Large Pyroelectric Effect in Relaxor-Based Ferroelectric Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals

The pyroelectric properties of (1− x )Pb(Mg_1/3Nb_2/3)O_{3− x} PbTiO₃ (PMN− x PT) single crystals with various compositions and orientations have been investigated using a dynamic method. Excellent pyroelectric performances can be achieved in 〈111〉-oriented rhombohedral PMN− x PT (0.24≤ x ≤0.30) crystals, where the measurement direction corresponds to the polar axis of the crystal. At room temperature, the pyroelectric coefficient and the detectivity figure of merit ( F _d ) for the 〈111〉-oriented PMN–0.28PT single crystal are 8.55 × 10⁻⁴ C·(m²·K)⁻¹ and 9.89 × 10⁻⁵ Pa^−1/2 (100 Hz), respectively, superior to those of the widely used pyroelectric materials. They are also weak temperature dependent and nearly independent of frequency. These outstanding pyroelectric performances make the single crystals a promising candidate for uncooled infrared detectors and thermal imagers.     

Iron and Spinel Precipitation in Iron-Doped Sapphire

Single crystals of Al₂O₃ containing 0.5 wt% Fe were exposed to low p o₂ atmospheres at 1500°C to produce precipitate phases. Analytical TEM identified the precipitate phases as spinel (hercynite) and iron, with the following orientation relationships: 〈001〉_Fe‖〈2 2 01〉_s with {1 1 0}_Fe‖{11 2 0}_s, 〈111〉_Fe‖〈10 1 0〉_s with {0 1 1}_Fe‖ (0001)_s, and 〈1 1 0〉_H‖〈01 1 0〉_s with {111}_H‖ (0001)_s. The three phase fields observed — (Fe, Al)₂O₃, spinel +α-Al₂O₃, and iron +αAl₂O₃— are in accordance with phase stability diagrams. Precipitation kinetics indicate that oxygen is mobile in the reduced region of the crystal.     

Effect of Water Vapor on Dielectric Loss in MgO

A dielectric loss study of porous MgO indicates that H₂O absorption on MgO probably leads to the formation of surface defects as well as hydroxide ions. The ac conductivity, σ_ac followed the equation σ_ac=σ₁ + KP _H2O^0.27 from 550° to 800°C when the water partial pressure was varied between 7 × 10⁻⁵ and 3 × 10⁻² atm.     

Dislocation-Containing Planar Faults in Metastably Retained Hexagonal Barium Titanate

Planar faults, designated F ₁– F ₆ and F _a , with intermixed dislocations in metastably retained hexagonal-BaTiO₃ ceramics, were found and analyzed by transmission electron microscopy. Only faults with one, two, and four extra c -layers parallel to the basal plane have been identified. Fault vectors R_F1=R_Fa=1/6[02 2 1], R_F2=R_F3=1/3[0 1 11], R_F4=1/3[01 1 2], and R_F'1=R_F5= R_F6=R_F'a=1/6[0 2 21] were determined adopting the 2πg·R=0 (or 2 n π) criteria in combination with high-resolution imaging. Further, the embedded dislocations were half-partials with Burgers vectors b=1/3〈10 1 0〉 determined by the g·b=0 effective invisibility criteria in conjunction with the eligible fault vectors. A rotation by 60° about the c -axis was found between fault segments with R_F1=1/6[02 2 1] and R_F'1=1/6[20 2 1] located on either side of a partial. Basal dislocations with b_B=1/3〈1 2 10〉 have dissociated into two prism-plane Shockley half-partials with b_Pr=1/3〈1 1 00〉 by glide in the fault plane (0002) according to 1/3〈1 2 10〉→1/3〈1 1 00〉+1/3〈0 1 10〉. The fault segment F'₁ encompassed by two half-partials is an extrinsic complex stacking fault.     

