The effect of slip casting parameters on the green density of MgAl2O4 spinel

The aim of this paper was to investigate the effect of slip casting parameters on the green density of MgAl₂O₄ spinel. In order to obtain samples with suitable mechanical and optical properties, it is necessary to prepare bulk samples with a fine grain size along with a low level of impurity and high density. Slip casting is widely used in the processing of optical ceramics to achieve a body with high green density and low sintering temperature. In the present study, several spinel suspensions with similar solid content but different viscosities and particle sizes (90, 150, 300 and 500 nm) were prepared and shaped into a dense body. Viscosity of suspension depended on dispersant content, such that the addition of dispersant firstly caused viscosity to decrease, but it was increased by further dispersant addition, irrespective of the suspension particle size. The green density range of samples was 36–67% of the theoretical value. Rheological behaviour and green density measurements showed that powder particles smaller than 90 nm were unsuitable for slip casting because agglomeration of powder particles led to high viscosity and hence, low green density. The optimal particle size for slip casting was found to be 150 nm.     

Additive Manufacturing of Dense Ceramic Parts via Direct Ink Writing of Aqueous Alumina Suspensions

Additive manufacturing of near‐net‐shaped dense ceramic components has been established via room‐temperature direct writing of highly loaded aqueous alumina suspensions in a layer‐by‐layer fashion. The effect of alumina solid loading on rheology, specimen uniformity, density, microstructure, and mechanical properties was studied. All suspensions contained a polymer binder (~5 vol.%), dispersant, and 51–58 vol.% alumina powder. Rheological measurements indicated all suspensions to be yield‐pseuodoplastic, and both yield stress and viscosity were found to increase with increasing alumina solid loading. Shear rates ranging from 19.5 to 24.2/s, corresponding to viscosities of 9.8 to 17.2 Pa·s, for the 53–56 vol.% alumina suspensions were found to produce the best results for the 1.25‐mm tip employed during writing. All parts were sintered to >98% of true density, with grain sizes ranging from 3.2 to 3.7 μm. The average flexure strength, which ranged from 134 to 157 MPa, was not influenced by the alumina solid loading.     

Slip casting of highly concentrated ZnO suspensions: Rheological studies,two-step sintering and resistivity measurements

The paper presents research on elaboration of well dispersed and stable aqueous suspensions of ZnO fine powder. Within the work the influence of the type and concentration (0.2 wt% - 1.2 wt%) of selected dispersing agents (i.a. poly(acrylic acid)-based polyelectrolyte and tetramethylammonium hydroxide), solid loading (30 - 50 vol%) and milling time (1–3 h) on the rheological properties of the slurries was investigated. Two-step sintering (970/920 °C, 2 h) was applied to sinter the green bodies obtained by slip casting.The lowest viscosity of ZnO suspensions was obtained for the addition of 0.4 wt% of poly(acrylic acid)-based polyelectrolyte (PAA) and TMAH. ZnO suspension containing PAA had negative zeta potential in the whole pH range. The highest solid loading obtained in the study was 50 vol%. The applied two-step sintering allowed to obtain samples of high density (above 96% of TD) and homogeneous microstructure of average grain size of 640 nm. ZnO sintered bodies were characterized by different electric properties at the core part and outer part of the sample which was caused by the differences in concentration of oxygen vacancies.     

Rheological properties of nanosized barium titanate prepared by HGRP for aqueous tape casting

The conditions for the preparation of stable nanosized barium titanate suspensions with high solids content for the production of aqueous tape casting are identified. The rheological behavior of colloidal barium titanate suspension with Ammonium polyacrylate (NH₄-PAA) as a dispersant to aid the powder dispersion has been investigated. Nanosized barium titanate powder was synthesized by a continuous high-gravity reactive preparation (HGRP) technique, and then annealed at 900 °C for 2 h. Measuring the zeta potential, the particle size distributions and ball-milling time, assessed the optimum conditions of the suspension with low viscosity and stability. An isoelectric point (IEP) at pH = 2.8 was found. Particle size distribution tests identified an optimum pH value about 10 and an optimum dispersant addition about 1.2 wt.% (based on the dry powder weight). As the ball-milling time was longer than 8 h, the amount NH₄-PAA adsorbed on the barium titanate reached to saturation. The maximum solid content attained during this work was 45 vol.% at pH of 10, with dispersant addition 1.2 wt.%. High green density value (up to ∼55.4% of the theoretical density) in BaTiO₃ sheet was achieved with a solid content 40 vol.%. After sintering at 1200 °C for 2 h a final density of 95% is reached.     

