Thermal Expansion Anomalies Research Articles

Strong uniaxial pressure dependencies evidencing spin-lattice coupling and spin fluctuations in Cr2Ge2Te6

Single crystals of Cr$_2$Ge$_2$Te$_6$ were studied by high-resolution capacitance dilatometry to obtain in-plane ($B\parallel ab$) and out-of-plane ($B\parallel c$) thermal expansion and magnetostriction at temperatures between 2 and 300 K and in magnetic fields up to 15 T. The anomalies in both response functions lead to the 'magnetoelastic' phase diagrams and separate the paramagnetic (PM), ferromagnetic low-temperature/low-field (LTF) and aligned ferromagnetic (FM) phases. The presence of two distinct thermal expansion anomalies at small fields $B\parallel ab$ of different magnetic field dependence clearly supports the scenario of an intermediate region separating PM and LTF phases and is indicative of a tricritical point. Simulations of the magnetostriction using the Stoner-Wohlfarth model for uniaxial anisotropy demonstrate that the observed quadratic-in-field behavior in the LTF phase is in line with a rotation of the spins from the preferred $c$ direction into the $ab$ plane. Both the LTF and the PM phase close to T$_{\rm C}$ exhibit very strong pressure dependencies of the magnetization, ${\partial}\ln{M_{\rm ab}}/{\partial}p_{\rm ab}$, of several hundred %/GPa and also the transition from the LTF to the FM phase strongly depends on $p_{\rm ab}$ ($\sim -$280%/GPa), indicating a strong decrease of the uniaxial anisotropy under applied in-plane pressure. Our data clearly demonstrate the relevance of critical fluctuations and magnetoelastic coupling in Cr$_2$Ge$_2$Te$_6$.

Features of thermal expansion in substitution alloys based on heavy rare-earth metals <span class="inline-formula"><span class="math">\({\mathbf{R}}_{{{\mathbf{1}} - x}}^{{\mathbf{I}}}{\mathbf{R}}_{x}^{{{\mathbf{II}}}}{\mathbf{F}}{{{\mathbf{e}}}_{{\mathbf{2}}}}\)</span></span>

We consider the features of the behavior of thermal expansion and magnetostriction in magnetically ordered substitutive alloys based on heavy rare earth metals, namely: TbFe2, Tb0.8Zr0.2Fe2, Tb0.8Sm0.2Fe2 and Gd0.8Sm0.2Fe2. It is found that the of thermal expansion anomalies observed in alloys are mainly due to the competition of exchange interactions. In TbFe2 and Tb0.8Zr0.2Fe2 alloys invar-type features are observed in a wide temperature range.

Charge density wave transitions, soft phonon, and possible electronic nematicity in BaNi2(As1−xPx)2

A detailed investigation of ${\mathrm{BaNi}}_{\text{2}}{({\mathrm{As}}_{1\ensuremath{-}x}{\mathrm{P}}_{x})}_{\text{2}}$ single crystals using high-resolution thermal-expansion, heat-capacity, Young's-modulus, and resistivity measurements is presented. The phase diagram of ${\mathrm{BaNi}}_{\text{2}}{({\mathrm{As}}_{1\ensuremath{-}x}{\mathrm{P}}_{x})}_{\text{2}}$ is shown to be much richer than suggested by the original data of Kudo et al. [Phys. Rev. Lett. 109, 097002 (2012)]. The transition to the commensurate charge density wave (C-CDW) is always preceded by a fourfold symmetry-breaking transition associated with the long-range ordering of a strongly fluctuating unidirectional incommensurate charge density wave (I-CDW). Significant precursors above the I-CDW and C-CDW transitions are seen in the thermal expansion and resistivity and are particularly evident in the temperature dependence of the $c/a$ ratio of the lattice parameters. Heat-capacity measurements of the crystals with a higher P content and a higher critical temperature of 3.2 K uncover a Debye-like behavior of a soft-phonon mode with a very low ${\mathrm{\ensuremath{\Theta}}}_{\text{Debye}}$ of roughly 50 K. Associated with this soft phonon are unusually large thermal-expansion anomalies, resulting in logarithmically diverging uniaxial phonon Gr\"uneisen parameters. Young's-modulus data of these higher-${T}_{c}$ crystals exhibit a significant softening in both ${B}_{1g}$ and ${B}_{2g}$ channels, which is argued to be incompatible with nematic criticality and is rather associated with a broad phase transition to an hitherto unknown structure. Possible origins of the increase in the superconducting critical temperature with P substitution are discussed.

