The dielectric properties of the low and high density amorphous ices are discussed in terms of those for supercooled water and crystalline ices, and also used to evaluate the transition behaviour upon pressure cycling at 130 K. The dielectric relaxation of the high density amorphous ice is described well by the symmetrical Cole–Cole function with an almost pressure independent relaxation time τ ∼ 2 s at 133 K and a relaxation time distribution factor of 0.7. At the high to low density amorphous ice transition, the dielectric relaxation time increases by about two orders of magnitude despite a ∼30% decrease in density, and τ of the low density amorphous ice is in the range 102–103 s at 130 K. The relaxation time behaviour of the high density amorphous ice is similar to that of supercooled liquid water, whereas τ of the low density amorphous ice appears to be prolonged by the ice rules, in correspondence to that of the crystalline ices.
The knowledge of the existence of liquid water under extreme conditions and its concomitant properties are important in many fields of science. Glassy water has previously been prepared by hyperquenching micron-sized droplets of liquid water and vapor deposition on a cold substrate (ASW), and its transformation to an ultraviscous liquid form has been reported on heating. A densified amorphous solid form of water, high-density amorphous ice (HDA), has also been made by collapsing the structure of ice at pressures above 1 GPa and temperatures below approximately 140 K, but a corresponding liquid phase has not been detected. Here we report results of heat capacity C(p) and thermal conductivity, in situ, measurements, which are consistent with a reversible transition from annealed HDA to ultraviscous high-density liquid water at 1 GPa and 140 K. On heating of HDA, the Cp increases abruptly by (3.4 ± 0.2) J mol-1 K-1 before crystallization starts at (153 ± 1) K. This is larger than the Cp rise at the glass to liquid transition of annealed ASW at 1 atm, which suggests the existence of liquid water under these extreme conditions.
The effect of deuteration on the thermal conductivity kappa of water, crystalline ice, and amorphous ices was studied using the pressure induced amorphization of hexagonal ice, ice Ih, to obtain the deuterated, D2O, forms of low-density amorphous (LDA), high-density amorphous (HDA), and very-high density amorphous (VHDA) ices. Upon deuteration, kappa of ice Ih decreases between 3% and 4% in the 100-270 K range at ambient pressure, but the effect diminishes on densification at 130 K and vanishes just prior to amorphization near 0.8 GPa. The unusual negative value of the isothermal density rho dependence of kappa for ice Ih, g = (d ln kappa/d ln rho)(T) = -4.4, is less so for deuterated ice: g = -3.8. In the case of the amorphous ices and liquid water, kappa of water decreases by 3.5% upon deuteration at ambient conditions, whereas K of HDA and VHDA ices instead increases by up to 5% for pressures up to 1.2 GPa at 130 K, despite HDA's and VHDA's structural similarities with water. The results are consistent with significant heat transport by librational modes in amorphous ices as well as water, and that deuteration increases phonon-phonon scattering in crystalline ice. Heat transport by librational modes is more pronounced in D2O than in H2O at low temperatures due to a deuteration-induced red-shift of librational mode frequencies. Moreover, the results show that kappa of deuterated LDA ice is 4% larger than that of normal LDA at 130 K, and both forms display an unusual temperature dependence of kappa, which is reminiscent of that for crystals (kappa similar to T (-1)), and a unique negative pressure dependence of kappa, which likely is linked to local-order structural similarities to ice Ih.
Type II clathrate hydrates (CHs) with tetrahydrofuran (THF), cyclobutanone (CB) or 1,3-dioxolane (DXL) guest molecules collapse to an amorphous state near 1 GPa on pressurization below 140 K. On subsequent heating in the 0.2-0.7 GPa range, thermal conductivity and heat capacity results of the homogeneous amorphous solid show two glass transitions, first a thermally weak glass transition, GT1, near 130 K; thereafter a thermally strong glass transition, GT2, which implies a transformation to an ultraviscous liquid on heating. Here we compare the GTs of normal and deuterated samples and samples with different guest molecules. The results show that GT1 and GT2 are unaffected by deuteration of the THF guest and exchange of THF with CB or DXL, whereas the glass transition temperatures (Tgs) shift to higher temperatures on deuteration of water; Tg of GT2 increases by 2.5 K. These results imply that both GTs are associated with the water network. This is corroborated by the fact that GT2 is detected only in the state which is the amorphized CH's counterpart of expanded high density amorphous ice. The results suggest a rare transition sequence of an orientational glass transition followed by a glass to liquid transition, i.e., kinetic unfreezing of H2O reorientational and translational mobility in two distinct processes.
Type II clathrate hydrates (CHs) were studied by thermal and dielectric measurements. All CHs amorphize, or collapse, on pressurization to 1.3 GPa below 135 K. After heating to 160 K at 1 GPa, the stability of the amorphous states increases in a process similar to the gradual high density to very high density amorphous ice (HDA to VHDA) transition. On a subsequent pressure decrease, the amorphized CHs expand partly irreversibly similar to the gradual VHDA to expanded HDA ice transformation. After further heating at 1 GPa, weak transition features appear near the HDA to low density amorphous ice transition. The results suggest that CH nucleation sites vanish on heating to 160 K at 1 GPa and that a sluggish partial phase-separation process commences on further heating. The collapsed CHs show two glass transitions (GTs), GT1 and GT2. GT1 is weakly pressure-dependent, 12 K GPa(-1), with a relaxation time of 0.3 s at 140 K and 1 GPa; it is associated with a weak heat capacity increase of 3.7 J H2O-mol(-1) K-1 in a 18 K range and an activation energy of only 38 kJ mol(-1) at 1 GPa. The corresponding temperature of GT2 is 159 K at 0.4 GPa with a pressure dependence of 36 K GPa(-1); it shows 5.5 times larger heat capacity increase and 4 times higher activation energy than GT1. GT1 is observed also in HDA and VHDA, whereas GT2 occurs just above the crystallization temperature of expanded HDA and only within its similar to 0.2-0.7 GPa stable pressure range.