The influence of solid loading in suspensions of a submicrometric alumina powder on green and sintered pressure filtrated samples

The present work deals with preparation of stable suspensions of a submicrometre alumina powder with different contents of solid for pressure filtration. The optimum dispersant content (2.2 wt.% of Darvan C-N) was determined by sedimentation tests and viscosity measurements. By modification of the solid loading and dispersant content two kinds of aggregation were observed. One type of aggregates is related to the use of excessive solid loading in suspension. In samples prepared from these suspensions only minor effect on sintered microstructure was observed, which increased with increasing volume fraction of hard aggregates. In case of excess dispersant addition weak aggregates formed as the result of depletion flocculation. Weak aggregates had stronger negative effect on green microstructure, with consequent negative impact on sinterability.     

Aqueous and Nonaqueous Colloidal Processing of Difficult‐to‐Densify Ceramics: Suspension Rheology and Particle Packing

Aqueous and nonaqueous colloidal processing of zirconium diboride (ZrB₂) and boron carbide (B₄C) has been investigated. The aqueous and nonaqueous ZrB₂ and B₄C suspension formulations have been optimized. The suspensions were cast into green bodies using slip casting. The correlation between the state of dispersion with the rheological properties of the suspensions and the resulting packing density was observed in both aqueous and nonaqueous processing. The attractive interactions between powder particles in water were difficult to overcome with electrical double layer or electrosteric repulsion. Reasonably low viscosity aqueous ZrB₂ suspensions up to 45 vol% solids could be prepared. It was not possible to produce low viscosity (viscosity below 1 Pa·s at shear rate of 100 s^?1) aqueous B₄C suspensions with solid content above 30 vol%. Slip casting of the weakly aggregated ZrB₂ suspensions resulted in low packing densities (~55% relative density) of the green bodies. On the other hand, dispersion of powder particles in nonaqueous media (cyclohexane and dodecane) enabled suspensions with lower viscosities and a higher maximum solid concentration (up to 50 vol%) to be prepared. The well‐dispersed nonaqueous suspensions promoted an efficient particle packing, resulting in higher green densities (64% and 62% relative density for ZrB₂ and B₄C, respectively) compared to aqueous processing. The significantly high green densities are promising to allow densification of the materials at lower sintering temperature.     

Dense m-Li2ZrO3 formed by aqueous slip casting technique: Colloidal and rheological characterization

An aqueous colloidal processing method was proposed to prepare m-Li₂ZrO₃ bodies, with high green density and a homogenous microstructure, employing a pressureless forming technique. For this purpose, the preparation conditions of m-Li₂ZrO₃ aqueous suspensions were optimized considering colloidal processing variables, such as milling time (0–40 min), dispersant concentration (1–10 wt% of the solids content) and maximum solid loading (41–74 wt%). Particle size distributions and steady-state flow curves of the slips were analyzed, together with phase composition and microstructure of the ceramic bodies. The results show that after planetary ball milling for 30 min, the aqueous suspension with 63.1 wt% of m-Li₂ZrO₃, and a dispersant content equal to 10 wt% of the solid loading, yielded green bodies with bulk densities close to 66% TD by slip casting. Then, after the heat treatment process at 1100 °C for 12 h, bulk densities close to 88% TD were achieved. It was found that density values and microstructure of the green and sintered products bear a direct relationship to the particle size and the consistency of the slips.     

Rheological characteristics of alumina platelet–Hydroxyapatite composite suspensions

The rheological behaviour of aqueous suspensions of alumina platelet–hydroxyapatite mixtures for slip casting was investigated. The stabilisation of the suspensions requires the use of a dispersing agent and the breakdown of powder agglomerates. The addition of alumina platelets to the HAP powder does not modify significantly the behaviour of the suspensions which remains always quasi-Newtonian. Nevertheless, this behaviour becomes shear-thinning at low shear rates for high alumina contents when platelets of small size are used. The viscosity increases at low shear rates with the increase of small platelets content. These modifications are assumed to result from orientation phenomena of alumina disks under shear stress in the direction of flowing. The disk-shaped morphology of alumina is detrimental to the preparation of high density green composites. Suspensions containing between 50 and 70 wt% of powder are castable but the best rearrangement of solid particles during the casting process is reached for suspensions containing 65 wt% of powder.     