Thermal expansion anisotropy of CuIn11Se17 single crystals

Homogeneous single crystals of CuIn11S17 with 14 mm in diameter and 40 mm in length were grown by directional crystallization of the melt (vertical Bridgman method). The composition and structure of the obtained single crystals were determined by the X-ray microanalysis and the X-ray diffraction analysis, respectively. It is shown that the obtained single crystals crystallize in a hexagonal structure. The anisotropy of thermal expansion was investigated for single crystals oriented parallel and perpendicular to the main crystal axis in the temperature range of 120–600 K. It was found that anomalies of thermal expansion are observed in the indicated single crystals oriented parallel to the main crystal axis.

Negative-stiffness composite systems and their coupled-field properties

Composite materials consisting of negative-stiffness inclusions in positive-stiffness matrix may exhibit anomalous effective coupled-field properties through the interactions of the positive and negative phases, giving rise to extremely large or small effective properties. In this work, effective viscoelastic properties of a continuum composite system under the effects of negative inclusion Young’s modulus ratio $$\lambda _E = E_{\text {inc}}/E_{\text {matrix}}$$ are studied with the finite element method. Furthermore, effective coupled-field properties, such as thermal expansion coefficient, dielectric constants and piezeoelectric constants, are numerically calculated under the effects of negative inclusion bulk modulus ratio $$\lambda _K=K_{\text {inc}}/K_{\text {matrix}}$$ . Stability boundaries are determined by applying small dynamic perturbation to the systems through boundary surfaces, and the system is unstable if its field variables become divergent in time. For viscoelastic composite systems containing small volume fractions, less than $$V_i = 1.5 \%$$ , the systems can be stable up to $$\lambda _E \approx -0.3$$ in 0.3 s under 10 Hz driving frequency. For $$V_i = 5.1 \%$$ case, its stability boundary is around $$\lambda _E \approx 0$$ . Larger inclusion volume fraction reduces allowable negative stiffness in the viscoelastic system. All anomalous peaks found in the coupled-field properties are in the unstable regime, except for the piezoelectric and thermal-expansion anomalies in the composite system with electrically insulated inclusions and large inclusion volume fraction $$V_i = 26.81 \%$$ . Insulated inclusions may cause charge accumulation at the inclusion–matrix interface and boundary surface effects may serve as stabilizing agents to the composite system. Since it is known that negative-stiffness composite is unstable in the purely elastic system in statics, stability enhancement found here in the negative-stiffness systems with viscoelastic and coupled-field effects may be considered as multiphysics-induced stabilization.

Strong spin-lattice coupling in tetragonal-like BiFeO3 films with thermal expansion anomalies

The evidence for a spin-lattice coupling in a tetragonal-like BiFeO3 (BFO) film is derived from thermal expansion measurements. Taking the advantage of La doping, the Néel temperature (TN) of the BFO film can be further adjusted over a broad range of temperatures. The lattice parameters exhibit anomalies near the Néel temperatures. The Bi0.8La0.2FeO3 film has a spin order-to-disorder transition at the TN without a structural phase transition, suggesting that a spin-lattice coupling drives the thermal expansion anomalies. The spin-lattice coupling can be enhanced by the coexistence of phases in the thicker BFO films. The density functional theory calculations show a smaller lattice constant of the c axis in the spin-order state than that in the spin-disorder state for the same tetragonal-like phase, which supports that the thermal expansion anomalies are a consequence of the spin-lattice coupling. Our findings may have application prospects for functional materials with controllable thermal expansions.

Structural, magnetic, electronic, and dilatation properties of the ordered solid solutions Ln0.2Sr0.8CoO3-δ (Ln = Sm, Gd, Dy) with the same oxygen nonstoichiometry index δ

Single-phase samples of the layered perovskite-like cobalt oxides Ln0.2Sr0.8CoO3-δ (Ln = Sm, Gd, Dy) with the same oxygen nonstoichiometry index δ = 0.37 ± 0.01 were synthesized. All samples are characterized by a tetragonal unit cell with the space group I4/mmm. The structural, magnetic, electric transport and dilatation properties of the obtained samples are investigated. The studied samples are characterized by two anomalies in magnetic properties, a high-temperature maximum near Тm = 350 К with magnetic field hysteresis below Tm, and a diffuse peak in the intermediate temperature range, which shifts with ionic radius decrease of the rare-earth element to higher temperatures. The high-temperature maxima of the magnetic susceptibility correlate with anomalies in thermal expansion, heat capacity and the features in the temperature dependences of the electrical resistivity, pointing to a strong relationship between the structural, magnetic and electronic degrees of freedom. The given comparative analysis of the experimental data of various substituting rare-earth elements with the same oxygen nonstoichiometry has been carried out for the first time.

