Low temperature heat release,sound velocity and attenuation,specific heat and thermal conductivity in polymers

We have measured the long time (t = 5 to 200 h) heat release of Polymethylmethacrylate (PMMA) and Polystyrene (PS) at 70 mK T 300 mK. After cooling from a charging temperature of 80 K the heat release in PMMA shows a t^–1 dependence in the measured time and temperature ranges in agreement with the tunneling model. In contrast, for PS we observe strong deviations from at ^–1 dependence and a factor of ten smaller heat release than in PMMA in apparent contradiction to specific heat and thermal conductivity data for PS. To compare the heat release with other low temperature properties and to verify the consistency of the tunneling model we have measured also the acoustical properties (sound velocity and attentuation), the specific heat and the thermal conductivity of PMMA and PS in the temperature range 70mKT 100 mK, 70mKT200 mK and 0.3 KT4K, respectively. We show that the anomalous time dependence of the heat release of PS is due to the thermally activated relaxation of energy states with excitation energies above 15 K.     

A scaled equation of state for real fluids in the critical region

A scaled equation of state is proposed for real fluids in the critical region which incorporates asymmetry with respect to the critical isochore. In the range of reduced densities 0.65(/ _c)1.4 and for reduced temperatures (T/T _c)1.2, the equation represents P-V-T data for steam within the experimental accuracy.     

A generalized scaled equation of state for n-alkanes (methane to n-nonane) in the critical region

A generalized scaled equation of state has been developed to calculate thermodynamic properties of n-alkanes from methane (CH₄) to n-nonane (C₉H₂₀) in the critical region. The equation is valid in the reduced density range 0.7 _c1.3 at T=T _c and up to 1.2T _c at = _c.     

Fermi liquid behaviour of the viscosity of3He-4He mixtures

We have investigated³He-⁴He mixtures at³He-concentrations 0.98%x9.5% by the vibrating wire technique in the temperature range 1 mKT 100 mK and at pressures 0 bar p 20 bar. In the degenerate regime of the mixtures the Landau theory of Fermi liquids predicts a temperature dependence of the viscosity proportionalT ^–2. We report on the first observation of this behaviour at 3 mKT 10 mK for all investigated concentrations and pressures. At temperatures below about 20 mK slip corrections had to be taken into account due to the increase of the quasiparticle mean free path at very low temperatures. The low-temperature cut-off in T ² = constant indicates the transition into the ballistic regime of the mixtures, where the mean free path of the quasiparticles exceeds the radius of the vibrating wire. Our results for the pressure dependence of the viscosity as well as for its magnitude show substantial differences from predictions based on pseudopotential theory. However, a calculation of with the quasiparticle interaction potential of recent solubility measurements in mixtures agrees well with our experimental data, in particular the pressure independence of .     

Y xBayCuzO7− δ solid solutions

Y_xBa_yCu_zO_7– ceramics forming at isobaric conditions were studied by x-ray diffraction analysis, dynamic magnetic measurements and potentiometric titration. It was established that compositions: 0.8 x 1.2 y=2, z=3; x-1, 1.8 y 2.2, z=3; x=1, y=2, 2.7 z 3.4: are in the homogeneity range of 123. It was found that compositions with nonstoichiometric cations rations have minimum T_c.     

X-ray,electrical conductivity and magnetic hysteresis studies of the chalcogenide system Zn1−xCuxCr2Se4

X-ray diffraction studies performed here indicated solid-solution formation between ZnCr₂Se₄ and CuCr₂Se₄, and all the compounds could be indexed on the basis of cubic spinel lattice. The compositions between 0 x 0.8 showed semi-conducting behaviour, while CuCr₂Se₄ (x=1.0) exhibited metallic conductivity. Seebeck measurements showd P-type behaviour for 0 x 1. Magnetic hysteresis indicated a ferromagnetic nature for all the compounds except ZnCr₂Se₄ (x=0). The shapes of/ _i plotted againstT exhibited single domain behaviour, and Curie temperatures showed an increase with increasing copper concentration.     

