Yield Stress Measurement of Silicon Nitride Suspensions

Yield stress values of silicon nitride suspensions were measured via a novel slotted plate device and a constant stress rheometer and the results were compared. Test platform velocity, associated with the slotted plate method, was found to have a substantial effect on dynamic yield stress but not on static yield stress. The effects of suspension concentration and temperature on yield stress values were investigated. Yield stress measurements on mixtures of silicon nitride and alumina particles, as well as creep tests were performed.     

Nonaqueous Aluminum Nitride Extrusion: I, Die-Entry Flow Behavior

Simultaneous orifice and capillary rheometry at 160°C was used to determine flow parameters of aluminum nitride extrudates plasticized with a polyethylene–mineral-oil binder. Data were analyzed using the Benbow model for square-entry ram extrusion. Variables included the powder concentration, polymer molecular weight and concentration, and lubricant concentration. Die-entry rheology was explained in terms of the mean interparticle separation, polymer spatial requirements, and lubricant adsorption. Particles and polymer were observed to not pack independently. The yield stress of the body increased rapidly as the solids loading approached the critical volume limit of extrudability. An increase in polymer molecular weight or partial decrease of adsorbed lubricant increased the yield stress of the body and produced a satisfactory extrudate.     

Effect of Acid Cleaning and Calcination on Rheological Properties of Concentrated Aqueous Suspensions of Silicon Nitride Powder

The powder characteristics of two types of Si₃N₄ (referred to as FD1 and FD2), as well as the rheological properties of their aqueous suspensions, were studied in this paper. There are distinctive differences in size distribution, soluble counterions, and surface groups. Highly concentrated aqueous slurries could not be prepared from these two as-received powders. Acid cleaning and calcination improved the solids loading of their aqueous slurries, but the improvement varied with the powder. For the as-received FD1 powder, poor dispersibility was caused by high-valence counterions, which can be eliminated through acid-cleaning. However, for the as-received FD2 powder, it was the surface group of amine structures and carbon-hydrogen bonding that limited the dispersibility. The calcination of FD2 can remove the amine structure and carbon-hydrogen bonding and improve the slurry's rheological properties almost perfectly. For acid-cleaned and calcined FD1, and calcined FD2, the solids loading of their aqueous suspensions reached 50 vol% with a viscosity below 300 mPa·s.     

In Situ Rheological Investigation of the Coagulation in Aqueous Alumina Suspensions

Electrostatically stabilized alumina suspensions can be destabilized by the enzyme-catalyzed decomposition of urea (direct coagulation casting). Depending on the conditions, this reaction can shift the pH of a suspension to the buffer pH of the reaction products or increase the ionic strength at the buffer pH. The coagulation for both mechanisms was investigated using in situ rheological measurements. Using a vane tool in oscillation mode, the measuring conditions were optimized to find a reasonable method for time-dependent measurements. Constant parameters (stress or strain) proved to be unsuitable, because the linear viscoelastic region shifted considerably during the coagulation. Furthermore, the gel structure produced on coagulation via increase of ionic strength (Δ I ) was very sensitive to the oscillation. Therefore, for long-time experiments, a short continuous measurement with a low strain was followed by amplitude sweeps with increased intervals to determine the linear values of G ' and G ". In this way, the increase of the moduli G ' and G " could be followed for longer times, and it was possible to demonstrate two results. First, the final G ' of the network was about 10 times higher for Δ I -coagulated material than for suspensions coagulated via pH shift (ΔpH). Second, particle rearrangement processes took place in Δ I -coagulated networks even after the chemical changes were finished, whereas ΔpH-coagulated samples were "frozen-in" when approaching the isoelectric point and showed no further physical changes afterward.     

Aqueous Gel-Forming of Silicon Nitride Using Carrageenans

Much effort has been devoted recently to the development of near-net-shaping processes in water. Agarose has been demonstrated to be a suitable gelling agent for aqueous forming. However, its high cost and the difficulties in controlling the rheological properties have restricted large-scale applications. In this work a novel gelling binder, namely carrageenan, is proposed as a low-cost and high-gel-strength additive for gel-forming ceramic powders. The capability to obtain silicon nitride parts by carrageenan gelation is described. Aqueous silicon nitride slips are prepared at pH >11 to a solids content of 70 wt% using tetramethylammonium hydroxide as a dispersant. Dissolution and gelation of carrageenan are studied by continuous measurements of viscosity with temperature for solutions prepared at different pH values. The final injection slips prepared by mixing at <60°C the previously heated suspension and the carrageenan solution are rheologically characterized also. After the blend is injected into cooled nonporous molds, gelling occurs in a few seconds and samples can be dried in air for 24–48 h. Green densities of 52% of theoretical are obtained.     