Order/disorder processes and electromechanical properties of monoclinic GdCa4O(BO3)3

Abstract Large single crystals of GdCa4O(BO3)3 (space group Cm) were grown by the Czochralski method. Dielectric, piezoelectric and elastic coefficients at room temperature as well as specific heat capacity, thermal expansion and cation disorder were studied employing a variety of methods including resonant ultrasound spectroscopy, differential scanning calorimetry, dilatometry and X-ray diffraction techniques. The electromechanical parameters (4 dielectric, 10 piezoelectric and 13 elastic stiffness coefficients) obtained on different samples are in excellent agreement indicating high internal consistency of our approach, whereas the values reported in literature differ significantly. The elastic behaviour of GdCa4O(BO3)3 resembles the one of structurally related fluorapatite, i.e. the elastic anisotropy is relatively small and the longitudinal effect of the deviations from Cauchy-relations exhibit a pronounced minimum along the direction of the dominating chains of cation polyhedra. GdCa4O(BO3)3 exhibits a maximum longitudinal piezoelectric effect of 7.67 × 10−12 CN−10, a value in the order of that of langasite-type materials. Significant changes of the calcium/gadolinium distribution on the 3 independent cation sites accompanied by characteristic anomalies of heat capacity and thermal expansion suggest processes of nonconvergent cation ordering above about 900 K in GdCa4O(BO3)3.

Magnetic phase transition, crystal electric field and zero thermal expansion in ab-plane of thulium carboboride TmB2C

Abstract Temperature dependences of heat capacity CP(T) and lattice parameters a(T), b(T), c(T) of thulium carboboride TmB2C at 2–300 K were experimentally studied. Magnetic phase transition in the carboboride – ‘paramagnetic – antiferromagnetic’ at TN = 11.0 K was revealed. By comparison with the diamagnetic LuB2C the Schottky contribution to TmB2C heat capacity due to the crystal electric field (CEF) was calculated. The splitting scheme of Tm3+ ion f – level by the crystal field was suggested. It was obtained that in the temperature range under study (5–300 K) TmB2C carboboride thermal expansion in the basal plane is almost missing (anisotropic invar effect, linear thermal expansion coefficient αa(T) ≃ αb(T) ≃ 0). It is, seems, a common property of the lattice dynamics of layered carboborides. The anomalies in the thulium carboboride thermal expansion are due to the magnetic phase transition and the CEF influence.

Study of the Physical Properties and Electrocaloric Effect in the BaTiO3 Nano- and Microceramics

The specific heat, thermal expansion, permittivity, and electrocaloric effect in bulk of BaTiO3 (BT) samples in the form of nano- (nBT-500 nm) and micro- (mBT-1200 nm) ceramics fabricated using spark plasma sintering and solid-state plasma techniques have been investigated. The size effect has been reflected, to a great extent, in the suppression of the specific heat and thermal expansion anomalies and in the changes in the temperatures and entropies of phase transitions and permittivity, and a decrease in the maximum intensive electrocaloric effect: ΔTmaxAD = 29 mK (E = 2.0 kV/cm) for nBT and ΔTmaxAD = 70 mK (E = 2.5 kV/cm) for mBT. The conductivity growth at temperatures above 360 K leads to the significant irreversible heating of the samples due to the Joule heat release in the applied electric field, which dominates over the electrocaloric effect.

Magnetoelastic and magnetoelectric couplings across the antiferromagnetic transition in multiferroic BiFeO3

Clear anomalies in the lattice thermal expansion (deviation from linear variation) and elastic properties (softening of the sound velocity) at the antiferromagnetic-to-paramagnetic transition are observed in the prototypical multiferroic BiFeO3 using a combination of picosecond acoustic pump-probe and high-temperature X-ray diffraction experiments. Similar anomalies are also evidenced using first-principles calculations supporting our experimental findings. Those calculations in addition to a simple Landau-like model we also developed allow to understand the elastic softening and lattice change at T_N as a result of magnetostriction combined with electrostrictive and magnetoelectric couplings which renormalize the elastic constants of the high-temperature reference phase when the critical T_N temperature is reached.