Dispersion and densification of nano Si–(Al)–C powder with amorphous/nanocrystalline bimodal microstructure

The dispersion behavior and densification of nano Si–(Al)–C powder with amorphous/nanocrystalline bimodal microstructure were investigated. The Si–C powders synthesized by a mechanical alloying (MA) process had a near‐spherical shape with an average particle size of 170 nm. A solid loading of 62 vol% was achieved using polyethyleneimine (PEI) as a dispersant. The optimum dispersant amount was 1 wt% based on zeta potential, sedimentation, and viscosity analysis data. The high zeta potential value (73 mV) compared with that of the commercially available SiC (65 mV) was caused by modified surface properties and consequent promotion of the cationic dispersant adsorption. A Si–Al–C slurry containing 6.5 wt% of sintering additives with a solid loading of 60 vol% was also prepared. The relative density of the dried Si–Al–C slurry was 63.3% without additional compaction, which could be densified at 1650°C at a pressure of 20 MPa using a spark plasma sintering furnace.     

Physical characteristics and sintering behavior of ultrafine zirconia–ceria powders

Ultrafine zirconia–12 mol% ceria powders have been prepared by the coprecipitation technique. The azeotropic distillation with n-butanol has been carried out to ensure complete elimination of the residual water in the precipitate. This procedure has proved to be quite effective in preventing the formation of agglomerates, which are responsible for inhomogeneities in the sintered microstructure, and for non-densification at low temperatures. The crystallization of the solid solution occurs at 430 °C as determined by thermal analyses. The specific surface of the calcined powder is 127.9 m² g⁻¹ and the pore size distribution exhibits only a maximum at approximately 9 nm. Total shrinkage of the compacted powder reached 30% at 1200 °C. Sintered specimens show six bands characteristics of the tetragonal phase in the Raman spectrum. Specimens with apparent densities >95% of the theoretical density and average grain size of 230–400 nm were obtained after sintering at 1200 °C.     

Stabilization of Nanoalumina Colloidal Slips

The processing of nanosized powders to produce dense components is a difficult task, mainly due to the strong agglomeration of nanoparticles. In this work, deagglomeration studies were carried out on sol–gel‐derived γ‐alumina suspensions through the addition of dispersant or dispersant in combination with ethylene glycol as binder and the proper wet ball‐milling. For this purpose, zeta‐potential, viscosity, and sedimentation studies were carried out, whereas dilatometric studies accompanied by XRD analyses were performed on the powders derived from the most stable suspensions. Sintering studies followed and the as received ceramics were evaluated by SEM. The optimum stabilization was achieved through the synergistic addition of 2.75 mg/g ammonium polymethacrylate with 1 wt% ethylene glycol. The respective powder, although it indicates a shift of the sintering start to higher temperature, leads to the densest ceramic with the finest (500 nm mean grain size) and the most homogeneous microstructure.     

Foaming inhibition of SiC-containing porcelain ceramics by using Si powders during sintering

Porcelain green bodies were prepared using porcelain stoneware tile powder as the major raw material, with silicon carbide (SiC) and Si powders as additives. These were fired at 1000–1200 °C. The effects of Si powder addition on the microstructure, crystalline phases, and relative density of SiC-containing porcelain bodies were systematically investigated, and the related mechanism was also discussed in detail. The results show that even with the addition of a small amount of Si powder, the foaming degree of the porcelain bodies containing SiC with particle size and content in a wide range can be effectively inhibited. In particular, this effect becomes more pronounced as the Si powder particle size is reduced. It is believed that this work will have important scientific value for the oxidation protection of SiC and the foaming inhibition during the direct recycling of large amounts of polishing porcelain tile residues in the world.     

