Influence of isotopic substitution on the diffusion and thermal diffusion coefficient of binary liquids

The mutual mass diffusion coefficient (D) and the thermal diffusion coefficient ( D _T) of the liquids acetone, benzene, benzene-d ₁, benzene-d ₃, benzene-d ₅, benzene-d ₆, benzene- ¹³C₆, n-hexane, toluene, 1, 2, 3, 4-tetrahydronaphtalene, isobutylbenzene, and 1, 6-dibromohexane in protonated and perdeuterated cyclohexane have been measured with a transient holographic grating technique at a temperature of 25 ^°C. The mass diffusion coefficient shows a pronounced concentration dependence. Perdeuteration of cyclohexane only leads to marginal changes of the mass diffusion coefficient. The Stokes-Einstein equation describes the limiting tracer diffusion coefficients well if the solute molecule is smaller than the solvent. It is not capable to describe the small isotope effect of a few percent. On the other hand, the isotope effect, which is independent of concentration, is in agreement with the Enskog theory, that does not provide the absolute value of the mass diffusion coefficient of the liquid mixtures. The thermal diffusion coefficient of all the binary mixtures shows a moderate and almost linear concentration dependence. Its isotope effect, which is the change of D _T upon deuteration of cyclohexane, varies with mole fraction. The thermophoretic force acting on any tracer molecule in cyclohexane changes by the same amount when cyclohexane is perdeuterated, irrespective of the magnitude of the thermophoretic force before deuteration. This change of the thermophoretic force is equal but of opposite sign to the difference between the thermophoretic forces acting on cyclohexane and perdeuterated cyclohexane as tracers in any of the above liquids.     

Study of the structure and refractive parameters of diethylamine and triethylamine

The refractive index (n) and thermal coefficient of the refractive index (dn/dt) are measured at four wavelengths for the diethylamine and triethylamine. The measurements are carried out using the Bellingham+Stanley model 60/ED high-accuracy Abbe refractometer. The optical permittivity (ε) and its variation with temperature are calculated. Applying the Cauchy equation, the following refractive properties are obtained: the optical dispersion dn/dλ, the dielectric dispersion dε/dλ, the variation of -dn/dT, dε/dT, as a function of wavelength (λ), and Cauchy's constants against temperature. Additionally, molar refractivity versus temperature and wavelength are determined.     

Spontaneous photorefractive effect in Sr1−x CaxTiO3 (x=0.014)

The temperature dependence of the principal values of the refractive index in Sr_1−x Ca_xTiO₃ (x=0.014) has been measured in the 17–275 K range under various conditions of sample illumination with 1.96 eV photons. The spontaneous photorefractive contribution δn ^ph to the temperature-induced variation of the refractive index of Sr_1−x Ca_xTiO₃, which appears after illumination of the sample in the ferrophase (transition temperature T _c=32 K) and persists in the paraphase under heating up to 150 K, has been separated. The photoinduced polarization has been estimated. Fiz. Tverd. Tela (St. Petersburg) 39, 711–713 (April 1997)     

Macroscopic and microscopic parameters of laser dye solvents: m-xylene and dioxane

For the laser designer and other users the optical, electrical and refractive parameters have been obtained for pure nonpolar laser dye solvents m-xylene and dioxane. The refractive index (n) and its thermo-optic constant (dn/dT) at argon laser wavelength 514.5 nm and He–Ne laser wavelength 632.8 nm, are measured. The values of n and dn/dT are used to calculate the optical permittivity ε=n² and its variation with temperature dε/dT. Applying Cauchy's equation the optical and dielectric dispersion (dn/dλ and dε/dλ) are determined. The variation of −dn/dT, −dε/dT, molar refractivity and thermal volume expansion coefficient as a function of wavelength are calculated and represented. Furthermore Cauchy's constants A and B as a function of temperature are plotted. The specific and molar refractivities, specific and molar dispersivity total polarizability, distortion polarizability, ratio of atomic to electronic polarizability, molecular radius, relaxation time, electric susceptibility characteristic impedance, and other physical parameters were calculated. Additionally, density, thermal linear expansion coefficient and molar polarization as a function of temperature were calculated at the laser wavelengths 514.5 nm.     

