Fracture of an Aluminosilicate Fiberboard

Mode-I fracture of aluminosilicate fiberboard that is used in large mirror casting molds was studied. The material was idealized as a transversely isotropic, layered composite that was composed of planar sheets of crosslinked fibers. Elastic constants, the toughness ( K_R ) curve, and the fracture work were measured at room temperature. The observed rising K_R behavior was attributed to crack bridging. Experimental measurements of the bridging stress were made using a specimen-renotching technique. Relationships between the bridging stress, K _R , and fracture work were explored and shown to be consistent.     

Assessment of Forchheimer's Equation to Predict the Permeability of Ceramic Foams

Correct estimation of the pressure drop in filtration processes that involve fluid velocity variations is of major importance, because it allows the filtration rate and/or the energy consumed on fluid flow to be more accurately controlled. Permeability of porous filters has been often described by Forchheimer's equation, which establishes a nonlinear dependence between pressure drop and fluid velocity. Two constants, k ₁ and k ₂, dependent only on the medium, quantify the viscous and inertial effects on the pressure drop curve. In this work, experimental data of airflow through 10 pores per linear inch ceramic foam filters are used to show that a single sample may have completely distinct permeability constants depending on the data range chosen for analysis. The Darcian permeability constant k ₁ displays higher variation than the non-Darcian permeability constant k ₂. The conclusion is that special attention must be taken to represent permeability of highly porous structures in a large velocity range. The predictability of Forchheimer's equation generally worsens when less data are included in the curve fitting, particularly at low velocities. Careful consideration should be made if constants k ₁ and k ₂ are intended to be used for permeability estimation beyond the fitting range.     

Influence of Sintering Temperature on Grain Growth and Phase Structure of Compositionally Optimized High-Performance Li/Ta-Modified (Na,K)NbO3 Ceramics

Microstructure characteristics, phase transition, and electrical properties of (Na_0.535K_0.485)_0.926Li_0.074(Nb_0.942Ta_0.058)O₃ (NKN-LT) lead-free piezoelectric ceramics prepared by normal sintering are investigated with an emphasis on the influence of sintering temperature. Some abnormal coarse grains of 20–30 μm in diameter are formed in a matrix consisting of about 2 μm fine grains when the sintering temperature was relatively low (980°C). However, only normally grown grains were observed when the sintering temperature was increased to 1020°C. On the other hand, orthorhombic and tetragonal phases coexisted in the ceramics sintered at 980°–1000°C, whereas the tetragonal phase becomes dominant when sintered above 1020°C. For the ceramics sintered at 1000°C, the piezoelectric constant d ₃₃ is enhanced to 276 pC/N, which is a high value for the Li- and Ta-modified (Na,K)NbO₃ ceramics system. The other piezoelectric and ferroelectric properties are as follows: planar electromechanical coupling factor k _p=46.2%, thickness electromechanical coupling factor k _t=36%, mechanical quality factor Q _m=18, remnant polarization P _r=21.1 μC/cm², and coercive field E _c=1.85 kV/mm.     

Optical and X-Ray Single Crystal Studies of the Monoclinic ⇌ Tetragonal Transition in ZrO2

The monoclinic ⇌ tetragonal phase transition in ZrO₂ single crystals was studied at temperature by transmission optical microscopy and X-ray diffraction techniques. A series of timelapse photographs illustrated the relations between the events that occur during the transition. The events themselves were recognized by direct observation using a high-temperature microscope stage and by scrutiny of several high-temperature Laue photographs. During heating the monoclinic phase transforms to the tetragonal by the motion of an interface parallel to the (100) _m plane; simultaneous twinning also occurs behind the advancing interface. The tetragonal phase is usually twinned on the (1 2) _bct or ( 12) _bct plane, and the extent of twinning is influenced by the heating rate. Cooling transforms the untwinned tetragonal form into a twinned monoclinic form with the orientation of the monoclinic twins parallel to the trace of the (001) _m plane when observations are made in the (100) _m plane. Transformation of a twinned tetragonal crystal results in twins on the {110} _m and {001} _m planes. Orientation relations in the ZrO₂ transformation are: (100) _m ‖(110) _bct , [010] _m ‖[001] _bct , and by the virtue of twinning, (100) _m ‖(110) _bct , [001] _m ‖[001] _bct . During cooling the same topotaxial relations are maintained.     

