Structural phase transitions in ‘hcp’ C70 single-crystals

The thermal expansion of vapor-grownC ₇₀ single crystals ahs been investigated using high-resolution capacitance dilatometry from 5–380 K. Measurements were made both parallel and perpendicular to the hexagonalc-axis. Three first-order phase transitions which we associate with the consecutive disordering of theC ₇₀ molecules are observed upon heating at 280 K (long-axis spinning), 300 K (long-axis precession) and 355 K (quasi-free rotation), respectively. The highest-temperature transition exhibits a very large (50 K) thermal hysteresis. Powder and single-crystal X-ray diffraction show that the crystals are predominantly hexagonal-close-packed (HCP) with an idealc/a1.63 above 360 K andc/a1.84 at 295 K.     

Comparative time-resolved study of solid-state and liquid ablation of polyethylene-glycol 1000: temperature, viscosity and surface tension dependence

Comparative study of solid and liquid phase ablation on the same sample by time-resolved investigations is presented in this paper. Polyethylene-glycol (PEG) 1000 having relatively low melting point (35 °C) was used in our experiments. By varying the sample temperature in the 20–80 °C range we could study the ablation mechanism in both solid and liquid (below and above the melting point) state of matter. An ArF excimer laser (λ=193 nm, FWHM=20 ns) was used for ablation at 1.95 J/cm² fluence. Ablation processes were observed by transmission fast photographic arrangement. It was demonstrated that plasma development and expansion (primer ablation, in 0–50 ns time range), formation and propagation parameters of shock wave and contact front did not depend on sample temperature and state of matter. The secondary material ejection (between 1–100 μs) showed a strong temperature dependence. Material ejection in the case of solid target occurred in the form of dense material cloud, and in the form of splashing for liquid (molten) sample. The ejection velocity of splashed jets depended on the sample temperature, significantly. This can be due to the change of molten PEG 1000 viscosity. Received: 1 November 1999 / Accepted: 17 April 2000 / Published online: 5 July 2000     

Frequency-dependent specific heat near the glass transition measured with the photoacoustic effect

For the supercooled salt melt 0.4 Ca(NO₃)₂–0.6 KNO₃ the photoacoustic amplitude and phase shift are measured in the glass transition region. The transition temperature is defined by the maximum in the phase angle. It is shifted to lower temperatures for lower frequencies. A frequency-dependent specific heat can be calculated from the data in the dispersion region. The frequency dependence of the transition temperature can be fitted by a power law with exponent =8.8±1.This work is part of a Ph. D. thesis at the Technische Universität München     

Pulsed laser-induced ablation of absorbing liquids and acoustic-transient generation

2 CrO₄ are irradiated by a KrF excimer laser (λ=248 nm, FWHM=24 ns) with moderate energy density (up to 100 MW/cm²) below the plasma-formation threshold. The ablation process, including the vapor-cavity formation and the acoustic-wave propagation is visualized by laser-flash photography. The ablation thresholds are determined by measuring the generated pressure transients and vapor-phase kinetics using a broadband piezoelectric pressure transducer and a simultaneous optical-transmission probe, respectively. The mechanisms of liquid ablation and acoustic-pulse generation are investigated based on the thermoelastic behavior of the liquid medium and the evaporation dynamics. A numerical model is proposed to describe the explosive-vaporization process at high laser fluences. The computation results are compared with the experiment. In short-pulse heating, ablation can be initiated at low laser fluences by the tensile component of the thermoelastic stress without a significant increase in the liquid temperature. On the other hand, if the heating rate is rapid enough to achieve a high degree of superheating of the liquid, the abrupt increase of the homogeneous-bubble-nucleation rate leads to explosive vaporization, which then plays the major role in the ablation dynamics. The pressure transient in the liquid is generated thermoelastically at low laser fluences, but the contribution of the vapor-phase expansion and/or the recoil momentum exerted by the ablation plume becomes significant at high laser fluences. Shock waves are formed in the ambient air in the case of explosive vaporization. The propagation of these wave fronts is in good agreement with the numerical-computation results. Received: 8 February 1998/Accepted: 10 February 1998     

