Effect of Polyethylenimine on Hydrolysis and Dispersion Properties of Aqueous Si3N4 Suspensions

The roles of polyethylenimine (PEI) in the hydrolysis and dispersion properties of aqueous Si₃N₄ suspensions were studied in terms of the hydrolysis, adsorption, electrokinetic, and rheological measurements. It was found that the pH change of the suspensions in the acidic environment could be minimized in the presence of ≥0.5 dwb% PEI. The ammonia and oxygen measurements suggest that this phenomenon is primarily attributed to the buffer mechanism generated by the ionized PEI, instead of the protection mechanism. The constant pH enables the suspensions to retain a better stability with time at acidic pH. The adsorption of PEI on Si₃N₄ is a high-affinity type at highly basic pH, but is a low-affinity type at acidic pH. As the PEI amount increases, the adsorption shifts the isoelectric point (IEP) of Si₃N₄ from pH 5.9 to pH ∼11 until complete coverage is attained. The stability of Si₃N₄ suspensions is found to depend strongly on the saturated adsorption of PEI, which is as a function of the pH and PEI amount. Once the saturated adsorption limit is reached, the excess free PEI molecules become more detrimental to the stability with increased solid loading. The stabilization mechanisms of Si₃N₄ suspensions by PEI were discussed in detail.     

Phase Equilibria in the System Na2SiO3-Li2SiO3-SiO2

Ternary phase relations have been studied and several modifications made to Kracek's phase equilibrium diagram. These include location of the primary phase fields of Na₆Si₈O₁₉ and Li₂Si₂O₅. Metastable phases and polymorphs were often encountered, notably a primary phase, δ-Na₂Si₂O₅, and a new polymorph of Li₂Si₂O₅.     

The System Si3N4-SiO2-Y2O3

Subsolidus phase relations were established in the system Si₃N₄-SiO₂-Y₂O₃. Four ternary compounds were confirmed, with compositions of Y₄Si₂O₇N₂, Y₂Si₃O₃N₄, YSiO₂N, and Y₁₀(SiO₄)₆N₂. The eutectic in the triangle Si₃N₄-Y₂Si₂O₇-Y₁₀(SiO₄)₆N₂ melts at 1500°C and that in the triangle Si₂N₂O-SiO₂-Y₂Si₂O₇ at 1550°C. The eutectic temperature of the Si₃N₄-Y₂Si₂O₇ join was ∼ 1520°C.     

Phase Relations in the System Al2O3─Ce2Si2O7 in the Temperature Range 900° to 1925°C in Inert Atmosphere

Equilibrium relationships in the system Al₂O₃-Ce₂Si₂O₇ in inert atmosphere have been investigated in the temperature range 900° to 1925°C. A simple eutectic reaction was found at 1375°C and 51 mol% Ce₂Si₂O₇. A high-low polymorphic transformation in Ce₂Si₂O₇ was observed at 1274°C. New XRD patterns are suggested for both polymorphs of cerium pyrosilicate. The melting point of Ce₂Si₂O₇ was found to be 1788°C. A value for ΔH°_m,Ce2Si2O7 of 36.81 kJ/mol was calculated from the initial slope of the experimentally determined liquidus in equilibrium with the pyrosilicate phase.     

Kinetics and Mechanism of Hot Corrosion of γ-Y2Si2O7 in Thin-Film Na2SO4 Molten Salt

γ-Y₂Si₂O₇ is a promising candidate material both for high-temperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9 × 10⁻⁶/K, 200°–1300°C), and low thermal conductivity (<3.0 W/m·K above 300°C). The hot corrosion behavior of γ-Y₂Si₂O₇ in thin-film molten Na₂SO₄ at 850°–1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y₂Si₂O₇ exhibited good resistance against Na₂SO₄ molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na₂SO₄ and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y₂Si₂O₇ in Na₂SO₄ molten salt with flowing air was evaluated to be 255 kJ/mol.     

Improvement in Mechanical Properties of Powder-Processed MoSi2 by the Addition of Sc2O3 and Y2O3

Additions of 1-20 mol% Sc₂O₃ or Y₂O₃ to MoSi₂ eliminate glassy SiO₂, which improves mechanical properties at both ambient and high temperatures. In particular, only 1 mol% ScO₃ additions dramatically enhance three-point bending strength from 521 to 1081 MPa. Vickers hardness, Young's modulus, fracture toughness, and high-temperature strength are also improved by this low level of additive. The improvement of mechanical properties is attributed to the formation of crystalline silicates: Sc₂Si₂O₇, Y₂Si₂O₇, Y₂SiO₅, and Y₄Si₃O₁₂, which are analyzed by XRD, SEM-EDS, and TEM-EDS methods.     