Optical properties of AsSe1.5−xTex glassy system

Thin AsSe_1.5−xTe_x films with 0x<1.5 have been prepared by a thermal vacuum evaporation technique onto quartz and glass substrates kept at room temperature (300 K). The optical constants, the refractive index, n, and the absorption index, k, of the films were determined for the investigated compositions of different thickness values (100–300 nm) using spectrophotometric measurements of the transmittance, T, and the reflectance, R, at normal incidence in the spectral range 400–2500 nm. The obtained values of both n and k were found to be independent of the film thickness within the above mentioned thickness range. The estimated indirect and direct optical energy gap decreased as tellurium content increased in the parent sample AsSe_1.5. The values of dispersion energy, E_d, and lattice dielectric constant, _L, of the system have been determined and correlated with the type and amount of chemical bonds and the relative proportion of the constituent elements in the examined compositions.     

Compositional effects on the optical and thermal properties of sodium borophosphate glasses

A series of sodium borophosphate glasses of the composition (1−x)NaPO₃−xB₂O₃ have been synthesised from Na₂CO₃, B₂O₃ and P₂O₅ and their optical and thermal properties investigated. The results show that refractive index (n) and glass transition temperature (T_g) show a maximum at about B/(B+P)=0.6 while thermal expansion coefficient (α) and thermo-optic coefficient (dn/dT) change monotonically with the B/(B+P) ratio. These observations can be interpreted based on the incorporation of BO₃ and BO₄ units into the glass structural network.     

Photoinduced effects on the optical constants of a-Ge–Se–Bi chalcogenide glassy thin films

In addition to the conversion from p-type to n-type conductivity that occurs in Ge–Se–Bi thin films when Bi is incorporated in a certain concentration. We found that, when these films were illuminated to UV light, after being annealed at glass transition temperature T _g, the photobleaching is dominant for Ge₂₀Se_80?x Bi _x (x=0, 2.5, and 5 at.%), while for Ge₂₀Se_72.5Bi_7.5 photodarkening is dominant. The photoinduced changes in the optical constants were studied. The refractive index (n) has been analysed according to the Wwmple–DiDominico single oscillator model and the values of E _o and E _d for exposed and unexposed films were determined, respectively. The photostructural effects were discussed in the light of single–double well model proposed by Tanaka and chemical bond approach.     

Dispersive optical constants of glassy AsSe1−xTex system

The compositional dependence of the optical constants, the refractive index n, and the absorption index k, of the AsSe_1−xTe_x thin films with 0<x<1.0 were determined in the spectral range of 400–2500 nm. The maximum value of the refractive index n, is shifted toward the long wavelength by increasing the Te content in the examined system. The values of the forbidden energy gap of the system have been determined and were correlated with the type and the amount of chemical bonds formed by the increasing Te content in the AsSe_1−xTe_x glassy system. The value of the dispersion energy E_d exhibits low value at the composition containing the same atomic percent of Se and Te.     

Measurements of the refractive indices and refractive index increment of a synthetic PMMA solutions at 488 nm

We describe a Mach–Zehnder interferometer (MZI) method for measuring the refractive index (RI) of polymethyl-methacrylate (PMMA) solution in both acetone and methyl-ethyl-ketone (MEK). The measurements are made as a function of concentration values 4, 8, 12, 16 and 20 g/l at a wavelength of 488 nm with a high degree of accuracy tends to 1.4×10⁻⁵. The refractive index increments (RIIs) dn/dc of PMMA in both investigated solvents are determined too. In addition, the RIIs Δn as a function of concentration and the RIIs at zero concentration (dn/dc)_c=0 are determined for both solvents accurately. The PMMA solutions in acetone and MEK solvents are chosen for laser light scattering investigations.     

