We investigated through noncommercial calorimetry and elastoacoustic Brillouin experiments the phase diagram of n-butanol and measured the specific heat and the thermal conductivity in a wide low-temperature range for its three different states, namely, glass, crystal, and the so-called "glacial" states. The main aim of the work was to shed light on the controversial issue of these allegedly polyamorphic transitions found in some molecular glass-forming liquids, first reported to occur in triphenyl phosphite and later in n-butanol. Our experimental results show that the obtained glacial state in n-butanol is not a homogenous, amorphous state, but rather a mixture of two different coexisting phases, very likely the (frustrated) crystal phase embedded in a disordered, glassy phase.
The effective thermal conductivity of the powder samples of xenon hydrate was measured in the interval 2 -170 K using the steady-state method. The thermal conductivity of the homogeneous Xe clathrate hydrate was estimated from the effective thermal conductivity using an empirical expression. The applicability of the formula was checked by comparing two powder samples with different grain size and porosity. The temperature dependence of the thermal conductivity ͑T͒ϳT n of Xe clathrate hydrate is divided into four distinct temperature regimes ͑I-IV͒ with different n. In the interval 55-97 K ͑III͒ the behavior of ͑T͒ shows an anomaly, where the thermal conductivity decreases by almost 50% as the temperature increases. This observation is attributed to the resonant scattering where the coupling of the lattice with "rattling" motions of Xe atom dominates the thermal resistivity at high temperature. Since the observed vibrational energy of Xe in the small cages is ϳ4 meV ͑or Ϸ46 K͒ the resonant scattering contribution to the thermal resistivity is expected to decrease in an interval of comparable temperature. The thermal conductivity in the low temperature regime ͑regimes I and II͒ is found to follow the prediction of the soft-potential model. The data on thermal conductivities of several gas clathrate hydrates are compared.
The heat capacity (C p ) and dilatation (α) of YB 12 and LuB 12 are studied. C p of the zone-melted YB 12 tricrystal is measured in the range 2.5-70 K, of the zone-melted LuB 12 single crystal in the range 0.6-70 K, and of the LuB 12 powder sample in the range 4.3-300 K; α of the zone-melted YB 12 tricrystal and LuB 12 single crystals is measured in the range 5-200 K. At low temperatures a negative thermal expansion (NTE) is revealed for both compounds: for YB 12 at 50-70 K, for LuB 12 at 10-20 K and 60-130 K. Their high-temperature NTE is a consequence of nearly non-interacting freely oscillating metal ions (Einstein oscillators) in cavities of a simple cubic rigid Debye lattice formed by B 12 cage units. The Einstein temperatures are ∼254 and ∼164 K, and the Debye temperatures are ∼1040 K and ∼1190 K for YB 12 and LuB 12 respectively. The LuB 12 low-temperature NTE is connected with an induced low-energy defect mode. The YB 12 superconducting transition has not been detected up to 2.5 K.
The thermal conductivity of all three disordered solid phases of ethyl alcohol has been measured. That for the orientationally disordered bcc phase is found to be remarkably close to that for the structurally amorphous solid, especially at low temperatures. The results, which emphasize the role of orientational disorder in phonon scattering, are discussed with the aid of computer simulations on single-crystalline models of both bcc and monoclinic crystals. DOI: 10.1103/PhysRevB.74.060201 PACS number͑s͒: 66.70.ϩf, 61.43.Ϫj, 63.50.ϩx, 65.60.ϩa Our current understanding of the mechanisms of heat transport in disordered media rests upon concepts grounded on clean experiments showing that acoustic phonons, especially those having transverse polarization, are the main heat carriers. 1 Work carried out over the last couple of decades has evidenced striking quantitative similarities in the characteristic thermal conductivity of bulk amorphous materials 2 between, say, 0.1 and 10 K, independent of chemical composition. Furthermore, such similarity also extends to a good number of disordered crystals, including a quasicrystal, 2,3 and from the set of collected data it has been inferred that the ratio of the wavelength of the acoustic wave to the mean free path l of all these solids ranges within 10 −2 -10 −3 , which suggests the presence of "universal" behavior of some sort. On such grounds, it becomes clear that the presence of "glassy dynamics" cannot be attributed in full to the absence of static translational long-range order ͑LRO͒.Some molecular crystals where the individual molecules have random static orientations while their centers of mass are at the nodes of a three-dimensional crystalline lattice are also known to exhibit glasslike excitations. Of those, solid ethyl alcohol is perhaps the most convenient benchmark to carry out a quantitative comparison of the effects caused by the complete lack of LRO, 4 on the most sensitive property to explore the propagation of excitations in condensed matter, the thermal conductivity. The material, apart from the wellknown monoclinic ͑fully ordered͒ crystalline ͑FOC͒ modification, can be prepared in three long-lived phases, an amorphous solid or glass, an orientationally disordered crystal ͑ODC͒ ͑or orientational glass͒ showing static orientational disorder but having translational LRO since the molecules are at the nodes of a bcc lattice, and a crystal with dynamic orientational disorder ͓rotator-phase crystal ͑RPC͔͒ which retains LRO as a bcc lattice still exists. Two glass transitions take place about 97 K between the glass and supercooled liquid and the ODC and RPC. 4 Here we report on measurements of the thermal conductivity of ethyl alcohol for all the solid phases. The relevance of such an exercise is twofold. First and foremost, as stated in a recent review, 2 the measurements will provide additional tests on claims of quantitative universality of the properties of heat propagation at low and intermediate temperatures in disordered matter brought forward by a cl...