Thermal conductivity of C60 and C70 crystals

We have performed thermal conductivity measurements on C₆₀ and C₇₀ crystals grown by sublimation. For single crystal C₆₀, the thermal conductivity k is 0.4 W/m K at room temperature and is nearly temperature independent down to 260K. We observed a sharp orientational phase transition at 260K, indicated by a 25% jump in k. Below 90K, k is time dependent, which manifests itself as a shoulder-like structure at 85K. The temperature and time dependence of k below 260K can be described by a simple model which accounts for the thermally activated hopping of C₆₀ molecules between two nearly degenerate orientations, separated by an energy barrier of 240 meV. It is found that solvents have a strong influence on the physical properties of C₇₀ crystals. For solvent-free C₇₀ crystal, k is about constant above 300K. There is a broad first-order phase transition in k at 300K with a 25% jump. We associate this transition with the aligning of the fivefold axes of the C₇₀ molecules along the c-axis of the hexagonal lattice. Upon further cooling, k increases and is time independent.     

Phase diagram of an Ising model with competitive interactions on a Husimi tree and its disordered counterpart

We consider an Ising competitive model defined over a triangular Husimi tree where loops, responsible for an explicit frustration, are even allowed. We first analyze the phase diagram of the model with fixed couplings in which a “gas of noninteracting dimers (or spin liquid) — ferro or antiferromagnetic ordered state” zero temperature transition is recognized in the frustrated regions. Then we introduce the disorder for studying the spin glass version of the model: the triangular ±J model. We find out that, for any finite value of the averaged couplings, the model exhibits always a finite temperature phase transition even in the frustrated regions, where the transition turns out to be a glassy transition. The analysis of the random model is done by applying a recently proposed method which allows us to derive the critical surface of a random model through a mapping with a corresponding nonrandom model.     

Phase transition in liquid crystal elastomers—A Monte Carlo study employing non-Boltzmann sampling

We investigate nematic-isotropic transition in liquid crystal elastomers employing a variant of Wang-Landau sampling. This technique facilitates calculation of the density of states from which other thermodynamic properties can be obtained. We consider a lattice model of a liquid crystal elastomer and a Hamiltonian which accounts for interactions among liquid crystalline units and interaction of local nematics with global strain. We investigate the effect of varying the strength of coupling between nematic and orientational degrees of freedom. When the local director is coupled strongly to the global strain, the transition is strongly first order. When the strength of the coupling decreases the transition becomes weakly first order. The transition temperature decreases when the coupling becomes weaker. We also report for the first time results on variation of free energy as a function of average energy at different temperatures and coupling constants.     

Synthesis and physical properties of negative thermal expansion materials Zr1−xMxW2O8−y (M=Sc, In, Y) substituted for Zr(IV) sites by M(III) ions

Zr_1−xM_xW₂O_8−y (M=Sc, In and Y) solid solutions substituted up to x=0.04 for Zr(IV) sites by M(III) ions were synthesized by a solid-state reaction. X-ray diffraction experiments from 90 to 560 K revealed that all solid solutions had a cubic crystal structure and showed negative thermal expansion coefficients. The lattice parameters of Zr_1−xM_xW₂O_8−y were smaller than that of ZrW₂O₈ probably due to oxygen defects, though the ionic radii of substituted M³⁺ ions were larger than that of Zr⁴⁺. Order-disorder phase transition temperatures of the substituted samples drastically decreased in the order of Y, In and Sc compared to the percolation theory, and decreased with increasing M content.     

Anomalous photoacoustic behavior of semiconductors: Evidence for thermally generated surface deformations

The photoacoustic signal measured for a solid sample is generally thought to originate from plane thermal waves, created by exposing the sample to modulated irradiation. For illumination of energy near or below the bandgap energy of a semiconductor, photoacoustic response was observed which could not be explained with conventional, thermal wave theory. This behavior can be explained if it is assumed that the signal is dominated by thermal deformations, generated at the semiconductor surface. This paper will show how this and other types of sample vibration can affect photoacoustic measurements of semiconducting materials.     

