Effect of pressure on thermal conductivity and pressure collapse of ice in a polymer-hydrogel and kinetic unfreezing at 1 GPa

We report a study of aqueous solutions of poly(vinylalcohol) and its hydrogel by thermal conductivity, κ, and specific heat measurements. In particular, we investigate (i) the changes in the solution and the hydrogel at 0.1 MPa observed in the 350-90 K range and of the frozen hydrogel at 130 K observed in the range from 0.1 MPa to 1.3 GPa, and (ii) the nature of the pressure collapse of ice in the frozen hydrogel and kinetic unfreezing on heating of its high density water at 1 GPa. The water component of the polymer solution on cooling either first phase separates and then freezes to hexagonal ice or freezes without phase separation and the dispersed polymer chains freeze-concentrate in nanoscopic and microscopic regions of the grain boundaries and grain junctions of the ice crystals in the frozen state of water in the hydrogel. The change in κ with temperature at 1 bar is reversible with some hysteresis, but not reversible with pressure after compression to 0.8 GPa at 130 K. At high pressures the crystallized state collapses showing features of κ and specific heat characteristic of formation of high density amorphous solid water. The pressure of structural collapse is 0.08 GPa higher than that of ice at 130 K. The slowly formed collapsed state shows kinetic unfreezing or glass-liquid transition temperature at 140 K for a time scale of 1 s. Comparison with the change in the properties observed for ice shows that κ decreases when the polymer is added.     

Correlation between thermodynamic and kinetic fragilities in nonpolymeric glass-forming liquids

A phenomenological relationship between reduced excess heat capacity of supercooled liquid DeltaC(p)(exc)(T(g))DeltaS(m) at the glass transition temperature T(g), fragility index m, and reduced glass transition temperature T(rg)=T(g)T(m), where T(m) is the melting (liquidus) temperature, was derived for fragile nonpolymeric glass-forming liquids under the assumptions that the fragile behavior of these liquids is described by the Vogel-Fulcher-Tammann (VFT) equation; the excess heat capacity of liquid is inversely proportional to the absolute temperature and the VFT temperature T(0) is equal to the Kauzmann temperature T(K). It was found that DeltaC(p)(exc)(T(g))DeltaS(m) is a composite function of m and T(rg), which indicates that the empirical correlation DeltaC(p)(exc)(T(g))DeltaS(m)=0.025m recently identified by Wang et al. [J. Chem Phys. 125, 074505 (2006)] is probably valid only for liquids which have nearly the same values of T(rg).     

Pressure and volume dependence of thermal conductivity and isothermal bulk modulus up to 1 GPa for poly(isobutylene)

The thermal conductivity λ and heat capacity per unit volume ρc_p of poly(isobutylene)s, one 2.8 in weight average molecular weight and one 85 kg mol⁻¹ in viscosity average molecular weight (PIB-2800 and PIB-85000), have been measured in the temperature range 170–450 K at pressures up to 2 GPa using the transient hot-wire method. At 297 K and atmospheric pressure, λ = 0.115 W m⁻¹ K⁻¹ for PIB-2800 and λ = 0.120 W m⁻¹ K⁻¹ for PIB-85000. The bulk modulus B_T has been measured in the temperature range 170–297 K up to 1 GPa. At atmospheric pressure, the room temperature bulk moduli B_T are 2.0 GPa for PIB-2800 and 2.5 GPa for PIB-85000 with dB_T/dp = 10 for both. These data were used to calculate the volume dependence of λ, At room temperature and atmospheric pressure (liquid phase) we find g = 3.4 for PIB-2800 and g = 3.9 for PIB-85000, but g depends strongly on temperature for both molecular weights. The difference in g between the glassy state and liquid phase is small and just outside the inaccuracy of g of about 8%. The best predictions for g are given by the theoretical model of Horrocks and McLaughlin. We have found that PIB exhibits two relaxations, where one is associated with the glass transition. The value for dT_g/dp at atmospheric pressure (for the main glass transition) is about 0.21 K MPa⁻¹ for both molecular weights. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1781–1792, 1998     

Computer simulation study of thermodynamic scaling of dynamics of 2Ca(NO3)2·3KNO3

