Controlled sintering and phase transformation of yttria-doped tetragonal zirconia polycrystal material

In this paper, 3 mol% yttria-doped tetragonal zirconia polycrystal material (3 mol% Y₂O₃–ZrO₂) was prepared using an optimised pressureless sintering process. The phase change and particle size distribution of Y₂O₃–ZrO₂ during sintering were studied, and the effect of sintering temperature on the properties of Y₂O₃–ZrO₂ was analysed. The raw materials and prepared samples were analysed using XRD, Raman spectroscopy, SEM, and Gaussian mathematical fitting. The results show that sintering encourages the transformation of the monoclinic phase into the tetragonal phase, thus improving the crystallinity of the sample. The relative content of the tetragonal phase in the sample increased from 57.43% to 99.80% after sintering at 1200 °C for 1 h. In the range of sintering temperatures studied in this paper (800–1200 °C), the zirconia material sintered at 1000 °C presented the lowest porosity and the best density.     

Suppression of nitridation of yttria-doped zirconia during flash sintering

The effect of direct current (DC) and alternating current (AC) on nitridation of 3 mol% Y₂O₃-doped ZrO₂ (3YSZ) after keeping in a flash state for 1 hour was investigated. The inside of the DC-flashed compact was confirmed to exhibit blacking. Scanning transmission electron microscopy, electron energy loss spectroscopy, and X-ray diffraction analysis revealed that zirconium nitrides formed in the blackened area. In contrast, a uniformly densified compact without blackening was obtained by AC fields. No zirconium nitrides formed in the compacts exposed to AC fields even when the flash state was maintained for 1 hour. Therefore, AC fields are effective to suppress nitridation of 3YSZ during flash sintering.     

Effect of withdrawal rate on the evolution of optical properties of dip-coated yttria-doped zirconia thin films

In this work, the Swanepoel method is described and applied for determining various optical parameters and thicknesses of dip–coated yttria–doped zirconia thin films. Using this method the influence of the withdrawal rate on optical parameters was studied. The characterization of the deposited thin films was carried out by optical microscopy and FT–IR spectrophotometry. As expected, coating thickness was closely related to the withdrawal rate and consequently influenced optical parameters such as refractive index, extinction coefficient, and absorption coefficient. Regarding the average refractive index of the prepared thin films, n is in the 2.0 – 2.2 range, the higher refractive index average value being obtained with films deposited at 25 mm min⁻¹ (n = 2.19). The value of the optical band gap was also studied, this increased with withdrawal rate and was quite similar to values reported by other investigators at 50, 25 and 10 mm min⁻¹. Thus, this study proposes analysing the influence of the withdrawal rate for the manufacture of different types of thin films with previously specified optical parameters.     

Ultrafast hole carrier relaxation dynamics in p-type CuO nanowires

Ultrafast hole carrier relaxation dynamics in CuO nanowires have been investigated using transient absorption spectroscopy. Following femtosecond pulse excitation in a non-collinear pump-probe configuration, a combination of non-degenerate transmission and reflection measurements reveal initial ultrafast state filling dynamics independent of the probing photon energy. This behavior is attributed to the occupation of states by photo-generated carriers in the intrinsic hole region of the p-type CuO nanowires located near the top of the valence band. Intensity measurements indicate an upper fluence threshold of 40 μJ/cm² where carrier relaxation is mainly governed by the hole dynamics. The fast relaxation of the photo-generated carriers was determined to follow a double exponential decay with time constants of 0.4 ps and 2.1 ps. Furthermore, time-correlated single photon counting measurements provide evidence of three exponential relaxation channels on the nanosecond timescale.     

Sintering of zirconia ceramics by intense high-energy electron beam

A comparative analysis of the efficiency of zirconia ceramics sintering by thermal method and high-energy electron beam sintering was performed for compacts prepared from commercial TZ-3Y-E grade powder. The electron energy was 1.4 MeV. The samples were sintered in the temperature range of 1200–1400 °C. Sintering of zirconia ceramics by high-energy accelerated electron beam is shown to reduce the firing temperature by about 200 °C compared to that in conventional heating technique. Ceramics sintered by accelerated electron beam at 1200 °C is of high density, microhardness and smaller grain size compared to that produced by thermal firing at 1400 °C. Electron beam sintering at higher temperature causes deterioration of ceramics properties due to radiation-induced acceleration of high-temperature recrystallization at higher temperatures.     

Determination of formation and relaxation of crazes by permeability measurements

Formation and relaxation of crazes on different polymeric films are determined by permeability measurements in a high pressure test cell. Thermal dependence of the films permeability has been studied and interpreted on the basis of segmental movement of the macromolecules. These permeability measurements also offer a way to determine the glass transition temperature of amorphous films.     

State of platinum in zirconia and sulfated zirconia catalysts

Platinum is present in a metallic state following activation in air at 725C of both 5 wt% Pt/ZrO₂ and 5 wt% Pt/SO ₄ ^2– /ZrO₂. Reduction of either catalyst at 725C produces a Pt-Zr alloy, and these reduced catalysts, upon recalcination in air at 725C, form metallic Pt crystallites. Likewise, reduction of these uncalcined catalysts at 725C in H₂ leads to a Pt-Zr alloy formation. However, treatment of these uncalcined catalysts in H₂ at 450C does not produce Pt crystallites large enough to detect by XRD.     