An Electronic Library as a Means of Science Publication on the Web: The Experience of Data Sharing on Anomalies of Thermal Expansion

The concept of a small-format electronic library (EL) is proposed, which permits the collected information on a project carried out in a scientific team to be disseminated on the Internet. The ABCD multilingual automation system for libraries and information centers was used as an effective software tool for building electronic libraries, the service capabilities of which were used to create a universal means of storing, organizing, and distributing scientific data. The developed library is used to exchange data and documents on thermal expansion anomalies on the web. The specificity of the subject area that implies the permanent emergence of new terms, ideas and concepts and expansion of the range of substances is reflected in the system of metadata that we adopted with the possibility of their continuous expansion.

Исследования физических свойств и электрокалорического эффекта в нано- и микрокерамике BaTiO-=SUB=-3-=/SUB=-

AbstractThe specific heat, thermal expansion, permittivity, and electrocaloric effect in bulk of BaTiO_3 (BT) samples in the form of nano- (nBT-500 nm) and micro- (mBT-1200 nm) ceramics fabricated using spark plasma sintering and solid-state plasma techniques have been investigated. The size effect has been reflected, to a great extent, in the suppression of the specific heat and thermal expansion anomalies and in the changes in the temperatures and entropies of phase transitions and permittivity, and a decrease in the maximum intensive electrocaloric effect: $$\Delta T_{{{\text{AD}}}}^{{\max }}$$ = 29 mK ( E = 2.0 kV/cm) for nBT and $$\Delta T_{{{\text{AD}}}}^{{\max }}$$ = 70 mK ( E = 2.5 kV/cm) for mBT. The conductivity growth at temperatures above 360 K leads to the significant irreversible heating of the samples due to the Joule heat release in the applied electric field, which dominates over the electrocaloric effect.

Anisotropy-governed competition of magnetic phases in the honeycomb quantum magnet Na3Ni2SbO6 studied by dilatometry and high-frequency ESR

Thermodynamic properties as well as low-energy magnon excitations of $S=1$ honeycomb-layered Na$_3$Ni$_2$SbO$_6$ have been investigated by high-resolution dilatometry, static magnetisation, and high-frequency electron spin resonance studies in magnetic fields up to 16 T. At $T_{\rm N}$ = 16.5 K, there is a tricritical point separating two distinct antiferromagnetic phases AF1 and AF2 from the paramagnetic regime. In addition, our data imply short-range antiferromagnetic correlations at least up to $\sim 5\cdot T_{\rm N}$. Well below $T_{\rm N}$, the magnetic field $B_{\rm C1}\approx$ 9.5 T is needed to stabilize AF2 against AF1. The thermal expansion and magnetostriction anomalies at $T_{\rm N}$ and $B_{\rm C1}$ imply significant magnetoelastic coupling, both of which associated with a sign change of $\partial L/\partial B$. The transition at $B_{\rm C1}$ is associated with softening of the antiferromagnetic resonance modes observed in the electron spin resonance spectra. The anisotropy gap $\Delta = 360$ GHz implies considerable uniaxial anisotropy. We conclude the crucial role of axial anisotropy favoring the AF1 spin structure over the AF2 one. While the magnetostriction data disprove a simple spin-flop scenario at $B_{\rm C1}$, the nature of a second transition at $B_{\rm C2}\approx$ 13 T remains unclear. Both the sign of the magnetostriction and Gr\"uneisen analysis suggest the short-range correlations at high temperatures to be of AF2-type.

The Phonon Mediated Anomalies of Thermal Expansion in Transition-Metal Componds and Emergent Nanostructures

Abstract. The negative expansion observed at low temperatures in specific crystallographic directions of complex structures with anisotropic interactions is explained by microscopic analysis within the tight-binding, quasi-harmonic approximation of lattice dynamics. The results agree with measurements on multilayer sandwiches of transition-metal dichalcogenides, high-temperature superconductors and relevant nanostructures including the carbon-based nanotubes.

