Further Consideration of Phases in the System Ba2SiO4–Ca2SiO4

The results of an investigation of the system Ba₂SiO₄–Ca₂SiO₄ by powder X-ray and electron diffraction suggest a greater complexity than supposed hitherto. The previously recognized phases α, α' h α' l , X, T, and the newly reported Y have room-temperature structures that are modulated distortions of hexagonal (or pseudohexagonal) parent structures. Each displays characteristic and distinctive modulations. The phases are more readily distinguished in this way than by their unit-cell dimensions and compositions which, for a given phase, can vary with bulk starting composition and thermal history.     

Hydration in the System Ca2SiO4–Ca3(PO4)2 at 90°C

Compositions along the Ca₂SiO₄–Ca₃(PO₄)₂ join were hydrated at 90°C. Mixtures containing 15, 38, 50, 80, and 100 mol% Ca₃(PO₄)₂ were fired at 1500°C, forming nagelschmidtite + a ¹-CaSiO₄, A -phase and silicocarnotite and a -Ca₃(PO₄)₂, respectively. Hydration of these produces hydroxylapatite regardless of composition. Calcium silicate hydrate gel is produced when Ca₂SiO₄≠ 0 and portlandite when Ca₂SiO₄ is >50%. Relative hydration reactivities are a -Ca₃(PO₄)₂ > nagelschmidtite > α ¹-Ca₂SiO₄ > A -phase > silicocarnotite. Hydration in the presence of silica or lime influences the amount of portlandite produced. Hydration in NaOH solution produces 14-A tobermorite rather than calcium silicate hydrate gel.     

Microstructure and Mechanical Properties of Sinter–Post-HIPed Si3N4–SiC Composites

The microstructural evolution and mechanical properties of Si₃N₄–SiC composites obtained by the sinter–post-HIP process were investigated. SiC addition prohibited β-Si₃N₄ grain growth; however, the grain growth followed the empirical growth law, with exponents of 3 and 5 for the c - and the a -axis directions, respectively. Mechanical properties were strongly influenced by SiC addition and sintering conditions. Short-crack propagation behavior was measured and analyzed by the indentation-strength in-bending (ISB) method. The present composites had high short-crack toughness, compared with the values for monolithic Si₃N₄. The enhanced short-crack toughness was attributed to crack-tip bridging by the SiC particles.     

The Join Ca2SiO4-CaMgSiO4

New data obtained on the join Ca₂SiO₄-CaMgSiO₄ established a limit of crystalline solubility of Mg in α-Ca₂SiO₄ corresponding to the composition Ca_1.90Mg_0.10SiO₄ at 1575°C. The α-α'Ca₂SiO₄ inversion temperature is lowered from 1447° to 1400°C by Mg substitution in the lattice. α'-Ca₂SiO₄ takes Mg into its lattice up to the composition Ca_1.94Mg_0.06SiO₄ at 1400°C and to Ca_1.96Mg_0.04SiO₄ at 900°C. A new phase (T) reported previously by Gutt, with the approximate composition Ca_1.70Mg_0.30SiO₄, was stable between 979° and 1381°C, and should be stable at liquidus temperatures in multicomponent systems involving CaO–MgO–SiO₂.     

Thermoelastic Behavior in Ca2SiO4 Solid Solutions

Dicalcium silicate solid solutions (C₂S(ss)) doped with Na₂O, A1₂O₃, and Fe₂O₃ were examined by high-temperature optical microscopy. Surface deformation caused by a possible martensitic transformation between a'_L and β phases was observed in situ under the microscope during temperature changes, indicating that the transformation was thermoelastic. Both the start and finish temperatures of the a'_L-to-β and β-to-a'_L transformations decreased with increased Na:(Na + Ca) ratio. Because of the athermal nature of the a'_L-to-β transformation, the a'_L phase, when cooled below the finish temperature, should have been completely converted to the β phase.     

Microstructure and Properties of Spark Plasma-Sintered ZrO2–ZrB2 Nanoceramic Composites

In a recent work, ¹ we have reported the optimization of the spark plasma sintering (SPS) parameters to obtain dense nanostructured 3Y-TZP ceramics. Following this, the present work attempts to answer some specific issues: (a) whether ZrO₂-based composites with ZrB₂ reinforcements can be densified under the optimal SPS conditions for TZP matrix densification (b) whether improved hardness can be obtained in the composites, when 30 vol% ZrB₂ is incorporated and (c) whether the toughness can be tailored by varying the ZrO₂–matrix stabilization as well as retaining finer ZrO₂ grains. In the present contribution, the SPS experiments are carried out at 1200°C for 5 min under vacuum at a heating rate of 600 K/min. The SPS processing route enables retaining of the finer t -ZrO₂ grains (100–300 nm) and the ZrO₂–ZrB₂ composite developed exhibits optimum hardness up to 14 GPa. Careful analysis of the indentation data provides a range of toughness values in the composites (up to 11 MPa·m^1/2), based on Y₂O₃ stabilization in the ZrO₂ matrix. The influence of varying yttria content, t -ZrO₂ transformability, and microstructure on the properties obtained is discussed. In addition to active contribution from the transformation-toughening mechanism, crack deflection by hard second phase brings about appreciable increment in the toughness of the nanocomposites.     