Cement Composition Effects on the Rheological Property Evolution in Concentrated Cement–Polyelectrolyte Suspensions

We have studied the rheological property evolution and hydration behavior of white and ordinary portland cement (type I) pastes and concentrated cement–polyelectrolyte suspensions. Cement composition had a marked effect on the elastic property evolution ( G '( t )) and hydration behavior of these suspensions in the presence of poly(acrylic acid)/poly(ethylene oxide) copolymer (PAA/PEO), even though their affinity to adsorb such species was nearly identical. Both white and ordinary portland cement pastes exhibited G '₀ values of ∼10⁴ Pa and fully reversible G '( t ) behavior until the onset of the acceleratory period ( t = 2 h), where the pastes stiffened irreversibly. In contrast, cement–PAA/PEO suspensions exhibited G '₀ values of ∼1 Pa and G '( t ) behavior comprised of both reversible and irreversible features. Interestingly, ordinary portland cement–PAA/PEO suspensions experienced a gel-to-fluid transition on high shear mixing at short hydration times (<1 h), and the particle network did not rebuild until ∼24 h of hydration. In sharp contrast, white portland cement–PAA/PEO suspensions remained weakly gelled throughout the initial stage of hydration even after high shear mixing. At longer hydration times (>1 h), both cement–PAA/PEO suspensions exhibited G ' _i ( t ) ∼ exp( t /τ_c) with τ_c values of 5.6 and 1.3 h for ordinary and white portland cement, respectively. Our observations suggest that hydration phenomena impact interparticle forces during early stage hydration and, ultimately, lead to initial setting through the formation of solid bridges at the contact points between particles within the gelled network.     

Comb Polymer Architecture Effects on the Rheological Property Evolution of Concentrated Cement Suspensions

We have studied the rheological behavior of concentrated cement suspensions in the absence and presence of comb polymers comprised of a polyacrylic acid (PAA) backbone and charge-neutral, poly(ethylene oxide) (PEO) teeth. These species possessed a uniform backbone molecular weight and graft density, with varying teeth molecular weight. Both PAA, a linear polyelectrolyte, and PAA/PEO comb polymers imparted initial stability to concentrated cement suspensions above a critical weight fraction, w * of 4 mg/(g of cement). Cement–PAA suspensions, however, set prematurely. Their rapid, irreversible stiffening stemmed from deleterious interactions between PAA and multivalent counterions in solution. Interestingly, the presence of PEO teeth comprised of only a few monomer units in length mitigated such interactions. The rheological property evolution of concentrated cement–PAA/PEO suspensions exhibited complex behavior ranging from the reversible gel-like response observed at short teeth lengths to a remarkable gel-to-fluid transition observed during the deceleratory period for systems comprised of longer PEO teeth. At longer hydration times, all cement–PAA/PEO suspensions exhibited initial elastic modulus values, G_i '∼ exp( t /τ_c) before the onset of the acceleratory period, followed by initial set. Their characteristic hydration time, τ_c, and set time depended strongly on the concentration of "free" carboxylic acid groups [COO⁻] arising from non-adsorbed polyelectrolyte species in solution.     

氮化硅浆料的胶体特性研究

本文研究了Si3N4浆料的胶体特性,结果表明:Si3N4悬浮粒子的等电点(isoelectric point,简称IEP)在pH=4.2处.分散介质的离子强度影响Si3N4粒子的Zeta电位.分散剂的引入有效地提高Si3N4粒子的Zeta电位,并引起IEP的位移.粉体经不同工艺的预处理后IEP均发生不同程度的位移.X光电子能谱(XPS)分析表面组成发现其IEP的位移与Si3N4粉体表面的氧化程度有关.同时,对Si3N4浆料在不同条件下的分散性进行了考察,表明其分散性与胶体特性具有很好的一致性.     

Effect of Surface-Active Substances on the Rheological Properties of Silicon Carbide Suspensions in Paraffin

In this paper, the possibility of stabilization of SiC suspensions in paraffin (hot-molding slips) was investigated from the colloid science point of view. By considering the surface properties of finely dispersed silicon carbide, surface-active agents (fatty amine and alkylsuccinimide) which are suitable for surface modification by chemical adsorption on SiC were selected. Adsorption of fatty amines and alkylsuccinimide was carried out in model experiments in chloroform. Increasing the length of the carbon–hydrogen chain caused the adsorption to decrease, and the adsorption area of one molecule in the saturated adsorption layer to increase. The stabilizing effect of surface-active agents resulted in improved flow behavior of hot-molding slips. The efficiency of surface-active agents increased with increased adsorption layer thickness. In highly concentrated SiC hot-molding slips, a combination of alkylsuccinimide and fatty amine proved to be very efficient. This synergistic effect of long- and short-chained surface-active agents is discussed in terms of an adsorption layer model.     

