On the solid state phases of poly(trans-1,4-butadiene)

Summary The method of semiempiric-atomistic calculations is applied to a polydiene. For this purpose a Coulomb term has to be added to a potential set used successfully for polyolefines. All stable 4 *p/q helices of poly(trans-1,4-butadiene) are calculated. This yields a conformation for the low temperature phase which is in agreement with X-ray data in the literature. Chain conformations are proposed for the high temperature phase carefully considering the energies (determined in the single chain approximation) and the packing properties.Experimentelly, the enthalpy and entropy differences between the phases, calculated only intramolecularly, are determined by high pressure dilatometry and calorimetry. A commercial material is investigated in the full pressure range up to 3 kbar; for low pressure dilatometry and calormetry a purely trans polymer, initially in extended chain conformation, is used. Experimental data are compared with calculated values and discrepancies are discussed.

---

Zusammenfassung Die Methode der semiempirisch-atomistischen Rechnung wird auf ein Polydien angewendet. Dazu wird ein bei Polyolefinen bewährter Potentialsatz um einen Coulombterm erweitert. Berechnet werden alle stabilen 4 *p/q Helices des Poly-trans-1,4-butadiens, und es ergibt sich eine Konformation für die Tieftemperaturphase, die mit Röntgendaten in der Literatur übereinstimmt. Für die Hochtemperaturphase werden Kettenkonformationen vorgeschlagen, bei denen die in der Einzelkettennäherung bestimmte Energie und die Packung berücksichtigt wird.Die Enthalpie- und Entropieunterschiede zwischen beiden Phasen, die bisher nur intramolekular berechnet sind, werden experimentell mit den Methoden der Hochdruckdilatometrie und der Kalorimetrie bestimmt. Dabei wird im Hochdruckbereich bis 3 kbar ein handelsübliches Material gemessen, im Niederdruckbereich und kalorimetrisch aber ein reines trans-Polymeres, das anfangs gestrecktkettig vorliegt. Die experimentellen Werte werden mit den berechneten verglichen, und ihre Unterschiede werden diskutiert.

     

Phase transition in LAMOX type compounds

La₂Mo₂O₉ (LMO) was synthesized at lower temperature 973 K (LT-phase) by ceramic route. Differential thermal analysis (DTA) scan of LT-phase of LMO showed α→β transition at 843 K during heating and β→α conversion via a metastable γ-phase during cooling. This was also confirmed by thermo-dilatometry and impedance spectroscopy. La₂Mo_1.95V_0.05O_9-δ (LMVO), La_1.96Sr_0.04Mo₂O_9-δ (LSMO) and La_1.96Sr_0.04Mo_1.95V_0.05O_9-δ (LSMVO) were prepared in a similar way. These compounds exhibited α→β transition on heating with shift in transition temperature, but the existence of γ-phase during cooling disappeared. Substitution increased the ionic conductivity of α-phase and reduced that of β-phase.     

Relationship between acoustic emission energy and the kinetics of martensite formation in plain carbon steels

The kinetics of the martensitic transformation in Fe-0.80C determined on the basis of dilatometry data is compared to the acoustic emission (AE) energy accompanying the transformation in the same steel reported in a previous study. The discrepancy between the AE energy and the volume fraction of martensite indicates that the mechanism for the generation of AE during the martensitic transformation is not solely dependent on the kinetics and the associated moving interfaces as suggested in previous studies. During the growth of martensite, slip takes place in order to relieve internal stresses, and dislocations are thought to be mainly introduced in the relatively soft austenite matrix. The quantitative analysis in this study demonstrates that the AE energy generated per unit time is a function of both the transformation kinetics and the volume fraction of remaining austenite. This strongly indicates that the moving dislocations associated with the plastic deformation of the austenite surrounding the as-formed martensite are the dominant sources of the generated acoustic waves. This improved AE source model is consistent with the well-accepted mechanism of AE during conventional plastic deformation due to an external load.     

Kinetics of radical polymerization of dimethylphenyl methacrylates

The kinetics of free radical polymerization of all six existing isomeric dimethylphenyl methacrylates were studied in bulk at 60°C, initiated by dilauroyl peroxide, using dilatometry. The different polymerization rates observed, resulting from the different monomer structures, are discussed in terms of steric and other effects, considering also the previous results for tolyl methacrylates. © 1993 John Wiley & Sons, Inc.     

Volume changes during stress relaxation in polyethylene

This paper presents the results of an experimental study of the stress relaxation behaviour of PE where the focus was on determination of the volume changes taking place during the relaxation process. The dimensions of the samples were followed using a specially designed non-disturbing extensometer. The extensometer data were confirmed in experiments where the volume was measured with a specially designed liquid stress dilatometer. The bulk of the results was obtained with LDPE and LLDPE. High density polyethylene was shown to behave similarly.The decrease in volume, corresponding to an increasing Poisson's ratio, during relaxation was approximately linear with log time. Volume vs. stress diagrams were linear; the values of the apparent bulk modulus calculated from them were only slightly higher than those obtained from the stress-strain curves. Grüneisen parameter was measured and compared with reported values. Possible similarities between the volume change during stress relaxation and that occuring during the process of physical ageing are discussed.     

