EPR study of a new low-temperature phase transition in Zn(ClO4)2·6H2O

From a temperature variation EPR study of Mn²⁺ doped single crystals of Zn(ClO₄)₂·6H₂O phase transition has been detected at T₂~290 K. The phase relationships in this crystal are as follows. Phase I transforms atT₂~346K to Phase II, which in turn transforms to Phase III at T₂ ~ 290K. The latter exists down to at least 220 K. The space group symmetry of crystal may be the same, i.e. Pmn2₁ both above and below T₂. The water-perchlorate sublattice symmetry below T₂ is found to be lower than the P6₃mc symmetry determined previously by X-ray measurements. The onset of a monoclinic or lower symmetry distortion of the water octahedron around a metal ion which starts just below T₂, is reflected through the observed temperature dependence of the rhombic distortion parameter E. It is felt that during this phase transition a change in the degree of configurational disorder associated with the perchlorate tetrahedra takes place, which in turn modifies the hydrogen bonded interaction in the crystal and consequently results in the onset of temperature dependent displacements of the mean positions of the oxygens of the water molecules.     

Critical behavior of heat capacity in the vicinity of phase transitions in [NH2(CH3)2]5Cd3Cl11

The heat capacity of a [NH₂(CH₃)₂]₅Cd₃Cl₁₁ crystal was studied calorimetrically in the temperature interval 100–300 K. The C _p (T) dependence indicates that, as the temperature is lowered, phase transitions occur at temperatures T ₁ = 176.5 K and T ₂ = 123.5 K. The thermodynamic characteristics of this crystal were determined. It is shown that the transition at T ₂ = 123.5 K is an incommensurate-commensurate phase transformation and that the transition at T ₁ = 176.5 K is a normal-incommensurate phase transition.     

Effect of γ-irradiation on the heat capacity of an [NH2(CH3)2]2 · CuCl4 crystal in the temperature range 80–300 K

The heat capacity of [NH₂(CH₃)₂]₂ · CuCl₄ crystals prior to and after γ-irradiation with doses of 1, 5, 10, and 50 MR is measured by the calorimetric method in the temperature range 80–300 K. It is found that, as the temperature decreases, the temperature dependence C _p (T) exhibits two anomalies which correspond to phase transitions from the incommensurate to the ferroelectric phase at T _c =281 K and from the ferroelectric to the ferroelastic phase at T ₁=255 K. The nature of the anomalies is typical of a first-order phase transition. In addition, a smeared anomaly in the form of a small increase in the heat capacity of the ferroelectric phase is observed at T≈275 K. It is demonstrated that when the dose of γ-irradiation increases, the anomalies decrease in magnitude and the phase transition temperatures are displaced: T _c increases and T ₁ decreases.     

Metal-nonmetal transition and superconductivity in frozen tin-hydrogen films

We have studied the d.c.-conductivity σ and the superconducting transition temperature T_c in frozen mixtures of Sn and molecular H₂ (Sn-H₂) or atomic H(Sn-H). The samples were prepared by co-deposition of Sn and H₂ (H) onto a sapphire substrate held at a temperature of about 5 K. Both systems show a quite different behaviour. While the Sn-H₂ system exhibits a metal-insulator transition at c_H2 = 0.6 which agrees well with percolation theory, the Sn-H samples show a metal-semiconductor transition already at c_H?0.32. Both systems have an increased T_c in the metallic region. H₂ seems to be mobile in Sn-H₂ films even down to 5 K after annealing of the samples at 10 K. Atomic H, on the other hand, is bound up to T?200 K.     

Thermal and magnetic properties of DyB62 at low temperatures

Temperature dependences of heat capacity C_P(T) and magnetization M(T) of an icosahedral dysprosium boride (DyB₆₂) single crystal have been experimentally investigated in the temperature range of 2-300 K. The magnetic susceptibility χ(T) of DyB₆₂ follows Curie-Weiss law with a paramagnetic Curie temperature of −3.7 K, which implies that the antiferromagnetic interactions are dominant in this material and suggests the possibility of magnetic ordering at low temperatures. This conjecture is supported by the temperature dependence of heat capacity C_P(T), which decreases upon heating from 2 to 7 K. The heat capacity of DyB₆₂ at 2 K is analyzed as a sum of magnetic, Debye, two-level system and soft atomic potential components.     

