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1.
The relaxation of electric field-induced polar orientation in a side-chain-bearing liquid-crystalline polysiloxane was measured by means of thermally stimulated depolarization currents. Different relaxation mechanisms were identified and characterized: the glass transition cooperative relaxation exhibits compensation behaviour. On the other hand, lowerT g and upperT g discharges were observed and their molecular nature is discussed. 相似文献
2.
Viorel Cîrcu Doina Mănăilă-Maximean Constantin Roşu Monica Iliş Yann Molard Florea Dumitraşcu 《Liquid crystals》2013,40(2):123-132
A series of ortho-metallated Pd and Pt complexes containing an imine ligand carrying three alkoxy chains and N-benzoylthiourea derivatives as co-ligands were prepared and their liquid crystalline properties investigated. Their structures were assigned based on elemental analysis, IR and 1H NMR spectroscopy, whereas thermal properties were investigated by differential scanning calotimetry and polarising optical microscopy. All the compounds exhibit monotropic transitions involving nematic and smectic A phases, with the mesomorphic behaviour strongly related to the type of N-benzoylthiourea as well as the metal centre used. The thermally stimulated depolarisation current technique was employed to determine the conduction mechanism, phase transition temperature and the activation energies for one of the ortho-metallated Pd complexes. 相似文献
3.
Joaquim J. Moura Ramos 《Molecular physics》2013,111(5):644-660
This study of the thermal behaviour of two glass formers showed that rofecoxib has a good ability to vitrify while celecoxib displays a moderate glass forming ability. On the other hand, celecoxib forms an instable glass while rofecoxib displays moderate glass stability. The α-relaxation of the two amorphous drugs was studied by differential scanning calorimetry (DSC) and thermally stimulated depolarization currents (TSDC). The values of the dynamic fragility obtained by the two techniques are in good mutual agreement and suggest that both drugs are moderately fragile glass formers. These values are however considerably lower than those obtained by dielectric relaxation spectroscopy (DRS) and published in the literature. In the present work we will compare the values of the dynamic fragility obtained by TSDC and DRS for a set of ~30 glass-forming liquids, in order to evaluate their relative suitability for the determination of the m-index. The observed differences are discussed and interpreted. Finally, secondary mobility modes were detected by TSDC in both celecoxib and rofecoxib. The kinetic parameters are identical in both cases and similar to those found by DRS for the slow-b relaxation of celecoxib. These secondary relaxations, that are precursors of the main relaxation on its lower temperature side, are believed to be Johari-Goldstein relaxations. 相似文献
4.
B. Chowdhury 《Journal of Thermal Analysis and Calorimetry》2001,64(2):433-441
Pyrolysis of normally insulating aromatic polyimide is known to impart electrical conductivity to the polymer due to the formation
of carbonized regions in an insulating matrix with a concomitant change in the polymer’s structural arrangement. The wholly
pyrolyzed polyimide is potentially useful for specific applications in certain types of semiconductor devices because of the
polyimide’s insulator/conductor transition which creates a barrier type conduction. Pyrolysis, however, degrades the required
mechanical integrity of the polyimide for construction of such devices. In order to evaluate the fundamental aspects of barrier
conduction by high voltage electron transfer from metal contact that can still produce measurable current in thermally treated
non-pyrolyzed polyimide, the nature of depolarization in Kapton was assessed by the thermally stimulated depolarization current
(TSDC) technique. The results show that thermal treatment of polyimide without pyrolysis and therefore without loss of mechanical
integrity offers a viable means of steady electron conduction for semiconductor operation.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
5.
S. Derbil M. W. Khemici A. Gourari N. Haine 《International Journal of Polymer Analysis and Characterization》2017,22(7):622-630
We will investigate the effect of γ-irradiation on the polymethyl methacrylate (PMMA) properties. The Fourier transform infrared spectroscopy technique in attenuated total reflexion mode (FTIR-ATR) results allowed us to show that the irradiated PMMA undergoes a scission in its lateral chain combined to an oxidation phenomenon. In fact, a decrease in the carbonyl index, versus the radiation dose, is observed. The differential scanning calorimetry and the thermostimulated depolarization currents revealed that the scission in the lateral chain provides a better flexibility to the PMMA chain and an increase in the free volume of the material. The consequences of these phenomena appear in the decrease of the activation energy of PMMA and the appearance of a local order in the material at a temperature Tc which decreases versus the radiation dose. 相似文献
6.
Joo F. Mano Natlia T. Correia Joaquim J. Moura Ramos Anabela C. Fernandes 《Journal of Polymer Science.Polymer Physics》1995,33(2):269-277
The technique of thermally stimulated depolarization currents was used to study the dipolar relaxation mechanisms in two side-chain liquid-crystalline polysiloxanes. The studied polymers have the same mesogenic side-group, but they differ in the number (or density) of side groups attached to the main chain. In both cases three different relaxations were observed: one in the vitreous state, one in the liquid crystalline phase, and the glass transition relaxation. The features of those thermally stimulated discharges are discussed and some suggestions are made concerning the attribution of those discharges at the molecular level. © 1995 John Wiley & Sons, Inc. 相似文献
7.