Pressure–volume–temperature properties and free volume parameters of PEO/PMMA blends

Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(methyl methacrylate (PEO/a-PMMA)) were prepared by melt-mixing and characterized by pressure–volume–temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 MPa and 20 to 200°C, respectively. The PVT data were analyzed in terms of two equations of state (EOS). The empirical Tait EOS was applied in the glassy, semicrystalline, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated from the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansivity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity. These findings are reconciled with composition-dependent free volume parameters, the free volume and cell volume as well as with self- and cross-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1061–1080, 1998     

Thermodynamic characterization of the oriented state of bisphenol A polycarbonate as it pertains to enhanced physical aging

It has recently been demonstrated that hot-drawn samples of bisphenol A polycarbonate (PC) have a 50% higher volume relaxation rate than their isotropic counterpart even though the oriented samples have a lower initial free volume (i.e., higher density).¹ In an attempt to better understand this paradox, samples of unaged, hot-drawn PC were characterized thermodynamically and kinetically as a function of orientation. Heat capacity, hole energy, and T_g data indicate that the chain mobility is actually decreasing slightly with orientation, possibly due to the hindered motion brought about by tighter packing, stronger intermolecular bonding, and reduced free volume. Nonetheless, this decrease in localized mobility is in contradiction to the enhanced volume relaxation rates observed for the oriented samples. In contrast, dynamic mechanical data indicate an increase in the relaxation strength of the β-transition (−100°C at 1 Hz) upon stretching for both the stretch and transverse directions. This implies that more segments are actively participating in the relaxation process for the oriented samples even though their individual localized mobility might be slightly lower. The net result is an increase in “effective” mobility for the oriented samples. It is conjectured that the enhanced relaxation strength of the oriented samples is a result of the stretching process somehow activating more of the chains into a higher energy state, and may be related to the physical aging concept of stress-induced rejuvenation/acceleration. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2111–2128, 1998     

In situ electrochemical dilatometry of carbide-derived carbons

The long life durability and extraordinary stability of supercapacitors are ascribed to the common concept that the charge storage is purely based on double-layer charging. Therefore the ideal supercapacitor electrode should be free of charge induced microscopic structural changes. However, recent in-situ investigations on different carbon materials for supercapacitor electrodes have shown that the charge and discharge is accompanied by dimensional changes of the electrode up to several percent. This work studies the influence of the pore size on the expansion behavior of carbon electrodes derived from titanium carbide-derived carbons with an average pore size between 5 and 8 Å. Using tetraethylammonium tetrafluoroborate in acetonitrile, the swelling of the electrodes was measured by in situ dilatometry. The experiments revealed an increased expansion on the negatively charged electrode for pores below 6 Å, which could be described with pore swelling.     

Electroconduction and linear expansion of solid electrolytes Ce1? x Sm x O2?δ ( x = 0.10?0.30)

A complex investigation of solid electrolytes Ce_1−x Sm _x O_2−δ (x = 0.10−0.30) is performed in a broad temperature interval by methods of x-ray diffraction analysis, electroconduction, dilatometry, differential scanning calorimetry, and thermogravimetry. Ceramic technology is used for the synthesis. The density of the obtained specimens is no lower than 95%. The dilatometry measurements reveal the presence of singularities in the curves obtained at temperatures in the region of 180–230°C, which may be ascribed to a phase transition of the type order-disorder of hypothetical phase Ce₇SmO_15.5. The electroconduction and dilatometry methods also point to the presence of singularities in the temperature dependences in the temperature interval extending from 800 to 870°C. Original Russian Text ? E.G. Vaganov, V.P. Gorelov, N.M. Bogdanovich, I.V. Korzun, V.A. Kazantsev, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 6, pp. 695–698. Based on the report delivered at the 8th International Meeting on Fundamental Problems of Solid-State Ionics, Chernogolovka (Russia), 2006.     

Impact of Pb substitution on the formation of high <Emphasis Type="Italic">T</Emphasis><Subscript>c</Subscript> superconducting phase in BSCCO system derived through sol-gel process

Sol-gel process was employed to synthesize the Pb-BSCCO system having general composition Bi_2−xPb_xSr₂Ca₂Cu₃O_10−δ, where x=0.2, 0.4 and 0.8. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), dilatometry and vibrating sample magnetometer (VSM) were employed to study the materials produced at different stages. Two-stage heating firstly at 300 and then 800°C was adopted in order to avoid the burning of the materials and formation of carbonates. The carbonate formation was avoided by heating the materials firstly at 300°C for 2 h and without intermediate cooling moved to the furnace having temperature 800°C and hold for 2 h. The sintering behaviour of samples was studied by dilatometry and the results revealed that the sample having x=0.4 was stabled up to a temperature of 700°C while samples having x=0.2 and 0.8 to a temperature of 625°C. The maximum shrinkage was observed at 850°C in all the samples. On the basis of dilatometry results, the samples were sintered at 845°C for 60 h to observe the superconducting phases. The highest volume fraction of high superconducting phase (2223) was noticed in the sample containing x=0.4 having onset T _c=110 K.