Optical waveguides in LiNbO3 formed by ion implantation

Abstract

Ion implantation in LiNbO₃ can be used to modify the refractive index. The change in indices, n ₀ n _e results from the damage formed by energy deposited by the (dE/dx)_nuclear collisions between the ions and the lattice and is independent of the ion species. A saturation change in index of some ?7% occurs after a deposition of 10²³ keV cm^?3 at 300K, greater changes of ?9 % occur with implants at 77K. Annealing studies indicate the optical absorption formed during irradiation is removed below 200°C whereas the index changes exist up to 400°C. For optical waveguide production a negative change in the index is not ideal as the damaged layer cannot directly act as the region of optical confinement. However the (dE/dx)_electronic term is unimportant and so we have been able to form optical waveguides by ion implantation with light energetic ions (e.g. MeV He⁺ ions) because the damaged layer is then formed beneath an unchanged high index surface layer. This retains the desirable electrooptic properties of the single crystal LiNbO₃. The experimentally observed waveguide modes are in accord with our theoretical predictions of the refractive index profiles.     

Wavelength and temperature dependence properties of human blood-serum

For biological importance and general scientific interest, the present paper studies the physical properties dependent on wavelength and temperature, for six different samples of human blood-serum, at two different laser wavelengths (514.5 and 632.8 nm). The properties are described in terms of scalar quantities, viz. refractive index or optical permittivity, optical and dielectric dispersion. A modified and high accurate laser Mach–Zehnder interferometric technique is used for measurement of the refractive index (n) and its gradient with temperature (dn/dT). The values of n and dn/dT are applied to calculate the optical permittivity () and its gradient with temperature d/dT. The refractive properties such as the variation of n, , −dn/dT and, −d/dT as a functions of wavelengths are determined. On the other hand, the optical properties such as reflectance, transmittance and absorptance as a function of light incident angle, temperature and wavelength are studied. Additionally the following dielectric parameters are calculated: specific refractivity, specific dispersivity, polarizability per unit volume, wave impedance, volume expansion coefficient and the electric susceptibility.     

Kinetic phenomena in zero-gap semiconductors CuFeS<Subscript>2</Subscript> and CuFeTe<Subscript>2</Subscript>: Effect of pressure and heat treatment

Electrical resistivity ρ and Hal coefficient R are measured as a function of the temperature (T = 1.7−310 K) and the magnetic field (up to H = 28 kOe) in zero-gap semiconductor CuFeS₂ samples subjected to hydrostatic compression and under various heat-treatment conditions. At low temperatures, anomalies are observed in the kinetic effects related to the presence of ferromagnetic clusters: the magnetoresistance at T = 4.2 K and T = 20.4 K acquires a hysteretic character and thermopower α changes its sign at T < 15 K. The temperature dependence of conduction-electron concentration n in CuFeS₂ has a power form in the temperature range T = 14−300 K, which is characteristic of the intrinsic conductivity in zero-gap semiconductors. In CuFeS₂, we have n(T) ∝ T ^1.2; in isoelectron compound Cu_1.13Fe_1.22Te₂, we have n(T) ∝ T ^1.93. Heat treatment is found to affect the intrinsic conductivity of CuFeS₂, as the action of hydrostatic compression (carrier concentration changes); that is, the carrier concentration changes. However, a power form of the n(T) and ρ(T) dependences is retained.     

Thermo-optical properties of a solar energy storage material

A dual wavelength laser Mach–Zehnder interferometric technique is applied for measuring the absolute values of refractive index n and its thermo-optic coefficients dn/dT for paraffin wax. The values of n and dn/dT are used to calculate a number of the decisive thermo-optic properties. Applying Maxwell’s equation (=n²) the optical permittivity and its thermal coefficient d/dT, specific refraction, specific dispersivity, polarizability per unit volume and the ratio of atomic to electronic polarizabilities are calculated. On the other hand the optical dispersion dn/dλ and dielectric dispersion d/dλ are calculated according to Cauchy’s equation. Different important relationships between −dn/dT, −dn/dλ, −d/dT and d/dλ as a function of wavelength and other important constants are calculated and graphically represented.     