Isochoric pvT measurements of SF6 in the density range 100 to 1200 kg · m−3

The pvT properties of SF₆ were determined by an isochoric method. The pressure p and the temperature T were measured in the pressure range 1.5 MPa p 9.0 MPa and in the temperature range 293 K T 340 K. The results are compared with data in the literature. The adsorption of SF₆ on glass and iron surfaces and its influence on the pvT measurements are also briefly discussed.Paper presented at the Tenth Symposium on Thermophysical Properties, June 20–23, 1988, Gaithersburg, Maryland, U.S.A.     

The viscosity and thermal conductivity of ethane in the limit of zero density

New representations of the viscosity and thermal conductivity of ethane in the limit of zero density are provided. The correlation for the viscosity extends over the temperature range 200 to 1000 K, whereas that for thermal conductivity extends from 225 to 725 K. The behavior of each property is represented by an independent correlation of the appropriate effective collision cross section as a function of temperature. The final results are compared with experimental data as well as with earlier correlations. The accuracy of the viscosity correlation is estimated to be ±0.5 % in the temperature range 300 KT600 K, increasing to ±1.5 and ±2.5% at 200 and 1000 K, respectively. The uncertainty associated with the thermal conductivity correlation is ±2 % in the temperature range 300 KT500 K, increasing to ±3% at either end. The results of this study indicate that there is an urgent need for additional high-precision measurements of thermal conductivity especially for temperatures above 400 K.     

Thermal transport properties in helium near the superfluid transition. III. Dilute3He-4He mixtures in the normal phase

An experimental study is presented for the thermal conductivity and the thermal relaxation for dilute mixtures of³He in⁴He with concentration 9×10^–4X(³He)5×10^–2 at saturated vapor pressure and in the normal phase near the superfluid transition. The conductivity results for are compared with predictions by Dohm and Folk from field-theoretic renormalization group(RG) theory. The conductivity _s =[^–1(T)–^–1(T)]^–1, is compared with Ahlers' phenomenological arguments, and also with predictions by Dohm and Folk and by Onuki. The temperature difference transient T(t) across the fluid, measured as a function of timet after switching on and off the heat current, is analyzed. The thermal diffusion ratiok _T and the mass diffusion coefficientD are obtained by fitting the calculated transient to the experimental one. The results are compared with the predictions that follow from the RG approach by Dohm and Folk. Very good agreement is obtained fork _T. The transient is not very sensitive toD, and hence the determination is not accurate. Yet within the uncertainty, the deducedD also agrees with predictions. Appendices give (1) the corrections to from finite heat effects, (2) the calculation of the concentration susceptibility (X/) _T,P , and (3) the calculation procedure for ,k _T, andD using the RG approach of Dohm and Folk.     

The preparation of high transition temperature superconducting Pb-Bi-Ge alloy filaments using the method of glass-coated melt spinning

The melt spinning of Pb-Bi-Ge alloys with Pyrex glass was investigated as a means of producing a superconducting long filament with highT _c. Continuous filaments with maximumT _c of more than 10 K of Pb_100-x-y Bi _x Ge _y (15x37 and 725) were obtained from the molten state at 1500 K with a winding speed of 0.95 m sec^–1. The Pb₄₉Bi₃₃Ge₁₈ filament, which was 34×10^–6 m diameter and a ductile material with a tensile strength of 20 MPa and elongation of 2.7%, exhibited superconductivity at the highestT _c of 14.3 K. These filaments were found to be polycrystalline with a grain size of more than 5000×10^–10 m and had a mixed structure of germanium (diamond) (h c p) and bismuth phases. The germanium element distributed homogeneously in the filament.     

On the calculation of second virial coefficients for nonspherical molecules

A self-consistent scheme is given for the calculation of the contributions of nonspherical molecular interactions to second virial coefficients. The usual longrange nonspherical interactions, which are asymptotically valid only at large separations, are modified by damping functions that render them valid at small separations as well. Numerical tables of new auxiliary functions J _n ^D (T^*) are given for 6n30 and 0.5T ^*10. These are designed to be used in the identical statistical-mechanical formalism for the second virial coefficient that had been developed for the undamped long-range nonspherical interactions.     