The thermal conductivity kappa of the ferroelectric, paraelectric, and incommensurate phases of polycrystalline Sn2P2S6 has been measured in the 0.1-0.7 GPa range. The thermal conductivity kappa of the ferroelectric phase decreases with increasing pressure p. This unusual behavior, which is found in only a few other phases, is attributed to a negative Gruneisen parameter. The temperature T dependence of kappa for the ferroelectric phase (kappa similar to T-1) is well described by the Debye model for kappa, with three-phonon Umklapp scattering serving as the dominant scattering mechanism near and above the Debye temperature (similar to 100 K) up to a few tenths of degrees below the ferro- to paraelectric phase transition, where kappa(T) gradually changes and becomes temperature independent upon further heating. The thermal conductivity of the paraelectric and incommensurate phases was temperature independent and indistinguishable. Possible causes for the unusually weak T dependence at high temperatures and implications of the p dependence of kappa are discussed.
The heat capacity of Sn2P2S6 ferroelectric crystals has been measured under quasihydrostatic pressures up to 0.7 GPa. The analysis of the heat-capacity and literature data for the birefringence shows that the tricritical point of Sn2P2S6 is in the 0.20–0.25 GPa range. Moreover, in the approximation of a linear change in the free-energy expansion coefficients, with respect to concentration and pressure, thermodynamic trajectories have been constructed for (PbySn1−y)2 P2(SexS1−x)6 solid solutions. We have thereby identified the region of the T-p-y-x diagram for (PbySn1−y)2 P2(SexS1−x)6 showing the tricritical Lifshitz point.
The potential hydrogen storage compound NH3BH3 has three known structural phases in the temperature and pressure ranges 110–300 K and 0–1.5 GPa, respectively. We report here the boundaries between, and the ranges of stability of, these phases. The phase boundaries were located by in situ measurements of the thermal conductivity, while the actual structures in selected areas were identified by in situ Raman spectroscopy and x-ray diffraction. Below 0.6 GPa, reversible transitions involving only small hysteresis effects occur between the room-temperature tetragonal plastic crystal I4mm phase and the low-temperature orthorhombic Pmn21 phase. Transformations of the I4mm phase into the high-pressure orthorhombic Cmc21 phase, occurring above 0.8 GPa, are associated with very large hysteresis effects, such that the reverse transition may occur at up to 0.5 GPa lower pressures. Below 230 K, a fraction of the Cmc21 phase is metastable to atmospheric pressure, suggesting the possibility that dense structural phases of NH3BH3, stable at room temperature, could possibly be created and stabilized by alloying or by other methods. Mixed orthorhombic Pmn21/Cmc21 phases were observed in an intermediate pressure-temperature range, but a fourth structural phase predicted by Filinchuk et al. [ Phys. Rev. B 79 214111 (2009)] was not observed in the pressure-temperature ranges of this experiment. The thermal conductivity of the plastic crystal I4mm phase is about 0.6 W m−1 K−1 and only weakly dependent on temperature, while the ordered orthorhombic phases have higher thermal conductivities limited by phonon-phonon scattering.
Type II clathrate hydrates (CHs) M·17 H2O, with M = tetrahydrofuran (THF) or 1,3-dioxolane, are known to collapse, or amorphize, on pressurization to ∼1.3 GPa in the temperature range 77–140 K. On heating at 1 GPa, these pressure-amorphized CH states show a weak, stretched sigmoid-shaped, heat-capacity increase because of a glass transition. Here we use thermal conductivity and heat capacity measurements to show that also type II CH with M = cyclobutanone (CB) collapses on isothermal pressurization and undergoes a similar, weak, glass transition upon heating at 1 GPa. Furthermore, we reveal for both THF CH and CB CH a second, much more pronounced, glass transition at temperatures above the thermally weak glass transition on heating in the 0.2–0.7 GPa range. This result suggests the general occurrence of two glass transitions in water-rich (94 mol %) pressure-collapsed CHs. Because of a large increase in dielectric permittivity concurrently as the weak heat capacity increase, the first glass transition must be due to kinetic unfreezing of water molecules. The thermal features of the second glass transition, measured on isobaric temperature cycling, are typical of a glass–liquid–glass transition, which suggests that pressure-amorphized CHs transform reversibly to liquids.
Ice is known to collapse to amorphous ice upon pressurization at low temperatures and shows the unusual feature of multiple distinct solid amorphous water states, which have inspired models of liquid water’s structure and unusual properties.Here, we use heat capacity Cp measurements to show that similarly collapsed ice clathrates display identical glass behavior as amorphous ice but that crystallization above the glass transition temperature Tg of ∼140 K at 1 GPa is inhibited. This effect of the homogeneously distributed “guest molecules” in water reveals a relatively strong reversible Cp increase above Tg but no further transition before crystallization at ∼190 K.This is consistent with a glass−liquid transition of water at Tg, which suggests a new path to study an ultraviscous liquid water network and evaluate water models
The low-temperature limiting value of the Grüneisen parameter for low-frequency phonons and the density dependence of the thermal conductivity (Bridgman parameter) of low-density amorphous (LDA) ice, high-density amorphous (HDA) ice, hexagonal ice Ih, and cubic ice Ic were calculated from high-pressure sound velocity and thermal conductivity measurements, yielding negative values for all states except HDA ice. LDA ice is the first amorphous state to exhibit a negative Bridgman parameter, and negative Grüneisen parameters are relatively unusual. Since Ih, Ic, and LDA ice all transform to HDA upon pressurization at low temperatures and share the unusual feature of negative Grüneisen parameters, this seems to be a prerequisite for pressure induced amorphization. We estimate that the Grüneisen parameter increases at the ice Ih to XI transition, and may become positive in ice XI, which indicates that proton-ordered ice XI does not amorphize like ice Ih on pressurization.
The vibrational state of a glass is naturally incompatible with its configurational state, which makes the glass structurally unstable. When a glass is kept at constant temperature, both the vibrational and configurational states of a glass change with time until it becomes metastable (equilibrium) liquid and the two states become compatible. The process, known as structural relaxation, occurs at a progressively higher rate during heating, and the properties of a glass change accordingly. We add to this incompatibility by depressurizing a glass that had been formed by cooling a liquid under a high pressure, p, and then investigate the effects of the added incompatibility by studying thermal conductivity, κ, and the heat capacity per unit volume ρCp of the depressurized glass.We use glycerol for the purpose and study first the changes in the features of κ and of ρCp during glass formation oncooling under a set of different p. We then partially depressurize the glass and study the effect of the p-induced instability on the features of and Cp as the glass is isobarically heated to the liquid state.At a given low p, the glass configuration that was formed by cooling at high-p had a higher κ than the glass configuration that was formed by cooling at a low p. The difference is more when the glass is formed at a higher p and/or is depressurized to a lower p. On heating at a low p, its κ decreases before its glass-liquid transition range is reached. The effect is the opposite of the increase in observed on heating a glass at the same p under which it was formed. It is caused by thermally assisted loss of the added incompatibility of configurational and vibrational states of a high-p formed glass kept at low p. If a glass formed under a low-p is pressurized and then heated under high p, it would show the opposite effect, i.e., its κ would first increase to its high p value before its glass-to-liquid transition range.
Irreversible transformation of the tetrahydrofuran ice clathrate at 130 K was studied by measuring thermal conductivity k with increase in pressure p. Initially, k increases slowly with p up to 0.75 GPa where it levels off, is roughly constant up to 0.95 GPa, then decreases up to 1.05 GPa. Pressure collapses the clathrate structure, plausibly beginning with lattice distortion, and k increases at 1.05 GPa in a sharp sigmoid-shape manner due to large densification until the transformation is complete at 1.25 GPa. This is the opposite of that found for ice whose k decreases first slowly with increase in p and then rapidly in an inverted sigmoidshape manner [O. Andersson and H. Suga, Phys. Rev. B 65, 140201 (2002)]. At 1.08 GPa and 131 K, k increases with time t (s) according to exp(t /2945), which is also the opposite of the collapse of ice [G. P. Johari and O. Andersson, Phys. Rev. B 70, 184108 (2004)]. The difference in its behavior is attributed to strong phonon scattering from the tetrahydrofuran guest molecules. k of the collapsed clathrate is 30% less than that for the collapsed ice, which is comparable with the 25% lesser k of the tetrahydrofuran-water solution from k of water at ambient pressure. On depressurizing at 130 K, k decreases progressively more rapidly and k of the collapsed state at 0.3 GPa is slightly lower than that of the as-made clathrate, showing that its original structure is not recovered.
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. 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.
Collapse of an ice clathrate of type II structure containing tetrahydrofuran as guest molecules has been studied at different pressures by dielectric spectroscopy. The sample was pressurized to 1.3 GPa at 130 K and the resulting collapsed state was pressure cycled. The dielectric relaxation time increases at a progressively rapid rate during pressurizing and then decreases slowly on depressurizing, but the dielectric relaxation time does not reach the value of the original state. With increase in pressure, the limiting high frequency permittivity due to orientation of H2O molecules first increases by about 5% until 0.75 GPa and then decreases slightly until 1 GPa, and finally it increases until ~1.2 GPa. The decrease is attributed to the loss of contribution from the reorientational motion of tetrahydrofuran molecules and the increase to densification as the structure mechanically collapses completely in the 1–1.25 GPa range. The relaxation time of the collapsed state is comparable with that of the high-density amorph formed on pressure collapse of ice.
We report thermal conductivity κ measurements of the pressure-induced collapse of two mixtures of ice and tetrahydrofuran (THF) clathrate hydrate formed by freezing aqueous solutions, THF·23 H2O and THF·20 H2O, one containing twice as much excess water than the other. On pressurizing, κ of the solid mixture first decreases at the onset pressure of 0.8 GPa, as occurs for collapse of pure ice, reaches a local minimum at a pressure of 1.0 GPa, and then increases as occurs for the collapse of the pure clathrate THF·17 H2O. This shows that in the apparently homogeneous mixture, the ice and the clathrate collapse as if the two were in a mechanically mixed state. The manner in which the clathrate aggregate can arrange in the solid indicates that ice occupies the interstitial space in the tightly packed aggregates and H2O molecules belonging to the lattice of one form hydrogen bond with that of the other, a feature that is preserved in their collapsed states. On decompression, the original clathrate is partially recovered in the THF·20 H2O mixture, but the collapsed ice does not transform to the low density amorph. We surmise that on irreversible transformation to the original clathrate, the aggregates expand. Any pressure thus exerted on the small domains of the collapsed ice with a hydrogen bonded interface with the clathrate aggregates could prevent it from transforming to the low density amorph. Measurements of κ are useful in investigating structural collapse of crystals when dilatometry is unable to do so, as κ seems to be more sensitive to pressure-induced changes than the volume.
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 ∼ 145 K exothermally to a phase whose relaxation rate and equilibrium dielectric permittivity increased. A second, but slower exothermic transformation also occurred at ∼ 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
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 k decreases according to a stretched exponential in time, and its limiting long time value k() varies with p and T. At 0.8 GPa and 128 K, k() remains 2.5 times the value observed for high-density amorph. Consequences of these findings for our understanding of amorphization are discussed.
On pressurizing at temperatures near 130 K, hexagonal and cubic ices transform implosively at 0.8–1 GPa. The phase produced on transformation has the lowest thermal conductivity among the known crystalline ices and its value decreases on increase in temperature. An ice phase of similar thermal conductivity is produced also when high-density amorphous ice kept at 1 GPa transforms on slow heating when the temperature reaches ∼155 K. These unusual formation conditions, the density and its distinguished thermal conductivity, all indicate that a distinct crystal phase of ice has been produced.
Type II clathrate hydrates (CHs), or ice clathrates, are inclusion compounds in which a hydrogen-bonded cage-like structure of H2O accommodates molecules of suitable size, known as guest molecules. CHs have similar local geometrical arrangements of the hydrogen-bonded water network as ice and both are known to collapse to amorphous states on isothermal pressurization at temperatures below about 140 K. Moreover, the collapsed CH states undergo a glass, or glass-like, transition at 140 K on heating at 1 GPa, which is identical to that of collapsed ice, or high density amorphous ice. Here we use thermal conductivity and dielectric measurements to study the transition behavior of two type II CHs with tetrahydrofuran and 1,3 dioxolane, respectively, as guest molecules. After their collapsed states have been heated to well above the glass transition at 1 GPa, we find transitions corresponding to the high to low density amorphous ice transition of ice with only slightly shifted temperature-pressure (T-p) coordinates compared to those of pure water. Thus, collapsed CHs show the same transition behaviors as cold water, which provide the basis for the model that explains the unusual temperature and pressure behaviors of waters properties in terms of two distinct types of liquid water. Collapsed CHs are, however, more stable than collapsed ice and can therefore be studied in a wider T-p interval. The results suggest sluggish homogenizing and phase separation processes, which affect the transition behaviors of collapsed CHs.
The orientational structure of C60 depends on pressure and temperature. Pressurization below the glass transition temperature Tg can freeze in non-equilibrium orientational structures. The relaxation of such structures on heating through Tg has been studied through thermal conductivity measurements and the effects observed are explained in a simple model.
The thermal conductivity λ of C60 shows anomalies near 260 K and 90 K which are associated with the well-established phase transition and glass transition, respectively. Both transition temperatures increase with pressure, at the rates 120 K GPa-1 and 62 K GPa-1, respectively. With increasing temperature, λ of the simple cubic (sc) phase increased below 170 K (glasslike behavior) but decreased above. The glasslike behavior of λ is probably due to a substantial amount of lattice defects. Possible reasons for the change of sign of dλ/dT near 170 K are discussed. In the face centered cubic (fcc) phase (T≳260 K at atmospheric pressure) λ was almost independent of temperature, a behavior which is far from that of an ordered crystal (λ∝T-1 for T≳Debye temperature). This result can be attributed to the molecular orientational disorder of the fcc phase. The relaxation behavior associated with the glassy state and its unusually strong dependence on thermal history are discussed briefly, and data which support a previously reported relaxation model are presented. At room temperature, the density dependencies of λ, (∂ lnλ/∂ lnρ)T, were 5.5 and 9.5 for the fcc and sc phases, which are values typical for an orientationally disordered phase and a normal crystal phase, respectively.
We have measured the thermal conductivity lambda of highly pure polycrystalline C60 in the range 50 to 300 K under pressures up to 1 GPa. The results are discussed in terms of the lattice structure and dynamics. In particular, we discuss the phase diagram as delineated by anomalies observed in lambda and cp at the f.c.c.-to-s.c. transition at 260 K and the glass transition at Tg = 90 K, and also the effect on lambda of the orientational motion in the s.c. phase. The results are found to be compatible with a p/T phase diagram recently suggested by us.
A low-temperature high-pressure apparatus was designed using commercial cryogenic equipment. Pressures up to 1 GPa and temperatures down to 40 K can be obtained in a volume of up to 30 cm3. The apparatus is of the piston-cylinder type with a piston diameter of 45 mm, and the pressure can be varied at all temperatures, An adaptive temperature control system keeps the temperature inside the pressure cylinder constant to within ±0.1 K.
The thermal properties and transition behavior of the host-guest inclusion compounds: urea, thiourea, Dianin’s compound, clathrate hydrates and hydroquinone have been reviewed. In particular, we summarize their thermal conductivities, heat capacities and transitions at high pressures. Two of the systems: urea inclusion compounds and clathrate hydrates, show unusual glass-like thermal conductivity k, i.e. their k is low and only weakly dependent on temperature despite their crystalline structure. Moreover, results for k of Dianin’s compound with guests such as ethanol and CCl4 indicate a change from glass-like k at atmospheric pressure to crystalline-like k at elevated pressure, whereas k of hydroquinone and thiourea inclusion compounds appears not to have been studied. Despite the technological and fundamental importance of the unusual glass-like k, e.g. the use of inclusion compounds as structural model systems for finding improved thermoelectrical materials, the origin of the glass-like k is not established. More specifically, the commonly employed rattling model, in which rattling guest motions cause resonance scattering of the acoustic host phonons, has recently been challenged, and we discuss alternative models. Heat capacity studies of these compounds reveal numerous transitions, which are associated with guest and host disorder-order transitions upon cooling and pressurization. A transition in hydroquinone may be of second order, or have only a small first-order component, which can explain discrepancies in the observed transition behavior. On pressurization at low temperatures, clathrate hydrates collapse to an amorphous state, which appears to be a glassy state of a water solution with perfectly spaced solute molecules.
Cellulose is a crystalline polymer with intriguing, amorphous-like, temperature dependence of thermal conductivity κ. To determine its origin, we have studied κ of cellulose nanocrystals (CNCs) derived from cotton by sulfuric acid hydrolysis, in both porous and nonporous states by pressure densification; κ increases weakly with increasing temperature and density, like in a fully amorphous material, and it is remarkably similar to that of cellulose fibers (CFs) and cellulose nanofibers (CNFs). For a powder derived from a natural material, like cellulose, amorphous-like κ may originate from poor thermal contact between particles or a high amorphous content, but the latter is not the case for CNCs. Moreover, the amorphous-like behavior is unaffected by densification and, therefore, improved thermal contacts. Instead, we attribute the behavior to CNCs' nanometer-sized fibrils, which limit the phonon mean free path to a few nanometers in a network of randomly oriented CNCs. This explains why κ is essentially the same in networks of CNCs, CFs, and CNFs, which are materials with the same structural unit-elementary fibrils of 3-5 nm in diameter. We obtain κ = (0.60 ± 0.01) W m-1 K-1 for a nonporous network of randomly oriented CNCs at 295 K and atmospheric pressure, and κ increases by only 14% GPa-1, which is unusually weak for a polymer. By using a model for such a network, we find κ = 1.9 W m-1 K-1 along a CNC and argue that this is a good estimate also along a CNF and a CF at room temperature.
Considering the growing use of cellulose in various applications, knowledge and understanding of its physical properties become increasingly important. Thermal conductivity is a key property, but its variation with porosity and density is unknown, and it is not known if such a variation is affected by fiber size and temperature. Here, we determine the relationships by measurements of the thermal conductivity of cellulose fibers (CFs) and cellulose nanofibers (CNFs) derived from commercial birch pulp as a function of pressure and temperature. The results show that the thermal conductivity varies relatively weakly with density (ρsample = 1340–1560 kg m–3) and that its temperature dependence is independent of density, porosity, and fiber size for temperatures in the range 80–380 K. The universal temperature and density dependencies of the thermal conductivity of a random network of CNFs are described by a third-order polynomial function (SI-units): κCNF = (0.0787 + 2.73 × 10–3·T – 7.6749 × 10–6·T2 + 8.4637 × 10–9·T3)·(ρsample/ρ0)2, where ρ0 = 1340 kg m–3 and κCF = 1.065·κCNF. Despite a relatively high degree of crystallinity, both CF and CNF samples show amorphous-like thermal conductivity, that is, it increases with increasing temperature. This appears to be due to the nano-sized elementary fibrils of cellulose, which explains that the thermal conductivity of CNFs and CFs shows identical behavior and differs by only ca. 6%. The nano-sized fibrils effectively limit the phonon mean free path to a few nanometers for heat conduction across fibers, and it is only significantly longer for highly directed heat conduction along fibers. This feature of cellulose makes it easier to apply in applications that require low thermal conductivity combined with high strength; the weak density dependence of the thermal conductivity is a particularly useful property when the material is subjected to high loads. The results for thermal conductivity also suggest that the crystalline structures of cellulose remain stable up to at least 0.7 GPa.
An important part of the new quantitative approach to elastohydrodynamic lubrication (EHL) is the use of reference liquids with well-characterized thermophysical properties. New measurements are reported for the thermal and rheological properties of squalane to high pressure and of high shear rate and high-frequency viscosity of squalane thickened with polyisoprene (SQL + PIP) at ambient pressure. The glass transition viscosity of squalane at ambient pressure was found from published viscosity measurements and new glass transition measurements by transient hot wire. The glass transition viscosity so determined was incorporated into the improved Yasutomi model and the calculated glass transition temperatures as a function of pressure are comparable to those directly measured, although the hybrid model yields better agreement. The glass transition viscosity of squalane by any definition must be substantially lower than the “universal value” of 1012 Pa·s. The second Newtonian inflection cannot be characterized in steady shear at ambient pressure for SQL + PIP due to cavitation; however, acoustic viscometry with matching layer does characterize the second Newtonian inflection. To form the analogy between steady and oscillatory shear requires that the steady shear rate be compared with the ordinary frequency rather than the angular frequency for SQL + PIP.
From crystalline tetrahydrofuran clathrate hydrate, THF-CH (THF·17H2O, cubic structure II), three distinct polyamorphs can be derived. First, THF-CH undergoes pressure-induced amorphization when pressurized to 1.3 GPa in the temperature range 77-140 K to a form which, in analogy to pure ice, may be called high-density amorphous (HDA). Second, HDA can be converted to a densified form, VHDA, upon heat-cycling at 1.8 GPa to 180 K. Decompression of VHDA to atmospheric pressure below 130 K produces the third form, recovered amorphous (RA). Results from neutron scattering experiments and molecular dynamics simulations provide a generalized picture of the structure of amorphous THF hydrates with respect to crystalline THF-CH and liquid THF·17H2O solution (∼2.5 M). Although fully amorphous, HDA is heterogeneous with two length scales for water-water correlations (less dense local water structure) and guest-water correlations (denser THF hydration structure). The hydration structure of THF is influenced by guest-host hydrogen bonding. THF molecules maintain a quasiregular array, reminiscent of the crystalline state, and their hydration structure (out to 5 Å) constitutes ∼23H2O. The local water structure in HDA is reminiscent of pure HDA-ice featuring 5-coordinated H2O. In VHDA, the hydration structure of HDA is maintained but the local water structure is densified and resembles pure VHDA-ice with 6-coordinated H2O. The hydration structure of THF in RA constitutes ∼18 H2O molecules and the water structure corresponds to a strictly 4-coordinated network, as in the liquid. Both VHDA and RA can be considered as homogeneous.
The high-pressure structural behavior of the noble gas (Ng) clathrate hydrates Ar·6.5H2O and Xe·7.2H2O featuring cubic structures II and I, respectively, was investigated by neutron powder diffraction (using the deuterated analogues) at 95 K. Both hydrates undergo pressure-induced amorphization (PIA), indicated by the disappearance of Bragg diffraction peaks, but at rather different pressures, at 1.4 and above 4.0 GPa, respectively. Amorphous Ar hydrate can be recovered to ambient pressure when annealed at >1.5GPa and 170 K and is thermally stable up to 120 K. In contrast, it was impossible to retain amorphous Xe hydrate at pressures below 3 GPa. Molecular dynamics (MD) simulations were used to obtain general insight into PIA of Ng hydrates, from Ne to Xe. Without a guest species, both cubic clathrate structures amorphize at 1.2 GPa, which is very similar to hexagonal ice. Filling of large-sized H cages does not provide stability toward amorphization for structure II, whereas filled small-sized dodecahedral D cages shift PIA successively to higher pressures with increasing size of the Ng guest. For structure I, filling of both kinds of cages, large-sized T and small-sized D, acts to stabilize in a cooperative fashion. Xe hydrate represents a special case. In MD, disordering of the guest hydration structure is already seen at around 2.5 GPa. However, the different coordination numbers of the two types of guests in the crystalline cage structure are preserved, and the state is shown to produce a Bragg diffraction pattern. The experimentally observed diffraction up to 4 GPa is attributed to this semicrystalline state.
The high pressure structural behavior of H2 and Ne clathrate hydrates with approximate composition H2/Ne·~4H2O and featuring cubic structure II (CS-II) was investigated by neutron powder diffraction using the deuterated analogues at ~95 K. CS-II hydrogen hydrate transforms gradually to isocompositional C1 phase (filled ice II) at around 1.1 GPa but may be metastably retained up to 2.2 GPa. Above 3 GPa a gradual decomposition into C2 phase (H2·H2O, filled ice Ic) and ice VIII’ takes place. Upon heating to 200 K the CS-II to C1 transition completes instantly whereas C1 decomposition appears sluggish also at 200 K. C1 was observed metastably up to 8 GPa. At 95 K C1 and C2 hydrogen hydrate can be retained below 1 GPa and yield ice II and ice Ic, respectively, upon complete release of pressure. In contrast, CS-II neon hydrate undergoes pressure-induced amorphization at 1.9 GPa, thus following the general trend for noble gas clathrate hydrates. Upon heating to 200 K amorphous Ne hydrate crystallizes as a mixture of previously unreported C2 hydrate and ice VIII’.
Three amorphous forms of Ar hydrate were produced using the crystalline clathrate hydrate Ar·6.5H2O (structure II, Fd3m, a ≈ 17.1 Å) as a precursor and structurally characterized by a combination of isotope substitution (36Ar) neutron diffraction and molecular dynamics (MD) simulations. The first form followed from the pressure-induced amorphization of the precursor at 1.5 GPa at 95 K and the second from isobaric annealing at 2 GPa and subsequent cooling back to 95 K. In analogy to amorphous ice, these amorphs are termed high-density amorphous (HDA) and very-high-density amorphous (VHDA), respectively. The third amorph (recovered amorphous, RA) was obtained when recovering VHDA to ambient pressure (at 95 K). The three amorphs have distinctly different structures. In HDA the distinction of the original two crystallographically different Ar guests is maintained as differently dense Ar–water hydration structures, which expresses itself in a split first diffraction peak in the neutron structure factor function. Relaxation of the local water structure during annealing produces a homogeneous hydration environment around Ar, which is accompanied with a densification by about 3%. Upon pressure release the homogeneous amorphous structure undergoes expansion by about 21%. Both VHDA and RA can be considered frozen solutions of immiscible Ar and water in which in average 15 and 11 water molecules, respectively, coordinate Ar out to 4 Å. The local water structures of HDA and VHDA Ar hydrates show some analogy to those of the corresponding amorphous ices, featuring H2O molecules in 5- and 6-fold coordination with neighboring molecules. However, they are considerably less dense. Most similarity is seen between RA and low density amorphous ice (LDA), which both feature strictly 4-coordinated H2O networks. It is inferred that, depending on the kind of clathrate structure and occupancy of cages, amorphous states produced from clathrate hydrates display variable local water structures.
Clathrate hydrates with the cubic structure II (CS-II) form typically with large guest molecules, such as tetrahydrofuran, trimethylamine oxide, or propane. However, CS-II is also realized for argon hydrate despite the comparatively small van der Waals diameter of the guest (around 3.8 angstrom). Here, the structure of deuterated argon hydrate was studied at ambient pressure in the temperature range 20-95 K using neutron diffraction and comparing natural Ar with Ar-36, which scatters neutrons more than 13 times more efficiently. The procedure allowed to unambiguously establish the positional disorder within the large cages of CS-H, while simultaneously refining host and guest structures. These cages are singly occupied and off-centered argon atoms distribute on two tetrahedron-shaped split positions with a ratio 3:1. Molecular dynamics (MD) simulations revealed that the crystallographic positional disorder structure is due to mobile argon atoms even at 20 K. The MD potential energy distribution confirmed the diffraction model. It is noted that the unit cell volumes of argon hydrate in the investigated temperature range are virtually identical to N-2 hydrate, which has a similar composition at ambient pressure, indicating a very similar (slightly attractive) host-guest interaction.
The type II clathrate hydrate (CH) THF·17 H2O (THF = tetrahydrofuran) is known to amorphize on pressurization to ∼1.3 GPa in the temperature range 77–140 K. This seems to be related to the pressure induced amorphization (PIA) of hexagonal ice to high density amorphous (HDA) ice. Here, we probe the PIA of THF-d8 · 17 D2O (TDF-CD) at 130 K by in situthermal conductivity and neutron diffraction experiments. Both methods reveal amorphization of TDF-CD between 1.1 and 1.2 GPa and densification of the amorphous state on subsequent heating from 130 to 170 K. The densification is similar to the transition of HDA to very-high-density-amorphous ice. The first diffraction peak (FDP) of the neutron structure factor function, S(Q), of amorphous TDF-CD at 130 K appeared split. This feature is considered a general phenomenon of the crystalline to amorphous transition of CHs and reflects different length scales for D-D and D-O correlations in the water network and the cavity structure around the guest. The maximum corresponding to water-water correlations relates to the position of the FDP of HDA ice at ∼1 GPa. Upon annealing, the different length scales for water-water and water-guest correlations equalize and the FDP in the S(Q) of the annealed amorph represents a single peak. The similarity of local water structures in amorphous CHs and amorphous ices at in situ conditions is confirmed from molecular dynamics simulations. In addition, these simulations show that THF guest molecules are immobilized and retain long-range correlations as in the crystal.
An in situ combined high-temperature high-pressure synchrotron radiation diffraction study has been carried out on LiBH4. The phase diagram of LiBH4 is mapped to 10 GPa and 500 K, and four phases are identified. The corresponding structural distortions are analyzed in terms of symmetry-breaking atomic position shifts and anion ordering. Group-theoretical and crystal-chemical considerations reveal a nontrivial layered structure of LiBH4. The layers and their deformations define the structural stability of the observed phases.
The polymerization of three typical aromatic solvent-doped fullerene materials with similar hexagonal closest packed (hcp) structures (mesitylene/C60, m-dichlorobenzene/C60 and m-xylene/C60 solvates) is studied under high pressure and high temperature (HPHT, 1.5 GPa, 573 K and 2 GPa, 700 K, respectively). Raman and photoluminescence spectroscopies reveal that the intercalated aromatic solvents play a crucial role in tailoring the extent of polymerization of C60 molecules. In the solvates, the solvents confine formation of covalent bonds between C60 molecules to the 001 direction and the (001) plane of the hcp lattices, leading to the formation of mixed polymeric phases of monomers, dimers, one-dimensional (1D) chainlike oligomers, and two-dimensional (2D) tetragonal phase polymers under suitable HPHT conditions. The type and number of substituent groups of the aromatic solvents are found to have significant influence, determining the amounts and types of polymeric phases formed. Our studies enrich the understanding of the formation mechanisms for controllably fabricating polymeric fullerenes and facilitate targeted design and synthesis of unique fullerene-based carbon materials.