Peculiarities of thermal expansion of quasi-two-dimensional organic conductor κ-(BEDT–TTF)2Cu[N(CN)2]Cl

Linear coefficient of thermal expansion α(T) of single crystal (BEDT–TTF)2Cu[N(CN)2]C1 was studied along the crystal layers using the method of precise capacitive dilatometry in the temperature range 2–285 K. It is positive in this direction over the entire temperature range. Anomalies of thermal expansion were observed at 29–30 K and 74–80 K. The anomaly near 30 K is, apparently, due to the transition between the paramagnetic phase and the antiferromagnetic insulator state. Peak of α(T) at 78 K corresponds to a phase transition related to orientational disordering of ethylene groups in dimers of BEDT–TTF. A broad maximum of α(T) in the temperature range 40–70 K, is apparently explained by fluctuations of charge within the dimers, and by spin fluctuations, which first increase with increasing temperature, and then decrease in process of thermal disordering of dimers.

Thermal Expansion Anomaly in TTB Ferroelectrics: The Interplay between Framework Structure and Electric Polarization.

Tetragonal tungsten bronze (TTB) makes up a large family of functional materials with fascinating dielectric, piezoelectric, or ferroelectric properties. Understanding the thermal expansion mechanisms associated with their physical properties is important for their practical applications as well as theoretical investigations. Fortunately, the appearance of anomalous thermal expansion in functional materials offers a chance to capture the physics behind them. Herein, we report an investigation of the thermal expansion anomalies in TTBs that are related to ferroelectric transitions and summarize recent progress in this field. The special role of Pb(2+) cation is elucidated. The interplay between the thermal expansion anomaly, electric polarization, and framework structure provides new insight into the structure-property relationships in functional materials.

Anomalies of thermal expansion and electrical resistivity of layered cobaltates YBaCo2O5 + x : The role of oxygen chain ordering

Layered cobaltates YBaCo2O5 + x have been investigated in the oxygen concentration range 0.23 ≤ x ≤ 0.52. It has been revealed that the oxygen ordering plays the key role in the appearance of anomalies in temperature dependences of structural parameters and electron transport. It has been shown that the orthorhombic lattice distortion caused by oxygen chain ordering is a necessary “trigger” for the phase transition from the insulating state to the metallic state at T ≈ 290–295 K, after which the orthorhombic distortion is significantly more pronounced. In the boundary region of the cobaltate compositions, where the oxygen ordering has a partial or local character, there are additional low-temperature (100–240 K) structural and resistive features with a large hysteresis. The observed anomalies can be explained by a change in the spin state of the cobalt ions, which is extremely sensitive to parameters of the crystal field acting on the ions, as well as by the spin-transition-induced delocalization of electrons.

Effect of Gd and Sr Ordering in A Sites of Doped Gd0.2Sr0.8CoO3−δ Perovskite on Its Structural, Magnetic, and Thermodynamic Properties

Magnetic and thermodynamic properties of perovskite Gd0.2Sr0.8CoO3−δ, with ordered and disordered states of Gd and Sr in the A-sites of the crystal lattice have been studied revealing remarkable differences in the physical properties of the ordered and disordered states. The ordered samples have larger oxygen nonstoichiometry, heat capacity, and thermal expansion anomalies, and abnormal temperature dependence of the magnetization around 350 K.

Raman spectra and anomalies of dielectric properties and thermal expansion of lead-free (1−x)Na0.5Bi0.5TiO3-xSrTiO3 (x = 0, 0.08 and 0.1) ceramics

ABSTRACTThermal expansion, Raman and dielectric properties of the lead-free (1−x)Na0.5Bi0.5TiO3-xSrTiO3 (x = 0, 0.08 and 0.1) ceramic solid solutions, fabricated by the conventional solid-state reaction method, were investigated. The Sr-doping results in an increase of the dielectric permittivity, broadening of the permittivity maximum, enhancement of the relaxation near depolarization temperature, broadening of the Raman bands and shift of all anomalies toward lower temperatures. The observed effects are attributed to an increase of the degree of cationic disorder and enhancement of the relaxor-like features. Anomalies in the thermal expansion strain were observed at the temperatures corresponding to the dielectric anomalies but not related to any phase transitions. These anomalies are supposed to follow changes of the averaged unit cell volume in the temperature interval of tetragonal and rhombohedral phase coexistence.