Crystallization kinetics of Zr-rich FexZr0−x0−x0−x(20 ⩽ x ⩽ 40) metallic glasses

The crystallization kinetics of the melt-spun Fe-Zr metallic glasses in the iron-rich region has been investigated by means of DSC and X-ray diffraction. The crystallization mode changes with iron concentration. In the lower iron region, 20 x 25, the Fe _x Zr100–x glasses crystallize into -Zr and Ti₂Ni-type FeZr₂ with an accompanying sharp and large exotherm at the first crystallization step and immediately after this step, they transform into orthorhombic FeZr₃. On the other hand, the alloys with 35 x 40 exhibit a gradual exotherm which initiates from a temperature far below the definite crystallization temperature (T _x). The Fe-Zr metallic glasses in this concentration region crystallize polymorphously into the oxygenstabilized Ti₂Ni-type FeZr₂ with accompanying relatively small and composite exotherms. The annealing at a temperature where the gradual exotherm occurs for the alloys with 30 x 40 does not cause any changes of X-ray halo pattern but results in the reduction of the heat of exotherm due to the crystallization.     

Substitution of Cu by Fe in the superconducting ceramic oxide EuBa2Cu3Oy: Structure, electrical conductivity, and microwave response

A series of EuBa₂(Cu_1–x Fe _x )₃O_y (0.0x0.15) ceramics were prepared and examined by thermogravimetric analysis, X-ray powder diffraction, electrical resistance measurements, and a magnetically modulated microwave absorption technique. The oxygen content (y=6.98±0.03), determined by thermogravimetric analysis in a reducing atmosphere, was independent of the iron concentration forx0.12. The introduction of iron into the EuBa₂Cu₃O _y lattice, via substitution into copper sites, effects a progressive decrease in the superconducting transition temperature with increasing iron concentration. Normal-state conductivity similarly progresses from a low resistivity and negative temperature coefficient behavior, to a semiconducting-like response at the high iron concentrations. X-ray powder diffraction measurements indicate that material containing 6% iron and above is tetragonal, yet it remains superconducting with up to at least 12% iron.     

Crystallization kinetics of bulk amorphous (Se65Te35)100−x Sb x

Kinetic studies of crystallization in (Se₆₅Te₃₅)_100–x Sb _x with 0x10 glasses, using the differential scanning calorimetry technique, were performed. Crystallization enthalpy data, H _c, were collected as a function of composition. The crystallization data were examined in terms of recent analyses developed for non-isothermal crystallization studies, to arrive at E _c. The results indicate bulk nucleation and crystallization with two- and three-dimensional growth, respectively, for the (Se₆₅Te₃₅)₉₈Sb₂ and (Se₆₅Te₃₅)₉₂Sb₈ glass composition.     

Heat capacity and magnetic properties in the (PdCO y )H x -system at low temperatures

Results of heat capacity measurements on (PdCo _y )H _x (y 2.5 at %; 0 x 0.8) in the temperature range from 2 to 12 K are reported. The dependence of the coefficient of the electronic heat capacity on the Co content and on the x value is considered. For the binary alloy PdCo _y a decreasing spin wave contribution to the heat capacity (T ^3/2) is found, which agrees well with the known ferromagnetic properties of the alloy. In contrast, for the phase of (PdCo _y )H _x a contribution to the heat capacity can be separated, probably caused by the thermal excitation of magnetic clusters. The temperature dependence of this cluster contribution can be well explained by means of an Einstein function. Conclusions are drawn with regard to the intercluster interaction and to the number of atoms per cluster.     

Critical review of the thermodynamics of the Na-Al-O system

The free energies of formation of various phases in the Na-Al-O systems are critically reviewed for the composition range between pure alumina and sodium-aluminate. The results clearly indicate that in the temperature range between 600 and 1100 K neither-alumina nor'-alumina (Na₂O.5Al₂O₃) are stable with respect to sodium; the most stable phase in that range being sodium aluminate. Least square fitting and statistical analysis of all the available data on the free energy of formation of-alumina deemed accurate yields G _form ⁰ (from oxides) = –8772+1.53T (J/mole of O) (600 T 1200K) If the composition of-alumina is assumed to be Na₂0.11Al₂O₃ then G _form ⁰ (Na_1/17Al_11/17O, from elements) = –565100+109.6T (J mole of O) (600 T 1200 K) If the composition is assumed to be 19 then: G _form ⁰ (Na_1/14Al_9/14O, from elements) = –564000+109.6T (J/mole of O) (600 T 1200K) Based on the only study to date, the best estimate for the free energy of formation of-alumina is G _form ⁰ (Na_1/8Al_5/8O, from the elements) = –567860+114T (J/mole of O) (600 T 1200 K)The uncertainty (95% confidence band) is estimated to be about ±200 J/mole of O. Based on these results-alumina should be thermodynamically stable at lower temperatures, but become unstable at temperatures >900 K and should, kinetics permitting, dissociate into-alumina and sodium aluminate. Experimental evidence, however exists that conclusively shows that-alumina is thermodynamically stable at much higher temperatures than 900 K which leads to the conclusion that G °_form for-alumina reported to date is too high and should be more negative.     