The System KAlSiO4–Mg2SiO4–KAlSi2O6

Schairer's study (1954) on phase relations in the system KalSi₂O₆–Mg₂SiO₄–SiO₂ was extended to include the system KalSiO₄–Mg₂SiO₄–KalSi₂O₆. It is shown that this join is ternary; however, the relatively high vapor pressure of the condensed phases prohibits study by the usual quenching techniques. The apparent intersection of the (KalSiO₄–Mg₂SiO₄–SiO₃) join with the primary phase volume of spinel is attributed to loss of the alkali-silicate constituents by vapor transport. This results in the effective bulk composition being moved away from this join toward the primary phase volume of spinel in the system K₂O–MgO–Al₂O₃–SiO₂.     

Structure Change of Ca2SiO4 Solid Solutions with Ba Concentration

A series of Ba-bearing Ca₂SiO₄ solid solutions (C₂S( ss )), (Ba _x Ca_{1− x} )₂SiO₄ with 0.075 x 0.30, were prepared and examined by X-ray and electron beam diffraction. They are all made up of orthorhombic domains 120° different in orientation around the common c axis of the former α phase. The C₂S solid solution with x = 0.075 shows a superstructure incommensurate along the a axis with λ (modulation wavelength) = 3.5 and commensurate along the c axis with Δ= 3. With x = 0.15, modulation is observed only along the a axis and Δ= 3.4. No evidence of superstructure is found with x = 0.24; the space group and cell dimensions are comparable with those of pure α '_H-C₂S. The C₂S( ss ) with x = 0.30 gives a superlattice with the cell-edge length of 3 b . All the C₂S( ss ), when reheated at 1000°C for 24 h, produced lamellae of the trigonal phase T nearly in parallel with (001) of the host α '_L phase. The crystallographic orientation between the two phases is

This indicates that the above Ba-bearing C₂S( ss ) phases occur as precursors to the thermodynamically more stable two-phase mixtures.     

Transitional Phase of Ca2SiO4 Solid Solution with Incommensurate Superstructure

Crystals of Ca₂SiO₄ doped with K, P, Al, and Fe were grown and examined by means of both X-ray and electronbeam diffraction. They are made up of domains 120° different in orientation around the c axis of the previous α phase. Each of the domains gives an orthorhombic superstructure whose cell is incommensurate with the underlying orthorhombic subcell with a=0.540, b=0.936, and c=0.681 nm. This orthorhombic phase, characterized by the cell edge length of 3.8a, is termed 3.8aC₂S(ss). Both the domain and the incommensurate structure strongly suggest that this is the precursor to a phase thermodynamically more advantageous at lower temperatures.     

Structure and Microtexture Changes in Phosphorous-Bearing Ca2SiO4 Solid Solutions

The crystal structure and microtexture of P-bearing Ca₂SiO₄solid solutions (C₂S( ss )) were studied as a function of x = P/(Si + P) ranging from 0.085 to 0.398. All the samples were prepared at the stable-temperature region of the α' _l -phase and quenched in air. The structures were described in terms of the orthohexagonal or hexagonal cell of the former α-phase. The crystal with x = 0.085 was composed entirely of the orthorhombic α' _l -phase, the modulation wavelength of which was N = 3 along the c -axis. With x = 0.118 and 0.156, the crystal grains were made up of both α' _l and incommensurate orthorhombic phases. The volume fraction of the α' _l -phase decreased with increasing x . With x = 0.197, the crystal was made up exclusively of the incommensurate phase, with the modulation wave vector k given by (1/ N ) a^*+ c^*. A good correlation N = 4.370 – 2.50 x was observed between N (3.75 ≤ N ≤ 4.09) and x (0.118 ≤ x ≤ 0.250). The crystal with x = 0.3.98 consisted of a single hexagonal phase. The modulation wavelength was N = 2 along the a-axis and N = 3 along the c -axis.     

Microstructure–Dielectric Properties Relationship in Ba0.6Sr0.4TiO3–Mg2SiO4–Al2O3 Composite Ceramics

0.60Ba_0.6Sr_0.4TiO₃(BST)–(0.40− x )Mg₂SiO₄(MS)– x Al₂O₃ ( x =0, 0.5, 3, 5wt%) composite ceramics exhibit excellent characteristics suitable for tunable device applications. With increasing amount of Al, the dielectric peak can be quantitatively broadened and suppressed; the "phase transition temperature" T _c or ( T _m) shifts to a lower temperature. Meanwhile, the tunability is still high in a wider temperature range. Far from T _c, pyroelectric effects are observed by using the Byer and Roundy technology and Slim polarization hysteresis loops are observed under high ac dielectric field at 10Hz. These proved the existence of spontaneous polarization in certain possible orientations in a broad temperature range above T _c in the paraelectric medium and reveal why 0.60BST–(0.40− x )MS– x Al₂O₃ have such remarkable dielectric nonlinearity.     

