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The document discusses various aspects of drying granular ceramics. It begins by describing the initial stages of drying a granular film, where particles on the outer edge consolidate to form a ring and liquid flows inward to maintain saturation. For drying granular films on rigid substrates, tensile stresses develop due to the substrate preventing shrinkage. Films can crack spontaneously above a critical thickness. The document then discusses drying of granular solids and defects from non-uniform drying, before covering debinding processes including capillary extraction, solvent extraction, and thermal debinding in multiple stages.
The document discusses various aspects of drying granular ceramics. It begins by describing the initial stages of drying a granular film, where particles on the outer edge consolidate to form a ring and liquid flows inward to maintain saturation. For drying granular films on rigid substrates, tensile stresses develop due to the substrate preventing shrinkage. Films can crack spontaneously above a critical thickness. The document then discusses drying of granular solids and defects from non-uniform drying, before covering debinding processes including capillary extraction, solvent extraction, and thermal debinding in multiple stages.
The document discusses various aspects of drying granular ceramics. It begins by describing the initial stages of drying a granular film, where particles on the outer edge consolidate to form a ring and liquid flows inward to maintain saturation. For drying granular films on rigid substrates, tensile stresses develop due to the substrate preventing shrinkage. Films can crack spontaneously above a critical thickness. The document then discusses drying of granular solids and defects from non-uniform drying, before covering debinding processes including capillary extraction, solvent extraction, and thermal debinding in multiple stages.
In the initial stage of drying, particles at the outer edge of the film undergo consolidation to form a ring As drying proceeds, liquid flows to the outer region to maintain a saturated state, a process driven by the capillary suction pressure of the ring. Particles in the liquid are deposited at the interface between the saturated ring and the supersaturated suspension. Granular Film Slip Casting Drying of Granular Ceramics Drying of Granular Film deposited on a Rigid Substrate Films deposited on a rigid substrate experience biaxial tensile stresses during drying because they cannot shrink in the plane of the film. The biaxial tensile stress develops during drying as a result of the capillary tension in the pore liquid as it stretches to cover the dried surface exposed by the evaporation of the liquid The capillary tension in the liquid will cause the film to shrink but the rigid substrate prevents the shrinkage in the plane of the film. Films produced from electrostatically stabilized, binder-free suspensions (0.5 m Al 2 O 3 particles) are observed to crack spontaneously regardless of the drying rate when the film thickness is above a certain critical value (50 m). The existence of a critical cracking thickness is explained by a linear elastic fracture model which states that a constrained film will crack when subjected to a stress only if the strain energy released in the process exceeds the energy required to form the crack. The critical cracking thickness depends on the capillary tension in the liquid: it increases with increasing particle size and with decreasing surface tension of the liquid. It also increases for a flocculated suspension but at the expense of a lower particle packing density in the dried film. The use of a binder provides an effective way for improving the critical cracking thickness Drying of Granular Ceramics Drying of Granular Solids The moisture content of articles produced by casting or extrusion is typically 2035%. Drying of Granular Ceramics Drying of Granular Solids In the CRP, the rate of evaporation is independent of the moisture content. As evaporation starts, a dry surface region is created, and the liquid stretches to cover the dry region. A tension develops in the liquid, which is balanced by compressive stresses on the solid phase. The compressive stresses cause the body to contract, and the liquid meniscus remains at the surface. As drying proceeds, the particles achieve a denser packing, and the body becomes stiffer. The liquid meniscus at the surface deepens, and the tension in the liquid increases. Eventually, the particles, surrounded by a thin layer of bound water, touch and shrinkage stops. The moisture content at this point is sometimes referred to as the leatherhard moisture content When shrinkage stops, further evaporation drives the meniscus into the body and the rate of evaporation falls. The point at which the rate starts to fall is the critical moisture content. In practice, the critical moisture content and the leatherhard moisture content are approximately equal. In the FRP1, the liquid still evaporates from the surface. Contiguous pathways exist along which liquid can flow to the surface. Eventually, the liquid column becomes isolated pockets into the body. Flow to the surface stops, and the liquid is removed predominantly by diffusion of the vapor. At this stage, drying enters the FRP2 Drying of Granular Ceramics Drying Defects Cracking and Warping Cracking and warping during drying are caused by differential strain due to (1) pressure gradients in the liquid and (2) inhomogeneities in the body produced by inadequate processing or forming operations
A tension develops in the liquid as it stretches to cover the dry region exposed by evaporation of the liquid. If the tension p in the liquid is uniform, there is no stress in the solid phase
However, when p varies through the thickness, the body tends to contract more where p is high, and the differential strain causes warping or cracking.
