Sintering: Densification, Grain Growth and Microstructure

2004

Part I

Basis of Sintering Science

Outline

Chapter 1: SINTERING PROCESSES

Chapter 2: THERMODYNAMICS OF THE INTERFACE2

Chapter 3: POLYCRYSTALLINE MICROSTRUCTURES

1

SINTERING PROCESSES

Publisher Summary

Sintering is categorized in the synthesis/processing element among the four basic elements of materials science and engineering. It is a processing technique employed to produce density-controlled materials and components from metal or/and ceramic powders by applying thermal energy. As material synthesis and processing have become crucial in recent years for materials development, the importance of sintering is increasing as a material processing technology. Sintering is one of the oldest human technologies, originating in the pre-historic era with the firing of pottery. Only after the 1940s, sintering was studied fundamentally and scientifically. Since then, remarkable developments in sintering science have been made. One of the most important and beneficial uses of sintering in the modern era is the fabrication of sintered parts of all kinds, including powder-metallurgical parts and bulk ceramic components. Sintering aims at producing sintered parts, with reproducible micro-structure, through the control of sintering variables. Micro-structural control means the control of grain size, sintered density, and size and distribution of other phases including pores. In most cases, the final goal of micro-structural control is to prepare a fully dense body with a fine grain structure.

1.1 WHAT IS SINTERING?

Sintering is a processing technique used to produce density-controlled materials and components from metal or/and ceramic powders by applying thermal energy. Hence, sintering is categorized in the synthesis/processing element among the four basic elements of materials science and engineering, as shown in Figure 1.1.¹ As material synthesis and processing have become crucial in recent years for materials development, the importance of sintering is increasing as a material processing technology.

Figure 1.1 The four basic elements of materials science and engineering.¹

Sintering is, in fact, one of the oldest human technologies, originating in the prehistoric era with the firing of pottery. The production of tools from sponge iron was also made possible by sintering. Nevertheless, it was only after the 1940s that sintering was studied fundamentally and scientifically. Since then, remarkable developments in sintering science have been made. One of the most important and beneficial uses of sintering in the modern era is the fabrication of sintered parts of all kinds, including powder-metallurgical parts and bulk ceramic components.

Figure 1.2 shows the general fabrication pattern of sintered parts. Unlike other processing technologies, various processing steps and variables need to be considered for the production of such parts. For example, in the shaping step, one may use simple die compaction, isostatic pressing, slip casting, injection moulding, etc., according to the shape and properties required for the end product. Depending on the shaping techniques used, not only the sintering conditions but also the sintered properties may vary considerably. In the sintering step, too, there are various techniques and processing variables; variations in sintered microstructure and properties can result.

Figure 1.2 General fabrication pattern of sintered parts.

Sintering aims, in general, to produce sintered parts with reproducible and, if possible, designed microstructure through control of sintering variables. Microstructural control means the control of grain size, sintered density, and size and distribution of other phases including pores. In most cases, the final goal of microstructural control is to prepare a fully dense body with a fine grain structure.

1.2 CATEGORIES OF SINTERING

Basically, sintering processes can be divided into two types: solid state sintering and liquid phase sintering. Solid state sintering occurs when the powder compact is densified wholly in a solid state at the sintering temperature, while liquid phase sintering occurs when a liquid phase is present in the powder compact during sintering. Figure 1.3 illustrates the two cases in a schematic phase diagram.* At temperature T1, solid state sintering occurs in an A–B powder compact with composition X1, while at temperature T3, liquid phase sintering occurs in the same powder compact.

Figure 1.3 Illustration of various types of sintering.

