Thermophysical study of structural phase transitions in Na<Subscript>0.95</Subscript>Li<Subscript>0.05</Subscript>NbO<Subscript>3</Subscript> solid solution

Temperature dependences of specific heat C_p(T) and coefficient of thermal expansion ;(T) for Na_0.95Li_0.05NbO₃ sodium-lithium niobate ceramic samples are investigated in the temperature range of 100–800 K. The C_p(T) and α(T) anomalies at T₃ = 310 ± 3 K, T₂ = 630 ± 8 K, and T₁ = 710 ± 10 K are observed, which correspond to the sequence of phase transitions N ? Q ? S(R) ? T2(S). The effect of heat treatment of the samples on the sequence of structural distortions was established. It is demonstrated that annealing of the samples at 603 K leads to splitting of the anomaly corresponding to the phase transition Q → R/S in two anomalies. After sample heating to 800 K, the only anomaly is observed in both the C_p(T) and ;(T) dependence. Possible mechanisms of the observed phenomena are discussed.     

Etude par effet Mössbauer de Ca2MnO4 dope a l'etain

The antiferromagnetic layer phase Ca₂MnO₄ doped with ¹¹⁹Sn⁴⁺ has been investigated by Mössbauer spectroscopy. Below the Néel temperature a hyperfine magnetic field transfered on the tin nucleus is observed with saturation value H(0)?38 kOe. The low value of the transfered field is attributed to the absence of e_g electrons on the 3d orbitals of Mn⁴⁺. Supposing the field to follow the power law H(T) = H(0)D[1 ? (T/T_N)]^β as the sublattice magnetizations usually do, the study of the temperature dependence of the field yields β = 0.44 ± 0.10. This value for the critical exponent is in rather good agreement with the value deduced from neutron measurements (β = 0.38 ± 0.06) as well as with those calculated from three dimensional Heisenberg and Ising models (0.31?β?0.38). It is anyway very different from the theoretical value for a two dimensional Ising model (β = 0.125) and from the experimental values for various two-dimensional antiferromagnets isostructural with Ca₂MnO₄ such as K₂MnF₄ (β = 0.15) or K₂NiF₄ (β = 0.14).     

A structural phase transition in squaric acid

Squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) is found to undergo a second order antiferrodistortive tetragonal to monoclinic phase transition at 97.7°C. The transition temperature for the fully deuterated compound is 243°C. The crystals are optically biaxial negative at room temperature, and the partial birefringence decreases with temperature as (n_z ? n_y)α(T_C ? T)^β, where β_H = 0.34 ± 0.02 and β_D = 0.37 ± 0.04.     

Magnetic order induced birefringence and critical behaviour of the long range order parameter in NiO

The optical linear magnetic birefringence of single-domain NiO crystals was measured at temperatures above and below the antiferromagnetic phase transition. The analysis of the experimental data yield a Néel temperature of T_N = (523.7 ± 0.2)K and a critical exponent β = 0.325^+0.01_-0.02 which determines the temperature behaviour of the magnetic long range order parameter $\text{S}\text{?}\text{～ (}\text{1?T}\text{T}{}_{\mathrm{N}}\text{)}{}^{\mathrm{\beta }}$. This critical behaviour of S? is found to be continued to temperatures well below T_N.     

Investigation of the ferroelastic phase transition in the SrMgF4 pyroelectric crystal

A SrMgF₄ compound has been synthesized and a high optical-quality crystal has been grown. Optical-polarization observations, X-ray diffraction analysis, and the measurement of the birefringence Δn _i (t) in the SrMgF₄ crystal have been carried out in the temperature range of 90–1200 K. A second-order improper ferroelastic phase transition accompanied by birefringence anomalies and the symmetry change P112₁ (Z = 12) ? Cmc2₁ (Z = 4) has been discovered at T ₀ = 478 ± 1 K. The crystal remains pyroelectric in both phases. Considerable contributions of the fluctuations of the order parameter have been observed in the temperature ranges of (T ₀ ? T) < 15 K and (T ? T ₀) < 60 K.     