If the evaporation rate is very high, the tension in the liquid can reach its maximum value and the total stress at the surface of the body is During the CRP, the boundary condition at the surface of the body is given by Drying of Granular Ceramics Drying Defects Cracking and Warping Conditions of Safe Drying For a given V E , p decreases with higher K and lower L . The permeability K increases roughly as the square of the particle (or pore) size. One approach would be to use a larger particle size or to mix a coarse filler with the particles. This approach is often impractical because it can lead to a reduction in densification rate during sintering. Another approach, based on a decrease in L is used practically in high humidity drying where the process is carried out at slightly elevated temperatures (70 0 C) and high ambient humidity in the drying atmosphere. Increasing the temperature leads to a decrease in L (by a factor of 2 at 70C) and to an increase in the rate of drying. However, the increase in the drying rate is counteracted by increasing the ambient humidity In this way a reasonable drying rate is achieved while keeping p small Drying of Granular Ceramics Drying Defects Cracking and Warping Even if the moist body were dried uniformly and at a safe rate, inhomogeneities produced by inadequate processing or forming operations can still lead to cracking and warping. Regions of the body with higher moisture content (above the critical value) undergo higher shrinkage. Differential shrinkage due to moisture gradients is a common source of cracking and warping. Gradients in the particle size caused, for example, by preferential settling can also lead to differential shrinkage. Pressure gradient Moisture gradient Particle segregation Drying of Granular Ceramics Debinding Process of binder removal by 1. Extraction by capillary flow 2. Solvent extraction 3. Thermal debinding Extraction by Capillary Flow: (Wicking) The green body is heated in a packed powder bed or on a porous substrate that absorbs the molten binder. The net time t for binder removal by wicking is given by, Where, L = thickness of the body, and LV = viscosity and specific surface energy, respectively, of the molten binder, V s = particle packing density of the body, D = particle size of the body, and D w = particle size of the powder bed.
Rapid binder removal by wicking is promoted by (1) small D w and (2) small L.
Because the viscosity of the binder increases with molecular weight, wicking is generally useful for waxes but not for high molecular weight polymers Drying of Granular Ceramics Solvent Extraction: Solvent extraction involves immersing the component in a liquid that dissolves at least one binder phase (~ 30 vol.%), leaving an open pore structure for subsequent binder burnout Full debinding is possible but not practical because the resulting powder mass will have almost no strength Debinding time, t: L = thickness of the body, = a factor that depends on the solubility of the binder in the solvent, V B = fraction of the binder to be removed, V s = particle packing density of the body, q = activation energy for the dissolution of the binder in the solvent, k = Boltzmann constant, and T = absolute temperature Interaction between the solvent and the binder can involve both swelling and dissolution It is necessary to choose a good solvent and perform the extraction above the theta temperature to reduce swelling Drying of Granular Ceramics Solvent Extraction: Extraction by Thermal Debinding The binder is removed as a vapor by heating at ambient pressure in an oxidizing or nonoxidizing atmosphere or under a partial vacuum. The process is influenced by both chemical and physical factors Chemically, the composition of the binder determines the decomposition temperature and the decomposition products. Physically, the removal of the binder is controlled by heat transfer into the body and mass transport of the decomposition products out of the body. In practice, binder systems consist of a mixture of at least two components that differ in volatility and chemical decomposition. The ceramic powder may alter the decomposition of the pure polymer Drying of Granular Ceramics Stages and Mechanism of Thermal Debinding: Stage I Involves heating of the binder to a point where it softens at 150200 0 C. Chemical decomposition and binder removal are negligible in this stage, but the occurrence of several other processes such as shrinkage, deformation, and bubble formation can seriously affect the ability to control the shape and structural uniformity of the body. Shrinkage occurs by a rearrangement process as the particles try to achieve a denser packing under the action of the surface tension of the polymer melt, and its magnitude increases with decreasing particle packing