Isomorphous phase transition and orientational freezing in hexagonal mixed crystal C 70(1 - x) C60x. A pseudospin model

A four-state pseudospin model is constructed for the isomorphous phase transition hcp-2↦hcp-1 in pure C₇₀ and in C₇₀-rich mixed crystal C _{70(1 - x)} C_60x. With the specific anisotropic pseudospin interactions adapted to the C₇₀ crystal the model is equivalent to a two-state Ising model in a temperature-dependent field. Replica symmetric state of the model is shown to approach the critical point when the width of distribution of random fields and/or of random bonds increases. The temperature of the phase transition and the phase equilibrium temperature then are practically constant, whereas the experiment shows their strong decrease with x. The main effect of dilution resides in an x-dependence of the model parameters. Dilatometric data on the hexagonal C _{70(1 - x)} C_60x are used to fit these parameters. A metastable disordered phase subsisting below the phase transition is discovered in a range of the model parameters and is shown to be responsible for the macroscopic behaviour of the system. A good agreement with experimental data is obtained for the spontaneous strain and for the x-dependence of the hysteresis. Received 20 April 2001 and Received in final form 26 September 2001     

The magnetic structures of NdCu2 determined by single crystal neutron diffraction

We investigated the magnetic structure of NdCu₂ by means of neutron diffraction as a function of temperature between 1.5 K and 8 K in zero external field. The diffraction data were obtained on two single crystals with different orientations using the triple-axis-spectrometer TAS6 at the DR-3 reactor at Risø. Two magnetic phases were observed between 1.5K andT _N =6.5K. From 1.5 K to 4.1 K the magnetic reflections can be described by the commensurate wave vector =(3/5 0 0) and its higher harmonics 3 and 5. Below 2.5K the structure is completely squared-up. For 4.1 KT6.5 K the magnetic structure is incommensurate with the chemical lattice and can be described by the wave vector=(3/5 0 0) and its higher harmonies 3 and 5M. Below 2.5 K the structure is completely squared-up. For 4.1 K T 6.5 K the magnetic structure is incommensurate with the chemical lattice and can be described by the wave vector ^*=(0.62 0.044 0). In both phases the Nd-moments are oriented along the easyb-direction.     

Pressure-induced structural phase transition in rare-earth trihydrides. Part III. Systematics: General and geometric approach

Systematics of hcp-fcc phase transition observed in a series of lanthanide and yttrium trihydrides has been established. Based on the established systematics the prediction of the hcp-fcc transition pressure for the rest of the lanthanide trihydrides has been made. The role of H-H repulsive interaction as a probable transition promoter is discussed.     

A quantum field theory of the liquid-glass transition in multi-component liquids

An established unified theory of the liquid-glass transition in one-component liquids is extended to multi-component liquids. The universal features such as the Kauzmann paradox, the Vogel-Tamman-Fulcher (VTF) law on the relaxation times and the transport coefficients, the jump of the specific heat at the glass transition temperature and the Boson peaks are elucidated. The Kauzmann entropy in a form of a Curie law with a negative sign comes from the mixing between the sound and the intra-band fluctuation entropies, where the critical temperature corresponds to the sound instability temperature at a reciprocal particle distance. The VTF law is constructed from the Einstein relation on entropy and probability so that the Kauzmann entropy is included as a normal form in exponent of the VTF law. The Kauzmann entropy explains the Kauzmann paradox and the jump of the specific heat so that the universal features of the glass transition are elucidated consistently.     

Size effects on the structure and phase transition behavior of baddeleyite TiO2

High-pressure structural transitions in nanocrystalline systems are of significant interest as models of first-order phase transitions. We demonstrate size-induced lattice expansion and significant atomic rearrangements in the crystal structure of nanocrystalline high-pressure baddeleyite-TiO₂. The α-PbO₂ structured TiO₂ recovered after dozens of pressure cycles in the α-PbO₂-baddeleyite pressure field displayed elongate 25-35 nm crystallites, compared to starting 34-nm anatase crystallites, suggesting crystallite coherency across anatase, baddeleyite, and α-PbO₂ structures and ‘single structural domain’ behavior of the nanocrystalline system.     