Anna A. Rugal Vladimir M. Gun’ko Valentina N. Barvinchenko Vladimir V. Turov Tatyana V. Semeshkina Vladimir I. Zarko 《Central European Journal of Chemistry》2007,5(1):32-54
Interaction of human plasma fibrinogen (HPF) with fumed nanosilica A-300 in a phosphate buffer solution (PBS) was studied
using 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial water in the temperature range of 210–273 K, TSDC
(90 < T < 265 K), adsorption, FTIR, and UV spectroscopy methods. An increase in concentration of HPF in the PBS leads to a decrease
in amounts of structured water (frozen at T < 273 K) because of coagulation of HPF molecules. Addition of nanosilica to the HPF solution strongly reduces the amounts
of structured water because of adsorption interaction of HPF molecules with silica nanoparticles, self-association of HPF
molecules, formation of denser packed hybrid agglomerates with HPF and silica, and lastly, because of conformational changes
of HPF. A monolayer adsorption capacity of A-300 corresponds to 156 mg of HPF per gram of silica. The FTIR and UV spectra
show that the HPF adsorption on silica leads to structural changes of the protein molecules. These changes and formation of
hybrid HPF/A-300 aggregates can increase the rate of clotting that is of importance on nanosilica application as a component
of tourniquet preparations.
相似文献
8.
Behaviour of pure water and water mixture with benzene or chloroform adsorbed onto ordered mesoporous silicas 总被引:1,自引:0,他引:1
Vladimir M. Gun’ko Vladimir V. Turov Alexander V. Turov Vladimir I. Zarko Vasiliy I. Gerda Victor V. Yanishpolskii Inna S. Berezovska Valentin A. Tertykh 《Central European Journal of Chemistry》2007,5(2):420-454
Structural characteristics of synthesized ordered mesoporous silicas MCM-41, MCM-48 and SBA-15 were studied using XRD, nitrogen
adsorption and FTIR methods. Pure water and mixtures with water/benzene and water/chloroform-d adsorbed onto silicas were studied by 1H NMR spectroscopy with layer-by-layer freezing-out of bulk and interfacial liquids. Concentrated aqueous suspensions of MCM-48
and SBA-15 were studied by thermally stimulated depolarization current (TSDC) method. Benzene and chloroform-d can displace a portion of water to broad pores from the pore walls and from narrower pores, especially in the case of a large
excess of an organic solvent. This process is accompanied by diminution of both interaction energy of water with an adsorbent
surface and freezing temperature depression of adsorbed water. The effect of nonpolar benzene on pore water is much stronger
than that of weakly polar chloroform-d. Modifications of the Gibbs-Thomson relation to describe the freezing point depression of mixtures of immiscible liquids
confined in pores allow us to determine distribution functions of sizes of structures with unfrozen pore water and benzene.
Former address: Pisarzhevskii Institute of Physical Chemistry, 31 Prospect Nauki, Kiev, Ukraine 相似文献
9.
Molecular motion and relaxation studies using a thermal windowing thermally stimulated depolarization current (TW‐TSDC) were performed for aliphatic polyureas 7 and 9. Global thermally stimulated depolarization current gave three characteristic major peaks corresponding to the α, β, and γ relaxation modes at 78.5, −44, and −136°C for polyurea 7 and at 80, −50, and −134°C for polyurea 9, respectively. The α relaxation is related to the large‐scale molecular motion due to micro‐Brownian motion of long‐range segments. This relaxation is significantly related to the glass‐transition temperature. The β relaxation is caused by the local thermal motion of long‐chain segments. The γ relaxation is caused by the limited local motion of hydrocarbon sections. Temperature dependence of relaxation times was expressed well using Vogel–Tammann–Fulcher (VTF) expression. 3‐D simulation of dielectric constants of dielectric strength and loss factor were performed in the frequency range from 10−6 to 104 Hz and temperature range from −150 to 250°C, using the relaxation parameters obtained from the TW‐TSDC method. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 88–94, 2000 相似文献
10.
M. C. Hernndez E. Laredo A. Bello M. A. Gmez C. Marco 《Journal of Polymer Science.Polymer Physics》1999,37(21):3038-3049
A family of four thermotropic polyesters starting with the poly(tetramethylene terephthaloyl bis-4-oxybenzoate), substituting either asymmetrically in the tetramethylene spacer or incorporating polar substituents onto the aromatic units of the mesogen, is studied by the Thermally Stimulated Depolarization Currents (TSDC) technique. The results are compared to the Dynamic-Mechanical Analysis at frequencies ranging from 0.1 to 1 Hz from 123 to 423 K. The unsubstituted polymer has a complex low-temperature TSDC spectrum corresponding to local reorientation modes due to the motion of the COO groups with different locations along the main chain. By comparing the effect of the Cl and CH3 substituents on the relative intensity and on the mean energies of the distribution of relaxation times determined by the DSA procedure, the lowest temperature mode is attributed to the COO peripheral groups and the modes located at higher temperatures, to the internal COO groups, which may be accompanied by adjacent segments. The mechanic and dielectric α-transitions are also very sensitive to the substituents, the addition of CH3 in the 1,4 flexible spacer shifting the glass transition temperature above room temperature. The existence of the three-dimensional order that is present in the materials with a linear spacer significantly broadens the α-relaxation. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3038–3049, 1999 相似文献