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1.
Broadband dielectric relaxation measurements of tris(dimethylsiloxy)phenylsilane were made at ambient pressure and at elevated pressures. The data show an anomalous behavior not previously seen in any other glass-formers; namely, the structural alpha-relaxation loss peak narrows with increasing pressure and temperature at constant peak frequency. Interpreted by the coupling model, the effect is due to reduction of intermolecular coupling at elevated pressures. This interpretation has support from the observed decrease of the separation between the alpha-relaxation and the Johari-Goldstein secondary relaxation, as well as the smaller steepness or "fragility" index m of the data obtained at 1.7 GPa than at ambient pressure. 相似文献
2.
Molecular dynamics simulations of the glass-forming liquid 2Ca(NO3)2.3KNO3 (CKN) were performed from high temperature liquid states down to low temperature glassy states at six different pressures from 10(-4) to 5.0 GPa. The temperature dependence of the structural relaxation time indicates that the fragility of liquid CKN changes with pressure. In line with recent proposal [Scopigno et al., Science 302, 849 (2003)], the change on liquid fragility is followed by a proportional change of the nonergodicity factor of the corresponding glass at low temperature. 相似文献
3.
Dielectric loss spectra of two glass-forming isomers, eugenol and isoeugenol, measured at ambient and elevated pressures in the normal liquid, supercooled, and glassy states are presented. The isomeric chemical compounds studied differ only by the location of the double bond in the alkyl chain. Above the glass transition temperature T(g), the dielectric loss spectra of both isomers exhibit an excess wing on the high frequency flank of the loss peak of the alpha relaxation and an additional faster gamma process at the megahertz frequency range. By decreasing temperature below T(g) at ambient pressure or by elevating pressure above P(g), the glass transition pressure, at constant temperature, the excess wing of isoeugenol shifts to lower frequencies and is transformed into a secondary beta-loss peak, while in eugenol it becomes a shoulder. These spectral features enable the beta-relaxation time tau(beta) to be determined in the glassy state. These changes indicate that the excess wings in isoeugenol and eugenol are similar and both are secondary beta relaxations that are not resolved in the liquid state. While in both isoeugenol and eugenol the loss peak of the beta relaxation in the glassy state and the corresponding excess wing in the liquid state shifts to lower frequencies on elevating pressure, the locations of their gamma relaxation show little change with increasing pressure. The different pressure sensitivities of the excess wing and gamma relaxation are further demonstrated by the nearly perfect superposition of the alpha-loss peak together with excess wing from the data taken at ambient pressure and at elevated pressure (and higher temperature so as to have the same alpha-peak frequency), but not the gamma-loss peak in both isoeugenol and eugenol. On physical aging isoeugenol, the beta-loss peak shifts to lower frequencies, but not the gamma relaxation. Basing on these experimental facts, the faster gamma relaxation is a local intramolecular process involving a side group and the slower beta relaxation mimics the structural alpha relaxation in behavior, involves the entire molecule and satisfies the criteria for being the Johari-Goldstein beta relaxation. Analysis and interpretation of the spectra utilizing the coupling model further demonstrate that the excess wings seen in the equilibrium liquid states of these two isomers are their genuine Johari-Goldstein beta relaxation. 相似文献
4.
The organic liquid ROY, i.e., 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile, has been a subject of detailed study in the last few years. One interest in ROY lies in its polymorph-dependent fast crystal growth mode below and above the glass transition temperature. This growth mode is not diffusion controlled, and the possibility that it is enabled by secondary relaxation had been suggested. However, a previous study by dielectric relaxation spectroscopy had not been able to find any resolved secondary relaxation. The present paper reports new dielectric measurements of ROY in the liquid and glassy states at ambient pressure and elevated pressure, which were performed to provide more insight into the molecular dynamics as well as the crystallization tendency of ROY. In the search of secondary relaxation, a special glassy state of ROY was prepared by applying high pressure to the liquid state, from which secondary relaxation was possibly resolved. Thus, the role of secondary relaxation in crystallization of ROY remains to be clarified. Notwithstanding, the secondary relaxation present is not necessarily the sole enabler of crystallization. In an effort to search for possible cause of crystallization other than secondary relaxation, we also performed crystallization kinetics studies of ROY at different T and P combinations while keeping the structural relaxation time constant. The results show that crystallization of ROY speeds up with pressure, opposite to the trend found in the crystallization of ibuprofen studied up to 1 GPa. The dielectric relaxation and thermodynamic properties of ROY with phenolphthalein dimethylether (PDE) are similar in many respects, but PDE does not crystallize. Taking all the above into account, besides the secondary relaxation, the specific chemical structure, molecular interactions and packing of the molecules are additional factors that could affect the kinetics of crystallization found in ROY. 相似文献
5.