In addition to solid state and liquid phase sintering, other types of sintering, for example, transient liquid phase sintering and viscous flow sintering, can be utilized. Viscous flow sintering occurs when the volume fraction of liquid is sufficiently high, so that the full densification of the compact can be achieved by a viscous flow of grain–liquid mixture without having any grain shape change during densification. Transient liquid phase sintering is a combination of liquid phase sintering and solid state sintering. In this sintering technique a liquid phase forms in the compact at an early stage of sintering, but the liquid disappears as sintering proceeds and densification is completed in the solid state. An example of transient liquid phase sintering may also be found in the schematic phase diagram in Figure 1.3 when an A–B powder compact with composition X1 is sintered above the eutectic temperature but below a solidus line, for example at temperature T2. Since the sintering temperature is above the A–B eutectic temperature, a liquid phase is formed through a reaction between the A and B powders during heating of the compact. During sintering, however, the liquid phase disappears and only a solid phase remains because the equilibrium phase under the given sintering condition is a solid phase.

In general, compared with solid state sintering, liquid phase sintering allows easy control of microstructure and reduction in processing cost, but degrades some important properties, for example, mechanical properties. In contrast, many specific products utilize properties of the grain boundary phase and, hence, need to be sintered in the presence of a liquid phase. Zinc oxide varistors and SrTiO3 based boundary layer capacitors are two examples. In these cases, the composition and amount of liquid phase are of prime importance in controlling the sintered microstructure and properties.

Figure 1.4 shows typical microstructures of partially sintered powder compacts without (a) and with (b) a liquid phase. In both cases, sintering has proceeded to the final stage in which pores are isolated. Such an isolated pore stage is generally reached quickly at usual sintering temperatures. The elimination of isolated pores is more time consuming and utilizes almost all of the sintering time.

Figure 1.4 Typical microstructures observed during (a) solid state sintering (Al2O3) and (b) liquid phase sintering (98W-INi-IFe(wt%)).

1.3 DRIVING FORCE AND BASIC PHENOMENA

The driving force of sintering is the reduction of the total interfacial energy. The total interfacial energy of a powder compact is expressed as γA, where γ is the specific surface (interface) energy and A the total surface (interface) area of the compact. The reduction of the total energy can be expressed as

(1.1)

Here, the change in interfacial energy (Δγ) is due to densification and the change in interfacial area is due to grain coarsening. For solid state sintering, Δγ is related to the replacement of solid/vapour interfaces (surface) by solid/solid interfaces. As schematically shown in Figure 1.5, the reduction in total interfacial energy occurs via densification and grain growth, the basic phenomena of sintering.

Figure 1.5 Basic phenomena occurring during sintering under the driving force for sintering, Δ(γA).

In general, the size of powders for sintering is in the range between 0.1 and 100 μm; the total surface energy of the powder is 500–0.5 J/mole. This energy is inconsiderably small, compared with the energy change in oxide formation which is usually in the range between 300 and 1500kJ/mole. If the desired microstructure of the sintered body is to be achieved by the use of such a very small amount of energy, it is necessary to understand and control the variables involved in the sintering processes.

1.4 SINTERING VARIABLES

The major variables which determine sinterability and the sintered microstructure of a powder compact may be divided into two categories: material variables and process variables (Table 1.1). The variables related to raw materials (material variables) include chemical composition of powder compact, powder size, powder shape, powder size distribution, degree of powder agglomeration, etc. These variables influence the powder compressibility and sinterability (densification and grain growth). In particular, for compacts containing more than two kinds of powders, the homogeneity of the powder mixture is of prime importance. To improve the homogeneity, not only mechanical milling but also chemical processing, such as sol-gel and coprecipitation processes, have been investigated and utilized. The other variables involved in sintering are mostly thermodynamic variables, such as temperature, time, atmosphere, pressure, heating and cooling rate. Many previous sintering studies have examined the effects of sintering temperature and time on sinterability of powder compacts. It appears, however, that in real processing, the effects of sintering atmosphere and pressure are much more complicated and important. Unconventional processes controlling these variables have also been intensively studied and developed (see Section 5.6 and Section 11.6).

Table 1.1

Variables affecting sinterability and microstructure

*Here, various types of sintering are explained using a schematic phase diagram, although, in most cases, the proper sintering type depends on the material system and/or the sintering purpose.