Alkali Strontium-Barium-Lead Niobate Systems with a Tungsten Bronze Structure: Crystallographic Properties and Curie Points

Crystallographic parameters, Curie points, and freezing temperatures are presented for a series of A⁺A₂²⁺Nb₅O₁₅ compositions with tungsten bronze-related structures, where A⁺=Na, K, or Rb, and A²⁺=Sr or Ba. Results are also reported for bronze solid solutions in the systems KNbO₃-PbNb₂O₆, K(Sr-Ba)₂Nb₅O₁₅, K(Ba-Pb)₂Nb₅O₁₅, K(Sr-Pb)₂Nb₅O₁₅, and (KSr₂-K₂La)Nb₅O₁₅. On the basis of these data, an empirical relation is shown between the ferroelectric transition temperature, T _c, and axial ratio °10 c _o/ a ₀. The T _c vs °10 c ₀/ a ₀ curve for compositions with polar axes perpendicular to [00l] has a negative slope, whereas that for compositions with polar axes parallel to [00l] has a positive slope of about the same magnitude. These results are compared with measurements of the temperature dependence of c ₀/ a ₀ for KSrPbNb₅O₁₅, and KBa₂Nb₅O₁₅; the latter is discussed in terms of the Devonshire free energy theory.     

Use of Crack Branching Data for Measuring Near-Surface Residual Stresses in Tempered Glass

An analytical procedure based on fracture mechanics is used to obtain the amount of residual stress in glass from measurements on the fracture surface. The technique utilizes the measurement of microcrack branching distances, known as the mirror — mist boundary, which occur at a critical crack branching stress intensity (K _m ) value. This procedurre shows that σ _A r _m ^1/2 Y _F (θ) =σ _R r ^1/2 _m +Ψ₀, where σ _A is the applied stress, r _m is the microcrack branching radius, σ _R is the residual stress, Y _F ( θ ) is the crack-border correction factor, and Ψ₀ is a material constant based on K _m . Thus, the equation is that of a straight line with the slope equal to the magnitude of the residual stress. Data for tempered glass from the literature are used to demonstrate the applicability of the technique.     

Effect of Oxygen Partial Pressure on the Formation of Metastable Phases from an Undercooled YbFeO3 Melt Using an Aerodynamic Levitator

The Yb₂O₃–Fe₂O₃ system was studied to investigate the effect of oxygen partial pressure on the formation of metastable phases over a wide range of oxygen partial pressures from 10⁵ to 10⁻¹ Pa. Two kinds of metastable phases, with space groups of P 6₃ cm and P 6₃/ mmc , were found through rapid solidification of an undercooled YbFeO₃ melt in an atmosphere with reduced P o₂. The crystal structure of the as-solidified samples changed from orthorhombic Pbnm to hexagonal P 6₃ cm and P 6₃/ mmc with decreasing P o₂. X-ray diffractometric and scanning electron microscopic results confirmed the existence of various phases in the as-solidified samples. The stabilities of each phase were studied by annealing the bulk sample in the thermogravimetric–differential thermal analysis (TG-DTA) furnace up to 1673 K, and the equilibrium phase diagram was constructed for the Yb–Fe–O system at 1473 K. TG analysis showed an increase of the sample mass during annealing and revealed that the existence of Fe²⁺, which has an ionic radius larger than that of Fe³⁺, decreases the tolerance factor and therefore destabilizes the perovskite structure.     