Reaction-Formed Porous Yb4Si2N2O7 Materials with Uniform Open-Cell Network Structure

A novel porous Yb₄Si₂O₇N₂ material with uniform open-cell network structure was fabricated from the reaction between Si₃N₄, Yb₂O₃, and SiO₂. The formation of Yb₄Si₂O₇N₂ during heating was studied using X-ray diffractometry. The porous structure was characterized using scanning electron microscopy and mercury porosimeter. It is shown that the formation of Yb₄Si₂O₇N₂ phase starts at ∼1150°C and completes at 1350°C for 4 h, accompanied by the development of open-cell network structure. The necks between Yb₄Si₂O₇N₂ particles become much thicker with increasing temperature because of the coarsening of Yb₄Si₂O₇N₂ particles, thus leading to a uniform three-dimensional network structure. Furthermore, the pore size can be well controlled by adjusting reacting temperature and altering atmosphere.     

Dispersion Behavior of ZrB2 Powder in Aqueous Solution

Dispersion conditions of ZrB₂ powder in water were investigated using poly(ethyleneimine) (PEI) as a dispersant. Pulverization of ZrB₂ powder to submicrometer size was difficult and a substantial amount of large particles remained after an intensive planatery milling for 72 h. The isoelectric point (IEP) of ZrB₂ powder was measured to be pH 5.8 by electrophoresis, which shifted to pH 6.2 after milling. The application of PEI changed the IEP of the boride slurry to ∼pH 11. Well-dispersed aqueous ZrB₂ slurries with a high solid loading (up to 45 vol%) were fabricated at pH 6.5–7.5 by the application of 1.5 wt% PEI.     

Synthesis of Celsian (BaAl2Si2O8) from Solid Ba-Al-Al2O3-SiO2 Precursors: I, XRD and SEM/EDX Analyses of Phase Evolution

An intimate Ba-Al-Al₂O₃-SiO₂ powder mixture, produced by high-energy milling, was pressed to 3 mm thick cylinders (10 mm diameter) and hexagonal plates (6 mm edge-to-edge width). Heat treatments conducted from 300° to 1650°C in pure oxygen or air were used to transform these solid-metal/oxide precursors into BaAl₂Si₂O₈. Barium oxidation was completed, and a binary silicate compound, Ba₂SiO₄, had formed within 24 h at 300°C. After 72 h at 650°C, aluminum oxidation was completed, and an appreciable amount of BaAl₂O₄ had formed. Diffraction peaks consistent with hexagonal BaAl₂Si₂O₈, BaAl₂O₄, β-BaSiO₃, and possibly β-BaSi₂O₅ were detected after 24 h at 900°C. Diffraction peaks for BaAl₂O₄ and BaAl₂Si₂O₈ were observed after 35 h at 1200°C, although SEM analyses also revealed fine silicate particles. Further reaction of this silicate with BaAl₂O₄ at 1350° to 1650°C yielded a mixture of hexagonal and monoclinic BaAl₂Si₂O₈. The observed reaction path was compared to prior work with other inorganic precursors to BaAl₂Si₂O₈.     

Phase Equilibria and Crystallization of Melts in the System Na2O-BaO-SiO2

Phase-equilibrium studies of the liquidus surface of the Na₂O-BaO-SiO₂ system are presented. The system contains 5 ternary compounds, Na₂Ba₄Si₁₀O₂₅, Na₂Ba₄Si₂O₆, Na₂Ba₂Si₂O₇, X (probably Na₂Ba₁₈Si₂₈O₇₅), and Y (probably Na₂Ba₄₅Si₇₃O₁₉₂), all of which melt incongruently. Twenty-three liquidus invariant points, including 13 peritectics, 4 eutectics, and 6 thermal maxima, were located. Metastable crystallization reactions are commonly encountered, and some of the metastable equilibria are described.     

