Untersuchungen der protonenresonanz von adsorbiertem wasser an zeolithen des faujasit-typs mit verschiedenen silicium-aluminium-verhältnissen

The line-widths of the proton magnetic resonance have been studied over the possible range of water contents of faujasite-type zeolites for ten samples with different silicium/ aluminium ratio between 1.18 and 2.5. The results show that the mobility of the sorbed water molecules at low coverages is restricted with increasing Si/Al ratio. This effect can be described by a picture of many flat potential wells for low Si/Al ratios and a few deep potential wells at high Si/Al ratios at the surface of the large cavities of the zeolite. The sorbed molecules at intermediate and high water contents rapidly exchange their protons with the sorbed molecules or possibly with OH groups at the walls of the cavities over hydrogen bonds. The line-widths at higher water contents therefore can be explained by an averaging process of the protons of the mobile water molecules with the molecules sorbed at the surface.     

Composition stability limits for the rocksalt-structure phase (Pb1−ySny)1−xTex from lattice parameter measurements

The lattice parameters at 25°C have been measured on powders with a precision of one part in 3(10⁴) for (Pb_1−ySn_y)_1−xTe_x for y = 1·0, 0·90, 0·80,and0·00 and values of x both without and, for the first threey-values, within the composition stability range. For the first threey-values, the composition stability limits for samples metal-saturated at 400°C is 0·5000 ± 0·0002, while those for samples Te-saturated at 356°C is x = 0·5070fory = 1·0, x = 0·5056fory = 0·90,andx = 0·5038fory = 0·80. The fine powders pick up oxygen quickly in air, which reacts with the Pb and Sn upon heating to deplete the telluride solid-solution of metal and consequently reduce its parameter by 2–3(10⁻³)Å. The metals are substantially all returned to the telluride phase upon H₂-reduction at 500–600°C. The present results for SnTe are used to extend the sources of data used in an analysis of SnTe. This analysis shows that the ratio of the number of valence band holes per Sn-vacancy, c, to the 77°K Hall factor, r, is 3·2 ± 0·3 over the entire range of 3(10¹⁹) to 1·8(10²¹) cm⁻³ in the apparent hole concentration. The results for the solid solutions are extrapolated to give the atomic fraction of Te in the 356°C, Te-saturated solid solution for y < 0·8. Comparison with the electrical measurements of others gives c/r equal to about unity for y = 0·27and0·13.     

Densification mechanism of polyacrylonitrile-based carbon fiber during heat treatment

Polyacrylonitrile (PAN)-based carbon fibers were heat treated at various temperatures for varying durations to simulate the graphitization process in the manufacture of C/C composites. Densification of the resulting fibers was confirmed by density measurement. The composition and structure of the fibers were investigated by means of elemental analysis, X-ray diffraction and Raman spectroscopy. For specified isothermal heat treatment time, the structural parameters depended strongly on heat treatment temperature. The nitrogen content decreased with increased heat treatment temperature and extended time at constant temperature. Nitrogen loss was complete at temperatures above 1900 °C. The graphite crystallite size increased rapidly with increasing heat treatment temperature, and slowly with extended isothermal heat treatment time. At 2100 °C a more ordered graphitic structure appeared. Denitrogenation induced “puffing”, which made the fibers expand. Decrease in density in the heat treatment temperature range 1500-1900 °C originated from the abrupt evolution of nitrogen, and above 1900 °C the graphitization transition induced steadily increasing density. Densification of the carbon fibers was determined both by the rate of denitrogenation and the rearrangement of carbon atoms.     

Temperature effect on water desorption from methylcellulose films studied by thermal FT-IR microspectroscopy