Preparation of Mesoporous Silicon Nitride via a Nonaqueous Sol–Gel Route

A silicon diimide gel Si(NH) _x (NH₂) _y (NMe₂) _z was prepared by an acid-catalyzed ammonolysis of tris(dimethylamino)silylamine. Pyrolysis of the gel at 1000°C under NH₃ flow led to the formation of an amorphous silicon nitride material without carbon contamination. All of the gel and pyrolyzed products exhibited a mesoporous structure with a high surface area and narrow pore-size distribution. The effective surface area of the pyrolyzed silicon nitride residues decreases with increasing temperature, but the heating rate during pyrolysis has little influence on the surface area and pore-size distribution of the final mesoporous ceramic Si₃N₄ products because of the highly cross-linked structures of the precursor silicon diimide gel.     

Si3N4及其复合材料强韧化研究进展

简述了氮化硅陶瓷的结构、性能和制备工艺，并分别通过自增韧补强、纤维／晶须强韧化、层状结构强韧化、相变强韧化以及颗粒弥散强韧化等方法对氮化硅陶瓷的强韧化研究进行了分类叙述。     

Gelation, Consolidation, and Rheological Properties of Boehmite-Coated Silicon Carbide Suspensions

We have studied the gelation, consolidation, and rheological properties of boehmite-coated SiC suspensions. A boehmite-coated SiC suspension consists of SiC particles covered with a boehmite layer of a few nanometers in thickness in the suspension. Similar to boehmite suspensions, the boehmite-coated SiC suspension can gel over time. The gelation, as well as the rheological behavior of the boehmite-coated SiC suspension with respect to pH, is shown to be similar to that of a boehmite suspension. However, because of the particle-size difference, a boehmite-coated SiC suspension gels more slowly than suspensions of smaller boehmite particles. The boehmite coating improves the consolidation density of SiC, increasing the sediment density from 39 to 52 vol% and the centrifuged density from 50 to 60 vol%. It, also, makes the consolidation behavior of a boehmite-coated SiC suspension with respect to pH more consistent with the rheological behavior; i.e., lower suspension viscosity and storage modulus correlate with a higher consolidated density. In contrast, suspensions containing SiC particles partially covered with boehmite and individual boehmite particles in the suspensions show no improvement in the sediment density and no systematic correlation between the consolidation density and the rheological properties. This indicates that the complete coating of boehmite on the SiC particles is critical to the improvement in consolidation density.     

Rheological Behavior of Slurries and Consolidated Bodies Containing Mixed Silicon Nitride Networks

Two particle networks, each formulated with a different interparticle potential, were mixed to control the rheological properties of ceramic slurries and to develop claylike plasticity in consolidated bodies. A weakly attractive network, containing silicon nitride powder, alkylated with hexadecanol, was mixed with a second slurry containing flocculated (nonalkylated) silicon nitride powder. The elastic modulus and apparent yield stress of concentrated suspensions containing each constituent and their mixtures were found to increase with volume fraction according to a previously reported power law function (exponents of 4.8 and 3.75, respectively). Because of the large difference in the relative strengths of the two networks, the flocculated network overwhelmingly controlled the behavior of the mixed slurries when its volume fraction (relative to total solids) exceeded 0.30. Slurries were consolidated by pressure filtration, and the saturated bodies were tested in uniaxial compression. Bodies containing only alkylated powder packed to a high volume fraction and deformed at a low flow stress. The addition of small amounts of the flocculated network increased the flow stress to produce a body with rheological properties similar to clay.     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

Effects of Boehmite-Coating Thickness on the Consolidation and Rheological Properties of Boehmite-Coated SiC Suspensions

We examined the effect of the boehmite coating thickness on the rheology and consolidation of boehmite-coated SiC suspensions. The thickness of the boehmite coating on SiC was varied by adjusting the boehmite concentration relative to SiC. For boehmite concentrations less than 10 wt%, the coating thickness increased with increasing boehmite concentration. For boehmite concentrations higher than 10 wt%, the coating thickness saturated. Further increase in the boehmite concentration led to the presence of small boehmite particles in the suspensions. All boehmite-coated suspensions gelled near their isoelectric points and the storage moduli of the gels with respect to pH exhibited a maximum near the isoelectric points. Below 10 wt% boehmite, the suspensions had very few small boehmite particles. The maximum storage modulus, G ^'_0,max, of the boehmite-coated SiC gel decreased with increasing coating thickness, t , as G ^'_0,max∝ t ⁻², in good agreement with our earlier theoretical prediction. Meanwhile, the maximum sedimentation densities, φ_max, of the coated suspensions occurred at around pH ∼ 4.0 and increased with increasing coating thickness from under φ_max= 25 vol% with 1 wt% boehmite to above φ_max= 65 vol% with 10 wt% boehmite due to increased zeta potential with increasing coating thickness. Above 10 wt% boehmite, the excess boehmite particles in the suspension increased the maximum suspension storage modulus, G ^'_0,max, and decreased the maximum sedimentation density, φ_max.     