Superionic transitions and conductivity anisotropy in Na4.6FeP2O8.6F0.4 single crystals

The cation conductivity in the directions parallel (σ_‖[001]) and perpendicular (σ_⊥[001]) to the [001] crystallographic direction of Na_4.6FeP₂O_8.6F_0.4 single crystals has been investigated at 293–734 K. The specific features of the ionic conductivity have been studied near two phase transitions at T _{tr, 1} ～ 450 K and T _{tr, 2} ～ 545 K. At T = T _{tr, 1}, the activation enthalpy for the dependences σ_‖[001](T) and σ_⊥[001](T) decreases from 0.45 ± 0.01 to 0.33 ± 0.02 eV, and the σ_‖[001](T) curve has a jump of the ionic conductivity by a factor of almost two at T = T _{tr, 2}; the jump is related to a manifestation of commensurate modulation of the crystal structure. In the Na_4.6FeP₂O_8.6F_0.4 crystals, the ionic transport is anisotropic with the ratio σ_‖[001]/σ_⊥[001] = 7.7, 5.2, and 6.6 at 293 K (T < T _{tr, 1}), 500 K (T _{tr, 1} < T < T _{tr, 2}), and 700 K (T < T _{tr, 2}), respectively. The mechanism of cation conductivity in the Na_4.6FeP₂O_8.6F_0.4 crystals is discussed.     

A novel double-peaked spin-glass susceptibility-temperature response in the ternary alloy Fe69Mn26Cr5

We have studied the low-field (B ≦ 10^?2 T) d.c. susceptibility χ of the austenitic stainless-steel alloy Fe₆₉Mn₂₆Cr₅ as a function of the magnetic field B and temperature T. χ(T) shows structure, strong B dependence, and typical irreversible effects. The range of temperatures studied comprises three distinct regions. In the high-temperature region (300 K ≦ T ≦ 380 K) a blunt peak in the susceptibility is noticed at T₂ = 340 K. T₂ was not sensitive to thermal cycling. χ(T) displayed a sharp cusp at T₁ = 200 K. This peak was sensitive to the thermal history of the sample and was strongly suppressed by B. Between T₁ and T₂ a shallow valley with some hysteresis was observed. We interpret this behavior to be due to a low-temperature pure spin-glass phase, a high temperature conventional paramagnetic phase, and coexisting antiferromagnetic and spin-glass phases between T₁ and T₂.     

An ESR study of phase transitions in crystals of M(BF4)2·6H2O (M = Fe,Co, Ni,Zn)

From a temperature dependent ESR study of Mn²⁺-doped crystals of M(BF₄)₂·6H₂O, M Zn, Co and Ni, new structural phase transitions have been detected and studied. First order structural phase transitions occur in Co(BF₄)₂·6H₂O at T₁ ~ 281K, T₂~189 K and T₃~172K (during cooling), in Zn(BF₄)₂·6H₂O at T₁ ~ 286 K and in Ni(BF₄)₂·6H₂O at T₁ ~ 301 K. A continuous phase transition occurs in Co(BF₄)₂·6H₂O at T_p ~ 257 K, in Zn(BF₄)₂·6H₂O at T_p ~ 277 K and in Ni(BF₄)₂·6H₂O at T_p ~ 294 K. The ESR spectral characteristics suggest similarities in the structures of these fluoroborate compounds in the phase above T₁ with the room temperature structure of Mg(ClO₄)₂·6H₂O. All these compounds are found to have a tendency to crystallise in a triply-twinned pseudo-hexagonal form, although the unit cell above T₁ is found to be orthorhombic. The structural changes related to the water octahedron around the metal at T₁ were found to be very small and basically the same for these three compounds. Although the unit cell structure of Fe(BF₄)₂·6H₂O above the first order phase transition temperature T₁ was found to be similar to that of the other fluoroborate compounds, the structural changes occurring at T₁ appeared to be quite different. The low temperature thermal behaviour differs considerably in the Co, Fe and Zn compounds.     

Magnetic properties of RPd5Al2 (R=Y, Ce, Pr, Nd, Sm, Gd)

Polycrystalline samples of a new rare-earth series RPd₅Al₂ crystallizing in the tetragonal ZrNi₂Al₅-type structure have been prepared. Their physical properties by electrical resistivity ρ, magnetic susceptibility χ, magnetization M and specific heat C_p measurements are reported. The ingots are composed of elongated grains preferentially aligned in the c direction; therefore, measurements were conducted parallel and perpendicular to the grains. Antiferromagnetic ordering appears in R=Ce, Nd, Gd, and Sm at low temperatures. CePd₅Al₂ has two AFM transitions at 4.1 and 2.9 K and ρ(T) indicates a Kondo metal behavior with large anisotropy. In PrPd₅Al₂ no magnetic transition was observed down to 0.4 K. The C_p(T) shows a broad peak around 13 K due to the CEF effect, suggesting a non-magnetic singlet ground state. In NdPd₅Al₂, χ(T) shows anisotropy and the C_p(T) shows a sharp peak at 1.2 K. The magnetic entropy at 3 K is very close to Rln2, indicating a Kramers doublet ground state. In SmPd₅Al₂, C_p(T) shows a magnetic transition at 1.7 K. C_p(T) for GdPd₅Al₂ shows a peak at 6 K, followed by a broad anomaly around 3 K. Within this series, T_N's for CePd₅Al₂ and NdPd₅Al₂ clearly deviate from the relation predicted by de Gennes scaling, which is ascribed to the CEF effect.     