Nonequilibrium solidification of poly(ethylene oxide)-sodium thiocyanate mixtures

Mixtures of polyethylene oxide (PEO) and sodium thiocyanate (NaSCN) were isothermally crystallized at temperatures between 7 and 37° C, below the eutectic temperature T _e=63° C. The stable phases are semicrystalline polyethylene oxide, SPEO, and a crystalline complex, CC, with the formula PEO₃ NaSCN; these two solids grow by different mechanisms. Salt mole fraction was varied between 0.067X0.143 for studies by optical microscopy and differential scanning calorimetry. Solidification was observed to proceed by primary growth followed by coupled growth at a nonequilibrium composition X_e much greater than the equilibrium eutectic composition X _e=0.026. The boundaries of this skewed coupled zone could not be determined because of a dependence of X_e on the nature of the primary phase.     

Optimum notch configurations for the chevron-notched four-point bend specimens

The failure sequence following crack formation in a chevron-notched four-point bend specimen is examined in a parametric study using the Bluhm slice synthesis model. Premature failure resulting from crack formation forces which exceed those required to propagate a crack beyond is examined together with the critical crack length and critical crack front length. An energy based approach is used to establish factors which forecast the tendency of such premature failure due to crack formation for any selected chevron-notched geometry. A comparative study reveals that, for constant values of ₁ and ₀, the dimensionless beam compliance and stress intensity factor are essentially independent of specimen width and thickness. The chevron tip position ₀ has its primary effect on the force required to initiate a sharp crack. Small values for ₀ maximize the stable region length, however, the premature failure tendency is also high for smaller ₀ values. Improvements in premature failure resistance can be realized for larger values of ₀ with only a minor reduction in the stable region length. The stable region length is also maximized for larger chevron base positions, ₁, but the chance for premature failure is also raised. Smaller base positions improve the premature failure resistance with only minor decreases in the stable region length. Chevron geometries having a good balance of premature failure resistance, stable region length, and crack front length are 0.20 ₀0.03 and 0.70₁0.80NASA Resident Research Associate at Lewis Research Center.     

Investigation of inter- and intra-molecular packing in the solid state for crystals of normal alkanes and homologous mixtures using FT-IR spectroscopy

Fourier transform-infrared spectroscopy has been used to detect conformational defects in certain crystalline n-alkanes (20 n 50) and homologous mixtures. The results indicate the existence of gauche conformers (trans-gauche, double gauche and king) in the lowtemperature solid-state structures of the single n-alkanes ( n-C₃₆H₆₈) and homologous mixtures; implying the existence of end-chain bending and folding. The data have been rationalized in terms of a model which incorporates surface melting and near-neighbour inter-molecular interactions.     

Nonlinear Response of a Continuous Wave NMR Spectrometer for Samples with a Large Magnetization

We present a new insight in the response of a CW NMR spectrometer for highly magnetized samples above 100 MHz. The spectrometer is a bridge made of a magic T. The output of the bridge is proportional to the reflection coefficient, , of a resonant circuit, which is built with a coil containing the sample. The sensitivity of the reflection coefficient to the complex susceptibility of the sample, () = () – j(), depends on the quality factor, Q, of the circuit and filling factor, . When the condition Q 1 is not fulfilled, we show indeed that the use of a simple crystal detector, which is only sensitive to || gives rise to a strong nonlinear response of the spectrometer. Measurements of the complex value of by means of phase sensitive detection allow to recover a linear behavior. We discuss and illustrate those issues with a few circuits we designed for our measurements on liquid ³ He with spin polarizations up to 15 %. A method is described to build in a reproducible and predictable way resonant circuits matched to 50 in the frequency range 100 – 400 MHz with a quality factor as high as 1000 at 4 K.