Effect of atomization methods on the size and morphology of Gd0.1Ce0.9O2−δ powder synthesized by aerosol flame synthesis

Nano-sized gadolinium doped ceria (GDC) powders were successfully synthesized by aerosol flame deposition (AFD) with two different atomization methods; ultrasonic and electrostatic atomization. The effect of the atomization method on the size and morphology of GDC particles were investigated. It was observed that the diameter range of the GDC small primary particles synthesized by the ultrasonic atomization method was 10–50 nm while with the electrostatic method was 5–25 nm. In addition, the size of primary large particle found to be decreased from 200 nm to 50 nm with increasing electric field up to 15 kV. The GDC powder synthesized by the electrostatic atomization exhibited reduced crystallite size, particle size, and similar electrical conductivity compared to GDC powder synthesized by ultrasonic atomization. This work demonstrated the benefits of the electrostatic atomization for producing smaller-sized GDC nanopowders for the application in intermediate temperature solid oxide fuel cells.     

Chemical Synthesis,Sintering and Piezoelectric Properties of Ba0.85Ca0.15 Zr0.1Ti0.9O3 Lead‐Free Ceramics

The preparation of Ba_0.85Ca_0.15 Zr_0.1Ti_0.9O₃ (BCZT) powders by wet chemical methods has been investigated, and the powders used to explore relationships between the microstructure and piezoelectric properties (d₃₃ coefficient) of sintered BCZT ceramics. Sol–gel synthesis has been shown to be a successful method for the preparation of BCZT nanopowders with a pure tetragonal perovskite phase structure, specific surface area up to 21.8 m²/g and a mean particle size of 48 nm. These powders were suitable for the fabrication of dense BCZT ceramics with fine‐grain microstructures. The ceramics with the highest density of 95% theoretical density (TD) and grain size of 1.3 μm were prepared by uniaxial pressing followed by a two‐step sintering approach which contributed to the refinement of the BCTZ microstructure. A decrease in the grain size to 0.8–0.9 μm was achieved when samples were prepared using cold isostatic pressing. Using various sintering schedules, BCZT ceramics with broad range of grain sizes (0.8–60.5 μm) were prepared. The highest d₃₃ = 410.8 ± 13.2 pC/N was exhibited by ceramics prepared from sol–gel powder sintered at 1425°C, with the relative density of 89.6%TD and grain size of 36 μm.     

纳米钛酸钡粉体的分散及水基悬浮体制备

通过测定超重力法制备的纳米钛酸钡悬浮体的Zeta电位和团粒尺寸分布,确定了纳米BaTiO3在水中稳定分散的基本条件,制备了不同体积分数的悬浮体并研究了其流变学特性. 该纳米BaTiO3在水中的等电点约为pH 2.8,加入分散剂PAA-NH4后,颗粒零电点向更低pH值移动;当分散剂用量为干粉量的1.2%(w)时,悬浮体中平均团粒尺寸最小,分散效果最佳. FT-IR分析证明颗粒表面上PAA-NH4的吸附为物理化学吸附. 制备了体积分数高达45%的纳米BaTiO3悬浮体,其流变特性表现为剪切变薄行为,流延成型的BaTiO3陶瓷生坯片具有较高的相对密度(55.4%).     

Gelcasting of alumina suspensions containing nanoparticles with glycerol monoacrylate

An acrylic monomer of low toxicity containing two hydroxyl groups has been synthesized and used for gelcasting in water. The results have been compared to those achieved with the use of a commercially available monomer (2-hydroxyethyl acrylate). Due to the chemical structure of the synthesized monomer, no addition of the crosslinking agent was necessary for gelation and similar results in terms of rheology of suspensions, density and microstructure of the bodies were obtained with respect to those obtained with the commercial monomer. However, higher time for gelation was observed.Two alumina powders with very different particle sizes were used in this study: a commercial submicron-sized powder (d₅₀ = 0.35 μm) and a nanometer-sized alumina obtained by freeze-drying from aluminum sulphate solutions. The rheological behavior of concentrated suspensions was studied in order to establish their stability and to analyse the effect of the different monomers used in the process. Once the suspensions were optimized, the influence of the size of the powder on the gelation process was studied. The sintered density of submicrometer-sized alumina was higher (99%) than that measured when the bimodal suspension was used due to the difficulty to obtain highly concentrated suspensions from nanometric powder.     