Temperature-induced desorption behavior of water from methylcellulose (MC) film was investigated by a novel microscopic Fourier transform infrared (FT-IR) spectroscopy equipped with thermal analyzer (thermal FT-IR microscopic system) and thermogravimetric analysis (TGA). The result indicates that the weight loss of water from MC film was markedly correlated to the IR spectral changes of OH stretching (3000-3800 cm⁻¹) and bending (1649 cm⁻¹) modes of water molecules. The shift of OH stretching mode from 3461 to 3481 cm⁻¹ was accompanied with the water loss from MC film induced by temperature effect. Two stages of water desorption from MC film were proposed: the first stage within the 35-65 °C had a dramatic IR peak shift from 3461 to 3477 cm⁻¹ and accompanied with a largest weight loss of water from MC film, which might be mainly due to the desorption of free water with minor weakly hydrogen-bonded water; the second stage beyond 65 °C would be desorption of moderately hydrogen-bonded bound water, due to the gradual IR spectral shift from 3477 to 3481 cm⁻¹ and a slower weight loss of water from MC film. The changes in peak area ratio of 1649 cm⁻¹/1374 cm⁻¹ with the temperature also confirmed the IR spectral peak shift of the OH stretching mode via the water loss from MC film. The temperature-dependent dissociation of intermolecular and intramolecular hydrogen bonds within water molecules and/or between water/MC interaction might be responsible for the desorption kinetics of water from MC film.     

The decomposition pressure,congruent melting point and electrical resistivity of cerium nitride

The melting point of CeN in nitrogen was determined at pressures between 10⁻² and 21 atmospheres. Congruent melting was observed at T = 2575 ± 20°C and P = 5 ± 1 atmospheres. With lower nitrogen pressures, the melting point was related to the applied (or decomposition) pressure by the equation log P_atmos(N₂) = 18·5 − 5·1 × 10⁴/T. The electrical resistivities of samples prepared from these melts were measured at temperatures between 150–900°K. The room temperature resistivity of congruently melted samples was 21 μΩ-cm, which may be compared with the value of 75 μΩ-cm for cerium metal at this temperature. These samples had a positive (metallic) temperature dependence of resistivity of 0·11 μΩ-cm/°C at room temperature and increased with temperature to a value of 0·22 μΩ-cm/°C at a temperature of 700°K. The noncongruently melted samples had a similar behavior, but with somewhat higher values of resistivity. The room temperature Seebeck coefficients for both types of samples were approximately + 5 μV/°C, relative to platinum.     

Transparent and conducting Zn-Sn-O thin films prepared by combinatorial approach

Zn-Sn-O (ZTO) films with continuous compositional gradient of Sn 16-89 at.% were prepared by co-sputtering of two targets of ZnO and SnO₂ in a combinatorial method. The resistivities of the ZTO films were severely dependent on oxygen content in sputtering gas and Zn/Sn ratio. Except for the films with Sn 16 at.%, all the as-prepared films were amorphous and maintaining the stable amorphous states up to the annealing temperature of 450 °C. Annealing at 650 °C resulted in crystallization for all the composition, in which ZnO, Zn₂SnO₄, ZnSnO₃, and SnO₂ peaks were appeared successively with increasing Sn content. Above Sn 54 at.%, the ZTO films were deduced to have a local structure mixed with ZnSnO₃ and SnO₂ phases which were more conductive and stable in thermal oxidation than ZnO and Zn₂SnO₄ phases. The lowest resistivity of 1.9 × 10⁻³ Ω cm was obtained for the films with Sn 89 at.% when annealed at 450 °C in a vacuum. The carrier concentrations of the amorphous ZTO films that contained Sn contents higher than 36 at.% and annealed at 450 °C in a vacuum were proportional to the Sn contents, while the Hall mobilities were insensitive to Sn contents and leveling in the range of 23-26 cm²/V s.     

Transport properties and in-situ Raman spectroscopy study of BaCe0.9Y0.1O3 − δ as a function of water partial pressures

The total conductivity of BaCe_0.9Y_0.1O_3 − δ material was measured under air, in a large p(H₂O) range up to 0.30 bar. The defect concentrations (OH_O^·, V_O^· · and h^·) and electrical conductivities were calculated on the basis of chemical constants (diffusion coefficients and equilibrium constants reported in the past literature) and compared to the experimental data. Protonic transport number as high as 0.8 was found at 700 °C, under air containing 0.30 bar of water, which allows a possible extension of the protonic temperature range of this material using water rich atmosphere. In-situ Raman spectroscopy under wet and dry air was performed from room temperature up to 700 °C in two wavenumber ranges. At low wavenumber, characteristic of lattice vibrations, this study clearly shows that no significant changes occur upon water insertion while at high wavenumbers, characteristic of OH vibrations, two contributions to the OH vibrations were found. This is discussed in terms of proton environment and transient hydrogen bonds. Moreover, this in situ study confirms that, at moderate p(H₂O), water insertion becomes significant at temperature below 650 °C.     