Structural Phase Transition and the Dielectric Permittivity of the Model Lipid Bilayer [(CH2)12(NH3)2]CuCl4

Structural phase transitions in the lipid-like bilayer material [(CH₂)₁₂(NH₃)₂]CuCl₄ have been observed using differential thermal scanning. The compound shows an irreversible thermochromic transition at ? 465 K and three reversible transitions at T ₁ = 433 ± 4 K and T ₂ = 411 ± 2 K and T ₃ = 358 K. The transition at 350 K is ascribed to chain melting. The other two correspond to crystalline phase transformation.

Phase (IV) T₃ = 358 ± 2K Phase (III) T₂ = 411 ± 2K Phase (II) T₁ = 433 ± 4K Phase (I)

Dielectric permittivity is studied as a function of temperature in the range 300-440 K and frequency, range (60 Hz-100 kHz). It confirms the observed transitions. The dielectric permittivity reflects rotational and conformational transitions for the compound. The variation of the real part of the conductivity with temperature is thermally activated in the temperature range above 350 K, with frequency-dependent activation energy, the values of activation energy lie in the range of ionic hopping. The dependence of the conductivity on frequency follows the universal power law σ = σ₀ + A(T) ω ^{s ( T )} with 0<s<1. Comparison of this material with other members of the series is discussed     

Hyperfine magnetic interactions of 57Fe nuclei in NaFeAs arsenide

The results of the Mössbauer effect studies of layered NaFeAs arsenide in a wide temperature range are presented. The measurements at T > T _N demonstrate that the main part (～90%) of iron atoms are in the low-spin state Fe²⁺. The other atoms can be attributed to the impurity NaFe₂As₂ phase or to the extended defects in NaFeAs. The structural phase transition (at T _S ≈ 55 K) does not produce any effect on hyperfine parameters (δ, Δ) of iron atoms. At T < T _N, the spectra exhibit the existence of a certain distribution of the hyperfine magnetic field (H _Fe) at ⁵⁷Fe nuclei, indicating the inhomogeneity of the magnetic environment around iron cations. The analysis of the temperature behavior of the distribution function p(H _Fe) allows us to determine the temperature of the magnetic phase transition (T _N = 46 ± 2 K). It has been found that the magnetic ordering in the iron sublattice has a two-dimensional type. The analysis of the H _Fe(T) dependence in the framework of the Bean-Rodbell model reveals a first-order magnetic phase transition accompanied by a drastic change in the electron contributions to the main component (V _ZZ ) and the asymmetry parameter (η) of the tensor describing the electric field gradient at ⁵⁷Fe nuclei.     

Magneto-optical measurement on the layer type magnet (CH2)2(ND3)2MnCl4

The linear birefringence (LB) of the antiferromagnet (CH₂)₂(ND₃)₂MnCl₄ has been measured as a function of temperature and in magnetic fields up to 100 kOe. The temperature dependence of the LB points to a pronounced two dimensional magnetic behaviour. No anomaly corresponding to the effect of three dimensional ordering could be detected at T_N. In theffield dependent measurements the spin flop at H_SF = 33.6 ± 1 kOe (T = 4K) could clearly be detected.     

The antiferromagnetic structure of TbB4

The magnetic structure of the rare earth tetraboride TbB₄ (crystallographic space group P4/mbm) has been determined by neutron diffraction on a polycrystalline sample. Below the experimentally determined Néel temperature of T_N = (43±1) K TbB₄ is ordered antiferromagnetically. The data refinement yielded a magnetic moment value of (7.7 ± 0.2) μ_B/Tb ion at 4.2 K which we interpret as Tb⁴⁺. The magnetic structure is antiferromagnetic collinear with the moments perpendicular to the tetragonal axis.     