We present a dynamic and thermodynamic study of the orientational glass former Freon 113 (1,1,2-trichloro-1,2,2-trifluoroethane, CCl 2 F-CClF 2 ) in order to analyze its kinetic and thermodynamic fragilities. Freon 113 displays internal molecular degrees of freedom that promote a complex energy landscape. Experimental specific heat and its microscopic origin, the vibrational density of states from inelastic neutron scattering, together with the orientational dynamics obtained by means of dielectric spectroscopy have revealed the highest fragility value, both thermodynamic and kinetic, found for this orientational glass former. The excess in both Debye-reduced specific heat and density of states (boson peak) evidences the existence of glassy low-energy excitations. We demonstrate that early proposed correlations between the boson peak and the Debye specific heat value are elusive as revealed by the clear counterexample of the studied case. DOI: 10.1103/PhysRevLett.118.105701 When a structurally disordered system is rapidly cooled to avoid crystallization, some properties, such as viscosity, show a dramatic increase down to the glass transition where the material reaches viscosity values comparable to those of a solid (10 12 Pa s), i.e., relaxation times of ≈100 s. Such behavior contrasts with that typical for most liquids at high temperatures, which usually exhibit a simple Arrhenius behavior of the relaxation time, τ ¼ τ 0 expðE a =k B TÞ, where the activation energy is temperature independent.Decreasing temperature relaxation time shows a stronger increase, faster than that of the Arrhenius law and accompanied with an increase of some characteristic cooperativity relaxation length. The viscosity (or τ) increase is generally characterized by recourse to the concept of the kinetic fragility [1,2], m ¼ fð∂ log τÞ=½∂ðT g =TÞg T¼T g , which accounts for the deviation of the Arrhenius temperature dependence.In terms of fragility index m, materials for which τ follow an Arrhenius law are known as "strong" glass formers, whereas "fragile" glass formers are those exhibiting super-Arrhenius behavior. For such cases, the temperature dependence of τ is given through the Vogel-FulcherTammann (VFT) expression,where the temperature T 0 is associated with an ideal glass transition and even with the so-called Kauzmann temperature [3], and the fragility strength parameter D is linked to the fragility parameter by. Typical strong glass formers (m ≈ 16, or D ≥ 100) are tetrahedral network liquids as SiO 2 or GeO 2 . The highest values of fragility for organic materials (exception made of polymers) have been found in cis-or trans-decahydronaphthalene (m ¼ 147 [4]). Another group of materials exhibiting glasslike properties is that of crystals with positional order and orientational disorder [5]. Such plastic phases are formed from the liquid and can be supercooled, giving rise to the so-called orientational glasses (OG) or "glassy crystals" [6][7][8][9]. They show typically low fragility, as cyclooctanol (m ¼ 33) [10,11]
The heat capacity and thermal conductivity of the monoclinic and the fully ordered orthorhombic phases of 2-adamantanone (C10H14O) have been measured for temperatures between 2 and 150 K. The heat capacities for both phases are shown to be strikingly close regardless of the site disorder present in the monoclinic crystal which arises from the occupancy of three nonequivalent sites for the oxygen atom. The heat capacity curves are also well accounted for by an evaluation carried out within the harmonic approximation in terms of the g(ω) vibrational frequency distributions measured by means of inelastic neutron scattering. Such spectral functions show however a significant excess of low frequency modes for the crystal showing statistical disorder. In contrast, large differences are found for the thermal conductivity which contrary to what could be expected, shows the substitutionally disordered crystal to exhibit better heat transport properties than the fully ordered orthorhombic phase. Such an anomalous behavior is understood from examination of the crystalline structure of the orthorhombic phase which leads to very strong scattering of heat-carrying phonons due to grain boundary effects able to yield a largely reduced value of the conductivity as well as to a plateau-like feature at intermediate temperatures which contrasts with a bell-shaped maximum shown by data pertaining the disordered crystal. The relevance of the present findings within the context of glassy dynamics of the orientational glass state is finally discussed.
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