Calorimetric Study of Nickel Molybdate: Heat Capacity, Enthalpy, and Gibbs Energy of Formation

The thermodynamic properties of the α and β polymorphs of NiMoO₄ were directly investigated by calorimetry. The standard entropies of formation, Δ_f S ° _T , of α and β were determined from measuring the molar heat capacity, C _p,m, from near absolute zero (2 K) to high temperature (1380 K) by a relaxation method and differential scanning calorimetry. The standard enthalpies of formation, Δ_f H ° _T , of α and β were determined by combining C _p,m with the standard enthalpy of formation, Δ_f H °₂₉₈, at 298 K obtained from drop solution calorimetry in molten sodium molybdate at 973 K. The standard Gibbs energies of formation, Δ_f G ° _T , of α and β were determined from their Δ _f S ° _T and Δ _f H ° _T values. The Δ _f G ° _T values indicate that the polymorphic transformation from α to β occurs at 1000 K, consistent with the observed phase transformation at 1000 K.     

Stoichiometry Effects on the Fracture of TiO2−x

Fracture characteristics of TiO_{2− x} were studied as a function of Stoichiometry. With increasing x , the fracture toughness K _{I e} and the fracture surface energy γ _f decrease and the amount of transgranular cleavage increases, corresponding to the increased concentration of planar defects within the grains. Increasing nonstoichiometry also shifted the ( K _I- V ) diagram to lower K _I values, commensurate with the K_{I e} decrease. Water accelerated stress corrosion by promoting intergranular failure during subcritical crack growth.     

ON LINEAR PROCESSES WITH GIVEN MOMENTS

Abstract. Let X _t = c ₀ Y _t + c ₁ Y _{t -1}+… be a linear process with known coefficients c _k , where Y _t is a strict white noise. Let m ₁, …, m _2r be given numbers. A method is presented to determine whether there exists a distribution of Y _t such that EX ^k _t = m _k for k = 1, …, 2 r . In the positive case, such a distribution of Y _t is described. Some explicit formulas for AR(1) and AR(2) models are derived. The results can be used for simulating a process with given moments of its stationary distribution. The procedure also enables proof that some stationary distributions cannot belong to the given linear process.     

Ink Jet Printing of Microdot Arrays of Mesostructured Silica

We report a process for preparing microdot arrays of SiO₂ from a tetraethoxysilane precursor containing either a cationic (CTAB) or non-ionic surfactant. Controlling the ink jet deposition parameters and precursor hydrolysis made it possible to obtain mesoporous silica with a Pm 3 n cubic structure, using CTAB, or an Fmmm orthorhombic structure, using a non-ionic surfactant. The addition of hydrophobic organosilane F₃C(CF₂)₅CH₂CH₂Si(OC₂H₅)₃ leads to the most regular and best-defined three-dimensional microdot array with a constant diameter of 155 μm and a regular space of 250 μm.     

Long-Ultraviolet-Excited White-Light Emission in Rare-Earth-Activated Yttrium-Oxyorthosilicate

White-light emission was achieved by activating yttrium oxyorthosilicate with two rare-earth elements, (Y_{1− m − n} Ce _m Tb _n )₂SiO₅. Ce³⁺ strongly absorbs at λ _ex =358 nm and produces a broad, mainly blue emission with a tail that extends out to 600 nm (orange), and transfers energy efficiently to Tb³⁺, which produces strong green-line emissions at 550 nm and some red emission around 650 nm. At λ_{e x} =358 nm, chromaticity coordinates of the optimally activated (Y_0.9625Ce_0.0075Tb_0.03)₂SiO₅ were found to be x =0.266, y =0.365 with a color temperature 8512 K. Upon mixing in another red-emitting phosphor, (Y_0.955Bi_0.005Eu_0.04)₂O₃, the chromaticity and color rendering index values were improved.     

