Phase transitions in chlorobenzene-cis-decalin mixtures

The dielectric constant ?' and loss tangent tan δ of chlorobenzene-cis-decalin mixtures have been measured in the temperature range 77 K to 330 K and frequency range 0.1 to 100 kHz. On cooling, ?' increases with decreasing temperature upto about 135 K, after which it drops rapidly with decreasing T followed by a slow decrease. This indicates that the liquid mixture goes to an amorphous phase which transforms to a glass phase of restricted dipole rotation below T_g; however, the peak in ?' is due to relaxation in the amorphous phase (α relaxation) and does not give an exact T_g. On heating, the behaviour of the cooling curve is retraced upto 160 K, after which ?' drops suddenly to a value lower than that at 77 K in the glass phase. This indicates the transition to a crystalline phase in which dipole rotational freedom is completely lost. The crystalline phase changes to a eutectic liquid phase of high ?' at a temperature (200 K) lower than the melting point of chlorobenzene and cis-decalin. Dielectric dispersion is observed only in the glass and amorphous phases. The dielectric relaxation time is independent of the concentration of chlorobenzene.     

Dielectric study of polyacrylonitrile,poly-2-hydroxyethyl methacrylate and their copolymers

A dielectric study on polyacrylonitrile (PAN), poly-2-hydroxyethyl methacrylate (P-HEMA) and copolymers of acrylonitrile and HEMA in the temperature range 30–150° is reported. The loss peaks occur in the frequency region 0.1–100 kHz at temperatures between 110° and 140 for PAN. In copolymers of acrylonitrile with HEMA, these loss peaks were present although their positions on temperature scale and their peak heights depended on the HEMA content. For P-HEMA no relaxation peak was observed in this range of frequency and temperature. The results for copolymers compared with those for the homopolymers suggest that the loss peaks in PAN are due to molecular motion in amorphous regions.     

The application of small polaron theory to transition metal oxide glasses

A review of the experimental data on a range of transition metal oxide glasses shows a strong relationship between activation energy and site spacing for glasses based on V₂O₅. The behaviour confirms that transport in amorphous V₂O₅ and vanadate glasses is by adiabatic hopping with an appreciable polaron bandwidth, while non-adiabatic hopping between isolated centres is apropriate for glasses based on most other transition metal oxides. The behaviour of vanadium is linked to the retention of a well-defined VO^5? structural unit in the glass network and to optimisation of the packing of this unit within the glass.     

Phase Transitions in Chlorobenzene-Cis-Decalin Mixtures: A Nuclear Magnetic Resonance,Thermal Analysis and Phase Diagram Study

Using nuclear magnetic resonance and differential scanning calorimetry we have been able to observe the molecular rotation properties of chlorobenzene-cis-decalin mixtures in their glassy, amorphous and crystalline phases. The results indicate: that in “rapidly” cooled samples the behavior of the host dominates the properties of the mixtures; that reorientation of the guest molecule is less restricted in the amorphous phase than in the glassy phase; that when the material crystallizes from the amorphous phase on warming, reorientation again becomes severely restricted. The temperatures at which these phenomena occur agree with the phase diagram that has been determined for these materials. Similar experiments on t butyl chloride-cis-decalin mixtures support the above conclusions. These conclusions are in agreement with the previous dielectric studies.

Our magnetic resonance and thermal analysis experiments support the argument that the behavior of the CD host dominates the behavior of guest polar molecules in rapidly cooled mixtures. At the lowest temperature (110 K) CD forms a glassy phase unaccompanied by any heat of crystallization. On warming this glassy phase transforms near 150 K to an amorphous phase where considerable motion of both host and guest molecules occurs. Above 160 K the material crystallizes and reorientation is once again severely restricted up to the eutectic melting of 210 K. There appears to be no time dependence to these transformations and, as long as one stays below the crystallization temperature, the glassy-amorphous transition is reversible.     

