Effect of Moisture on the Structure and Fracture Strength of Ceramic Green Bodies

To study independently the effects of moisture on the structure and the mechanical strength of the binder in green bodies, specimens of the system alumina/PVA were formed with spray-dried granules of various moisture contents. The structure and fracture strength of these specimens then were examined after their moisture contents had been adjusted to specified values. As moisture content increased in the granules during compaction, the density and strength of the green body also increased. The accompanying change in the fracture mode, from intergranular to transgranular, showed that the strength of the green bodies was affected more significantly by bonding between granules than by bonding between powder particles.     

Influence of Granule Character on Strength and Weibull Modulus of Sintered Alumina

Alumina specimens were prepared by compacting well-characterized spray-dried alumina granules of excellent deformability, followed by sintering. The strength and Weibull modulus were measured and microstructure was evaluated for specimens prepared from granules with different density and morphology. Compacts of spheroidal granules with lower density and lower granule strength sintered to 98% relative density and had fewer microstructural defects than compacts prepared from spheroidal or hollow granules of higher density. Flexural strength of sintered material was found to depend on initial granule size but not density or morphology of the granules. Weibull moduli of 18–20 were independent of particular granule characteristics.     

Mechanical Properties of Dry-Pressed Ceramic Green Products: The Effect of the Binder

The strength of alumina green samples prepared by uniaxial pressing of powders spray-dried with two binders such as poly(ethylene glycol) or poly(vinyl alcohol) is discussed in terms of (i) the adhesive properties of the polymer-rich external layer of spray-dried granules and (ii) the mechanical properties of this layer. A transition from intra- to intergranular fracture is observed when the glass transition temperature of the binder increases. The influence of the binder on the defect size distribution in the green products is investigated using the classical Weibull statistics.     

Fracture Toughness of Spray-Dried Powder Compacts

The strengths and fracture toughness values were measured for alumina powder compacts containing two different binder systems. Diametral compression was used to measure both the tensile strength and the fracture toughness (through-thickness notch). This methodology was very useful in linking processing parameters, such as binder choice and compaction stress, to the quality of the green bodies. Observations of the compact structure before and after fracture showed that the binders segregated to the region between the spray-dried granules. The presence of the excess binder in this region was linked to both the failure mode and the creation of secondary cracks.     

Effect of Organic Binder Segregation on Sintered Strength of Dry-Pressed Alumina

The influence of binder systems on the structure and properties of alumina ceramics was examined. Two types of binders were used to prepare alumina granules by spray drying: poly-acrylic acid (PAA) and poly-vinyl alcohol (PVA). PVA segregated to the surface and subsurface of the granules, whereas PAA was homogeneously distributed. Compaction tests on a single granule showed that the PAA binder provides lower yield stress of granules than PVA. In the die compaction process, the relative density of the compact body started to increase at a lower pressure, and a more homogeneous internal structure was observed in the green compact prepared with the PAA binder than PVA. The homogeneous structure resulted in a sintered body with a strength of 580 vs 485 MPa when PVA was used.     

Comparison of freeze drying and spray drying to obtain porous nanostructured granules from nanosized suspensions

This work studies the spray drying and freeze drying of different nanosized ceramic materials and the physicochemical characteristics of the obtained granules. Colloidal suspensions of alumina, titania, and a 87/13 mixture were studied. The influence of temperature, pressure, nozzle diameter, and solids loading on the morphology and characteristics of dried granules were evaluated. It was demonstrated that these processing parameters have practically no influence, and the only parameter determining the granules characteristics is the solids content of the suspensions, in both processes. Spray drying leads to a monomodal distribution with higher granule size, while freeze drying produces more porous granules, with a bimodal intragranular distribution. The flowability of spray-dried powder is better than that of the freeze-dried powder and suit better the requirements of a feedstock targeted to obtain coatings by plasma thermal spraying whereas freeze drying can produce high porosity, softer granules.     

Compaction Behavior of Spray-Dried Alumina

Compaction behavior and resultant porosity of spray-dried alumina were examined over a range of pressures from 18 to 345 MPa. The variability in pressed density and pore size was measured as a function of spray-dried granule size, binder concentration, and powder moisture content. An exponential behavior was found between pressed density and compaction pressure, density increasing with the logarithm of the compaction pressure. Pore size also displays an exponential behavior, pore diameter decreasing with the log of increasing pressure. The distribution width about the median pore size was noted to decrease approximately in a log-log response to increasing compaction pressure. The behavior of the compaction and porosity curves is related to the degree to which the polymer binder is plasticized which, in turn, affects the pressure at which the spray-dried granules begin to crush. This apparent yield pressure, although dependent on amount of binder and powder moisture, is intrinsically dependent on the water/binder ratio. Finally, by analogy to soil mechanics, an empirical equation relating compact density, yield pressure, and slope is presented.     