Surface Chemistry, Dispersion Behavior, and Slip Casting of Ti3AlC2 Suspensions

The surface chemistry and dispersion properties of aqueous Ti₃AlC₂ suspension were studied in terms of hydrolysis, adsorption, electrokinetic, and rheological measurements. The Ti₃AlC₂ particle had complex surface hydroxyl groups, such as ≡Ti–OH,=Al–OH, and −OTi–(OH)₂, etc. The surface charging of the Ti₃AlC₂ particle and the ion environment of suspensions were governed by these surface groups, which thus strongly influenced the stability of Ti₃AlC₂ suspensions. PAA dispersant was added into the Ti₃AlC₂ suspension to depress the hydrolysis of the surface groups by the adsorption protection mechanism and to increase the stability of the suspension by the steric effect. Ti₃AlC₂ suspensions with 2.0 dwb% PAA had an excellent stability at pH=∼5 and presented the characteristics of Newtonian fluid. Based on the well-dispersed suspension, dense Ti₃AlC₂ materials were obtained by slip casting and after pressureless sintering. This work provides a feasible forming method for the engineering applications of MAX-phase ceramics, wherein complex shapes, large dimensions, or controlled microstructures are needed.     

Crystallization and Seeding Effect in BaAl2Si2O8 Gels

Two sol-gel routes have been used to prepare celsian (BaAl₂Si₂O₈) precursors. The crystallization behaviors of unseeded gels and the gels seeded with 5 wt% feldspar, rutile, LiAISi₂O₂, and ZrO₂ crystals as well as SrAl₂Si₂O₈ gel have been studied using X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermal gravimetric and differential thermal analyses (TGA and DTA). It was found that metastable hexacelsian, rather than the preferred monoclinic celsian, was the major crystallization product in the two unseeded gels. Seeding largely enhanced the crystallization of monoclinic celsian, but the mechanisms involved were different for seeding with different crystals. SrAl₂Si₂O₈ gel and ZrO₂ crystals acted as normal heterogeneous centers and had little catalytic effect on monoclinic celsian crystallization. Feldspar and rutile crystals worked as epitaxial substrates for monoclinic celsian and produced pure monoclinic celsian in some temperature regions. LiAISi₃O₈ seeds lowered the glass transition temperature of the immediately adjacent gel matrix and led to the crystallization of pure monoclinic celsian.     

Phase Relations and Stability Studies in the Si3N4-SiO2-Y2O3 Pseudoternary System

Composite powders were hot-pressed to determine the phase relations in the Si₃N₄-SiO₂-Y₂O₃ pseudoternary system. Four quaternary compounds, Si₃Y₂O₃N₄, YSiO₂N, Y₁₀Si₇O₂₃N₄, and Y₄Si₂O₇N₂, were identified. Studies of polyphase and single-phase materials in this system showed that these 4 compounds are unstable under oxidizing conditions. Materials within the Si₃N₄-Si₂N₂O-Y₂Si₂O₇ compatibility triangle precluded the unstable compounds, and are extremely resistant to oxidation.     

Phase Equilibria in the System Si3N4-SiO2-BeO-Be3N2

The 1780°C isothermal section of the reciprocal quasiternary system Si₃N₄-SiO₂-BeO-Be₃N₂ was investigated by the X-ray analysis of hot-pressed samples. The equilibrium relations shown involve previously known compounds and 8 newly found compounds: Be₆Si³N₈, Be₁₁Si₅N₁₄, Be₅Si²N₆, Be₉Si₃N₁₀, Be₈SiO₄N₄, Be₆O₃N₂, Be₈O₅N₂, and Be₉O₆N₂. Large solid solubility occurs in β-Si₃N₄, BeSiN₂, Be₉Si₃N₁₀, Be₄SiN₄, and β-Be₃N₂. Solid solubility in β-Si₃N₄ extends toward Be₂SiO₄ and decreases with increasing temperature from 19 mol% at 1770°C to 11.5 mol% Be₂SiO₄ at 1880°C. A 4-phase isotherm, liquid +β-Si₃N₄ ( ss )Si₂ON₂+ BeO, exists at 1770°C.     

Phase Equilibria in High-Alumina Part of the System CaO–MgO–Al2O3–SiO2

Results are presented of a study of phase equilibria among crystalline and liquid phases in the quaternary system CaO–MgO-Al₂O₃–SiO₂ at Al₂O₃ contents greater than 35%. Equilibrium diagrams shown are for the five triangular joins CaAl₂Si₂O₃-Ca₂Al₂SiO₇-MgAl₂O₄, Ca₂Al₂SiO₇-MgAl₂O₄-Al₂O₃, CaAl₂Si₂O₈-MgO-Al₂O₃, CaAl₂Si₂O₈-Mg₂SiO₄-MgAl₂O₄, and CaAl₂Si₂O₈-MgO-Mg₂SiO₄. The composition and nature of the four quaternary peritectic points and the relationships of univariant lines and primary phase volumes are discussed.     

