Spool valve mechanism used in a 20 K Gifford-McMahon cycle cryorefrigerator and its effect on the P-V diagram

The design and fabrication of a spool valve for a two-stage Gifford-McMahon cycle cryorefrigerator is described. The effect of this valve on the P-V diagram and practical methods of reducing the P-V degradation are also discussed.

Two stage Gifford-McMahon cycle cryorefrigerator operating at 20 K

A two stage Gifford-McMahon cycle cryorefrigerator operating at 20 K is described. This refrigerator uses a very simple ‘spool valve’ and a modified indigenous compressor to compress helium gas. This cryorefrigerator reaches a lowest temperature of 15.5 K; it takes ≈ 50 min to reach 20 K and the cooling capacity is ≈ 2.5 W at 25 K. The cool-down characteristics and load characteristics are presented in graphical form. The effect of changing the operating pressure ratio and the second stage regenerator matrix size are also reported. Pressure-volume (P-V) diagrams obtained at various temperatures indicate that P-V losses form the major fraction of the total losses and this becomes more pronounced as the temperature is decreased. A heat balance analysis shows the relative magnitudes of various losses.

Determination of the thermodynamic properties of xMgO + (1 x)MnO (s, sln) from a solid-electrolyte galvanic cell in the temperature range 1163 to 1318 K

The thermodynamic activities of MgO in the NaCl-type solid solutions which can exist in xMgO + (1 x)MnO have been determined in the temperature range 1163 to 1318 K from a solid-state galvanic cell incorporating MgF2 as the solid electrolyte. The activities of MnO have been calculated by a graphical Gibbs-Duhem integration method. The activities of both the components exhibit positive deviations from ideality over the entire composition range. The excess molar enthalpies are found to be positive. Further, xMgO + (1 - x)MnO does not conform to regular-solution behaviour. The origin of the excess thermodynamic properties is discussed in relation to the cationic size disparity and the crystal-field effects.

A new synthetic procedure for the preparation of pyridinium tetrafluoroborate and hexafluorosilicate

Pyridinium tetrafluoroborate (C5H5NHBF4) and pyridinium hexafluorosilicate [(C5H5NH)2SiF6] have been prepared in good yields and high purity by the reaction of pyridinium poly(hydrogen fluoride) with oxides and acids of boron and silicon respectively. The salts have been characterised by melting points, IR, 1H and 19F NMR spectroscopy and chemical analysis.

Phase relations between Al2O3---Cr2O3 and FeAl2O4---FeCr2O4 solid solutions at 1823 K

Tie-lines between the corundum and spinel solid solutions have been determined experimentally at 1823 K. Next, activities of FeCr2O4 and FeAl2O4 in the spinel solid solution were determined by combining the tie-line data with literature values for the activities of Cr2O3 and Al2O3 in the corundum phase. Activities and the Gibbs energy of mixing for the spinel solid solution were also obtained from a model based on cation distribution between nonequivalent crystallographic sites in the oxide lattice. The difference between the Gibbs energy of mixing obtained experimentally and from the model has been attributed to a strain enthalpy term which is relatively unchanged in magnitude from the reported at 1373 K. The integral enthalpy of mixing obtained from experimental data at 1373 and 1823 K using the second law is compared with the model result.

Spinel-Corundum Phase Equilibria in the Systems Mn-Cr-Al-O and Co-Cr-Al-O at 1373 K

The tie lines delineating ion-exchange equilibria between MCr2O4-MAl2O4 spinel solid solution, where M is either Mn or Co, and Cr2O3-Al2O3 solid solution with the corundum structure were determined at 1373 K by electron microprobe and E0AX point count analysis of the oxide phases equilibrated with metallic Co and Au-5% Mn. The component activities in the spinel solid solutions are derived from the tie lines and the thernodynamic data for Cr2O3-Al2O3 soiid solutions available hi the literature. The Gibbs free energies of mixing calculated from the experimental data are discussed in relation to the values derived from the cation distribution a.odel based on the site preference energies and assuming random mixing on both tetrahedral and octahedral sites. Positive deviations from ideality observed in this study suggest a miscibility gap for both series of spinel solid solutions at low temperatures in the absence of oxidation.

Improved bounds on the radius and curvature of the K pi scalar form factor and implications to low-energy theorems

We obtain stringent bounds in the < r(2)>(K pi)(S)-c plane where these are the scalar radius and the curvature parameters of the scalar K pi form factor, respectively, using analyticity and dispersion relation constraints, the knowledge of the form factor from the well-known Callan-Treiman point m(K)(2)-m(pi)(2), as well as at m(pi)(2)-m(K)(2), which we call the second Callan-Treiman point. The central values of these parameters from a recent determination are accomodated in the allowed region provided the higher loop corrections to the value of th form factor at the second Callan-Treiman point reduce the one-loop result by about 3% with F-K/F-pi = 1.21. Such a variation in magnitude at the second Callan-Treiman point yields 0.12 fm(2) less than or similar to < r(2)>(K pi)(S) less than or similar to 0.21 fm(2) and 0.56 GeV-4 less than or similar to c less than or similar to 1.47 GeV-4 and a strong correlation between them. A smaller value of F-K/F-pi shifts both bounds to lower values.