Effect of Externally Applied Plasticizer on Compaction Behavior of Spray-Dried Powders

The effects of an externally applied plasticizer on compaction behavior and green microstructure quality of spray-dried powders was investigated. The plasticizer was applied to the external surfaces of already spray-dried powders by spraying it on tumbling spray-dried granules. The apparent yield point of the spray-dried powder was reduced when the plasticizer was added. Microstructures of compacts made from these granules (with and without the externally applied plasticizer) were compared at different compaction pressures. Better knitting across granule interfaces and fewer defects were obtained for the granules with the externally applied plasticizer.     

Effect of Forming Pressure on the Internal Structure of Alumina Green Bodies Examined with Immersion Liquid Technique

Green bodies prepared by compaction of alumina granules were made transparent by an immersion liquid technique, and the internal structure was characterized with an optical microscope to study the effect of forming pressure on the internal structure. Clear images obtained by the technique provide more detailed information than other existing methods for structures ranging from one to tens of micrometers. Intergranular pores were present between unfractured granules. Their sizes and concentration tended to decrease with increasing forming pressure. However, pores were clearly present even in the green body prepared at 600 MPa. A rod- and needlelike feature was also found and was concluded to correspond to a high-density region. The significance of large pores and high-density regions on processing as well as the details of the technique is discussed.     

Crack-reduced alumina/aluminum titanate composites additive manufactured by laser powder bed fusion of black TiO2−x doped alumina granules

Laser powder bed fusion is an emerging industrial technology, especially for metal and polymer applications. However, its implementation for oxide ceramics remains challenging due to low thermal shock resistance, weak densification and low light absorptance in the visible or near-infrared range. In this work, a solution to increase the powder absorptance and to reduce cracking during laser processing of alumina parts is given. This is achieved by the use of a homogeneously dispersed and reduced titanium oxide additive (TiO_2?x) within spray-dried alumina granules leading to formation of aluminum titanate with improved thermal shock behavior during powder bed fusion. The impact of different reduction temperatures on powder bed density, flowability, light absorption and grain growth of these granules is evaluated. Crack-reduced parts with a density of 96.5%, a compressive strength of 346.6 MPa and a Young's modulus of 90.2 GPa could be manufactured using powders containing 50 mol% (43.4 vol%) TiO_2?x.     

氧化锆料浆性能对其喷雾造粒粉料性质的影响

本文研究了料浆含固量和粘度对其喷雾造粒粉料性质影响。结果表明：氧化锆料浆含固量是喷雾造粒（ＳＤ．）粉料填充密度的主要控制因素，高含固量料浆能得到高填充密度喷雾造粒粉料，且其颗粒显微结构相对致密；随着ＺｒＯ２料浆含固量、粘度增加，喷雾造粒粉料平均粒径增大，粗颗粒含量增多，细颗粒含量减少。     

Effect of Internal Lubricants on Defects in Compacts Made from Spray-Dried Powders

The role of internal lubricants in the closure of large intergranular pores during dry-pressing was investigated. Alumina was spray-dried with and without an internal lubricant to yield granules with similar characteristics other than lubricant effects. Green and sintered microstructures were evaluated at different compaction pressures. The defects were quantified by evaluating the fracture surface of ∼90% dense sintered compacts. The samples that contained an internal lubricant had higher green densities and fewer defects at comparable compaction pressures. The internal lubricant did not cause any significant reduction in green strength or increase in springback.     

Morphology of alumina granules obtained by spray freeze drying with twin-fluid atomization

This study presents the results of the morphological dependence of alumina granules obtained by spray freeze drying (SFD) with twin-fluid atomization. It is shown that the introduction of 1-, 2- and 4-wt.% polyvinyl alcohol (PVA) as a binder in an alumina suspension leads to the formation of irregular granules. Depending on atomization conditions, spherical, “tadpole-like,” granule-satellite and granule aggregates may form during SFD. Increasing the flight time of droplets before the fixing of their shape when they come in contact with liquid nitrogen effectively contributes to the spheroidization of alumina granules. Compacting PVA-free SFD granules leads to the formation of diagonal flaws in a green-body structure. Adding PVA prevents the abovementioned defects by increasing the strength of alumina granules. Increasing the amount of PVA leads to an increase in “tadpole-like” granule content and, consequently, a decrease in a green-body density.     