Spectroscopic investigation of rare-earth chromium borates RCr3(BO3)4 (R = Nd, Sm)

The optical absorption spectra of single crystals of neodymium and samarium chromium borates are studied. A magnetic phase transition in NdCr₃(BO₃)₄ (at T _c = 8 ± 1 K) and SmCr₃(BO₃)₄ (at T _c = 5 ± 1 K) is observed. The effective magnetic field acting on the Nd³⁺ ion from the side of the ordered magnetic subsystem of chromium is estimated.     

Spektroskopische Untersuchungen an DyAsO4

DyAsO₄ undergoes a crystallographic phase transition atT _D=11.2K which is induced by a cooperative Jahn-Teller-effect. As deduced from the optical absorption spectra the distance between the two lowest lying Kramers doublets of the Dy³⁺ ion is increased from (6.1±0.5) cm^?1 aboveT _D to (25.0±0.5) cm^?1 at 4.2 K. BelowT _D the splitting factor of the lowest doublet becomes nearly uniaxial with a maximum value ofg _b =17.5±1.0 along the crystallographicb-axis. AtT _N=2.44 K the crystals order antiferromagnetically. The absorption lines of Er³⁺ ions in DyAsO₄ show already a splitting immediately belowT _D which is explained by magnetic short range ordering of the Dy³⁺ ions in the temperature rangeT _{N D} .     

Magnetization behaviour of DyAl2 single crystals

We report the theoretical interpretation of the magnetization and the magnetocrystalline anisotropy of ferromagnetic DyAl₂ single crystals between 4.2 and 60 K and magnetic fields up to 15 T. Good agreement between theory and experiment is obtained by using three temperature independent parameters: the two crystal field parameters B₄ = (?0.50 ± 0.05) × 10^?4 meV, B₆ = ? (0.51 ± 0.05) × 10^?6 meV and the Curie temperature T_c = (62 ± 2) K.     

Neutron scattering investigation of the tricritical point in DyPO4

Neutron scattering experiments on DyPO₄ were performed without and with external field at temperatures between 1.65 and 3.5 K in order to determine the phase diagram and critical properties. In contrast to previous results the M(H)-curve shows typical first order behaviour fot T ? 2 K and H ? 4.2. kG. The H_c(T)-curve agrees quite well with the previous results. Critical scattering was observed at 1.65 K around the (110) magnetic Gragg-peak. A structure refinement at room temperature was also done mainly in order to check for the importance of extinction.     

Fluctuations of the order parameter in R 0.55Sr0.45MnO3 manganites near the metal-insulator phase transition

The magnetic phase transformations induced by changes of the composition, external magnetic field strength, and temperature in manganites with a nearly half-filled conduction band in the vicinity of the metal-insulator phase transition have been investigated experimentally. It has been found that the substitution of rare-earth ions (Sm) for Nd ions with a larger ionic radius in R _0.55Sr_0.45MnO₃ manganites leads to a linear decrease in the Curie temperature T _C from 270 to 130 K and a transformation of the second-order ferromagnetic (FM) phase transition into a first-order phase transition. The results of measurements of the alternating-current (ac) magnetic susceptibility in the (Nd_{1 ? y} Sm _y )_0.55Sr_0.45MnO₃ system indicate the existence of a Griffiths-like phase in samples with a samarium concentration y > 0.5 in the temperature range T _C < T < T* (where T* ～ 220 K). For samples with y > 0.5, the magnetization isotherms at temperatures above T _C exhibit specific features in the form of reversible metamagnetic phase transitions associated with strong fluctuations of the short-range ferromagnetic order in the system of Mn spins in the high-temperature Griffiths phase consisting of ferromagnetic clusters. According to the results of measurements of the ac magnetic susceptibility in the (Sm_{1 ? y} Gd _y )_0.55Sr_0.45MnO₃ system for a gadolinium concentration y = 0.5, there is an antiferromagnetic (AFM) phase with an unusually low critical temperature of the spin ordering T _N ? 48.5 K. An increase in the external static magnetic field at 4.2 K leads to an irreversible induction of the ferromagnetic phase, which is stable in the temperature range 4.2–60 K. In the temperature range 60 K < T < 150 K, there exists a high-temperature Griffiths-like phase consisting of clusters (correlations) with a local charge/orbital ordering. The metastable antiferromagnetic structure is retained in samples with gadolinium concentrations y = 0.6 and 0.7, but it is destroyed with a further increase in the gadolinium concentration upon the transition to the spin-glass state. The magnetization isotherm obtained with variations in the external static magnetic field in the field range ±70 kOe at 4.2 K and the temperature dependence of the ac-magnetic susceptibility χ suggest that, in the Gd_0.55Sr_0.45MnO₃ ceramics, there is a mixed two-phase low-temperature state consisting of the quantum Griffiths phase with a characteristic divergence of χ(T) near T = 0, which was embedded in the spin-glass matrix with the spin “freezing” temperature T _G ? 42 K. The low-temperature state with quantum fluctuations exists in the (Sm_{1 ? y} Gd _y )_0.55Sr_0.45MnO₃ system for y ≥ 0.5.     