Magnetic and bioactivity evaluation of ferrimagnetic ZnFe2O4 containing glass ceramics for the hyperthermia treatment of cancer

Glass ceramics of the composition xZnO·25Fe₂O₃·(40−x)SiO₂·25CaO·7P₂O₅·3Na₂O were prepared by the melt-quench method using oxy-acetylene flame. Glass-powder compacts were sintered at 1100 °C for 3 h and then rapidly cooled at −10 °C. X-ray diffraction (XRD) revealed 3 prominent crystalline phases: ZnFe₂O₄, CaSiO₃ and Ca₁₀(PO₄)₆(OH)₂. Vibrating sample magnetometer (VSM) data at 10 KOe and 500 Oe showed that saturation magnetization, coercivity and hence hysteresis area increased with the increase in ZnO content. Nano-sized ZnFe₂O₄ crystallites were of pseudo-single domain structure and thus coercivity increased with the increase in crystallite size. ZnFe₂O₄ exhibited ferrimagnetism due to the random distribution of Zn²⁺ and Fe³⁺ cations at tetrahedral A sites and octahedral B sites. This inversion/random distribution of cations was probably due to the surface effects of nano-ZnFe₂O₄ and rapid cooling of the material from 1100 °C (thus preserving the high temperature state of the random distribution of cations). Calorimetric measurements were carried out using magnetic induction furnace at 500 Oe magnetic field and 400 KHz frequency. The data showed that maximum specific power loss and temperature increase after 2 min were 26 W/g and 37 °C, respectively for the sample containing 10% ZnO. The samples were immersed in simulated body fluid (SBF) for 3 weeks. Scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) and XRD results confirmed the growth of precipitated hydroxyapatite phase after immersion in SBF, suggesting that the ferrimagnetic glass ceramics were bioactive and could bond to the living tissues in physiological environment.     

Thermally stimulated depolarization of a phosphate glass

Thermally stimulated depolarization (TSD) of phosphate glass of the composition 72·9% P₂O₅, 8·5% Al₂O₃, 18·6% CaO, 0·23% MnO has confirmed the existence of two types of slow relaxation. Migration polarization leads to TSD maximum near 0 °C, while the high temperature TSD maximum at 113 °C probably corresponds to space charge polarization. An analysis of the high temperature maximum shows that it is formed by a spectrum of relaxations with a single activation energy 1·0 eV, distributed over the dipole frequency factors with the most probable value ₀ 10¹⁰ sec^–1. Strong dispersion of permittivity points to the space charge polarization, though it is found that the effect is linear and independent of the sample geometry.The authors thank Dr. A.Bohun for the samples and for valuable advice.     

Investigation of the effect of power ultrasound on the nucleation of water during freezing of agar gel samples in tubing vials

Nucleation, as an important stage of freezing process, can be induced by the irradiation of power ultrasound. In this study, the effect of irradiation temperature (−2 °C, −3 °C, −4 °C and −5 °C), irradiation duration (0 s, 1 s, 3 s, 5 s, 10 s or 15 s) and ultrasound intensity (0.07 W cm⁻², 0.14 W cm⁻², 0.25 W cm⁻², 0.35 W cm⁻² and 0.42 W cm⁻²) on the dynamic nucleation of ice in agar gel samples was studied. The samples were frozen in an ethylene glycol-water mixture (−20 °C) in an ultrasonic bath system after putting them into tubing vials. Results indicated that ultrasound irradiation is able to initiate nucleation at different supercooled temperatures (from −5 °C to −2 °C) in agar gel if optimum intensity and duration of ultrasound were chosen. Evaluation of the effect of 0.25 W cm⁻² ultrasound intensity and different durations of ultrasound application on agar gels showed that 1 s was not long enough to induce nucleation, 3 s induced the nucleation repeatedly but longer irradiation durations resulted in the generation of heat and therefore nucleation was postponed. Investigation of the effect of ultrasound intensity revealed that higher intensities of ultrasound were effective when a shorter period of irradiation was used, while lower intensities only resulted in nucleation when a longer irradiation time was applied. In addition to this, higher intensities were not effective at longer irradiation times due to the heat generated in the samples by the heating effect of ultrasound. In conclusion, the use of ultrasound as a means to control the crystallization process offers promising application in freezing of solid foods, however, optimum conditions should be selected.     