Influence of Li-rich vapor transport equilibration on surface refractive index and Mg concentration of MgO (5 mol%)-doped LiNbO3 crystal

The Li-rich vapor transport equilibration (VTE) effect on surface refractive index of MgO (5 mol%)-doped LiNbO₃ crystal is studied at the wavelengths of 473, 632.8 and 1536 nm. The results show that in the early stage of VTE the ordinary index n _o decreases substantially with the VTE duration t, then recovers slightly, and tends to a constant for t>80 h. The extraordinary index n _e shows a similar VTE effect but reveals a relatively weak dependence on the VTE duration. Secondary ion mass spectrometry analysis shows that the VTE induces Mg diffusion within the crystal and hence an inhomogeneous Mg depth profile, depending on the VTE duration. As the VTE is prolonged the Mg homogeneity is improved. The surface Mg concentration, determined from the measured surface n _o and energy dispersive X-ray analysis, shows a substantial VTE duration dependence, which is responsible for the substantial VTE effect on surface index. Neutron activation analysis shows that the VTE hardly induces the MgO loss from the crystal. It appears that the Mg ions counter diffuse to the crystal surface in the early stage of VTE and then diffuse slowly back into the bulk of the crystal toward equilibrium as Li concentration tends to equilibrium. Gravimetric measurement shows that the Li₂O content in the crystal increases with the VTE duration in the early stage of VTE and saturates for t>60 h, and the Li₂O content increase in the saturation regime is about 2.25 mol%.     

The refractive index dispersion of Hg1−xCdxTe by infrared spectroscopic ellipsometry

The refractive indices of Hg_1−xCd_xTe (x=0.276, 0.309, and 0.378) bulk samples in the region below, in, and above the fundamental band gap have been measured by infrared spectroscopic ellipsometry at room temperature. A refractive index peak, in which the corresponding energy equals approximately the band gap energy, is observed for each refractive index spectrum with different compositions. Above the band gap, the refractive index drops quickly near the gap, then decreases slowly as photon energy increases. The refractive index n above the band gap is found to follow the Sellmeier dispersion relationship n²(λ)=A+B/λ²+C/λ⁴+D/λ⁶ as a function of the wavelength of light λ.     

NMR relaxation times and proton motion in HxWO3

The relaxation timesT ₁,T _1q,T _1D, andT ₂ for¹H in the tetragonal-A phase of H_xWO₃ have been measured over the temperature range 190 to 490 K. The¹H relaxation behaviour appears to be governed by diffusion over inequivalent jump distances, approximating to a short range planar diffusion and a long range isotropic diffusion. Parameters for the latter motion are estimated asE _a = 68 kJ/mol and ₀=2.5×10^–13 s. The powder X-ray diffraction pattern for this phase of H_xWO₃ has been studied over the temperature range 300–470 K. The tetragonal distortion diminishes with temperature and H_0.43 WO₃ becomes cubic at about 435 K. Volumetric studies of hydrogen evolution show that decomposition accelerates at approximately this temperature.     

Investigation of the mass dependence of self-diffusion coefficients by molecular dynamics calculations: binary and ternary isotopic mixtures of atoms