Layered zinc hydroxides (LZHs) with the general formula (Zn2+)x(OH–)2x−my(Am–)y·nH2O (Am– = Cl–, NO3–, ac–, SO42–, etc) are considered as useful precursors for the fabrication of functional ZnO nanostructures. Here, we report the synthesis and structure characterization of the hitherto unknown “binary” representative of the LZH compound family, Zn5(OH)10·2H2O, with Am– = OH–, x = 5, y = 2, and n = 2. Zn5(OH)10·2H2O was afforded quantitatively by pressurizing mixtures of ε-Zn(OH)2 (wulfingite) and water to 1–2 GPa and applying slightly elevated temperatures, 100–200 °C. The monoclinic crystal structure was characterized from powder X-ray diffraction data (space group C2/c, a = 15.342(7) Å, b = 6.244(6) Å, c = 10.989(7) Å, β = 100.86(1)°). It features neutral zinc hydroxide layers, composed of octahedrally and tetrahedrally coordinated Zn ions with a 3:2 ratio, in which H2O is intercalated. The interlayer d(200) distance is 7.53 Å. The H-bond structure of Zn5(OH)10·2H2O was analyzed by a combination of infrared/Raman spectroscopy, computational modeling, and neutron powder diffraction. Interlayer H2O molecules are strongly H-bonded to five surrounding OH groups and appear orientationally disordered. The decomposition of Zn5(OH)10·2H2O, which occurs thermally between 70 and 100 °C, was followed in an in situ transmission electron microscopy study and ex situ annealing experiments. It yields initially 5–15 nm sized hexagonal w-ZnO crystals, which, depending on the conditions, may intergrow to several hundred nm-large two-dimensional, flakelike crystals within the boundary of original Zn5(OH)10·2H2O particles.
TiO2-II is a high pressure form of titania with a density about 2% larger than that of rutile. In contrast to the common polymorphs anatase, brookite and rutile its electronic structure and optical properties are poorly characterized. Here we report on a comparative electron-energy-loss-spectroscopy (EELS) study for which high resolution valence-loss and core-loss EELS data were acquired from nanocrystalline (<75 nm sized) titania particles with an energy resolution of about 0.2 eV. Electronic structure features revealed from titanium L3,2 and oxygen K electron energy loss near-edge structures show a strong similarity of TiO2-II with both rutile and brookite, which is attributed to similarities in the connectivity of octahedral TiO6 units with neighboring ones. From combined valence-loss EELS and UV-VIS diffuse reflectance spectroscopy data the band gap of TiO2-II was determined to be indirect and with a magnitude of ∼3.18 eV, which is very similar to anatase (indirect, ∼3.2 eV), and distinctly different from rutile (direct, ∼3.05 eV) and brookite (direct, ∼3.45 eV).
The aim of this paper is to study the effects of pressure and temperature dependence of a conventional lubricant's thermal properties on the behaviour of heavily loaded thermal elastohydrodynamic lubrication (TEHL) contacts. For this purpose, a typical mineral oil (Shell T9) is selected and the dependence of its transport properties on pressure and temperature is investigated. Appropriate models are then developed for these dependencies. The latter are included in a TEHL solver in order to investigate their effect on the behaviour of circular EHD contacts. The results reveal the necessity of a thermal analysis including the pressure and temperature dependence of thermal properties for a good estimation of film thicknesses and mostly traction coefficients in circular EHD contacts operating under severe conditions. Numerical results are compared with experiments, showing a very good agreement over the considered ranges. This thorough validation of a thermal EHL framework for the calculation of film thickness and friction offers a previously unavailable opportunity to investigate the effects of variations in material properties.
A new method for stirring under high pressure conditions has been developed and tested. The key component is a Teflon cell assembly equipped with magnetic stirring function, which is capable to operate across a wide pressure range, up to at least 2 GPa, in a large volume press. The setup enables adjustable stirrer rotation rate and detection of stirring in a sample,e.g.to observe liquid-solid phase transitions at high pressure. The viscosity limit of stirring is ca. 500 times that of water at room temperature (i.e.similar to 500 mPas). Moreover, we show that zinc oxide nanoparticles hydrothermally synthesized at 0.5 GPa and 100 degrees C under stirring conditions show an order of magnitude smaller size (100 nm) compared to those synthesized under non-stirring conditions (1 mu m). The wide pressure range for stirring of viscous media opens interesting possibilities to produce novel materials via hydrothermal synthesis and chemical reactions.
Glass formation/crystallization phenomena were studied in water and glycerol mixtures using adiabatic calorimetry. The sample was cooled rapidly from room temperature and its thermal response was followed on heating from 80 to 300 K. The binary mixtures with the glycerol contents more than 55% (w/w) (19 mol%) yielded the homogeneous glassy states, consisting of randomly mixed water and glycerol molecules. Their glass transition temperatures showed the composition dependence of the Gordon-Taylor equation, and extrapolated exactly to that of pure water (135 K). The mixtures in the 0-55% (w/w) glycerol range crystallized partly on cooling and exhibited three anomalies in the temperature drift rate on heating. The first of these three is associated with the onset of reorientational motions of water molecules in the hexagonal ice which increases from 107 to 120 K on increasing the glycerol composition. The second is the composition independent temperature of 164 K that corresponds to the mixture with 76% (w/w) glycerol (38 mol%, known as the maximally freeze-concentrated solution), which is the mixture with the maximum composition of water that can be cooled without crystallization. The third is associated with the ice crystallization followed by ice dissolution in the range 185-202 K. In addition, the sample with 60% (w/w) glycerol composition (23 mol%) exhibited two distinguishable exothermic peaks on heating. The initial one is large and is attributed to crystallization into a novel two-dimensionally ordered structure of ice, and the second is due to the transformation of the layered structures into the hexagonal ice.