Study of recrystallisation of CdGeAsMnx glass

It is shown that CdGe₀₃As₃Mn_x. can be prepared in glassy form up to the content of Mnx = 0·15. This glass is stable up to the temperature of 275 °C. Greater amount of Mn or heat treatment at temperatures higher than 275°C leads to the nucleation of crystalline phases, namely MnAs and CdAs₂.     

Surface modification by vacuum annealing for field emission from heavily phosphorus-doped homoepitaxial (1 1 1) diamond

The relationship between field emission properties and C 1s core level shifts of heavily phosphorus-doped homoepitaxial (1 1 1) diamond is investigated as a function of annealing temperature in order to optimize surface carbon bonding configurations for device applications. A low field emission threshold voltage is observed from surfaces annealed at 800 °C for hydrogen-plasma treated surface, while a low field emission threshold voltage of wet-chemical oxidized surface is observed after annealing at 900 °C. The C 1s core level by X-ray photoelectron spectroscopy (XPS) showed a shoulder peak at 1 eV below the main peak over 800 and 900 °C annealing temperature for hydrogen-plasma treated and wet-chemical oxidized surfaces, respectively. When the shoulder peak intensity is less than 10% of the main peak intensity, lower threshold voltages are observed. This is due to the carbon-reconstruction which gives rise to a small positive electron affinity. By increasing annealing temperature, the shoulder peak ratios also increase, which indicates that a surface graphitization takes place. This leads to higher threshold voltages.     

Electron spin resonance in carbon-doped boron nitride

It is shown that carbon impurity is responsible for the yellow color and paramagnetism in boron nitride which has been heated to 1800–2300°C in graphite furnaces. The yellow BN powders exhibited 10-line ESR spectra with spin concentrations up to 10¹⁹/g. Annealing the yellow BN at 1800–2300°C in a carbon-free environment removed the yellow color and reduced the spin concentration below the observable limit of 10¹⁶/g. Such pure white BN was unaffected by prolonged irradiation with u.v., 50 kV X-rays or 1 MeV γ-rays, whereas other less pure types of BN showed a large enhancement of ESR signal after relatively short exposures to such radiation. The ESR spectra from pure white BN doped with C¹³-enriched carbon were identical to those from BN doped with normal carbon. These results suggest that the yellow color in BN is due to an F-center produced by a carbon impurity ionization mechanism. The anisotropy of the ESR was studied in carbon-doped specimens of highly oriented BN. The room temperature hyperfine splitting at 9·151 GHz was found to vary as (a + b cos²θ), where a = 7·85 ± 0·07 G and b = −1·27 ± 0·07 G. The g-value obeyed a similar relation: g = g_⊥ + Δg cos²θ, where g_⊥ = = 2·00321 ± 0·00002 and Δg = g_∥ − g_⊥ = (−9·5 ± 0·2) × 10⁻⁴.     

Surface heterogeneity of polysiloxane xerogels functionalized by 3-aminopropyl groups

DRIFT spectra of xerogels synthesized by co-condensation of tetraethoxysilane (or 1,2-bis(triethoxysilyl)ethane) and 3-aminopropyltriethoxysilane have been measured using termoevacuation in the temperature range 50-350 °C. The disappearance of bands related to the vibrations of water molecule with temperature growth and shifts of absorption band related to the deformation vibrations of amino groups to the high-frequency region have been observed. The formation of a new band in the range of 3650-3660 cm⁻¹ has been attributed to stretching vibrations of silanol groups. The simplest change of surface layer composition in the amino-containing xerogels by water removal results in transformation of one type of hydrogen bond to another. The first type is associated with forming of cyclical structure with participation of 3-aminopropyl and silanol groups and water molecule, [≡Si(CH₂)₃H₂N···HO(H)···HOSi≡], the other type is associated with the interaction of amino groups between each other.     