Microstructures and Properties of Three Composites of Alumina, Mullite, and Monoclinic SrAl2Si2O8

Three composites that were 96% alumina were mixed and uniaxially dry-pressed into bars and pellets; all had monoclinic SrAl₂Si₂O₈ as an intergranular phase. The diffraction patterns, microstructure, density, dielectric properties, strength, and toughness were measured. The first composition, which contained crystalline SrCO₃, Al₂O₃, and SiO₂, in a 1:1:2 molar ratio, as the 4% component, densified but was generally inferior to the second and third compositions, which contained strontium aluminosilicate (SrAl _x Si _y O _z , SAS) glass as the 4% component, in terms of mechanical properties, defects, and monoclinic SrAl₂Si₂O₈ transformation. The second composition, which lacked B₂O₃, was very tough and was comparable to commercial alumina, in terms of the dielectric constant. The third, which contained 0.068% of B₂O₃ that was dissolved in the SAS glass as a sintering aid, had high strength and toughness and no macroscopically visible defects. Mullite formed, in addition to monoclinic SrAl₂Si₂O₈ in all three composites. Alumina–monoclinic SrAl₂Si₂O₈ composites of the third composition had room-temperature properties that were comparable to commercial aluminas that contained 96% alumina and also had potential for mechanical and refractory applications.     

The System K2O-BaO-SiO2

Phase equilibrium studies of compound formation and liquidus and solidus surfaces of the system K₂O-BaO-SiO₂ are presented. The system contains 3 ternary compounds: K₄BaSi₃O₉, K₈BaSi₁₀O₂₅, and K₂Ba₃Si₈O₂₀. Both high and low polymorphs of the third have fields on the ternary liquidus surface. Solid solution with SiO₂ depresses the high-low inversion from 1030°C at K₂Ba₃Si₈O₂₀ to 835°C at 70.2 mol% SiO₂. Data for 20 liquidus invariant points were found; 8 are thermal maxima and 12 are eutectics or peritectics. The isofracts of quenched glasses were determined.     

γ-Y2Si2O7, a Machinable Silicate Ceramic: Mechanical Properties and Machinability

In this paper, the mechanical properties of bulk single-phase γ-Y₂Si₂O₇ ceramic are reported. γ-Y₂Si₂O₇ exhibits low shear modulus, excellent damage tolerance, and thus has a good machinability ready for metal working tools. To understand the underlying mechanism of machinability, drilling test, Hertzian contact test, and density functional theory (DFT) calculation are employed. Hertzian contact test demonstrates that γ-Y₂Si₂O₇ is a "quasi-plastic" ceramic and the intrinsically weak interfaces contribute to its machinability. Crystal structure characteristics and DFT calculations of γ-Y₂Si₂O₇ suggest that some weakly bonded planes, which involve Y–O bonds that can be easily broken, are the sources of the low shear deformation resistance and good machinability.     

Processing and Properties of in Situ-Reinforced α-SiAlONs Stabilized with Y2O3 and Lu2O3

α-SiAlONs with equiaxed and elongated microstructures stabilized with Y₂O₃ and Lu₂O₃ were produced by hot pressing, and the phase structure and room- and high-temperature mechanical properties were assessed. Additional liquid added to the starting composition in the form of 5 wt% rare-earth monosilicate resulted in the formation of elongated microstructures and improvements in room-temperature strength and fracture toughness. The elongated grain growth was promoted by the additional liquid phase, which crystallized to form a secondary grain-boundary phase thought to be J ' (Re₄Si_{2– x} Al _x O_{7+ x} N_{2– x} ). For the equiaxed and the elongated samples, those sintered with Lu₂O₃ showed higher hardness than the comparable Y₂O₃-sintered materials, and, at elevated temperature, the strength retention of the elongated Lu₂O₃ SiAlON was much higher than that of the Y₂O₃ sample, which was attributed to properties of the residual grain-boundary phase associated with the difference in the cationic radius of the stabilizing cation.     

Optimization of a Nanoparticle Suspension for Freeze Casting

Poly(acrylic acid) (PAA) dispersant concentration, suspension pH, and Al₂O₃ solids loading effects on PAA adsorption onto Al₂O₃ nanoparticles were studied; the stability and rheology of the Al₂O₃ nanoparticle suspensions were examined. The most desirable suspension conditions were 7.5–9.5 for pH and 2.00–2.25 wt% of Al₂O₃ for the PAA concentration. Electrical double-layer thickness and PAA adsorption layer thickness comparison showed that electrosteric stabilization was dominant. 45.0 vol% Al₂O₃ solids loading can be achieved for freeze casting. The maximum solids loading was predicted to be 50.7 vol%. The freeze-cast sample showed that pre-rest before freezing was critical for achieving desirable microstructures.