High-temperature superconductivity in the 100 K region in perovskite-related oxides of the Ln-Ba-Cu-O (Ln=Y or La) system

Oxides of the Y-Ba-Cu-O system are found to show onset of superconductivity in the 100–120 K region.

Study of strontium compounds and minerals by X-ray absorption spectroscopy. I. K-edge shifts

The chemical shifts in the X-ray K-absorption edge of strontium in various compounds and in six minerals are measured using a single crystal X-ray spectrometer. Besides valence, the shifts are found to be governed by ionic charges on the absorbing ions, which are calculated employing Pauling's method. For the minerals the plot of chemical shift against the theoretically calculated ionic charges is used to determine the charges on the strontium ions.

TlCaBa2Cu2O7: The 1122 (90 K) superconductor in the new Tl(Ca,Ba)n+1CunO2n+3 seriesstar, open

The 1122 (n=2) member of the Tl(Ca,Ba)n+1CunO2n+3 series containing a single Tl-O layer is shown to be associated with a Tc of 90 K. This value of Tc is significantly lower than that of the 2122 phase (Tcnot, vert, similar110 K) with two Tl-O layers.

Vapour composition and activities in Mg-Zn liquid alloy at 923 K

Vapour species effusing from a magnesia Knudsen cell containing Mg-Zn alloy at 923 K were condensed on a water cooled copper plate. The equilibrium composition of the vapour phase over the alloy was determined from chemical analysis of the condensate. The activity coefficients of both components in the alloy have been derived from the data using a modified Gibbs-Duhem relation. The ratio of saturation vapour pressures of pure Zn and Mg obtained from the analysis of alloy data agree well with values from the literature, providing an internal check on the accuracy of data obtained in this study. Both components of the alloy exhibit negative deviations from Raoult's law. The concentration-concentration structure factor of Bhatia and Thomton at zero wave vector, evaluated from the measurements, indicate the presence of MgZn2 type complex in the liquid state. The associated regular solution model has been used for the thermodynamic description of liquid Mg-Zn alloys.

Synthesis and physico-chemical properties of diruthenium(III, II) tetra-aryl carboxylato compounds

Monochloro-tetra-μ-aryl-carboxylatodiruthenium(III, II) compounds Ru2Cl (O2CAr)4 (Ar = -C6H5; -C6H4-p-OCH3), are prepared and characterized. The compounds have magnetic moments that correspond to three unpaired spins per dimer. The Rusingle bondRu bond order is 2.5 and the ground electronic configuration is σ2π4δ2(δ*π*)3. The visible spectral band is observed at ca 450 nm along with a shoulder near 580 nm in DMF solution. The compounds undergo a one-electron Ru(III)Ru(II) → Ru(II)Ru(II) quasi-reversible reduction in DMF near 0.0 V vs sce.

Estimation Of Properties Of Rare-Gas Solids From Compression Characteristics Of Closed-Shell Ions

We present a unified approach to repulsion in ionic and van der Waals solids based on a compressible-ion/atom model. Earlier studies have shown that repulsion in ionic crystals can be viewed as arising from the compression energy of ions, described by two parameters per ion. Here we obtain the compression parameters of the rare-gas atoms Ne. Ar. Kr and Xe by interpolation using the known parameters of related equi-electronic ions (e.g. Ar from S2-. Cl-, K- and Ca2-). These parameters fit the experimental zero-temperature interatomic distances and compressibilities of the rare-gas crystals satisfactorily. A hightemperature equation of state based on an Einstein model of thermal motions is used to calculate the thermal expansivities, compressibilities and their temperature derivatives for Ar. Kr and Xe. It is argued that an instability at higher temperatures represents the limit to which the solid can be superheated. beyond which sublimation must occur.

Elastic Constants of Sodium Nitrate from 77 to 300 K

The six independent elastic constants of sodium nitrate are determined using 10 MHz ultrasonic pulse echo superposition technique over the temperature interval 77 to 300 K. The values obtained at 300 K are C11 = 5.71, C12 = 2.16, C33 = 3.3, C13 = 1.66, C44 = 1.24, C14 = 0.82, and at 77 K C11 = 6.63, C12 = 2.07, C33 = 3.99, C13 = 1.67, C44 = 1.69, C14 = 1.16 all expressed in units of 1011 dyn/cm2.