Electron paramagnetic resonance study of partially oriented clay platelets intercalated with copper(II) 1,4,8,11-tetraazacyclotetradecane

Electron paramagnetic resonance (EPR) spectra of powder and oriented films of montmorillonite, hectorite, and saponite intercalated with [Cu(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) exhibit three components: an orientation-dependent component without hyperfine features, an orientation-dependent component with hyperfine features, and an orientation-independent component without hyperfine feature. EPR spectra of [Cu(cyclam)](2+)-saponite, which exhibit only two components and the best resolved hyperfine features, were simulated. The spectra indicate that a large portion of the saponite platelets are inclined to the glass surface, although they tend to align with their basal planes parallel to the glass surface. The orientation-dependent spectra could be simulated by introducing a Gaussian distribution with a standard deviation of 20 degrees for the inclination angle. The standard deviation may be used as a disorder parameter for the microcrystals assembled on glass plates. Spectral simulation also shows that the CuN(4) plane of [Cu(cyclam)](2+) is parallel to the clay layers. EPR spectra of some other partially oriented systems are also discussed.     

High oxygen pressures and the stabilization of a new mixed valence Cu(III)/Cu(IV)

Abstract

The Cu(III) oxides were investigated first for the unusual copper oxidation state and then for the high-Tc superconductivity. In the last case this property is observed when a mixed copper valence is stabilized : Cu(I)/Cu(II) or Cu(II)/Cu(III). A new mixed valence Cu(III)/Cu(IV) has been stabilized in the three dimensional lattice of the perovskite-type oxide Lal_-xSr_xCuO₃ (0 ≥ ′ ≥ 0,25). Chemical analysis and XPS study confirm the mixed valence. This compound shows metallic properties with an broadening of the conduction band compared to LaCu0₃. Such a behaviour can be explained either by the increase of the covalence of the average Cu-0 bond or by the decrease of the structural distortion induced by the substitution of Sr(II) for La(III). No superconducting property has been detected down to 4K.     

Leakage current and pyroelectric properties of compositionally graded (Pb,Ca)TiO<Subscript>3</Subscript> films

Highly (100)-oriented, compositionally graded (Pb,Ca)TiO₃ (PCT) thin films with a Ca content from 0 to 24 mol% on Pt/Ti/SiO₂/Si substrates were prepared by a sol-gel process. The graded structure of the Au/PCT/Pt film capacitor showed a well-saturated hysteresis loop at an applied field of 500 kV/cm with remanent polarization (P_r), and coercive electric field (E_c) values of 9.35 C/cm² and 130 kV/cm, respectively. At 100 kHz, the dielectric constant and dielectric loss of the film were 129 and 0.024, respectively. The leakage current density of the graded PCT film was less than 1.0×10^-7 A/cm² over a voltage range from 0 to 4 V. The conduction current depended on the voltage polarity. At low electric field (110 and 180 kV/cm, respectively, for Pt and Au electrodes biased negatively), the Au/PCT and PCT/Pt interfaces form a Schottky barrier. At high electric field (>110 kV/cm), the Au electrode biased negatively shows space-charge-limited current (SCLC) behavior. The temperature dependencies of the pyroelectric coefficients of the graded PCT film were measured by a dynamic technique. From 20 to 82 °C, the pyroelectric coefficients of graded PCT film remain steady in the range 106 to 118 C/m²K. The detectivity figure of merit (F_D) of the graded PCT film was 6.7×10^-6 Pa^-0.5. PACS 77.80.-s; 77.70.+a; 77.22.-d; 51.50.+v; 68.37.-d     

Structure evolution and stoichiometry control of Pb(Zr, Ti)O3 thick films fabricated by electrospray assisted vapour deposition

Well-crystallized and stoichiometric Pb(Zr, Ti)O₃ (PZT) films, typically ∼5 μm thick, with pure perovskite-type rhombohedral structures have been successfully prepared via an electrospray assisted vapour deposition (ESAVD) method. Control of the deposition temperature within a narrow range of 300-400 °C resulted in films with the most desirable phases. PZT films with close stoichiometric match with the expected composition ratio and uniform element distribution were obtained by adding the appropriate levels of excess Pb in the precursor solutions. The annealed films were uniform, dense, compact and adherent to the substrates. The dielectric constant, ?_r, and loss tangent, tan δ, of the fabricated PZT films measured at 10 kHz were 442 and 0.09, respectively. The ESAVD deposited PZT films showed a remanent polarization, P_r, of 15.3 μC/cm² and coercive field, E_c, of 86.7 kV/cm. These results demonstrate the clear potential of the ESAVD method as a promising technique for the fabrication of thick PZT films.     