Dielectric relaxation spectra of a metastable crystal phase formed on implosive and exothermic transformation of pressure-amorphized hexagonal ice have been measured in situ at 0.97 GPa pressure over a range of temperature. The metastable phase showed no relaxation peak at 130 K and 0.97 GPa. When heated at a fixed pressure of 0.97 GPa, it began to transform at approximately 145 K exothermally to a phase whose relaxation rate and equilibrium dielectric permittivity increased. A second, but slower exothermic transformation also occurred at approximately 175 K. After keeping at 213 K, the relaxation rate and equilibrium permittivity reached the known values of these two quantities for ice VI. Thus the metastable phase transformed to ice VI in two stages. It is conjectured that the intermediate phase in this transformation could be ice XII. The rate of transformation is not determined by the reorientational relaxation rate of water molecules in the ices. 相似文献
6.
Characteristic temperatures and structural relaxation times for different classes of glass-forming polymer liquids are computed using a revised entropy theory of glass formation that permits the chain backbone and the side groups to have different rigidities. The theory is applied to glass formation at constant pressure or constant temperature. Our calculations provide new insights into physical factors influencing the breadth of the glass transition and the associated growth of relaxation times. 相似文献
7.
Rivera-Calzada A Kaminski K Leon C Paluch M 《The journal of physical chemistry. B》2008,112(10):3110-3114
We investigate ion dynamics under pressure in the ionic liquid 1-butyl-1-methylpyrrolidinium bis[oxalate]borate (BMP-BOB) by conductivity relaxation measurements in the temperature range 123-300 K and varying pressures from 0.1 MPa up to 0.5 GPa. We report on the influence of pressure on the relaxation times and on the spectral shape of the conductivity relaxation process. We also analyze the pressure dependence of the glass transition temperature and find that the dynamic response under pressure in this ionic liquid shows remarkable similarities to nonionic glass formers. The main relaxation process shows temperature-pressure superposition while a secondary relaxation process, very weakly depending on pressure, is observed. The spectral shape of the main relaxation broadens with increasing pressure or decreasing temperature, but is found to be the same when the relaxation time is the same, independently of the particular pressure and temperature values. 相似文献
8.
《Chemical physics letters》2003,367(3-4):259-264
Dielectric spectra were obtained at ambient and elevated pressures for three ‘type-A’ glass formers, which exhibit excess intensity on the high frequency side of the structural relaxation peak. The response to pressure of the peak maximum and the excess wing suggests categorization of such glass formers into two groups: associated liquids, in which the α-relaxation and the excess wing have a different pressure dependence, and van der Waals liquids, which at fixed value of the α-relaxation time, conform to temperature–pressure superpositioning. This distinction is believed to arise from the change in the number of intermolecular bonds (non-dispersive interactions) with volume. 相似文献
9.
Broadband dielectric spectroscopy was used to study the relaxation dynamics in bis-5-hydroxypentylphthalate (BHPP) under both isobaric and isothermal conditions. The relaxation dynamics exhibit complex behavior, arising from hydrogen bonding in the BHPP. At ambient pressure above the glass transition temperature T(g), the dielectric spectrum shows a broad structural relaxation peak with a prominent excess wing toward higher frequencies. As temperature is decreased below T(g), the excess wing transforms into two distinct peaks, both having Arrhenius behavior with activation energies equal to 58.8 and 32.6 kJmol for slower (beta) and faster (gamma) processes, respectively. Furthermore, the relaxation times for the beta process increase with increasing pressure, whereas the faster gamma relaxation is practically insensitive to pressure changes. Analysis of the properties of these secondary relaxations suggests that the beta peak can be identified as an intermolecular Johari-Goldstein (JG) process. However, its separation in frequency from the alpha relaxation, and both its activation energy and activation volume, differ substantially from values calculated from the breadth of the structural relaxation peak. Thus, the dynamics of BHPP appear to be an exception to the usual correlation between the respective properties of the structural and the JG secondary relaxations. 相似文献
10.