Diimide nanoclusters play hole trapping and electron injection roles in organic light-emitting devices

We report thermally stable diimide nanoclusters that could potentially replace the conventional thick electron transport layer (ETL) in organic light-emitting devices (OLEDs). Bis-[1,10]phenanthrolin-5-yl-bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic diimide (Bphen-BCDI) was synthesized from the corresponding dianhydride and amine moieties, and its purified product exhibited a high glass transition temperature (232 °C) and a wide band gap (3.8 eV). The Bphen-BCDI subnanolayers deposited on substrates were found to form organic nanoclusters, not a conventional layer. The OLED made with a subnanolayer of Bphen-BCDI nanoclusters, instead of a conventional ETL, showed greatly improved efficiency (about 2-fold) compared with an OLED without the diimide nanoclusters. The role of the BPhen-BCDI nanoclusters was assigned to hole trapping and electron injection in the present OLED structure.     

Effect of ultrasound on thermoset polyurethane: NMR relaxation and diffusion measurements

Recycling of rubber-based materials is of increasing industrial environmental importance. In order to characterize the effect of ultrasound on polymer networks, nuclear magnetic resonance (NMR) relaxation and pulsed-gradient diffusion measurements were made at 70.5 °C in polyurethane rubber (PUR) and foam after subsequent treatment by intense ultrasound. The proton transverse relaxation decay was analyzed in terms of molecular and segmental mobilities of all motional species, a chemical and physical network as well as diffusing sol. The diffusivity spectrum, measurable in foams, reflected the changing molecular weight distribution of low-molecular weight sol and oligomers. It was observed that the effect of ultrasound was less pronounced in PUR than rubbers like SBR, PDMS and BR owing to its low degree of unsaturation. The investigation on the foams is the first of its kind to be reported.     

Characterization of rubber-cellulose-fibre composites by mechanical measurements and electron microscopy

Mechanical measurements, SEM micrographs and crosslink density measurements on cellulose-fibre-filled natural rubber suggest that there are bonds between untreated cellulose fibres and the rubber matrix. Mechanical tests indicate that the dispersion or lack of dispersion of the fibres in the matrix is at least as influential a parameter in determining the strength of the composite as is the adhesion between fibre and matrix. Stress/strain measurements indicate that there is no obvious correlation between adhesion and the shape of the stress/strain curve unless the curve is clearly jagged.     

Discrepancy between TPD- and FTIR-based measurements of Brønsted and Lewis acidity for sulfated zirconia

Temperature-programmed desorptions (TPD) of isopropylamine (IPA), NH₃, and pyridine were compared with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of pyridine to determine the effect of H₂O on the Brønsted and Lewis acidities of two sulfated zirconia (SZ) catalysts. Although the traditional interpretation of pyridine infrared spectra showed an apparent increase in Brønsted acidity upon treating SZ with H₂O, TPD spectra showed that H₂O displaced IPA from approximately one-fifth of the Lewis sites with no corresponding increase in Bronsted acidity. Water treatment prior to TPD displaced similar amounts of both NH₃ and pyridine. The primary effect of H₂O is displacement of weakly adsorbed basic probe molecules from Lewis sites, rather than the conversion of Lewis sites to Brønsted sites. Finally, different types of analyses (e.g. infrared or TPD) of catalyst acidity yield dramatically different conclusions regarding Brønsted and Lewis acidity.     

Asymmetric electron hole distribution in single-layer graphene for use in hydrogen gas detection

We demonstrate a highly sensitive hydrogen gas sensor using single-layer graphene exfoliated from highly oriented pyrolytic graphite, which one side of it was covered by palladium. In this asymmetric graphene sensor, the electrons generated from reaction between palladium and hydrogen accumulate at the interface between palladium and graphene, and these accumulated electrons changed the carrier density of graphene beneath the palladium film from hole-dominated to neutralized graphene. This half-neutralized and half hole-dominant graphene showed asymmetrical I–V characteristics in a hydrogen atmosphere. Moreover, this device showed promising sensing performance in hydrogen gas including good sensitivity, a few second response time, and a few minute recovery time from 50 to 20,000 ppm hydrogen depending on the current direction. The fact that the response of the sensor satisfies Sievert’s law, suggests that graphene with lithographically patterned palladium on one half can exhibit direction dependent asymmetrical electric current performance in a hydrogen atmosphere and also can act as a highly sensitive sensor for the quantitative detection of hydrogen molecules over broad concentration ranges.     