density in the green body. Deformation is enhanced by a lower particle packing density, higher binder content, and lower melt viscosity. Bubble formation results from the decomposition of the binder as well as from residual solvent, dissolved air, or air bubbles trapped within the green body during forming, and it provides a possible source of failure or defect formation during thermal debinding Stage II Drying of Granular Ceramics Stages and Mechanism of Thermal Debinding: Occurs at 200400 0 C where most of the binder is removed by chemical decomposition and evaporation. Capillary flow of the molten binder accompanies the evaporation process. The nature of the decomposition reactions depends on the chemical composition of the binder and on the atmosphere. In inert atmospheres such as nitrogen or argon, polymers such as poly(ethylene) undergo thermal degradation by chain scission at random points in the main chain to form smaller segments, which leads to a reduction in the polymer viscosity. With continued thermal degradation, the chain segments become small enough (i.e., their volatility increases) that evaporation is promoted. Other polymers such as poly(methyl methacrylate) undergo depolymerization reactions to produce a high percentage of volatile monomers chain scission depolymerization In oxidizing atmospheres, degradation by oxidation occurs in addition to thermal degradation. Oxidative degradation commonly occurs by a free radical mechanism to produce decomposition products that contain a high percentage of volatile, low molecular weight compounds such as water, carbon dioxide, and carbon monoxide. Compared to thermal degradation, oxidation reactions generally lead to decomposition at lower temperatures and lead to an increase in the rate at which the binder is removed Stage II Drying of Granular Ceramics Stages and Mechanism of Thermal Debinding: Stage III The left out binder in the body is removed by evaporation and decomposition at temperatures above 400 0 C. Binder removal is facilitated by the highly porous nature of the body, but the atmosphere must be carefully chosen to avoid the retention of an excessive amount of binder residue. Drying of Granular Ceramics Models of Thermal Debinding: 1. Evaporation 2. Thermal Degradation followed by Evaporation 3. Oxidative Degradation followed by Evaporation The evaporation model differs from the thermal degradation model only as far as the concentration of the volatile species is concerned. In the evaporation model, the volatile species are present in the binder at some initial concentration and the concentration decreases as debinding proceeds. In the thermal degradation model, the volatile species have a concentration that is initially zero but increases with degradation of the binder and then decreases as the volatile species evaporate. The thermal degradation model is therefore expected to describe the main features of the evaporation of low molecular weight binders Binder removal during thermal degradation has features that are similar to those encountered in the drying of a moist granular material Drying of Granular Ceramics Models of Thermal Debinding: Even though the pores have different radii (r L and r S ), initially liquid evaporates from them at the same rate so that the radii of the menisci (r m ) are equal. The capillary tension in the liquid is given by Young and Laplace equation: If the radii of the menisci are different, the capillary tension will also be different, and liquid would flow from one pore to the other until the menisci become equal again. As evaporation from the surface proceeds, the radius of the menisci decreases. But no shrinkage of the body occurs because the particles touch each other A point is reached where the radius of the menisci is equal to the radius of the large pore, i.e., r m = r L (Fig b) Further evaporation forces the liquid to retreat into the large pore. However, the radius of the meniscus, r m , will continue to decrease in the small pore, and the capillary tension will suck liquid from the large pore (Fig. c). In this way the large pore empties first and the small pore remains full of liquid. After the large pore has been emptied, the small pore starts to empty. In practice, a distribution of pore sizes and pore shapes exist in the body, but the same principles will apply. Considerable redistribution of the liquid would therefore be expected to occur during thermal degradation. The evaporation front is not expected to move uniformly into the body. Instead, pore channels first develop deep into the body as liquid from the larger pores is drawn into the smaller pores. Trends in porosity development and liquid redistribution have been observed in binder burnout studies. Drying of Granular Ceramics Models of Thermal Debinding: