Influence of Viscous Deformation at the Contact Point of Primary Particles on Compaction of Alkoxide-Derived Fine SiO2 Granules under Ultrahigh Isostatic Pressure

Viscous deformation and the adhesion force at the contact point between amorphous silica particles under ultrahigh isostatic pressure (up to 1 GPa) are important in the densification of powder compacts. The amount of viscous deformation and the strength of adhesion force have been changed in the present study by altering the calcination temperature and particle diameter, and the new values have been determined successfully using a diametral compression test. The diameter of spherical and monosized alkoxide-derived silica powders has been controlled within the range of 10–400 nm. Close-packed granules of these powders have been produced by spray drying. Because of viscous deformation, as-spray-dried ultrafine silica powders without calcination could be consolidated into highly dense compacts (>74% of theoretical density) by applying ultrahigh isostatic pressure (1 GPa). Relatively high temperature in the calcined particles (400°C) causes viscous deformation at the contact point to disappear almost completely and clearly increases the adhesion force, because of neck growth that has resulted from viscous sintering. At temperatures >200°C, the green density of the calcined powders decreases to 65% of theoretical density, even under 1 Gpa pressure. The relationship between green density and viscous deformation in silica particles at the point of contact has been analyzed quantitatively by the Hertz and Rumpf model. On the other hand, if relatively low isostatic pressure ( P c < 100 MPa) is applied, the green density and intergranular pore volume depend on the strength of the spray-dried granules. The relationship between granule strength and neck growth at the contact point with calcination has been estimated quantitatively.     

Densification of Sol-Gel-Derived Mullite Ceramics after Cold Isostatic Pressing up to 1 GPa

Molecular-designed ultrafine mullite precursor powders with a stoichiometric composition were prepared by copolymerization of alkoxides. The precursor powders were calcined in the range from 800° to 1200°C and consolidated by ultra-high-pressure cold isostatic pressing up to 1 GPa. Ultrahigh isostatic pressure of 1 GPa led to a closed packing structure in the green compacts. Interaggregate pores in the green compacts were collapsed by the ultrahigh cold isostatic pressure to reduce the pore size below 6 nm. As a result, the maximum density of the green compacts reached 70% of theoretical. These closely packed green compacts of precursor powders with a stoichiometric composition and calcined at relatively low temperatures could be sintered to >95% of theoretical at 1500°C. Relatively low-temperature sintering below the liquid formation temperature resulted in fine microstructure of the resultant mullite ceramic with a grain size below 300 nm.     

Compaction and Pressureless Sintering of Zirconia Nanoparticles

Four nanometer-sized zirconia powders stabilized by 3 mol% Y₂O₃ were used for the preparation of dense bulk ceramics. Ceramic green bodies were prepared by cold isostatic pressing at pressures of 300–1000 MPa. The size of the pores in ceramic green bodies and their evolution during sintering were correlated with the characteristics of individual nanopowders and with the sintering behavior of powder compacts. Only homogeneous green bodies with pores of <10 nm could be sintered into dense bodies (>99% t.d.) at a sufficiently low temperature to keep the grain sizes in the range <100 nm. Powders with uniform particles 10 nm in size yielded green bodies of required microstructure. These nanoparticle compacts were sintered without pressure to give bodies (diameter 20 mm, thickness 4 mm) with a relative density higher than 99% and a grain size of about 85 nm (as determined by the linear intercept method).     

Influence of forming methods on the microstructure of 3Y-TZP specimens

Nanosized 3Y-TZP powders with particle size of 10–40 nm were formed by gelcasting, dry pressing and cold isostatic pressing. The influence of particle size as well as forming methods on the microstructure and mechanical properties of specimens were investigated. Both SEM images and the analysis on pore size distribution reveal that the gelcast sample possessed more homogenous microstructure. 3Y-TZP powders with particle size of 10 nm have been gelcast with green density as 37.5% of theory and sintered density as high as 96% was achieved. Its fracture toughness was up to 11.9 MPa m^1/2 and the hardness value HV₁₀ is of 15.2 GPa. The difference of microstructure and mechanical properties is explained in terms of the differences in grain size and the forming methods.     

Influence of particles packing in granules on the particles orientation in compacts

Particles orientation during compaction was studied in alumina granules of different packing structures and deformation properties. These granules were classified mainly in two types: loose granules prepared with flocculated slurries and dense granules prepared with dispersed slurries. Particles orientations in the granules and in the compacts were examined quantitatively with the cross-polarized light microscopy. A large difference was noted in the packing structures of granules and compacts. Orientation of particles was detected only in the surface vicinity of the dense granules. These dense granules show only a slight change in particle orientation locally and its initial structures were mostly preserved even after compaction. As a result, the green compacts containing these granules also show very low net particles orientation. In contrast, loose granules show no orientated particles. However, a major rearrangement of the particles was noted during compaction, resulting in a high net particle orientation in the compacts. The particles orientation in the green compacts affected the anisotropy in the sintering shrinkage significantly; high anisotropy was observed in compacts of high particle orientation fabricated from the loose granules.     

Influence of solid loading and particle size distribution on the porosity development of green alumina ceramic mouldings

Alumina ceramic mouldings with different solid contents ranging from 55 to 70 vol% and different ratios of coarse/fine powders, i.e. 0.4 μm (fine) and 3 μm (coarse), respectively, were prepared by compression moulding at 75 °C under a compressive stress of 10 MPa. The porous parameters, such as porosity, pore size and pore size distribution, of the green compacts were evaluated after removal of organic vehicles. Experimental evidence showed that the green density, as well as the sintered density, of the moulded alumina increased linearly with increased solid loading to an optimum of 65 vol% and decreased roughly linearly with increased coarse/fine ratio. Further increase in solid loading reduced particle packing efficiency, resulting in lower green and fired densities. No considerable improvement in green and sintered density of the moulded alumina was achieved by adjusting the coarse/fine ratio, which is due to the fact that coarse particles suppress the driving force of densification. The green compacts generally showed a bimodal pore size distribution character which may be the most important factor in dominating the densification of the powder compacts. The peak frequency at larger pore region is approximately 20–35 μm in diameter and at the smaller pore region is ˜50–95 nm in diameter. The larger pores are believed to be due to the presence of internal voids originating from entrapped gas and are probably caused by the removal of organic vehicles.     

Influence of Particle Diameter on Surface Silanol Structure, Hydration Forces, and Aggregation Behavior of Alkoxide-Derived Silica Particles

The effects of silica particle diameter on dispersion and aggregation behavior in water were analyzed, using alkoxide-derived silica powders with particle diameters of 8–260 nm. The present study focused on the relationships between the surface silanol structure and the interaction forces between solid surfaces in water. The surface silanol structure and interaction between particles were determined using Fourier transform infrared spectroscopy, Fourier transform near-infrared spectroscopy, and atomic force microscopy. For relatively large particles (>30 nm in diameter), the surface silanols primarily were hydrogen-bonded silanols, and isolated silanols disappeared. The hydrogen-bonded silanols formed a hydrogen-bonded water layer on the particle surface; therefore, the additional hydration force was strong between these relatively large particles. In contrast, the surface density of isolated silanols increased as the particle diameter decreased to <30 nm, and the additional hydration force between ultrafine powders disappeared. The aggregation behaviors of alkoxide-derived silica powders were dependent on the hydration force, which was changed by the surface silanol structure.     

Synthesis of spherical mesoporous silica nanoparticles with nanometer-size controllable pores and outer diameters

Spherical mesoporous silica particles with tunable pore size and tunable outer particle diameter in the nanometer range were successfully prepared in a water/oil phase using organic templates method. This method involves the simultaneous hydrolytic condensation of tetraorthosilicate to form silica and polymerization of styrene into polystyrene. An amino acid catalyst, octane hydrophobic-supporting reaction component, and cetyltrimethylammonium bromide surfactant were used in the preparation process. The final step in the method involved removal of the organic components by calcinations, yielding the mesoporous silica particles. Interestingly, unlike common mesoporous materials, the particle with controllable pore size (4–15 nm) and particle diameter (20–80 nm) were produced using the method described herein. The ability to control pore size was drastically altered by the styrene concentration. The outer diameter was mostly controlled by varying the concentration of the hydrophobic molecules. Relatively large organic molecules (i.e. Rhodamine B) were well-absorbed in the prepared sample. Furthermore, the prepared mesoporous silica particles may be used efficiently in various applications, including electronic devices, sensors, pharmaceuticals, and environmentally sensitive pursuits, due to its excellent adsorption properties.     

Powder Processing for the Fabrication of Si3N4 Ceramics: I, Influence of Spray-Dried Granule Strength on Pore Size Distribution in Green Compacts

The effect of spray-dried granule strength on the micro-structure of green compacts obtained by isostatic pressing was quantitatively analyzed. The fracture strength of single granules of Si₃N₄ powder made with ultrafine A1₂O₃ and Y₂O₃ powders was measured directly by diametral compression. It was found that fracture strength increased notably with the increasing relative density of the granule and the decreasing size of agglomerates in suspension before spray-drying. Even when green bodies were prepared at an isostatic pressure of 200 MPa, intergranular pores, which negatively affected densification of the sintered bodies, occurred between unfractured granules. The volume and size of these pores in the green compacts increased with the increasing fracture strength of the granules. In the case of closely packed granules, an isostatic pressure of 800 MPa was required to completely collapse the intergranular pores. A simple equation was derived to calculate the isostatic pressure necessary for complete collapse of intergranular pores in the green compacts, and it was determined that granule strength must be kept as low as possible to obtain uniform green compacts.     

Diamond-like carbon sintered compacts formed by spark plasma sintering

A spark plasma sintering (SPS) method was utilized for the novel production of diamond-like carbon (DLC) compacts. Two amorphous carbon powders with different particle sizes (45 μm and 24 nm diameter) were employed as starting materials for the sintering experiments. The carbon powders were sintered using a SPS system at various sintering temperatures and holding times. The structural properties of the sintered compacts were evaluated using X-ray diffraction (XRD) analysis and high-resolution transmission electron microscopy (HRTEM). Disk-shaped compacts were obtained by sintering the powder with a particle diameter of 45 μm, although the compacts were very brittle and easily broken. However, sintering of the 24 nm diameter powder particles at temperatures of 1473 to 1573 K with a holding time of 300 s led to the successful production of sintered compacts without breakage. Reflection peaks related to graphite structure were observed in XRD patterns of the compacts sintered from the 24 nm diameter particles. HRTEM analysis revealed that the compacts sintered at 1473 K with a holding time of 300 s had an amorphous structure and consisted of 34% sp³ carbon bonding. Evaluation of the structural properties indicated that sintered compacts with DLC structure could be created by the SPS method with 24 nm diameter amorphous carbon particles.     

Obtaining of silica nanopowders from natural hydrothermal solutions

Obtaining of nanodispersed silica powders from natural hydrothermal solutions is described. Hydrothermal solutions contain colloid silica forming as a result of the polycondensation of the molecules of orthosilicic acid. Via ultrafiltration with a membrane concentration of hydrothermal solutions, silica sols with SiO2 contents up to 600 g/dm³ (43.0 wt %) and particle radii of 29–135 nm are obtained. The silica powders with the specific surface area of 110–400 m²/g, average pore diameter of 3–10 nm, and pore volume of 0.2–0.3 cm³/g are obtained via the cryochemical vacuum-sublimation drying of sols with the use of liquid nitrogen. The particle size in the powders is in the range from 10 to 100 nm.     

Facile syntheses of nanoporous organosilica spherical particles

Well-defined spherical particles of silica, containing phenyl group, with the diameter of ca. 2 microns were prepared by the co-condensation of tetraethoxysilane with phenyltriethoxysilane in basic aqueous methanol solutions of hexadecyltrimethylammonium chloride. The products were hydrophobic. The content of phenyl group was controlled by the ratio of tetraethoxysilane and phenyltriethoxysilane in the starting solution. Hexadecyltrimethylammonium was extracted with methanolic HCl to obtain nanoporous silica spherical particle containing phenyl group. The spherical particle possessed pore size of 1.8 nm and the BET surface area of 750 m² g^?1.     

义眼台用羟基磷灰石的制备和性能

采用均相共沉淀法直接合成了高纯度羟基磷灰石粉体,通过改变反应物加入方式和反应时间调控粉体形貌和组成,分析了体系pH值对产物纯度的影响;以硅溶胶为粘结剂、尿素为造孔剂,室温下压制成型,高温烧结制备了孔隙度高、力学性能良好的多孔羟基磷灰石块体,考察了粉体粒径、造孔剂含量对孔隙度和抗压强度等性能的影响。结果表明,纳米粉有利于块体成型,随造孔剂含量增加,块体密度减小、孔隙度增加,当羟基磷灰石与尿素质量比为1.5:1时,孔隙度达69%,抗压强度达8 MPa,满足义眼台应用需求。     

Exploring the Elastic Behavior of Core–shell Organic–Inorganic Spherical Particles by AFM Indentation Experiments

Monodispersed polystyrene (PS)-silica core–shell composite particles were synthesized via the hydrolysis and condensation of tetraethoxysilane (TEOS) on PS colloids at acidic medium. The thickness of silica coating was controlled by the amount of the addition of TEOS during the shell growth process. Transmission electron microscopy results confirmed that a continuous amorphous network of homogenous coating of silica was formed on the PS colloids. After coating by silica, the particle diameter increased from ca. 221 nm for uncoated PS cores to ca. 243–286 nm for PS-silica composite particles observed by scanning electron microscopy, indicating that the silica shell thickness was 11–32 nm. The elastic behavior of the obtained products was investigated by means of atomic force microscopy. The elastic moduli of samples were calculated by fitting the retract curves in force-separation plots based on the Hertzian contact model. The average moduli were 4–8 GPa for the PS-silica composite particles which were much lower than the that of the pure silica (72–75 GPa) and closed to that of the PS cores (2.1 ± 0.5 GPa). The elastic moduli of the PS-silica hybrids increased with increasing of silica shell thickness, suggesting that the elasticity of the PS-silica composite particles might be attributed to the PS cores and the silica shell was stiffening the polymer cores. These results provide a basis for exploring the mechanical properties of core–shell PS-silica hybrids in the application of novel abrasives for chemical mechanical polishing.     

Pressureless sintered Al2O3–SiC nanocomposites

Al₂O₃ + 5 vol% SiC composite ceramics were prepared via a conventional powder processing route followed by pressureless sintering. Commercially available Al₂O₃ and SiC powders were milled together in an aqueous suspension. The slurry was freeze granulated, and green bodies were obtained by cold isostatic pressing of the granules. Pressureless sintering was carried out in a nitrogen atmosphere at 1750 and 1780 °C. Near full density (>99%) was achieved at 1780 °C. Densification at the lower sintering temperature was promoted by smaller additions of MgO. Vickers hardness and indentation fracture toughness varied around 18 GPa and 2.3 MPa m^1/2 after sintering at 1780 °C. Transmission electron microscopy revealed that the SiC particles were located predominantly to the interior of the matrix grains and well distributed throughout the composite microstructures. The intragranular particles had sizes in the range 50–200 nm while the intergranular particles were larger, typically 200–500 nm in diameter.     

Optical properties of dense and porous spheroids consisting of primary silica nanoparticles

The light scattering by granular and macroporous silica spheroids consisting of nanometer-sized primary particles was systematically investigated using a laser particle counter coupled with a pulse height analyzer. The shape- and porosity-controlled spheroids as model particles were prepared using spray drying method by changing the particle size of colloidal suspension. The effect of shape and porosity of dense and porous spheroidal particles on electrical mobility was also studied using a differential mobility analyzer and an electron microscope. The electrical mobility equivalent diameter of particles classified by the differential mobility analyzer was estimated by measuring Feret diameter and the projected area equivalent diameter from the SEM micrographs. The electrical mobility diameter of the spheroids was in good agreement with the projected area equivalent diameter regardless of the primary particle size and porosity. The measured partial scattering cross section of dense and porous silica particles with same mobility diameter showed significant differences. As the primary particle size of granules and the porosity of porous particles increased at parity of electrical mobility diameter, the scattering intensity decreased. The effective refractive indices of dense and porous particles were computed by best fitting of the scattering intensity measurements. The porosities of dense and porous spheroids were calculated using the effective refractive indices as obtained by the effective medium theory. The porosities were also measured by a comparison of particle size before and after annealing at 1700°C. By comparing these porosities, the effective refractive indices of the spheroidal particles were confirmed.     

Effect of compaction pressure on the sinterability of submicron powders of tetragonal zirconium dioxide

Conclusions We studied the effect of compaction pressure on the pore structure of the paniculate compacts obtained using two types of agglomerated submicron powders of tetragonal zirconium dioxide, on the structure evolution during the sintering process, and on the strength of the obtained material. It was established that the characteristics of the agglomerates present in the powders have a significant effect on their behavior during compaction and sintering. At a given compaction pressure, the powders having weaker agglomerates densify up to a higher density and give a more uniform distribution of pores in the preform. The low-density compacts obtained using agglomerated powders having a high specific surface area sinter faster and attain high strength levels at a lower temperature; however, the sintered materials obtained from such compacts contain several structural defects in the form of large pores and have a lower strength. The uniformity of the distribution of pore volume with respect to size (or the specific content of the interagglomerate pores) forms the main criterion of the quality of particle packing in the compacts obtained from agglomerated powders. The compacts having a low content of the interagglomerate pores give a defect-free dense and strong material after sintering. The presence of the anion impurities in the original powders leads to a decrease of density during the sintering process after the attainment of a threshold density at which formation of closed porosity occurs. Pressure sintering (HIP) forms an effective method of suppressing the decrease of density.Translated from Ogneupory, No. 2, pp. 5–11, February, 1993.     

Effects of Particle Packing Characteristics on Solid-State Sintering

Alumina compacts fabricated with different green densities and different pore size distributions were characterized and the changes of the pore characteristics during solid-state sintering were studied. A critical ratio of pore size to mean particle size for pore shrinkage was determined. Porosity in the compact could be classified into two classes: the first class contains pores smaller than the critical ratio, and the second class contains pores larger than the critical ratio. Pores belonging to a different class of porosity behaved differently during sintering. Pores larger than the critical ratio were not totally eliminated during sintering. The first class of porosity controlled the ultimate sintering shrinkage, and the second class of porosity controlled the final sintered density.     

Analysis of agglomerated packings

Results of computer simulation of the packing of particles in compacts from agglomerated powders are presented. The effect of the characteristics of agglomerated powders, such as the number of particles in the agglomerates, the size distribution of agglomerates, and the volume share of the fine fraction (individual particles) on the factors that determine the sinterability of compacts, i.e., the density, the mean number of contacts per particle, and the mean size and the mean coordination number of the pores, is investigated. It is established that compared to compacts from individual particles the presence of agglomerates sharply worsens the packing characteristics. The worst effect is due to agglomerates containing less that 30 – 40 particles. The packing characteristics can be improved by using powders with a wide size distribution of agglomerates or by adding unagglomerated particles. It is interesting that computer models of powder compacts can be used for predicting the strength properties of the materials sintered from these powders. Data on the influence of the packing characteristics on the mean strength and the Weibull modulus are presented.Translated from Ogneupory, No. 4, pp. 14–17, April, 1995.     

Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2'-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles, and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites, followed by HF etching. Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica particle incorporated. N₂ adsorption-desorption, scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials. Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through templating effect of silica nanoparticles. The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm. The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%. The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.