DC conduvtivity of V2O5TeO2 glasses

The dc conductivity of semiconducting vanadium tellurite glasses of compositions in the range 50 to 80 mol% V₂O₅ has been measured in the temperature region 77 to 400 K. Measurements have been made on annealed samples at different annealing temperatures. Annealing the samples at temperature of about 250°C causes the appearance of a complex crystalline phase resulting in an increase of conductivity. Results are reported for amorphous samples of different compositions. The conductivity of tellurite glasses is slightly higher than the corresponding composition of phosphate glasses, but the general trend of the increase of conductivity and decrease of high temperature activation energy with increasing V₂O₅ content is similar in the two systems. The data have been analysed in the light of existing models of polaronic hopping conduction. A definite conclusion about the mechanics of conduction (adiabatic or nonadiabatic) is difficult in the absence of a precise knowledge of the characteristic phonon frequency v₀. Adiabatic hopping is indicated for v₀～10¹¹ Hz, however this value leads to unreasonably low value for the Debye temperature θ_D, and higher values for v₀～10¹³ hz satifiies the conditions for nonadiabatic hopping which appears to be the likely mechanism of conduction in V₂O₅TeO₂ glasses. The low temperature data (< 100 K) can be fitted to Mott's variable range hopping, which when combined with ac conductivity data gives reasonable values of α, but a high value for the disorder energy.     

Low frequency dielectric relaxation in lightly doped VO2 single crystals

The relative effects of intrinsic and extrinsic defects on the dielectric relaxation of VO₂ crystals have been investigated by measurement of the dielectric parameters of undoped crystals and crystals doped with Ti, Cr and Al. Measurements have been made in the temperature range 77–250 K and the frequency range 50–100 kHz. The dielectric data is described by a Cole-Cole distribution function with a distribution parameter α ? 0.45 which decreases with increasing temperature. However, the distribution of activation energies g(E) derived from α is almost independent of temperature. The overall dielectric relaxation behaviour is determined primarily by the intrinsic defect structure of VO₂, and the effect of impurities is observed only in changes in the low frequency limiting (static) value of the dielectric constant. The same transport mechanism is found to determine the dc conductivity and the dielectric relaxation and evidence is presented that the dielectric relaxation is of dipolar origin.     

Phase transitions and low-frequency dielectric dispersion in the solid phase of bromoform

Phase transitions in the solid phase of bromoform have been studied by dielectric and differential scanning calorimetric techniques. Two modifications of the solid phase, solid I and solid II, have been observed above and below about ?35°C respectively. Solid phase I exhibits clear Debye-type dispersion in the 0.5 to 100 kHz frequency region, while solid phase II exhibits complete dipole freezing.     

Ligating characteristic of an unstable phosphorus(III) derivative diphenylisothiocyanatophosphine; Synthesis and characterization of its chelates with transition metal ions

Summary Diphenylisothiocyanatophosphine prepared in CHCl₃ solution from Ph₂PCl and AgSCN yields stable complexes with MCl₂, Cu₂Cl₂, [Ni(Ph₃P)₂Cl₂] or [Cu(Ph₃P)₃Cl] which have the stoichiometry [MLCl₂], [M=Ni(1) or Cu(2)], [CuLCl](3), [Ni(Ph₃P)-(Ph₂PNCS)Cl₂](4) and [Cu(Ph₃P)(Ph₂PNCS)Cl](5) respectively characterized by physicochemical methods. The>PNCS moiety retains its entity in the complexes providing both P and S as chelating centres. The geometry of the complexes has been determined from magnetic susceptibility and electronic spectral measurements.     

Molybdenum doping of semiconducting vanadium phosphate glasses

The DC conductivity and dielectric properties of glasses of composition (70 ? x) V₂O₅ : x MoO₃ : 30 P₂O₅ have been measured as a function of temperature and frequency for O × 5 mol %. An increase in conductivity by two orders of magnitude is observed for 1 mol % MoO₃ and this is correlated with changes in activation energy and dielectric constant. The results can be explained in terms of small polaron theory, with the main interaction being through the local electronic polarizability at any site. The results indicate that percolation considerations have to be taken into account in describing the electrical properties of transition metal glasses.     

Dielectric relaxation in vanadium phosphate glasses

An asymmetric distribution of relaxation times has been inferred from an increase in the Cole-Cole distribution parameter α with increasing values of ωτ in 62% v₂O₅–38% P₂O₂ glass. The conventional Debye type relaxation loss peaks in the frequency range 10²–10⁵ Hz are observed in this sample above 85°K. The extrapolated values of dielectric constant and relaxation time below 100°K seem unexpectedly large while the high temperature extrapolated values of ?' are close to ?_∞ as expected. Probably the conventional dielectric loss peaks are observed only above a critical temperature at which the carriers gain sufficient energy to be excited to the conduction band edge. Below this temperature hopping of carriers within kT of the Fermi level may dominate and conventional Debye type dielectric loss peaks may lose their significance as envisaged in the models of frequency dependent ac conductivity.