The electrodeposition behaviors and magnetic properties of Ni-Co films

Ni-Co films with different compositions and microstructures were produced on ITO glasses by electrodeposition from sulphate bath at 25 °C. Cyclic voltammograms give a result that the increase in the Co²⁺ concentration displaces Ni-Co alloy oxidation peaks to negative potential with high Co current distributions. It is observed that the content of cobalt in the films increases from 22.42% to 56.09% as the molar ratio of CoSO₄/NiSO₄ varying from 0.015/0.085 to 0.045/0.055 in electrolyte. XRD patterns reveal that the structure of the films strongly depends on the Co content in the deposited films. The saturation magnetization (M_s) moves up from 144.84 kA m⁻¹ to 342.35 kA m⁻¹ and coercivity (H_c) falls from 15.27 kA m⁻¹ to 7.27 kA m⁻¹ with the heat treatment temperature increasing from 25 °C to 450 °C. The saturation magnetization (M_s) and coercivity (H_c) move up from 340.97 kA m⁻¹ and 7.98 kA m⁻¹ to 971.58 kA m⁻¹ and 18.62 kA m⁻¹ with the Co content increasing from 22.42% to 56.09% after annealing at 450.     

Variable temperature FT-IR studies on hydrogen adsorption on the zeolite (Mg,Na)-Y

Variable-temperature infrared spectroscopy was used for the thermodynamic studies on the adsorption of hydrogen on the zeolite (Mg,Na)-Y. Adsorption renders the HH stretching mode infrared active, and simultaneous measurement of IR absorbance and hydrogen equilibrium pressure, over a range of temperature, allowed adsorption enthalpy and entropy to be determined. The standard adsorption enthalpy and entropy resulted to be ΔH° = −18.2(±0.8) kJ mol⁻¹ and ΔS° = −136(±10) J mol⁻¹ K⁻¹, respectively. The adsorption enthalpy is substantially higher than the hydrogen liquefaction heat, which suggests that magnesium-containing porous materials are potential candidates in the search for suitable adsorbents for reversible hydrogen storage.     

Tunable polymer waveguide Bragg filter fabricated by direct patterning of UV-curable polymer

Tunable polymer wavelength filters are demonstrated using a silicon-nitride grating which gives high refractive index contrast with polymers. The polymer waveguides are defined using direct patterning of a liquid-state UV-curable polymer by proximate-contact lithography technique. The wavelength filter exhibits a narrow bandwidth of less than 1.0 nm and a transmission dip of more than −15 dB. The peak wavelength is shifted over 10 nm in the temperature range of 25-70 °C and the thermal tuning efficiency is −0.212 nm/°C.     

Static susceptibility and heat capacity studies on V3O7·H2O7 nanobelts

V₃O₇·H₂O nanobelts were prepared by a hydrothermal method at 190 °C using V₂O₅·nH₂O gel and H₂C₂O₄·2H₂O as starting agents. The obtained nanobelts have diameters ranging from 40 to 70 nm with lengths up to several micrometers. Measurements of the static magnetic susceptibility and the specific heat show a discontinuous phase transition at around T=145 K, which separates two regions of paramagnetic behavior.     

A novel method for the assembly of nano-zeolite crystals on porous stainless steel microchannel and then zeolite film growth

A new method that is simple, efficient, and clean was developed for seeding surfaces with a monolayer of covalently bonded zeolite seeds. This method was used to seed the microchannels fabricated on porous stainless steel with NaA nano-zeolites enabling the deposition and growth of defect-free zeolite film. The NaA nano-zeolites were attached to the surface of the stainless steel via alkoxysilane linkers (e.g., 3-chloropropyltrimethoxysilane and 3-aminopropyltrimethoxysilane) grafted on the stainless steel. The NaA zeolite grown on the microchannel by hydrothermal synthesis consists of intergrown, (1 1 1)-oriented pyramidal NaA crystals that completely clad the stainless steel grains. The zeolite cladding the grains grew uniformly until the zeolite layers of neighboring grain impinges, then intergrew to fully bridge the gaps between the grains forming a defect-free film layer. A separation factor of 10,000 and a flux of 0.04 kg m⁻² h⁻¹ were obtained for water pervaporation from a 3 wt% water-benzaldehyde solution at room temperature.