Silicon Nitride Colloidal Probe Measurements: Interparticle Forces and the Role of Surface-Segment Interactions in Poly(acrylic acid) Adsorption from Aqueous Solution

Direct measurements of forces between silicon nitride surfaces in the presence of poly(acrylic acid) (PAA) are presented. The force-distance curves were obtained at pH > pH_iep with an atomic force microscopy (AFM) colloidal-probe technique using a novel spherical silicon nitride probe attached to the AFM cantilever. We found that PAA adsorbs onto the negatively charged silicon nitride surface, which results in an increased repulsive surface potential. The steric contribution to the interparticle repulsion is small and the layer conformation remains flat even at high surface potentials or high ionic strength. The general features of the stabilization of ceramic powders with PAA are discussed; we suggest that PAA adsorbs onto silicon nitride by sequential adsorption of neighboring segments ("zipping"), which results in a flat conformation. In contrast, the long-range steric force found in the ZrO₂/PAA system at pH > pH_iep arises because the stretched equilibrium bulk conformation of the highly charged polymer is preserved via the formation of strong, irreversible surface-segment bonds on adsorption.     

Rheological Property Evolution in Concentrated Cement-Polyelectrolyte Suspensions

We have studied the rheological property evolution and hydration behavior of pure white portland cement (Type I) pastes and concentrated cement-polyelectrolyte suspensions. Polyelectrolyte species have a marked effect on the initial stability, elastic property evolution ( G '( t )), and hydration behavior of this cement system. Pure cement pastes exhibited an initial G ' value of ∼10⁴ Pa and fully reversible G '( t ) behavior until the onset of the acceleratory period ( t ∼ 2 h), where the pastes stiffened irreversibly. In contrast, cement-polyelectrolyte suspensions exhibited initial G ' values of ∼1 Pa and G '( t ) behavior comprised of both reversible and irreversible features. Their initial G ' values, measured after disrupting the particle network under high shear conditions, grew exponentially with hydration time, where G _i'= G _i,0' exp( t /τ_c) and τ_c corresponds to the characteristic hydration time determined from calorimetry measurements. Our observations of these cement-polyelectrolyte systems suggest that hydration phenomena impact interparticle forces during early stage hydration and, ultimately, lead to initial setting through the formation of solid bridges at the contact points between particles within the gelled network.     

Pulsed Electric Current Sintering of Silicon Nitride

Pulsed electric current sintering (PECS) has been used to densify α-Si₃N₄ powder doped with oxide additives of Y₂O₃ and Al₂O₃. A full density (>99%) was achieved with virtually no transformation to β-phase, resulting in a microstructure with fine equiaxed grains. With further holding at the sintering temperature, the α-to-β phase transformation took place, concurrent with an exaggerated grain growth of a limited number of elongated β-grains in a fine-grained matrix, leading to a distinct bimodal grain size distribution. The average grain size was found to obey a cubic growth law, indicating that the growth is diffusion-controlled. In contrast, the densification by hot pressing was accompanied by a significant degree of the phase transformation, and the subsequent grain growth gave a broad normal size distribution. The apparent activation energy for the phase transformation was as high as 1000 kJ/mol for PECS, almost twice the value for hot pressing (∼500 kJ/mol), thereby causing the retention of α-phase during the densification by PECS.     

Machinability of Silicon Nitride/Boron Nitride Nanocomposites

The machinability and deformation mechanism of Si₃N₄/BN nanocomposites were investigated in the present work. The fracture strength of Si₃N₄/BN microcomposites remarkably decreased with increased hexagonal graphitic boron nitride ( h -BN) content, although machinability was somewhat improved. However, the nanocomposites fabricated using the chemical method simultaneously had high fracture strength and good machinability. Hertzian contact tests were performed to clarify the deformation behavior by mechanical shock. As a result of this test, the damage of the monolithic Si₃N₄ and Si₃N₄/BN microcomposites indicated a classical Hertzian cone fracture and many large cracks, whereas the damage observed in the nanocomposites appeared to be quasi-plastic deformation.