Cation Ordering and Domain Boundaries in Ca[(Mg1/3Ta2/3)1−xTix]O3 Microwave Dielectric Ceramics

Cation ordering and domain boundaries in perovskite Ca[(Mg_1/3Ta_2/3)_{1− x} Ti _x ]O₃ ( x =0.1, 0.2, 0.3) microwave dielectric ceramics were investigated by high-resolution transmission electron microscopy (HRTEM) and Rietveld analysis. The variation of ordering structure with Ti substitution was revealed together with the formation mechanism of ordering domains. When x =0.1, the ceramics were composed of 1:2 and 1:1 ordered domains and a disordered matrix. The 1:2 cation ordering could still exist until x =0.2 but the 1:1 ordering disappeared. Neither 1:2 nor 1:1 cation ordering could exist at x =0.3. The space charge model was used to explain the cation ordering change from 1:2 to 1:1 and then to disorder. A comparison between the space charge model and random layer model was also conducted. HRTEM observations showed an antiphase boundary inclined to the (111) _c plane with a projected displacement vector in the 〈001〉 _c direction and ferroelastic domain boundaries parallel to the 〈100〉 _c direction.     

Anisotropic Thermal Expansion of β-Ca2SiO4 Monoclinic Crystal

Crystals of β-Ca₂SiO₄ (space group P 12₁/ n 1) were examined by high-temperature powder X-ray diffractometry to determine the change in unit-cell dimensions with temperature up to 645°C. The temperature dependence of the principal expansion coefficients (α_i) found from the matrix algebra analysis was as follows: α₁= 20.492 × 10⁻⁶+ 16.490 × 10⁻⁹ ( T - 25)°C⁻¹, α₂= 7.494 × 10⁻⁶+ 5.168 × 10⁻⁹( T - 25)°C⁻¹, α₃=−0.842 × 10⁻⁶− 1.497 × 10⁻⁹( T - 25)°C⁻¹. The expansion coefficient α₁, nearly along [302] was approximately 3 times α₂ along the b -axis. Very small contraction (α₃) occurred nearly along [     01]. The volume changes upon martensitic transformations of β↔α_L' were very small, and the strain accommodation would be almost complete. This is consistent with the thermoelasticity.     

Texture Development in Barium Titanate and PMN–PT Using Hexabarium 17-Titanate Heterotemplates

Bulk BaTiO₃ ceramics with 〈111〉-texture have been prepared by the modified templated grain growth method, using platelike Ba₆Ti₁₇O₄₀ particles as templates, and the mechanism of texture development is examined. The Ba₆Ti₁₇O₄₀ particles induce the abnormal growth of BaTiO₃ grains, and a structure similarity between {001} of Ba₆Ti₁₇O₄₀ and {111} of BaTiO₃ gives 〈111〉-texture to abnormally grown BaTiO₃ grains. Thus, the 〈111〉-texture develops in the BaTiO₃ matrix. The use of platelike Ba₆Ti₁₇O₄₀ particles has been extended to a 0.65Pb(Mg_1/3Nb_2/3)O₃–0.35PbTiO₃ matrix, but the matrix phase is decomposed by extensive chemical reactions between the matrix and template phases.     

Vibrational Spectra of Hydrothermally Prepared Hydroxyapatites

Apatites can be used as bioceramic materials for tooth and bone implants. Infrared (4000 to 400 cm⁻¹) and laser-Raman spectra were obtained for hydrothermally prepared hydroxyapatites with the general formula X₁₀(PO₄)₆(OH)₂ where X= Ca²⁺ Sr²⁺, Ba²⁺, or Pb²⁺ Fundamental vibrational modes were identified and empirical band assignments made. Analysis of the vibrational spectra led to the reassignment of the v₂ mode to a higher wave-number, lower-intensity band (e.g. ∼470 cm⁻¹ for Ca hydroxyapatite). Effects of solid-state interaction were noted in the vibrational spectra and interpreted by factor-group analysis. An "effective" factor group C_6h, which neglects the locations of the OH⁻ ions, best describes the vibrational spectra of the hydroxyapatites.     

π-Rotation Faults in Hexagonal BaTiO3

Planar defects in the metastably retained h-BaTiO₃ exhibiting α-fringe pattern have been characterized via transmission electron microscopy (TEM). The eligible fault vectors were determined by adopting the invisibility criteria of 2πg·R = 0 or 2 n π augmented by high-resolution imaging. Three stacking faults, F₁, F₂, and F₃, of the extrinsic nature have been fully analyzed. The eligible fault vectors for faults F₁ and F₃ contained a basal component respectively of ⅓[0001] and ⅙[0001] and a common prismatic component of ⅓〈10[1-macr]0〉. However, only three of the 〈10[1-macr]0〉 vectors are the eligible prismatic component for the fault vectors R_F1=⅓[0[1-macr]11], ⅓[10[1-macr]1], and ⅓[[1-macr]101], and R_F3=⅙[02[2-macr]1], ⅙[2[2-macr]01], and ⅙[[2-macr]021] that have fulfilled the invisibility criteria. On the other hand, all fault vectors R_F21=⅙〈[4-macr]223〉 for fault F₂, containing six vectors of the 〈[2-macr]110〉 family, is eligible. Unlike the faults of πR_F=⅙〈[2-macr]203〉 found in the D0₁₉ intermetallics of Ni₃Sn and Co₃W, neither fault F₁ nor F₃ is the π-rotation type. Fault F₂, however, is a π-rotation fault since a 60°-rotation clockwise about [0001] has produced another eligible fault vector.     

Knoop Microhardness Anisotropy of Single-Crystal Stoichiometric MgAl2O4 Spinel

Microhardness anisotropy profiles for the (100) and (111) planes of single-crystal stoichiometric MgAl₂O., spinel were determined at room temperaturé. The (100) microhardness profile has ahardness maximum in tiie [001] and a minimum in the [O11], which supports the previous suggestion that the primary slip system is the {111}〈11¯0〉. The microhardness of the (111) plane is independent of indenter orientation, also consistent, with a {111}〈11¯0〉 primary slip system. It is concluded that these microhardness profiles are in accord with other experimental observations that the {111}〈11¯0〉 is the primary slip system in stoichiometric MgAl₂O₄ spinel.     

Growth and Morphology of Magnesium Oxide Whiskers

Magnesium oxide crystals and whiskers were grown by vapor phase reactions between MgO and tungsten, hydrogen, and carbon. The large number of morphologies obtained are described in terms of two, three, and fourfold growth symmetry and are related to the growth conditions by current heterogeneous nucleation theory. Threefold (or 〈111〉) growth occurred principally with MgO + H₂ reactions, and in all experiments 〈100〉 and 〈110〉 growth occurred under closely similar conditions of temperature and vapor supersaturation. Observations of growth steps suggest that {100} surfaces are favored only at the highest vapor supersaturation. Tensile strength measurements of whiskers with l/d ratios of about 300 show increasing strength with decreasing cross section. A value of 8.13 × 10⁴ psi was observed for a whisker 9.76μ in diameter. The results are of particular interest to the formation of refractory oxides crystallizing in the simple cubic NaCl structure.     

Thermal Expansion of the Low-Temperature Form of BaB2O4

Thermal expansion of the low-temperature form of BaB₂O₄ (β-BaB₂O₄) crystal has been measured along the principal crystallographic directions over a temperature range of 9° to 874°C by means of high-temperature X-ray powder diffraction. This crystal belongs to the trigonal system and exhibits strongly anisotropic thermal expansions. The expansion along the c axis is from 12.720 to 13.214 Å (1.2720 to 1.3214 nm), whereas it is from 12.531 to 12.578 Å (1.2531 to 1.2578 nm) along the a axis. The expansions are nonlinear. The coefficients A, B , and C in the expansion formula L _t = L ₀(1 + At + Bt ²+ Ct ³) are given as follows: a axis, A = 1.535 × 10⁻⁷, B = 6.047 × 10⁻⁹, C = -1.261 × 10⁻¹²; c axis, A = 3.256 × 10⁻⁵, B = 1.341 × 10⁻⁸, C = -1.954 × 10⁻¹²; and cell volume V, A = 3.107 × 10⁻⁵, B = 3.406 × 10⁻⁸, C = -1.197 × 10⁻¹¹. Based on α _t = (d L _t /d t )/ L ₀, the thermal expansion coefficients are also given as a function of temperature for the crystallographic axes a , c , and cell volume V.     

Use of Stress To Produce Highly Oriented Tetragonal Lead Zirconate Titanate (PZT 40/60) Thin Films and Resulting Electrical Properties

Thin films of Pb(Zr_0.4Ti_O.6)O₃ produced by chemical solution deposition were used to study the effects of stress from different platinized single-crystal substrates on film orientation and resulting electrical properties. Films deposited on MgO preferred a (001) orientation due to compressive stress on the film during cooling through the Curie temperature ( T _C). Films on Al₂O₃ were under minimal stress at T _C, resulting in a mixture of orientations. Those on Si preferred a (111) orientation due to templating from the bottom electrode. Films oriented in the 〈001〉 direction demonstrated lower dielectric constants and higher P _r and − d ₃₁ values than (111) films.     

High-Temperature Defect Structure of Acceptor-Doped Strontium Titanate

The defect structure of acceptor-doped (Fe, Al, Cr) polycrystalline strontium titanate was investigated by measuring the equilibrium electrical conductivity as a function of oxygen activity (10⁻²¹≤a_o2≤1) and temperature (85°C≤ T ≤ 1050°C). The electrical conductivity was n type with ∼−1/4 dependence on a ₀₂ for a₀₂<10⁻¹⁰. For a₀₂>10⁻⁸, the observed data for Fe- or Al-doped samples were proportional to ∼1/4.5 power of a₀₂. In this region for Cr-doped samples, the value of m in.σp αa₀₂^+1/m varies from ∼4.80 to ∼9.00 as the concentration of Cr is increased from 460 to 10 000 ppm. The onset of p -type conductivity depends on the amount. of acceptor impurity added to the sample. The absolute values of the conductivity in the acceptor-doped samples were lower in the n-type region than those for undoped SrTiO₃. The conductivity minima shift toward lower oxygen activity with increasing acceptor concentration. For the entire oxygen activity rangae used in this study, the defect structure of SrTiO₃ is dominated by the added acceptor impurities.     

Effect of Divalent Cation Additives on the γ-Al2O3-to-α-Al2O3 Phase Transition

The effect on the γ-Al₂O₃-to-α-Al₂O₃ phase transition of adding divalent cations was investigated by differential thermal analysis, X-ray diffractometry, and surface-area measurements. The cations, Cu²⁺, Mn²⁺, Co²⁺, Ni²⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, were added by impregnation, using the appropriate nitrate solution. These additives were classified into three groups, according to their effect: (1) those with an accelerating effect (Cu²⁺ and Mn²⁺), (2) those with little or no effect (Co²⁺, Ni²⁺, and Mg²⁺), and (3) those with a retarding effect (Ca²⁺, Sr²⁺, and Ba²⁺). The crystalline phase formed by reaction of the additive with γ-Al₂O₃ at high temperature was a spinel-type structure in groups (1) and (2) and a magnetoplumbite-type structure in group (3). In groups (2) and (3), a clear relationship was found between the transition temperature and the difference in ionic radius of Al³⁺ and the additive (Δ r ): The transition temperature increased as Δ r increased. This result indicates that additives with larger ionic radii are more effective in suppressing the diffusion of Al³⁺ and O²⁻ in γ-Al₂O₃, suppressing the grain growth of γ-Al₂O₃, and retarding the transformation into α-Al₂O₃.     

Energy Transfer Process for the Blue Up-Conversion in Calcium Aluminate Glasses Doped with Tm3+ and Nd3+

Excitation of Tm³⁺ to ³ H ₄ using the 791 nm pump source showed the frequency up-converted blue emission (∼480 nm) due to the Tm³⁺:¹ G ₄→³ H ₆ transition in Tm³⁺/Nd³⁺ codoped CaO·Al₂O₃ glasses. Intensity and lifetime changes with rare-earth concentrations suggested the efficient energy transfer of Tm³⁺:³ H ₄→ Nd³⁺:⁴ F _5/2 and Nd³⁺:⁴ F _3/2→ Tm³⁺:¹ G ₄. The latter transfer enabled Tm³⁺ to reach its ¹ G ₄ level, and the blue emission became possible through the ¹ G ₄→³ H ₆ transition. Quantitative analysis with rate equations proved that these two transitions were the most efficient among all the possible energy transfer routes between Tm³⁺ and Nd³⁺. Calculated up-conversion efficiency of the Tm³⁺/Nd³⁺ combination in CaO·Al₂O₃ glass was 6.6 × 10⁻³, and it was ∼4 orders of magnitude larger than those reported for other oxide glasses.     