Molecular dynamics (MD) simulations of the glass-former 2Ca(NO(3))(2·3KNO(3), CKN, were performed as a function of temperature at pressures 0.1 MPa, 0.5 GPa, 1.0 GPa, and 2.0 GPa. Diffusion coefficient, relaxation time of the intermediate scattering function, and anion reorientational time were obtained as a function of temperature and densitiy ρ. These dynamical properties of CKN scale as ρ(γ)∕T with a common value γ = 1.8 ± 0.1. The scaling parameter γ is consistent with the exponent of the repulsive part of an effective intermolecular potential for the repulsion between the atoms at shortest distance in the equilibrium structure of liquid CKN, Ca(2+), and oxygen atoms of NO(3)(-). Correlation between potential energy and virial is obeyed for the short-range terms of the potential function, but not for the whole potential including coulombic interactions. Decoupling of diffusion coefficient and reorientational relaxation time from relaxation time take place at a given ρ(γ)∕T value, i.e., breakdown of Stokes-Einstein and Debye-Stokes-Einstein equations result from combined thermal and volume effects. The MD results agree with correlations proposed between long-time relaxation and short-time dynamics, lnτ ∝ 1∕, where the mean square displacement concerns a time window of 10.0 ps. It has been found that scales as ρ(γ)∕T above and below the glass transition temperature, so that thermodynamic scaling of liquid dynamics can be thought as a consequence of theories relating short- and long-time dynamics, and the more fundamental scaling concerns short-time dynamical properties.     

Pressure effects on the transitions between disordered phases in supercooled liquid silicon

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.     

Water's polyamorphic transitions and amorphization of ice under pressure

Transformations of water's high density amorph (HDA) to low density amorph (LDA) and of LDA's to cubic ice (Ic) have been studied by in situ thermal conductivity kappa measurements at high pressures. The HDA to LDA transformation is unobservable at p of 0.07 GPa, indicating that, for a fixed heating rate, an increase in pressure increases the temperature of HDA to LDA transformation and decreases that of LDA to ice Ic, causing thereby the two transformations to merge, and HDA appears to convert directly to ice Ic. Thus either LDA forms but converts extremely rapidly to ice Ic, or LDA does not form. At a fixed p and T, in the range of pressure amorphization of hexagonal ice, kappa continues to decrease with time. Therefore, the amorphization of ice Ih is kinetically controlled. When HDA at 1 GPa was heated from 130 to 157 K and densified to very HDA, its kappa increased by 3%. Our findings and a scrutiny of earlier reports show that a reversible transition between HDA and LDA does not occur at approximately 135 K and approximately 0.2 GPa. Since there is no unique HDA, it is difficult to justify the conjecture for a second critical point for water.     

Molecular alloy with diluted magnetic moments-molecular Kondo system

[Ni(1-x)Cu(x)(tmdt)(2)] (tmdt = trimethylenetetrathiafulvalenedithiolate) was prepared for realizing molecular Kondo systems. Magnetic moments (S = (1)/(2)) are considered to exist at the central {CuS(4)} parts of Cu(tmdt)(2) molecules. The χT-versus-T curve of the system with x ≈ 0.15 showed a broad peak at ~10 K. The decrease in the χT value below 10 K is consistent with a singlet ground state, as expected for a Kondo system. However, in the system with x ≈ 0.27, the χT value decreased when the temperature was lowered to 2 K, indicating antiferromagnetic interactions between magnetic moments through π-d interactions. Although the susceptibility anomaly suggested that the π-d interactions become important at T < 20 K, the observed resistivity (ρ(obs)) showed no resistivity minimum characteristic of a Kondo system down to 4.2 K. However, the differential resistivity Δρ(T) = ρ(obs) - ρ(L)(T) showed a logarithmic resistivity increase at 8-20 K with decreasing temperature, where ρ(L)(T) is a fitted function of ρ(obs) obtained at T > 50 K that is considered to represent approximately the temperature dependence of the resistivity without spin scattering of the conduction electrons.     

Time-dependent amorphization of ice at 0.8-0.9 GPa

Thermal conductivity measurements show that ice continues to amorphize for several days when kept at a fixed pressure p in the 0.79-0.88 GPa range, and fixed temperature T in the 127-130 K range. Thermal conductivity kappa decreases according to a stretched exponential in time, and its limiting long time value kappa( infinity ) varies with p and T. At 0.8 GPa and 128 K, kappa( infinity ) remains 2.5 times the value observed for high-density amorph. Consequences of these findings for our understanding of amorphization are discussed.     

Crystal structure of the new FeSe(1-x) superconductor

The newly discovered superconductor FeSe(1-x) (x approximately 0.08, T(c)(onset) approximately 13.5 K at ambient pressure rising to 27 K at 1.48 GPa) exhibits a structural phase transition from tetragonal to orthorhombic below 70 K at ambient pressure-the crystal structure in the superconducting state shows remarkable similarities to that of the REFeAsO(1-x)F(x) (RE = rare earth) superconductors.     

Thermal, pressure and light induced spin transition in the two-dimensional coordination polymer [Fe(pmd)2[Cu(CN)2]2

A complete structural, calorimetric, and magnetic characterisation of the 2D coordination spin crossover polymer [Fe(pmd)(2)[Cu(CN)(2)](2)] is reported. The crystal structure has been investigated below room temperature at 180 K and 90 K, and at 30 K after irradiating the sample at low temperature with green light (lambda = 532 nm). The volume cell contraction through the thermal spin transition is only 18 A(3) which is lower than the usually observed value of around 25-30 A(3) while the average Fe-N bond distances decrease by the typical value of about 0.19 A. The structural data of the irradiated state indicate that the high spin state is well induced since the cell parameters are consistent with the data at 180 K. Calorimetric and photo-calorimetric experiments have also been performed. The entropy content for the thermal spin transition, DeltaS = 35-37 J mol(-1) K(-1) lies in the lowest range of the typical values and correlates with the low volume cell contraction. The combination of the crystallographic and calorimetric data predicts, in accordance with a mean-field approach, a linear pressure dependence of the critical temperature with a slope of 302 K GPa(-1). Magnetic measurements under pressure reveal an anomalous behaviour since the critical temperature and hysteresis do not change up to 0.22 GPa but an apparent linear dependence is obtained for higher pressures (up to 0.8 GPa) with a slope two times higher than the mean-field estimation.     

Hysteretic spin crossover between a bisdithiazolyl radical and its hypervalent σ-dimer

The bisdithiazolyl radical 1a is dimorphic, existing in two distinct molecular and crystal modifications. The α-phase crystallizes in the tetragonal space group P4?2(1)m and consists of π-stacked radicals, tightly clustered about 4? points and running parallel to c. The β-phase belongs to the monoclinic space group P2(1)/c and, at ambient temperature and pressure, is composed of π-stacked dimers in which the radicals are linked laterally by hypervalent four-center six-electron S···S-S···S σ-bonds. Variable-temperature magnetic susceptibility χ measurements confirm that α-1a behaves as a Curie-Weiss paramagnet; the low-temperature variations in χ can be modeled in terms of a 1D Heisenberg chain of weakly coupled AFM S = (1)/(2) centers. The dimeric phase β-1a is essentially diamagnetic up to 380 K. Above this temperature there is a sharp hysteretic (T↑= 380 K, T↓ = 375 K) increase in χ and χT. Powder X-ray diffraction analysis of β-1a at 393 K has established that the phase transition corresponds to a dimer-to-radical conversion in which the hypervalent S···S-S···S σ-bond is cleaved. Variable-temperature and -pressure conductivity measurements indicate that α-1a behaves as a Mott insulator, but the ambient-temperature conductivity σ(RT) increases from near 10(-7) S cm(-1) at 0.5 GPa to near 10(-4) S cm(-1) at 5 GPa. The value of σ(RT) for β-1a (near 10(-4) S cm(-1) at 0.5 GPa) initially decreases with pressure as the phase change takes place, but beyond 1.5 GPa this trend reverses, and σ(RT) increases in a manner which parallels the behavior of α-1a. These changes in conductivity of β-1a are interpreted in terms of a pressure-induced dimer-to-radical phase change. High-pressure, ambient-temperature powder diffraction analysis of β-1a confirms such a transition between 0.65 and 0.98 GPa and establishes that the structural change involves rupture of the dimer in a manner akin to that observed at high temperature and ambient pressure. The response of the S···S-S···S σ-bond in β-1a to heat and pressure is compared to that of related dimers possessing S···Se-Se···S σ-bonds.     

Phase separation in dilute LiCl-H2O solution related to the polyamorphism of liquid water

When an emulsified 4.8 mol % LiCl-H2O solution was cooled under a pressure of 0.35 or 0.45 GPa and decompressed to 0.1 GPa at 142 K, slightly above its glass transition temperature (approximately 140 K at 0.1 GPa), its volume increased suddenly. This was regarded as an appearance of the low-density amorphous ice in the liquid solution as suggested by x-ray and Raman measurements, and this appearance corresponded to the high-to-low-density polyamorphic transition of pure H2O. Hysteresis was considered to accompany this volumetric change. The hysteresis of the liquid transition proves its first-order nature and, as for the solution, this suggests that the transition is a polyamorphic phase separation.     

Several routes to the glassy states in the one component soft core system: revisited by molecular dynamics

Molecular dynamics simulations have been performed to study the glass transition for the soft core system with a pair potential φ(n)(r) = ε(σ∕r)(n) of n = 12. Using the compressibility factor, PV/Nk(B)T=P?(ρ*), its phase diagram can be represented as a function of a reduced density, ρ? = ρ(ε∕k(B)T)(3∕n), where ρ = Nσ(3)∕V. In the present work, NVE relaxations to the glassy or crystalline states starting from the unstable states in the phase diagram have been revisited in details and compared with other processes. Relaxation processes can be characterized by the time dependence of the dynamical compressibility factor (PV/Nk(B)T)(t)?(≡g(ρ(t)*)) on the phase diagram. In some cases, g(ρ(t)*) reached a crystal branch in the phase diagram; however, metastable states are found in many cases. With connecting points for the metastable states in the phase diagram, we can define a glass branch where the dynamics of particles are almost frozen. The structures observed there have common properties characterized as glasses. Although overlaps of glass forming process and nanocrystallization process are observed in some cases, these behaviors are distinguishable to each other by the characteristics of structures. There are several routes to the glass branch and we suggest that all of them are the glass transition.     

Glass transition temperature of glucose, sucrose, and trehalose: an experimental and in silico study

Isothermal-isobaric molecular dynamics simulations are used to calculate the specific volume of models of different amorphous carbohydrates (glucose, sucrose, and trehalose) as a function of temperature. Plots of specific volume vs temperature exhibit a characteristic change in slope when the amorphous systems change from the glassy to the rubbery state. The intersection of the regression lines of data below (glassy state) and above (rubbery state) the change in slope provides the glass transition temperature (T(g)). These predicted glass transition temperatures are compared to experimental T(g) values as obtained from differential scanning calorimetry measurements. As expected, the predicted values are systematically higher than the experimental ones (about 12-34 K) as the cooling rates of the modeling methods are about a factor of 10(12) faster. Nevertheless, the calculated trend of T(g) values agrees exactly with the experimental trend: T(g)(glucose) < T(g)(sucrose) < T(g)(trehalose). Furthermore, the relative differences between the glass transition temperatures were also computed precisely, implying that atomistic molecular dynamics simulations can reproduce trends of T(g) values in amorphous carbohydrates with high quality.     

Structure-property relationships in the crystals of the smallest amino acid: an incoherent inelastic neutron scattering study of the glycine polymorphs

Incoherent inelastic neutron scattering spectra for the three crystalline polymorphs (alpha- P2(1)/n, beta- P2(1), gamma- P3(1)) of glycine (C2H5NO2) at temperatures between 5 and 300 K (using the time-of-flight (ToF) spectrometer NEAT at HMI) and at pressures from ambient up to 1 GPa (using the ToF spectrometer IN6 at the ILL) were measured. Significant differences in the band positions and their relative intensities in the density of states (DoS) were observed for the three polymorphs, which can be related to the different intermolecular interactions. The mean-squared displacement, (T), dependence reveals a change in dynamic properties at about the same temperature (150 K) for all the three forms, which can be related to the reorientation of the NH3 group. Besides, a dynamic transition in beta-glycine at about 230-250 K on cooling was also observed, supporting previously obtained adiabatic calorimetry data. This behavior is similar to that already observed in amorphous solids, on approaching the glass transition temperatures, as well as in biological systems. It suggests the onset of degrees of freedom most likely related to transitions between slightly different conformational orientations. The DoS obtained as a function of pressure has confirmed the stability of the alpha-form with respect to pressure and also depicted a sign of the previously reported reversible beta-beta' glycine phase transition in between 0.6 and 0.8 GPa. Moreover, a remarkable kinetic effect in the pressure-induced phase transition in gamma-glycine was revealed. After the sample was kept at 0.8 GPa for an hour in the neutron beam, an irreversible transition into a high-pressure form (different from the beta'-form) occurred, although previously in X-Ray diffraction and Raman spectroscopy experiments a gamma- to delta-glycine phase transition was observed above 3.5 GPa only.     

Comment on "Heat capacity, enthalpy fluctuations, and configurational entropy in broken ergodic systems" [J. Chem. Phys. 133, 164503 (2010)

A critical examination shows that the specific heat and shear modulus relaxation spectra do not support the notions of continuously broken ergodicity and loss of configurational contribution on isothermal glass transition, nor does the long-known result that C(p) → 0 as T → 0 K prove that S(conf) → 0. Spectra show variation of the real and imaginary components due to phase lag and not due to loss of configurational degrees of freedom. The high-frequency shear modulus, G(∞), of glass increases with time as its fictive temperature decreases and dG(∞)∕dT decreases when a glass forms.     

Effect of branching architecture on glass transition behavior of hyperbranched copolystyrenes: the experiment and simulation studies

By controlling the feed ratio of CMS/styrene and the polymerization time, a series of hyperbranched copolystyrenes(HBCPS) were synthesized with comparable weight-averaged molecular weights(Mw) but different degree of branching(DB) through atom transfer radical self-condensing vinyl copolymerization(ATR-SCVCP) with Cu Br/2,2?-bipyridyl as the catalyst. The resulting HBCPS samples were used to investigate the effect of branching architecture on their glass transition behavior. With the DB increased, the glass transition temperatures(Tg) of HBCPS samples measured by DMA and DSC both decreased. Their spin-lattice relaxation times(1H T1r) of protons displayed the same downtrend with increasing DB. Besides, a correlation between the Tgs and the DB was well established by all-atom molecular dynamics(MD) simulations. The values of MD-determined Tgs are little higher than the corresponding experimental ones. However, the dependence of Tgs on DB is in good agreement with the experimental results, i.e., Tg decreases both in experiments and simulations with increasing DB.     

Novel method to detect the volumetric glass --> liquid transition at high pressures: glycerol as a test case

We report a novel method of detecting the glass --> liquid transition at high pressures, which comprises measuring the relative volume change incurred upon heating glassy samples into the liquid state. We show data on glycerol in the pressure range 0.050-1.00 GPa to demonstrate the viability of the method. The reversible glass --> liquid transition is observed by means of a kink in the relative volume change on heating the sample isobarically, which is attributed to the glass --> liquid transition temperature Tg. This kink can only be observed in the second and subsequent heating cycles since it is superposed by a compaction in the first heating cycle. The isobaric thermal expansivity beta, which is closely related to the first derivative of this curve, shows the features expected for a glass --> liquid transition, including a sharp rise of beta(glass) in a narrow temperature interval to beta(viscous liquid) and an accompanying overshoot effect. Both Tg and the size of the overshoot effect vary in accordance with theory upon changing the ratio of cooling to heating rates. From the shape of this curve the onset, inflection, overshoot peak, and endpoint of the glass --> liquid transition can be extracted, which can be employed to calculate the reduced glass transition width as a measure for the fragility of the liquid. Comparison with literature data allows quantifying the accuracy of the liquid's thermal expansivity beta to be at least +/-10%, while the error in beta is significantly larger for the expansivity of the glassy state. The reproducibility of the glass --> liquid transition temperature Tg is better than +/-2 K. Our glycerol data confirms literature studies showing a nonlinear increase of Tg with increasing pressure (approximately 35 K/GPa on average), which is accompanied by an increase in fragility.     

聚合温度对聚氯乙烯树脂结构和性能的影响

采用凝胶渗透色谱法、¹³H NMR和DSC法测定了悬浮聚合PVC树脂的平均分子量、间规度、结晶度和玻璃化温度.结果表明:聚合温度下降,PVC的平均分子量上升,分子量的对数值与聚合温度的倒数成正比;PVC的间规度和结晶度均增大,在形成结晶的间规链段的最短长度(ξ_min)为6时,由间规度计算的结晶度理论值与测定值接近;分子量和结晶度增加的共同作用,使PVC的玻璃化转变温度上升.     

Ion dynamics under pressure in an ionic liquid

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.