering tasks is to manage reactive systems, especially where a transient phase forms. Copper-tin is the most famous of these, where during heating tin melts, forms intermetallic compounds, and the compounds subsequently melt or dissolve. Although complicated, this system is fundamental to sintered oil-less bronze bearings and control of the events is crucial to successful functioning.
1.9 Thermodynamics, stages and mechanisms of mass flow
Transport mechanisms tell how mass flows to lower the system energy during sintering. There are two classes of sintering mechanisms: surface transport and bulk transport. Each is composed of several atomistic events that contribute to bonding. The pores are large accumulations of vacancies, so the sintering mechanisms describe vacancy motion and annihilation during heating. Vacancies and atoms move along particle surfaces (surface diffusion), across pores (evaporation-condensation), along grain boundaries (grain boundary diffusion), and through the lattice (viscous flow or volume diffusion). Also, vacancies couple with dislocations via plastic flow and dislocation climb.
Surface transport processes give neck growth without a change in particle spacing (no shrinkage or densification) since the mass flow originates and terminates at the particle surface. The atoms are rearranged, but no annihilation of vacancies takes place. Surface diffusion and evaporation-condensation are two contributors to surface transport controlled sintering. Surface diffusion dominates the low-temperature sintering of many metals and ceramics, while evaporation- condensation is active when the vapor pressure is high.
Bulk transport processes promote neck growth and shrinkage during sintering. For densification to occur, the mass must originate from the particle interior with deposition at the neck. The vacancy annihilation takes place on the grain boundary by particle rotation and rearrangement. Bulk transport mechanisms include volume diffusion, grain boundary diffusion, dislocation climb, plastic flow and viscous flow. Plastic flow is important during the heating period, especially for compacted powders where the initial dislocation density is high. Without rapid heating, surface tension stresses are generally insufficient to generate new dislocations and the dislocations are annihilated once they intersect a grain boundary or free surface. Thus, the role of plastic flow decreases as the dislocations are annealed out at high temperatures. In contrast, amorphous materials, such as glasses and polymers, sinter by viscous flow, where the particles coalesce at a rate that depends on the particle size and material viscosity. A form of viscous flow is also possible for metals with liquid phases on the grain boundaries. Grain boundary diffusion is fairly important to densification for most crystalline materials, and appears to dominate the densification of many common systems. Volume diffusion is most active in cooperation with dislocation climb. Relative to the melting temperature, bulk transport processes are dominant at higher temperatures and surface transport processes are dominant at lower temperatures.
The sinter bond between the contacting particles is the critical region. It is the point where atoms are deposited to reduce the surface energy. Generally all of the key sintering measures relate to the mass transport rates and how they influence neck growth and change the pores and grains. Models for solid–state sintering have subdivided the treatments into specific combinations of the sintering stage and mass transport mechanism, such as surface diffusion during initial stage sintering or grain boundary diffusion during intermediate stage sintering.
Amorphous materials exhibit a decreasing viscosity (increased flow) as temperature increases. Under the action of an applied stress a viscous material flows. Both glasses and polymers densify by viscous flow. The lower the viscosity the more rapid the sintering process, so temperature is a key control parameter. If an external stress is applied, then the rate of sintering increases in proportion to the applied stress [1].
The two-particle sintering situation is different for amorphous materials when compared to crystalline solids, since amorphous materials lack grain boundaries. As neck growth occurs, amorphous materials reach a neck size ratio of approximately X/D = 2/3 where sintering often stops. In most cases the powder is fully densified by this point. Many early models of sintering associated viscous flow with creep and volume diffusion processes. The Stokes-Einstein relation effectively relates the volume diffusion coefficient to an effective viscosity, so such an idea is widely accepted. If a sintering body is measured for effective viscosity during periods of rapid sintering, the viscosity of 10 GPa-s is about the same as that of a viscous child’s toy known as Silly Putty®.
Vapor transport during sintering leads to the repositioning of atoms located on the particle surface, without densification. Evaporation preferentially occurs from a convex surface and transport takes place across the pores to deposit mass on a nearby convex surface. The result is a reduction in the surface area as bonds grow between touching particles, but there is no change in the distance between particle centers. The fraction of atoms on surface sites decreases over time as the concave surfaces are filled using mass from the convex surfaces. Vapor pressure increases with temperature, following the Arrhenius behavior. Higher temperatures give a higher vapor pressure and more vapor phase transport during sintering. Because the vapor pressure changes with surface curvature, deposition occurs at the concave necks between particles where the vapor pressure is slightly below equilibrium. Materials with a large sintering contribution from evaporation-condensation include NaCl, PbO, TiO2, H2O, Si3N4, BN and ZrO2. All of these systems exhibit weight loss during
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