Phase-Transformation-Induced Anti-Phase Boundary Domains in Barium Cerate Perovskite

Anti-phase boundary (APB) domains resulting from the orthorhombic ( o ₁, Ibmm (No. 74)) to orthorhombic ( o ₂, Pbnm (No. 62)) phase transformation at ∼290°C in pressureless-sintered barium cerate (BaCeO₃) ceramics have been investigated by transmission electron microscopy and large-angle convergent beam electron diffraction (LACBED). APB exhibiting symmetric π-fringe patterns in both bright-field and dark-field images, lying in {011) with the fault vector R =1/2〈111〉, were determined adopting the invisibility criteria of 2π g · R =0 or 2 n π. The curved boundaries due to symmetry change can be related to the low symmetry phase by a pure translation upon phase transition. The displacement vector, R , relating the domains is the translational symmetry element from the origin to the lattice point that was lost upon transition. The formation of such domains induced by the o ₁→ o ₂ phase transition is discussed in terms of change in the Bravais lattice and loss of lattice point upon the transition. The identification has also confirmed the existence of a higher symmetry orthorhombic o ₁ phase along the transition sequence of R 3 c → Ibmm → Pbnm . The increased spatial frequency of APB domains is attributed to A-site ordering due to vacancies created by BaO loss and/or disordering of the B-site substitutional defects generated extrinsically when doped with either a Y³⁺-acceptor or a Nb⁵⁺-donor.     

Hardness and Depth-Dependent Microstructure of Ion-Irradiated Magnesium Aluminate Spinel

Stoichiometric polycrystalline magnesium aluminate spinel has been irradiated at 25° and 650°C with 2.4-MeV Mg⁺ ions to a fluence of 1.4 × 10²¹ ions/m² (∼35 dpa (displacement per atom) peak damage level). Microindentation hardness measurements and transmission electron microscopy combined with energy dispersive X-ray spectroscopy measurements were used to characterize the irradiation effects. The room-temperature hardness of spinel increased by about 5% after irradiation at both temperatures. There was no evidence for amorphization at either irradiation temperatures. Interstitial-type dislocation loops lying on {110} and {111} planes with Burgers vectors along 〈110〉 were observed at intermediate depths (∼1 μm) along the ion range. The 〈110〉{111} loops are presumably formed from 〈111〉{111} loops as a result of a shear on the anion sublattice. Only about 0.05% of the calculated displacements were visible in the form of loops, which indicates that spinel has a high resistance to aggregate damage accumulation. The peak damage region contained a high density of dislocation tangles. There was no evidence for the formation of voids or vacancy loops. The specimen irradiated at 650°C was denuded of dislocation loops within ∼1 μm of the surface.     

ON THE CONSISTENCY OF LEAST SQUARES ESTIMATORS FOR A THRESHOLD AR(1) MODEL

Abstract. For the SETAR (2; 1,1) model

where {a_t(i)} are i.i.d. random variables with mean 0 and variance σ²(i), i = 1,2, and {a_t(l)} is independent of {a_t(2)}, we consider estimators of φ₁, φ ₂ and r which minimize weighted sums of the sum of squares functions for σ²(1) and σ²(2). These include as a special case the usual least squares estimators. It is shown that the usual least squares estimators of φ₁, φ₂ and r are consistent. If σ²(1) ≠σ²(2) conditions on the weights are found under which the estimators of r and φ₁ or φ₂ are not consistent.     

Electronic Conductivity of La-Doped Ceria Ceramics

Lanthanum-doped ceria powder with a composition Ce_0.8La_0.2O_1.9 was prepared by heating the oxalate solid solution (Ce_0.8La_0.2)₂(C₂O₄)₃ at 873 K in air. As-prepared powder was densified to 96%–97% relative density by sintering in air at 1773 K for 4 h. The electronic current of the disk sample was measured in a temperature range from 773 to 1113 K by the direct current polarization method using a Hebb–Wagner ion-blocking cell. A linear relationship, which was theoretically predicted, was measured between log σ_e (electronic conductivity) and E (applied voltage) in the applied voltage range of 0.2–1.0 V. The σ_e was proportional to P _O2^−1/4.3≈ P _O2^−1/4.6 in the oxygen partial pressure range of 10⁻²–10⁻⁸ Pa, and to P _O2^−1/6.7≈ P _O2^−1/7.1 in the oxygen partial pressure range of 10^−7.5–10⁻²² Pa. The apparent activation energy of the electronic conduction was 1.87–1.94 eV. The hole conduction was also measured in the P o₂ range of 10²–10⁵ Pa. The transport number of oxide ion was 0.96–1.00 at 773–1113 K under an oxygen partial pressure of 10⁻⁵ Pa.