2

THERMODYNAMICS OF THE INTERFACE²

Publisher Summary

Surface is the plane between condensed matter and a vapor phase or vacuum, such as solid/vapor and liquid/vapor interfaces. The existence of an interface means the presence of excess interface energy over the bulk energy. The driving force for sintering is the reduction of the total interfacial energy of the system concerned; it is useful to understand the thermodynamic characteristics of interfacial energy. The surface tension of a liquid is because of the interatomic distance that is greater at the surface than in the bulk. For liquids, increase in surface area is achieved by the fast supply of atoms from the bulk to the surface and the atom arrangement with surface area increase is invariable, and isotropic as the increase occurs. For solids, surface area increase is achievable by atom supply from the bulk and by an increase in interatomic distance at the surface. The thermodynamic driving force for sintering is the reduction in total interfacial energy. The three kinds of thermodynamic phenomena—differences in bulk pressure, vapor pressure, and vacancy concentration—occur simultaneously.

2.1 SURFACE ENERGY AND ADSORPTION

2.1.1 Surface Energy

In what follows ‘surface’ is defined as the plane between condensed matter and a vapour phase or vacuum, such as solid/vapour and liquid/vapour interfaces. In a broader sense, the term ‘interface’ is used for the dividing plane between any two different phases. The existence of an interface means, by itself, the presence of an excess interface energy over the bulk energy. Since the driving force for sintering is the reduction of the total interfacial energy of the system concerned, it will be useful to understand the thermodynamic characteristics of interfacial energy.

Figure 2.1(a) is a schematic of a system containing an interface. Here, σ is the interface and α and β homogeneous phases. The interface in a real system can be represented thermodynamically as a dividing surface σ, although the variation in chemical composition at the interface occurs across multiatomic layers, as shown schematically in Figure 2.1(b). For the system in Figure 2.1(a), any extensive thermodynamic property ¢ can then be expressed as the sum of the properties of the bulk phases and that of the interface.

Figure 2.1 Schematic of (a) a system containing a phase α, a phase β and an interface σ, and (b) atom density near the interface.

(2.1)

Here, Φσ may be regarded as an additional term due to the presence of a transition layer which is determined by the curvature and area of the interface.

Hence, an infinitesimal change in the internal energy at the surface, which is an excess surface quantity, can be expressed as

(2.2)

if we choose a dividing surface where the effect of curvature is negligible. Here, S is the entropy, μi the chemical potential of component i and ni the number of moles of component i. It can be seen from Eq. (2.2) that surface energy γ is the partial derivative of surface internal energy Eσ with respect to surface area A. The surface energy can also be expressed as the change in the total internal energy of the system.

(2.3)

where P is the pressure and V the volume. Hence,

(2.4)

Equation (2.4), the thermodynamic definition of γ, shows that γ is the reversible work required to create a unit area of the surface.

The internal energy at surface Eσ is expressed as

(2.5)

From this equation and Eq. (2.2),

(2.6)

where Γi is the number of excess moles of i adsorbed at a unit surface area. Equation (2.6) is known as the Gibbs adsorption equation.

2.1.2 Surface Energy and Thermodynamic Potential

The thermodynamic potential Ω is defined as

(2.7)

where F is the Helmholtz free energy, and represents the reversible work in a system at constant temperature, volume and chemical potential. Since

(2.8)

for bulk homogeneous phases, Ωα = −PαVα and Ωβ=–PβVβ. Then, the surface excess potential Ωσ is expressed as

(2.9)

Consequently,

(2.10)

This equation indicates that the surface energy is the work required to create unit surface area under constant temperature, volume and chemical potential.

2.1.3 Relative Adsorption

The relative adsorption of i , is defined as

(2.11)

are the numbers of moles of component i may be considered as the adsorption of i at the surface where the adsorption of 1 is zero. In this regard, γ = fα is simplified