Direct coagulation casting of silicon nitride suspension via a dispersant reaction method

A direct coagulation casting method for silicon nitride suspension via dispersant reaction was reported. Tetramethylammonium hydroxide (TMAOH) was used as dispersant to prepare silicon nitride suspension with high solid loading and low viscosity. Influences of TMAOH and pH value on the dispersion of silicon nitride powder were investigated. Glycerol diacetate (GDA) was used to coagulate the silicon nitride suspension. Influences of the concentration of glycerol diacetate on the viscosity and pH value of the suspension were investigated. It was indicated that high viscosity sufficient to coagulate the suspension was achieved by adding 1.0–2.0 vol% glycerol diacetate at 40–70 °C. The coagulation mechanism was proposed that the silicon nitride suspension was destabilized by dispersant reacting with acetic acid which was hydrolyzed from glycerol diacetate at elevated temperature. Coagulated samples could be demolded without deformation by treating 50 vol% silicon nitride suspensions with 0.2 wt% tetramethylammonium hydroxide and 1.0–2.0 vol% glycerol diacetate at different temperatures. Dense silicon nitride ceramics with relative density above 98.8% had been prepared by this method using glycerol diacetate as coagulating agent sintered by different methods.     

Preparation and rheology of biochar, lignite char and coal slurry fuels

Slurries of an Oil Mallee biomass char, a low rank coal char and sub-bituminous coals were prepared by mixing the finely milled solids with water and a range of additives including polyacrylic acid, charged copolymers D101 and D102, and sucrose. The resultant slurries were subjected to rheological characterizations including apparent viscosity and yield stress. The effect of the solid type, particle size distribution, and the additives on preparation of highly loaded slurries with the desired rheological behaviour were systematically examined in terms of apparent viscosity and yield stress. The additives D101 and D102 were found to be most effective in producing highly loaded suspensions with a low apparent viscosity and yield stress. Particle size distributions were manipulated to improve the solid loading. Suspensions produced by powder mixture containing equal weight precent of 30 min and 1 min milled powders gave a broad size distribution and is very effective in increasing the solid loading in slurries. The significant improvement in the solid loading was shown to be achieved by (i) increasing particle packing density via size distribution control and (ii) minimising the strength and number of the interactions between colloidal particles. The maximum solid loading of flowable (or relatively low apparent viscosity) slurries achieved with the Oil Mallee char is ∼40 wt.%, with the sub-bituminous coals 56-63 wt.%, and with the lignite char ∼65 wt.%. This study has shown that for low rank coals such as lignite, thermal and densification treatment is essential to achieve the solid loading of slurry fuel.     

Characterization of rheological properties of colloidal zirconia

Dynamic viscosity of aqueous suspensions of nanosized zirconia (ZrO₂) have been studied for the low volume fraction range. The specific surface area of dry powder was determined from the BET method. The zeta potential of zirconia particles as a function of pH was measured by the microelectrophoretic method. The isoelectric point found in this way was 4.7. The particle density in aqueous suspensions was found by the dilution method. The dynamic viscosity of suspensions was measured by using a capillary viscometer that eliminated the sedimentation effects. Experimental data showed that for dilute zirconia suspension, the relative viscosity increased more rapidly with the volume fraction than that the Einstein formula predicts. This allowed one to calculate the specific hydrodynamic volume of particles in the suspensions and their apparent density. It was found that particles forming zirconia suspensions were composed of aggregates having porosity of 40–50%. The size of the primary particles forming these aggregates was 0.2 μm that agrees well with the BET specific surface data. The influence of an anionic polyelectrolyte:polysodium 4-styrenesulfonate (PSS) on zirconia suspension viscosity also was studied. First the PSS viscosity alone was measured as a function of its volume fraction for various ionic strength of the solutions. The data were interpreted in terms of the flexible rod model of the polyelectrolyte. Then, the viscosity of ZrO₂ in PSS solutions of fixed concentration was measured as a function of the concentration of zirconia. It was revealed that the viscosity of the mixtures was proportional to the product of the zirconia and polyelectrolyte viscosities taken separately.     

Effects of Particle Size on Soft Lithography Process,the Green and Sintered Micro Alumina Parts

Alumina micro parts were fabricated using powders in particle sizes of 1 μm, 2.0 μm, and 12.0 μm. The effects of particle size on soft lithography process, green bodies, and sintered characteristics were investigated, including process parameters affecting homogeneous and smooth surface. The effects of particle size were analyzed through suspensions, green, and sintered properties. It was found that the stability of suspensions, sintered density, Vickers micro hardness, surface roughness and edges resolution are significantly improved with the decrease in particle size. On the other hand, suspension viscosity, green density and shrinkage are degraded with the use of finer particles.