Effect of bias field on the dielectric properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 single crystals with different orientations

Microdomain-macrodomain transformations and phase transitions in 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ single crystals were investigated by studying their relative permittivity under various dc bias at constant heating and cooling rates. The orientation dependence of the bias field effect was revealed by examining the temperature dependence of relative permittivity as a function of crystal orientation (the 111, 011 and 001 directions) and dc bias field. The crystals have a microdomain rhombohedral ferroelectric state in the ferroelectric phase under zero dc bias. External bias field could modulate the domain state and induce a macrodomain state in the crystals. Also, it is proposed that the dc bias applied along the 001 or 011 direction could induce a tetragonal ferroelectric phase or an orthorhombic ferroelectric phase, respectively, in an intermediate temperature range. PACS 77.80.-e; 77.22.-d; 81.40.-z     

Pulsed-laser-deposited epitaxial aluminum nitride films on (111) Si for surface acoustic-wave applications

Epitaxial (001) aluminum nitride (AlN) thin films on (111) Si substrates are prepared using pulsed-laser deposition. The epitaxial structure of the as-prepared thin films is characterized by checking the X-ray-diffraction θ-2 θ scan and pole-figure, using scanning electron microscopy, infrared radiation (IR) spectroscopy and Raman spectroscopy. The surface acoustic-wave resonance at 345 MHz for a 1.5 μm thick AlN film on a (111) Si substrate is observed using an inter-digital electrode. Received: 18 September 2001 / Accepted: 29 January 2002 / Published online: 3 June 2002 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: liujm@nju.edu.cn     

Weakly compact operators on function spaces

S — E, F — . C(S, E) S E. : C(S, E) F C(S) . , C(S, E) C(S).     

Piezoelectric PMN-PT fibre hydrophone for ultrasonic transducer calibration

A newly developed ceramic fibre hydrophone with an active element as small as 0.25 mm in diameter is described in this work. Lead magnesium niobate-lead titanate (PMN-PT) ceramic fibre with a nominal composition of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ was fabricated by an extrusion method. PMN-PT single crystals were ground to a powder form and then mixed with poly(acrylic) acid to form a homogenous slurry. The fibre was extruded by pressing the slurry through a spinneret and then sintering at 1250 °C for crystallization. The electrical characteristics of the PMN-PT fibre were evaluated by measuring the relative permittivity and the impedance spectrum. A piezoelectric PMN-PT fibre hydrophone was fabricated and its sensitivity, angular response, and spatial resolution were evaluated. The fibre hydrophone provides good spatial resolution, angular response and receiving sensitivity. PACS 43.58.+z; 77.84.Dy     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

Ultrasonic transducers using electron-irradiated vinylidene fluoride-trifluoroethylene copolymers

Single-element, planar transducers have been fabricated using electron-irradiated poly(vinylidene fluoride-trifluoroethylene) 80/20 mol% copolymers with different electron dosage. Electrical field-induced strain response of copolymer film with 100 Mrad dosage has been studied at 5 kHz and the electrostrictive coefficient was calculated. The transmitting response of the air-backing and epoxy-backing transducers was evaluated with the application of high DC bias voltages. Clear ultrasonic amplitudes and high frequency spectrum (>20 MHz) were observed when driven from a standard ultrasonic voltage source through a decoupling circuit. It has also showed that larger generation of ultrasonic waves will be induced under high DC bias field, which is due to the increase of induced d(33) piezoelectric coefficient. Two different polar bias voltages, positive and negative, were applied to the transducers and inverse waveforms were received, which was coincident with the theoretical analysis of the strain response of electrostrictive film.