Synthesis and Friction Behavior of Chemically Vapor Deposited Composite Coatings Containing Discrete TiN and MoS2 Phases

Composite coatings containing discrete crystalline phases of TiN and MoS₂ were deposited on Si, graphite, and Ti-6A-14V alloy substrates by simultaneous chemical vapor deposition. MoF₆ and H₂S were utilized as the precursors for MoS₂ formation, while Ti((CH₃)₂N)₄ and NH₃ were used for TiN deposition. The composition and microstructure of the coatings were investigated by X-ray diffraction, Auger electron spectroscopy, and transmission electron microscopy. The molar ratios of TiN and MoS₂ in the composite microstructure could be controlled by adjusting the MoF₆concentration in the reagent mixture. Encouraging friction and wear characteristics against silicon nitride were obtained for a composite coating which was rich in MoS₂ at the coating surface, with TiN as the major phase near the substrate interface. Friction coefficients at room temperature in air were typically in the range of 0.07 to 0.3. The friction coefficients remained comparable at 573 K, but increased to 0.7 to 1.0 at 673 K. A friction coefficient value of −0.3 was, however, obtained from a composite coating tested at 973 K.     

Fabrication and Characterization of a (100) Three-Axis-Oriented Single-Crystal (Ba0.7Sr0.3)TiO3 Thin Film Prepared by the Chemical Solution Deposition Method

Epitaxially grown single-crystal perovskite (100) three-axis-oriented (Ba_0.7Sr_0.3)TiO₃ thin films were prepared on a (100) platinum-coated (100) magnesium oxide (MgO) single-crystal substrate by the chemical solution deposition method using a solution derived from Ba(CH₃COO)₂, Sr(CH₃COO)₂, and Ti(O- i -C₃H₇)₄.
The growth of the film was found to depend on the annealing condition. A (Ba,Sr)TiO₃ thin film annealed at 1073 K was found to be a single crystal by transmission electron microscope. The single-crystal film exhibited a (100) three-axis orientation that followed the (100) orientation of the Pt substrate, as observed from an X-ray pole figure measurement and selected area electron diffraction patterns.     

Sinterability of β-Calcium Orthophosphate Powder Prepared by Spray-Pyrolysis

Mixed solutions of Ca(NO₃)₂ and (NH₄)₂HPO₄ with Ca/P = 1.50 were spray-pyrolyzed at 600°C to produce β-calcium orthophosphate (β-Ca₃(PO₄)₂) powder; the spray-pyrolyzed powder was ground and then calcined at 600°C for 1 h. The best crystalline β-Ca₃(PO₄)₂ powder was obtained from the solution with 1.80 mol.L^–1 Ca(NO₃)₂, 1.20 mol.L^–1 (NH₄)₂HPO₄. The resulting powder was composed of primary particles with sizes of <0.5 μm. Dense β-Ca₃(PO₄)₂ ceramics with a relative density of 96.1% could be fabricated by firing this compressed powder at 1070°C for 5 h.     

Porous Glass-Ceramics with a Skeleton of the Fast-Lithium-Conducting Crystal Li1+xTi2−xAlx(PO4)3

Porous glass-ceramics with a skeleton of the fast-lithium-conducting crystal Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ (where x = 0.3–0.5) were prepared by crystallization of glasses in the Li₂O─CaO─TiO₂─Al₂O₃–P₂O₅ system and subsequent acid leaching of the resulting dense glass-ceramics composed of the interlocking of Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ and β-Ca₃(PO₄)₂ phases. The median pore diameter and surface area of the resulting porous Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ glass-ceramics were approximately 0.2 μm and 50 m²/g, respectively. The electrical conductivity of the porous glass-ceramics after heating in LiNO₃ aqueous solution was 8 × 10⁻⁵ S/cm at 300 K or 2 × 10⁻² S/cm at 600 K.     