Extensive molecular dynamics calculations have been used to study for the first time systematically the dependence of the self-diffusion coefficients D_i (i = 1, 2, 3) in binary and ternary atomic isotopic mixtures on the particle mass ratios m*₂ = m ₂/m ₁ and m*₃ = m ₃/m ₁ at different reduced temperatures T* and reduced particle number densities n*, using a Lennard-Jones 12-6 potential and a hard-soft-spheres potential. In addition, the dependence of D_i values of binary mixtures on the mole fraction x ₁ = 1—x ₂ was also investigated for some thermodynamic states. The calculated values of D_i can be represented quantitatively by exponential estimates of the form D_i = D* _i (m*₂)^ex _i in the case of binary mixtures and D_i = D ⁰ _i (m*₂)^{ex _i} (m ₃)^{ext _i} in the case of ternary mixtures. D ⁰ _i are the self-diffusion coefficients in reference mixtures of mass ratios m*₂ = m*₃ = 1. The dependence of the exponents ex _i (m*₂, T*, n*, x ₁) of binary mixtures on m*₂, T*, n*, and x ₁ and the dependence of the exponents ext _i (m*₂, m*₃, n*) of equimolar ternary mixtures at T* = 1.8 on the exponents ex _i of the constituent binary mixtures and on m*₂, m*₃, and n* are discussed.     

块体非晶合金的黏度与玻璃形成能力的关系

基于经典结晶理论讨论了非晶合金的晶化动力学因素和晶化热力学因素对玻璃形成能力（GFA）的影响.分析表明,合金的等温转变（TTT）曲线“鼻尖”温度T_n对应的黏度与晶化阻力因子成正比;重新加热时晶化开始温度T_x对应的黏度与晶化驱动力因子成反比.由此得到了新的GFA参数ω₀=（T_g-T₀）/（T_x-T₀）-（T_g-T₀）/（T_n-T₀）,其中T_g为玻璃转变温度,T₀为理想玻璃转变温度.统计结果显示,ω₀与临界冷却速率具有较高的相关性,R²高达09626.进一步分析表明：新提出的ω₀参数可以合理地解释过冷熔体的黏度、脆性、液相稳定性、热稳定性以及T_rg、ΔT_x、γ、γ_m、ΔT_rg、α、β、δ和φ等参数与GFA的关系. 关键词： 块体非晶合金 黏度 脆性 玻璃形成能力     

Dispersive optical constants of a-Se100−xSbx films

Thin films of amorphous Se_100−xSb_x (x=5,10 and 20 at%) system are deposited on a silicon substrate at room temperature (300 K) by thermal evaporation technique. The optical constant such as refractive index (n) has been determined by a method based on the envelope curves of the optical transmission spectrum at normal incidence by a Swanpoel method. The oscillator energy (E_o), dispersion energy (E_d) and other parameters have been determined by the Wemple–DiDomenico method. The absorption coefficient (α) has been determined from the reflectivity and transmitivity spectrum in the range 300–2500 nm. The optical-absorption data indicate that the absorption mechanism is a non-direct transition. We found that the optical band gap, E_g^opt, decreases from 1.66±0.01 to 1.35±0.01 eV with increase Sb content.     

Desorption kinetics and surface diffusion of potassium,rubidium and cesium on a silicon(111)7 × 7-surface

Using pulsed atomic beam technique and a surface ionization ion microscope, the desorption kinetics and the surface diffusion of the alkalis potassium, rubidium and cesium were investigated on a Si(111)7 × 7-surface at extremely low alkali coverages. In the temperature range 1120 … 800 K, the mean adsorption lifetime τ(T) = τ₀ · exp(E_desⁱ/kT) and the mean diffusion length x(T) - defined in the equilibrium between adsorption, diffusion and desorption - were measured. From these data the diffusion constant D(T) = D₀ · exp(-E_diff/kT) was obtained as D = x^?2/τ. For temperatures T ? 750 K, the diffusion constant was calculated from nonstationary alkali concentration profiles using the Boltzmann-Matano method. From the temperature dependence of these quantities the parameters of desorption (E_des,ⁱ τ₀) and surface diffusion (E_diff, D₀) for K, Rb and Cs on Si(111) were obtained. The values of E_diff and D₀ are comparably high and may be interpreted by non-localized diffusion according to a model proposed by Bonzel (Surf. Sci. 21 (1970) 45).