Temperature and electron density dependence of spin relaxation in GaAs/AlGaAs quantum well

Temperature and carrier density-dependent spin dynamics for GaAs/AlGaAs quantum wells (QWs) with different structural symmetries have been studied by using time-resolved Kerr rotation technique. The spin relaxation time is measured to be much longer for the symmetrically designed GaAs QW comparing with the asymmetrical one, indicating the strong influence of Rashba spin-orbit coupling on spin relaxation. D'yakonov-Perel' mechanism has been revealed to be the dominant contribution for spin relaxation in GaAs/AlGaAs QWs. The spin relaxation time exhibits non-monotonic-dependent behavior on both temperature and photo-excited carrier density, revealing the important role of non-monotonic temperature and density dependence of electron-electron Coulomb scattering. Our experimental observations demonstrate good agreement with recently developed spin relaxation theory based on microscopic kinetic spin Bloch equation approach.     

High temperature internal friction measurements of 3YTZP zirconia polycrystals. High temperature background and creep

This work focuses on the high-temperature mechanic properties of a 3 mol% yttria zirconia polycrystals (3YTZP), fabricated by hot-pressureless sintering. Systematic measurements of mechanical loss as a function of temperature and frequency were performed. An analytical method, based on the generalized Maxwell rheological model, has been used to analyze the high temperature internal friction background (HTB). This method has been previously applied to intermetallic compounds but never to ceramics, except in a preliminary study performed on fine grain and nano-crystalline zirconia. The HTB increases exponentially and its analysis provides an apparent activation enthalpy which correlates well with that obtained from creep experiments. This fact shows on the one hand the plausibility of applying the generalized Maxwell model to ceramics, and on the other hand indicates the possibility of using mechanical spectroscopy as a complementary helpful technique to investigate the high temperature deformation mechanism of materials.     

Discrepancy between TPD- and FTIR-based measurements of Brønsted and Lewis acidity for sulfated zirconia

Temperature-programmed desorptions (TPD) of isopropylamine (IPA), NH₃, and pyridine were compared with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of pyridine to determine the effect of H₂O on the Brønsted and Lewis acidities of two sulfated zirconia (SZ) catalysts. Although the traditional interpretation of pyridine infrared spectra showed an apparent increase in Brønsted acidity upon treating SZ with H₂O, TPD spectra showed that H₂O displaced IPA from approximately one-fifth of the Lewis sites with no corresponding increase in Bronsted acidity. Water treatment prior to TPD displaced similar amounts of both NH₃ and pyridine. The primary effect of H₂O is displacement of weakly adsorbed basic probe molecules from Lewis sites, rather than the conversion of Lewis sites to Brønsted sites. Finally, different types of analyses (e.g. infrared or TPD) of catalyst acidity yield dramatically different conclusions regarding Brønsted and Lewis acidity.     

Diffusion of niobium in yttria-stabilized zirconia and in titania-doped yttria-stabilized zirconia polycrystalline materials

Bulk and grain boundary diffusion of Nb⁵⁺ cations in yttria-stabilized zirconia (YSZ, 8 mol% Y₂O₃–92 mol% ZrO₂) and in titania-doped yttria-stabilized zirconia (Ti–YSZ, 5 mol% TiO₂–8 mol% Y₂O₃–87 mol% ZrO₂) was studied in air in the temperature range from 900 to 1300 °C. Experiments were performed in the B-type kinetic region. Diffusion profiles were determined using the secondary ion mass spectrometry (SIMS). The temperature dependencies of the bulk diffusion coefficient D and the grain boundary diffusion parameter D′δs for both the materials were calculated. The activation energies of these transport processes in YSZ amounts to 258 and 226 kJ mol⁻¹, respectively, and 232 and 114 kJ mol⁻¹ in Ti–YSZ. The results were compared to the diffusion data of other cations previously obtained for the same material.     

Acoustic relaxation and infrared spectroscopic measurements of the plasticization of poly(methyl methacrylate) by water

Measurements are reported on the acoustic attenuation and velocity of dry and wet samples of poly(methyl methacrylate) over a temperature range of 5° to 70°C and over a frequency range of 5 to 35 MHz. Lowering of the glass transition temperature with increase in water content was reflected in an increase in the acoustic attenuation and a lowering of the velocity at high temperature. Comparison of the infrared spectra of wet and dry thin films indicates that water exhibits spectroscopic characteristics of isolated rather than highly clustered molecules. A study of the temperature dependence of the diffusion coefficient of water into the polymer matrix provided an activation energy for the migration process. The data suggest that water plasticizes poly(methyl methacrylate) via specific local interactions with the backbone.     

A laser interferometric method for electron concentration measurements in stabilized plasmas

This work presents an interferometric means for measuring electron concentrations between 10¹² and 10¹⁶ electrons per cm³ in a stabilized ionized medium and an Argon plasma is used to illustrate the method. The interferometer is a 100 mW He-Ne laser emitting at 6,328 Å and 3.39 microns and a movable mirror is used to obtain the interferometric fringes required for calculation of the electron concenrations in the plasma The method uses the interesting feature of the He-Ne laser that both emissions at 6,328 Å and 3.39 microns originate at the same upper level so that variations in the 3.39 microns emission modulate the visible light (6,328 Å) output. This property has been used by a number of authors for measurements on plasmas in transient conditions; this paper presents an application of the method for stabilized plasmas, thus broadening the field of application