A Reexamination of the Polymorphism of Ca3SiO5

Polymorphic transitions in CasSiO₆ have been investigated by precise high-temperature X-ray diffractometer measurements and by differential thermal analyses. In addition to change caused by normal thermal expansion, three principal crystallographic transformations take place: α-triclinic–β–triclinic (sluggish) in the range 550° to 700°C; 8-triclinic-monoclinic at 910°± 10°C; and monoclinic-trigonal at 970°± 10°C. The sluggish 550° to 700° C reaction alternatively may be interpreted as two separate triclinic-triclinic transitions, accompanied by broad endothermic heat effects at 575° and 675°C.     

Mechanical Properties and Oxidation Behavior of Al2O3–AlN–TiN Composites

The study examines the effect which the composition of hot-pressed electroconductive ceramics has on their structure, mechanical properties, and oxidation behavior, for ceramics of the type AIN–Al₂O₃–42 wt% TiN, differing in the AIN/Al₂O₃ ratio. The results are physico-mechanical property data, including density, hardness, strength, fracture toughness, and wear resistance. A correlation was found between the wear resistance and fracture toughness. The analysis of oxidation products revealed the formation of α-Al₂O₃ and rutile in the temperature range from 600° to 1100°C and aluminum titanate above 1200°C. The spallation of the oxide layer caused low oxidation resistance of Al₂O₃-rich composites above 1250°C. The oxidation of composites was compared with the oxidation of pure TiN. The relationship is discussed between material properties, composition, phases, and processing parameters.     

Formation of Convoluted Silica Precipitates during Amorphous Phase Separation in the Ca3(PO4)2–SiO2–MgO System

Dispersed aggregates of peculiar morphology have been obtained in phase-separated glasses of the system Ca₃(PO₄)₂–SiO₂–MgO, where the separated phase is amorphous silica. The formation of such convoluted aggregates is tentatively explained in terms of a fast coalescence process of initial isolated quasi-spherical droplets which behave as a dispersed phase in an emulsion-like system.     

Microstructure and Dielectric Properties of a LaAlO3–TiO2 Diffusion Couple

Near-field scanning microwave microscopy was applied to investigate the dielectric properties and microstructure in a polycrystalline LaAlO₃–TiO₂ diffusion couple, which included three regions containing different phases and microstructures. Relatively low (La₂Ti₄Al₁₈O₃₈), high (α-La_2/3TiO₃), and intermediate (La₄Ti₉O₂₄) dielectric constant phases were distinguished at the inter-diffusion interface in optical, backscattered electron scanning electron microscopy, and scanning microwave microscopy (SMM) images. The relative ranking of dielectric constants based on SMM examination was as follows: TiO₂>α-La_2/3TiO₃>La₄Ti₉O₂₄>LaAlO₃>La₂Ti₄Al₁₈O₃₈. La_2/3TiO₃ and LaAlO₃ will form solid solutions in the LaAlO₃-rich region. The reaction paths leading to phase development are discussed.     

Investigation on the Microstructure and Dielectric Properties of BaTiO3–Nb2O5–Fe2O3 Materials Doped with La2O3

The influence of La₂O₃ doped on the microstructure and dielectric properties, including the phase structure, temperature dependence of permittivity, and the hysteresis loop of BaTiO₃–Nb₂O₅–Fe₂O₃ (BTNF) materials has been investigated in X-ray diffraction, SEM, and LCR analyzer, respectively. Experiments revealed that incorporation of proper content of La₂O₃ basically soluted in the lattice of BaTiO₃ and can control the grain-growth, reduce the dielectric loss of the BTNF materials. The development of microstructure promoted by the additives can result in the improvement of the dielectric constant. When the doping concentration of La₂O₃ was 3.846 wt%, the relative dielectric constant of the sample sintered at 1280°C only for 2 h could reach 4308, and improve the dielectric-temperature characteristics markedly. As a result, a novel Y5P can be achieved in the BTNF ceramics, which is very promising for practical use in Y5P multilayer ceramic capacitors.     

Properties of (Y)ZrO2–Al2O3 and (Y)ZrO2–Al2O3–(Ti or Si)C Composites

The effect of Al₂O₃ and (Ti or Si)C additions on various properties of a (Y)TZP (yttria-stabilized tetragonal zirconia polycrystal)–Al₂O₃–(Ti or Si)C ternary composite ceramic were investigated for developing a zirconia-based ceramic stronger than SiC at high temperatures. Adding Al₂O₃ to (Y)TZP improved transverse rupture strength and hardness but decreased fracture toughness. This binary composite ceramic revealed a rapid loss of strength with increasing temperature. Adding TiC to the binary ceramic suppressed the decrease in strength at temperatures above 1573 K. The residual tensile stress induced by the differential thermal expansion between ZrO₂ and TiC therefore must have inhibited the t - → m -ZrO₂ martensitic transformation. It was concluded that a continuous skeleton of TiC prevented grain-boundary sliding between ZrO₂ and Al₂O₃. In contrast, for the ternary material containing β-SiC in place of TiC, the strength decreased substantially with increasing temperature because of incomplete formation of the SiC skeleton.