Manifestation of quantum statistics in vibrational dynamics of poly(ethylene) crystals

The temperature dependences of the transverse expansion ?_⊥(T) and the longitudinal contraction ?_‖(T) (with respect to the axes of chain molecules) in large-sized poly(ethylene) (PE) crystal grains (100×60×60 nm) are measured using x-ray diffraction in the temperature range 5–380 K. The temperature dependence of the elongation of the molecular skeleton ?_C(T) is obtained by Raman spectroscopy. It is found that the dependences ?_⊥(T), ?_‖(T), and ?_C(T) exhibit a similar specific nonlinear behavior. Analysis of these dependences indicates that the nonlinearity is associated with the quantum statistics of transverse vibrations. The energies and amplitudes of zero-point (at T=0) transverse (torsional and bending) vibrations and the relevant zero-point components ?_‖(0) and ?_C(0) are estimated. It is revealed that the zero-point components make a considerable contribution to the dynamics of the PE crystal up to the melting temperature (～400 K).     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Relaxation effects and evidence for one dimensional ordering in KFeCl3 studied by Mössbauer spectroscopy

Mössbauer measurements of KFeCl₃ over the temperature range 4.2–293°K show a transition to a magnetically ordered phase at T_N ? 18.5°K and evidence for one-dimensional order above T_N. In the region 10–25°K striking relaxation effects appear. An approximate analysis of the quadrupole splitting data was used for the determination of the fine structure of the ⁵D levels below T_N which in turn was used for a theoretical reproduction of the relaxation spectra between 10–25°K.     

Specific heat anomaly of single phase YBa2Cu3O7-δ at superconducting transition temperature

The specific heat of single phase YBa₂Cu₃O_7-δ has been measured using non-adiabatic method between 4.2K and 120K. There is a specific heat anomaly Δc at 90K (about 3.2% of total specific heat) approximately, due to superconducting transition. From the measured value of ΔC and transition temperature T_c, the electronic density of state at Fermi level N(E_F) and Sommerfeld parameter γ calculated are 2.55±0.30states/eV.Cu-atom and 2.77±0.30 mJ/mole.K², respectively. The experimental result of N(E_F) is consistent with that of the band calculation by Mattheiss. The Debye temperature above T_c in this material deduced from Debye function is about 340K. Below 20K, the relation C=γ'T+βT³ is satisfied. But the value of γ' is smaller. That means, most of the electrons have formed superconducting Cooper pairs which give no contribution to specific heat below 20K.     

Errata

The Mössbauer effect has been used to study the behavior of the sublattice magnetization of the antiferromagnet RbFeF₄ near the Néel temperature T_N = 133.6 K. In the asymptotic critical region (1 ? T/T_N < 10^-2), a critical exponent β = 0.316 ± 0.005 was found, indicating a three-dimensional critical behavior.