Low-Temperature Structural Phase Transition in ZrO2–12 mol% CeO2 Studied by Infrared Spectroscopy and X-ray Diffractometry

The low-temperature tetragonal ( t ) to monoclinic ( m ) phase transition in ZrO₂–12 mol% CeO₂ was studied by Fourier-transform infrared spectroscopy and X-ray diffractometry (XRD). When the ZrO₂–12 mol% CeO₂ was cooled, the t → m phase transition occurred at about 120 K; this caused significant changes in the infrared reflectance spectra and X-ray diffractograms. As the phase transition proceeded, "difference spectra" obtained by subtracting the infrared spectra before and after the phase transition revealed two infrared modes at 575 and 740 cm⁻¹ which were assigned to the m phase. The volume fraction of the m phase (determined by XRD) and the subtraction coefficient (defined such that the difference spectra reproduced the infrared spectrum of m -ZrO₂) were consistent with each other; this revealed a marked discontinuity at about 120 K. Full width at half maximum of the ( 1 11) _m and (111) _t reflections also indicated a similar discontinuity at about 120 K.     

Density and Permeability of Sintered Slip-Cast Magnesia

Fused magnesia was ball-milled in ethanol for 14, 30, 48, and 100 hours, and particle-size distributions were determined. Specimens were slip-cast from the suspensions and were fired in air at 1300°, 1400°, and 1470°C, for times up to 8 hours, and gas-permeability and bulk density determinations were performed on the fired pieces. For all specimens the gas flow was essentially of the Knudsen type. The maximum bulk density, 96.7% of theoretical, was obtained by sintering a specimen, cast from the magnesia ball-milled for 100 hours, at 1470° for 3 hours. At this density the permeability was zero. The relation between permeability and porosity could be represented by the equation K _M = 6.9 ° 10⁻¹⁰( P_F )^2.54, where P_F is 100( d ₀ - d/do ). Here d is the bulk density and d ₀ is a constant representing the bulk density at which the permeability becomes zero. The foregoing equation fits the data for all specimens if it is assumed that do is a function of the particle-size distribution in the slip, varying from 3.36 g per cm³ for the magnesia ball-milled for 100 hours to 3.58 g per cm ³ for the magnesia ball-milled for 14 hours.     

Processing of Oriented K(Ta,Nb)O3 Films Using Chemical Solution Deposition

K(Ta,Nb)O₃ (KTN) thin films have been prepared by the chemical solution deposition method. KTN precursors consisted of a uniform mixture of K[Ta(OC₂H₅)₆] and K[Nb(OC₂H₅)₆] with interaction at the molecular level. Perovskite KTN thin films with the desired composition (Ta/Nb = 65/35, 50/50, and 35/65) were synthesized from the precursor solutions by the dip coating method. KTN thin films with (100) preferred orientation were successfully synthesized on MgO(100) and Pt(100)/MgO(100) substrates. X-ray pole figure measurements showed that grains of KTN films had a prominent three-dimensional regularity on MgO(100) and Pt(100)/MgO(100) surfaces. The Curie temperatures of KTN films decreased with increasing Ta/Nb ratio. Typical P-E hysteresis loops were observed for KTN thin films of three compositions on Pt(100)/MgO(100) substrates. The values of remanent polarization ( P _r) of KTN films increased as the Ta/Nb ratio changed from 65/35 to 35/65.     

Electrical Resistivities of Monocrystalline and Polycrystalline TiB2

The electrical resistivity of monocrystalline and polycrystalline TiB₂, was measured under an inert atmosphere by a four-point ac impedance technique over the range 298 to 1373 K. The results are expressed in the form ρ-ρ₂₉₈= m(T -298). The following values of ρ₂₉₈ (μω.cm) and m (nω.cm-K^-1) were determined: for polycrystalline TiB₂ (69% dense) 18.2 and 95; for polycrystalline TiB₂ (99% dense) 7.4 and 42; and for monocrystalline TiB₂, 6.6 and 34.9.