Growth of Co-Silicides from single crystal and evaporated Si

We have investigated the reaction of a thin Co film with a (100) Si (Si ^c ) or an evaporated Si (Si ^e , which is amorphous) substrate during thermal annealing. On either substrate, Co₂Si and CoSi form simultaneously and the growth of each phase has a square root of time dependence. Both silicides grow faster on Si ^c than on Si ^e . A model is proposed to calculate the effective diffusion constant in each silicide from the growth data of the silicides. The activation energies of the effective diffusion constants in Co₂Si and CoSi grown on Si ^c are 1.7±0.1 eV and 1.8±0.1 eV, respectively; while those on Si ^e are 1.85±0.1 eV and 1.9 ±0.1 eV, respectively. The differences observed for the two substrates are tentatively attributed to the presence of impurities in Si^e and to the microstructural differences of the silicides formed on either substrate.     

Pulsed dielectric spectroscopy of supercooled liquids

Pulsed dielectric spectroscopy is introduced as a technique for selectively emphasizing specific components of the non-exponential dielectric response of matter. Samples studied include supercooled liquid propanol, propylene carbonate, and poly(lauryl-methacrylate). It is shown that particular sequences of pulses can be used to emphasize the fast response regime, to produce a cross-over or memory effect, or to eliminate the response of selected components. Furthermore, for materials characterized by broad distributions of relaxation times, the technique facilitates the investigation of a relatively narrow band from that distribution. It is also shown that the time domain spectroscopy can be combined with conventional frequency domain techniques to provide the characterization of dielectric response over an extraordinarily broad spectral range.     

Non-destructive reading of laser-induced single-shot incubation in dielectric coatings

Two-dimensional photothermal displacement measurements were carried out on TiO₂, ZrO₂, and HfO₂ coatings to uncover single shot incubation produced by 248 nm laser light at fluences below the damage threshold. The incubation behavior of the three coatings differs and correlates with the ratio of band gap to photon energy. The non-destructive nature of the photothermal displacement technique, its high lateral resolution, and its sensitivity for reading single shot imprints by an excimer laser lends this scheme a capacity for use in optical storage.Alexander von Humboldt fellow 1991/92     

Overlap properties and adsorption transition of two Hamiltonian paths

We consider a model of two (fully) compact polymer chains, coupled through an attractive interaction. These compact chains are represented by Hamiltonian paths (HP), and the coupling favors the existence of common bonds between the chains. We use a (n=0 component) spin representation for these paths, and we evaluate the resulting partition function within a homogeneous saddle point approximation. For strong coupling (i.e. at low temperature), one finds a phase transition towards a “frozen” phase where one chain is completely adsorbed onto the other. By performing a Legendre transform, we obtain the probability distribution of overlaps. The fraction of common bonds between two HP, i.e. their overlap q, has both lower () and upper () bounds. This means in particular that two HP with overlap greater than coincide. These results may be of interest in (bio)polymers and in optimization problems. Received 4 December 1998 and Received in final form 10 March 1999     

Anomalies in low-temperature lattice parameters of ErFeO3 and ErAlO3 single crystals: correlation with magnetic properties

The paper presents the results of an experimental study of thermal expansion of isostructural orthorhombic ErFeO₃ and ErAlO₃ single crystals. Changes of lattice parameters have been investigated by X-ray measurements in the 10-300 K temperature range. Above ∼150 K, experimental results correspond well to the phonon mechanism. At low temperatures distinct anisotropic anomalies were observed in both compounds; and a correlation with the magnetic properties of the relevant ions is noted.     

Vibrational analysis of IR reflection-transmission from single crystal C60

We represent results of IR reflectivity and transmission measurements in the spectral range from 50 to 5000 cm^–1 for crystallographic {111} and {100} planes of C₆₀ single crystals between 80 K and 460 K. The spectra turned out to be highly anisotropic due to differences in geometric resonances. The geometries used allowed detailed simultaneous investigation of the four infrared activeF _1u fundamental modes together with some weak silent modes and the whole set of second- and third-order combination modes from an analysis of the reflection-transmission response. Photopolymerization is observed on the surface of the crystals after illumination in argon atmosphere. The orientational phase transition at 260 K is accompanied by a dramatic jump in the line widths within a fraction of a degree. This result is explained by a broadening mechanism due to collisions with librons and paralibrons for the low temperature phase and for the high temperature phase, respectively.