Density Measurements of Single Granules Using the Atomic Force Microscope

The density of single spray-dried granules has been determined with a new method based on atomic force microscopy (AFM). Spherical granules with a well-defined diameter are attached to the AFM cantilever, which acts as a beam-type spring, and the mass of a granule is estimated from the shift in the resonant frequency. The error of the measurements associated with the method was estimated to vary between 1% and 5%, depending on the size and shape of the granule. Density measurements of spray-dried WC–Co granules are presented, and the effect of a polymeric binder and dispersant on the consolidation during drying is discussed.     

不同辅料对芍甘颗粒喷干粉吸湿性的影响

为合理选择芍甘颗粒防潮性最佳的辅料和生产条件,在25℃,RH为75％的条件下,将喷干粉及喷干粉与几种常用辅料配伍,考察吸湿百分率、临界相对湿度。结果表明,防潮性最佳的辅料为乳糖,配比为喷干粉：乳糖=4：1。     

Young’s Modulus of Dry-pressed Ceramics: The Effect of the Binder

Measurements of Young’s modulus of green compacts prepared from spray-dried alumina powders containing two binders: polyvinyl alcohol or polyethylene glycol are reported. The variations of Young’s modulus with forming pressure are compared to those of mechanical strength and discussed in terms of glass transition temperature (T_g). When the T_g of the polymer is lower than the pressing temperature (case of PEG and moisture-plasticized PVA), the variation of the Young’s modulus is related to the evolution of the binder film covering the surface of primary particles inside the granules. Microcracking of the brittle external polymer-rich layer of granules seems to be responsible for a different evolution of Young’s modulus of green compact in the case of a binder with a T_g higher than the forming temperature (dry PVA).     

Spray drying of TiO2 nanoparticles into redispersible granules

We have demonstrated how titania nanoparticles can be spray-dried to produce redispersible granules. The evaluation of different dispersants using rheology, particle size and electrokinetic measurements showed that an anionic carboxylated polyelectrolyte, Dispex N40, was able to stabilize the primary aggregates of the titania nanoparticles with a size of about 180 nm at an addition of 2.4% dry-weight basis over a relatively large pH-range. Transmission electron microscopy showed that the commercial P-25 titania nanopowder could not be deagglomerated down to the individual crystallite size of 15-40 nm. Spherical granules with a size between 20 and 50 μm and a minimum amount of dusty fines could be produced by spray drying the aqueous titania dispersions in a configuration with internal bag filters. The granules could be completely disintegrated and redispersed in water by ultrasonication into a stable suspension with a size distribution that is identical to the as-received powder. The possibility to prepare redispersible nanoparticle granules by spray drying is a route to minimize the risk of airborne exposure and facilitate the handling of nanopowders.     

Wet size measurements for the evaluation of the deagglomeration behaviour of spray-dried alumina powders in suspension

Spray drying produces spherical agglomerates to obtain powders with good flowability. Three alumina powders of different size and/or specific surface area were spray-dried without any binder using either two-fluid or ultrasonic nozzle technology. Compared to the two-fluid nozzle, the ultrasonic one shows a better ability to form agglomerates from a coarse powder and increases the size of the agglomerates when spray drying is carried out under the same operating conditions. The redispersion of spray-dried agglomerates in solution was analysed by applying variable ultrasound durations during size measurement by wet laser diffraction. The initial state of the powder plays a predominant role in relation to the spray drying operating conditions both in terms of size characteristics and redispersion properties. Regardless of the alumina powders and spray drying conditions, a similar trend in deagglomeration behaviour was observed with first-order kinetics and a characteristic kinetic time depending on the initial powder properties.     

Influence of Slurry Parameters on the Characteristics of Spray-Dried Granules

A systematic study has been performed to determine how the characteristics of granules prepared by spray drying aqueous alumina slurries are influenced by processing parameters: binder type (PEG Compound 20M or PEG-8000), solids loading (30 or 40 vol%), ammonium polyacrylate deflocculant level (0.35-1.00 wt%), and spray-dryer type. Correlations between slurry rheology and granule characteristics have been made, and a model for granule formation is presented. The packing density of the primary particles within the granules is lower for slurries with higher yield stress and is dependent on the slurry solids loading. Granules prepared using 0.35 wt% deflocculant (0.14 mg/m²), which correspond to high slurry yield stress, are of solid morphology, whereas higher deflocculant levels result in hollow granules that contain a single large open pore or crater. The degree to which particles are able to rearrange during drying influences the final granule density and is determined by the strength of the floc structure, as indicated by the slurry yield stress. When the yield stress is low, a crater may form from the inward collapse of the surface of a forming granule when the particle packing density in a droplet continues to increase after the droplet size becomes fixed by the formation of a rigid shell, leaving an internal void with internal pressure lower than that of the surrounding atmosphere.