Employing frequency-dependent dielectric susceptibility we characterize the aging in two supercooled liquids, sorbitol and xylitol, below their calorimetric glass transition temperatures. In addition to the alpha relaxation that tracks the structural dynamics, the susceptibility of both liquids possesses a secondary Johari-Goldstein relaxation at higher frequencies. Following a quench through the glass transition, the susceptibility slowly approaches the equilibrium behavior. For both liquids, the magnitude of the Johari-Goldstein relaxation displays a dependence on the time since the quench, or aging time, that is quantitatively very similar to the age dependence of the alpha peak frequency. The Johari-Goldstein relaxation time remains constant during aging for sorbitol while it decreases slightly with age for xylitol. Hence, one cannot sensibly assign a fictive temperature to the Johari-Goldstein relaxation. This behavior contrasts with that of liquids lacking distinct Johari-Goldstein peaks for which the excess wing of the alpha peak tracks the main part of the peak during aging, enabling the assignment of a single fictive temperature to the entire spectrum. The aging behavior of the Johari-Goldstein relaxation time further calls into question the possibility that the relaxation time possesses stronger temperature dependence in equilibrium than is observed in the out-of-equilibrium state below the glass transition. 相似文献
11.
12.
C. Fanggao G. A. Saunders E. F. Lambson R. N. Hampton G. Carini G. Di Marco M. Lanza 《Journal of Polymer Science.Polymer Physics》1996,34(3):425-433
Electrical impedance measurements have been made in the frequency range 5 Hz to 10 MHz in pure poly(ethylene oxide) having a molecular weight of 600,000 from 12 K nearly up to the melting point of the crystalline phase (about 330 K). A pronounced relaxation peak in the dielectric loss and a corresponding step in the dielectric constant have been observed at about 240 K, which can be readily related to the glass-rubber transition in the amorphous region of the polymer. As the temperature approaches the melting point there are large increases in the real ϵ′ and imaginary e′ parts of the dielectric constant. The frequency dependence of ϵ′ is characterized by a primary relaxation process, whose frequency increases with increasing temperature as a consequence of decrease of the average structural relaxation time. There is strong evidence that this low-frequency dispersion arises mainly from the diffusive transport of ionic charge carriers rather than a purely orientation relaxation process. In addition, the effects of hydrostatic pressures (0–0.25 GPa) on the frequency dependencies of the real ϵ′ and imaginary ϵ′ parts of the dielectric constant have been measured in the temperature range from 254 to 329 K. An advantage of applying pressure is that it shifts the α𝒶 relaxation peak into an experimentally accessible frequency window of the equipment; the lowering of frequency results from a decrease in the relaxation volume and a consequent reduction in the mobility of the molecular units. Results are discussed in terms of theoretical models of the effect of pressure on the glass transition, providing information on the cooperative dynamics. © 1996 John Wiley & Sons, Inc. 相似文献
13.
Xiaorong Wang 《Macromolecular rapid communications》2002,23(9):530-534
Cooling a polymer glass through the glass transition temperature and then holding the material temporarily at an aging temperature produces a localized relaxation peak on its dynamic mechanical spectra. Clear evidence is provided that the aging‐induced structural relaxation is frequency‐temperature insensitive. The aging‐associated retardation time, if there is any, should therefore not relate to an activation process over temperature barriers or originate from a manipulation of the retardation spectra of the glass and the β‐transition. 相似文献
14.
RS McWilliams Y Kadry MF Mahmood AF Goncharov J Ciezak-Jenkins 《The Journal of chemical physics》2012,137(5):054501
The structural and chemical properties of the bi-molecular, hydrogen-bonded, nitrogen-rich energetic material triaminoguanidinium 1-methyl-5-nitriminotetrazolate C(3)H(12)N(12)O(2) (TAG-MNT) have been investigated at room pressure and under high pressure isothermal compression using powder x-ray diffraction and Raman and infrared spectroscopy. A stiffening of the equation of state and concomitant structural relaxation between 6 and 14 GPa are found to correlate with Raman mode disappearances, frequency discontinuities, and changes in the pressure dependence of modes. These observations manifest the occurrence of a reversible martensitic structural transformation to a new crystalline phase. The onset and vanishing of Fermi resonance in the nitrimine group correlate with the stiffening of the equation of state and phase transition, suggesting a possible connection between these phenomena. Beyond 15 GPa, pressure induces irreversible chemical reactions, culminating in the formation of a polymeric phase by 60 GPa. 相似文献
15.
We investigate the pressure effects on the transitions between the disordered phases in supercooled liquid silicon through Monte Carlo simulations and efficient methods to compute free energies. Our calculations, using an environment dependent interatomic potential for Si, indicate that at zero pressure the liquid-liquid phase transition, between the high density liquid and the low density liquid, occurs at a temperature 325K below melting. We found that the liquid-liquid transition temperature decreases with increasing pressure, following the liquid-solid coexistence curve. As pressure increases, the liquid-liquid coexistence curve approaches the region where the glass transition between the low density liquid and the low density amorphous takes place. Above 5 GPa, our calculations show that the liquid-liquid transition is suppressed by the glassy dynamics of the system. We also found that above 5 GPa, the glass transition temperature is lower than that at lower pressures, suggesting that under these conditions the glass transition occurs between the high density liquid and the high density amorphous. 相似文献
16.
Kinetic data for structural relaxation in silver iodomolybdates at the glass transition temperature (Tg) are obtained by high-pressure differential scanning calorimetry (HP-DSC) and are compared with activation energies (EA) and volumes (VA) obtained earlier from conductivities below Tg. The results are fitted to an empirical equation, EA = MVA, and displayed in the form of a master plot of EA versus VA, an approach previously applied to strongly coupled systems, including polymer electrolytes and molten salts above their glass transition temperatures. The parameter M emerges as a localized modulus, expressive of interatomic forces within the medium, linking together EA,sigma, VA,sigma and EA,s, VA,s, the "apparent" activation parameters for ionic conductivity and structural relaxation, respectively. The VA and EA values for ion transport are much smaller than the corresponding values for structural relaxation. However, remarkably close agreement emerges between the "process parameters", Ms and Msigma, both close to 8 GPa, thus establishing a quantitative link between ion transport and structural relaxation in this highly decoupled system. A new EA versus VA master plot is constructed, which points the way to a unified approach to ion transport in polymers and glasses. 相似文献
17.
Changes in the structure of water deduced from the pressure dependence of the Raman OH frequency 总被引:3,自引:0,他引:3
We report on the Raman spectra of water under high temperature and pressure conditions and show a discontinuity in the pressure dependence of the OH stretching frequency. As pressure increases, the strength of hydrogen bonding increases rapidly in the pressure ranges up to 0.4+/-0.1 GPa at 25 degrees C, 1.0+/-0.1 GPa at 100 degrees C, and 1.3+/-0.1 GPa at 300 degrees C and slowly above these pressures. This finding clearly demonstrates the existence of discontinuities in the pressure response of the hydrogen bonds of water, which suggests a possible structural change under these conditions. 相似文献
18.
Zinin PV Kudryashov I Konishi N Ming LC Solozhenko VL Sharma SK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(10):2386-2389
The new diamond-like B-C phase was obtained from the graphite-like BC phase in a laser-heated diamond anvil cell at high temperature 2230+/-140 K and high pressure 45 GPa. Raman spectra of the new phase measured at ambient conditions revealed a peak at 1315 cm(-1), which was attributed to longitudinal-optical (LO) mode. The X-Y Raman mapping was used to investigate spatial distribution of the diamond-like phases and was shown to be a powerful tool in studying the sp(2)-to-sp(3) phase transformations occurring in the diamond cell under high temperature and high pressure. 相似文献
19.
Data are presented for three glass formers, each having an excess wing in the low temperature dielectric loss spectra. Two
polychlorinated biphenyls, whose α relaxations have equivalent temperature dependences, exhibit excess wings that are clearly
different. Comparison of the spectra for glycerol at atmospheric pressure and at P=0.9 GPa reveals a different response of the α relaxation and the excess wing. These findings cannot be reconciled with the
notion that the excess wing is an inherent part of the α relaxation. Interpretation of the spectra as a superposition of distinct
α and β processes, however, is consistent with the observed behavior.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
20.
Many hydrogen-bonded liquids, especially glass-forming cases, display a dielectric relaxation behavior that differs qualitatively from that of other simple liquids. The majority of models aimed at explaining this unusual dielectric behavior associate the prominent Debye process with structural relaxation, viscous flow, and the glass transition. We perform dielectric and calorimetric studies of glass-forming mixtures of 2-ethylhexylamine and 2-ethyl-1-hexanol across the entire composition range. The kinetic glass transition temperature derived from the large dielectric Debye peak decreases, whereas that of the much smaller and asymmetrically broadened peak increases upon addition of amine. Only the latter feature coincides with the calorimetric glass transition results, implying that molecular structure and dielectric polarization fluctuate on time scales that can differ by orders of magnitude in many hydrogen-bonding liquids. 相似文献