Effect of surface temperature on the sorption of hydrogen by Pd(111)

Temperature programmed desorption (TPD) subsequent to various hydrogen exposure conditions indicates the formation of chemisorption, solid solution, and hydride phases of hydrogen in the near surface region of Pd(111). Variation of the sample exposure temperature (T_e) between 80 and 300 K has a strong effect on the subsequent TPD spectra. At T_e = 80 K a single desorption peak, β, appears at 310 K. Coverage variation of the β peak is consistent with second-order recombinative desorption of chemisorbed hydrogen. For T_e between 90 and 140 K a slight enhancement of the β peak occurs and a new peak, α, appears initially near 170 K. It does not saturate, exhibits near-zeroth-order desorption kinetics, and is assigned to the decomposition of a near surface palladium hydride phase. Population of the α peak is thermally activated with a maximum at T_e ≈ 115 K. For T_e, greater than 140 K, α disappears while the total amount of absorbed hydrogen increases significantly. At these temperatures, the concentration of absorbed hydrogen decreases significantly if the sample is held in vacuo at T_e after completion of the hydrogen exposure. At all exposure temperatures there is also a broad desorption feature near 800 K which is enhanced by higher T_e and is associated with hydrogen in solid solution.     

The properties of the (H2O)6 water cluster that depend on its density during temperature transitions

Water clusters (H₂O)₆ are simulated by the Monte Carlo method with the Metropolis function at various temperatures (T ₁ = 273 K, T ₂ = 298 K, and T′₁= 373 K) and densities (ρ₁ = 0.9998 g/cm³, ρ₂ = 0.9167 g/cm³, and ρ₃ = 0.00059 g/cm³) of the system. It is established that the number of retained most probable configuration types at ρ₁ = 0.9998 g/cm³ during temperature transitions from T ₁ = 273 K to T ₂ = 298 K and from T′₁ = 373 K to T ₂ = 298 K is smaller than at ρ₃ = 0.00059 g/cm³. This result was acquired on the background of the following invariable parameters of the system with the same temperature transitions for each of three values of density: (i) the average number of retained most probable configuration types, (ii) the average fraction of weight coefficients of the most probable configuration types, and (iii) the average potential energy. The configuration type that was retained among the most probable configuration types of the system for all values of density (ρ₁ = 0.9998 g/cm², ρ₂ = 0.9167 g/cm³, and ρ₃ = 0.00059 g/cm³) of the system for temperature transitions from T ₁ = 273 K to T ₂ = 298 K and from T′₁ = 373 K to T ₂ = 298 K was also revealed.     

Mössbauer effect of tin-119 doped in highT c Y−Ba−Cu−O superconductor

Mössbauer measurements at temperatures ranging from 12 K to 300 K have been carried out on highT _c superconductor YBa₂Cu₃O_6+δ samples doped with Sn (5,2 and 0.5 wt%). The temperature dependent recoilless fractionf(T) has a narrow and small drop nearby transition temperatureT _c which is dependent on the Sn-concentration and has a drop between 200–220 K. This indicates the occurrence of phonon softening at these temperatures. The Debye temperature θ_D of the samples containing 5, 2 wt% Sn atoms was determined as (290±25) K and (320±13) K respectively. These results show that phonons may play an important role for electron pairing in novel oxide superconductor.     

Nuclear spin-lattice and nuclear spin-spin relaxation time measurements in EuB6 at low temperatures using the spin-echo technique

Experimental results on the nuclear spin-lattice and nuclear spin-spin relaxation times in the ferromagnetic EuB₆ at temperatures below 4·2 K are presented using the external magnetic field,H _ext, in the range of 0 ⩽H _ext ⩽ 10 kG. Nuclear spin-spin relaxation time computed on the basis of the Suhl-Nakamura process turns out to be 3·2μs, which compares well with the experimental value 11·1μs obtained with the 10 kG magnetic field at 1·7 K. It is found that in the ferromagnetic EuB₆,T ₁ is approximately 5 × 10³ times larger thanT ₂ at 1·7 K with the 10 kG magnetic field. Thus the effect ofT ₁ onT ₂ can be neglected. From the experimental value ofT ₂, the value of the homogeneous line broadening is found to be 14 kHz. The corresponding value obtained from the cw method is 175 kHz. This evidently shows the presence of the inhomogeneous line broadening in the cw NMR.     

Charge density waves in layer structures: A NMR study on a 2HNbSe2 single crystal

We have studied by pulsed NMR a single crystal of 2HNbSe₂ at ambient pressure and under hydrostatic pressure of 21 kbar in the temperature range 4.2–273 K. Our results are consistent with the onset of incommensurate charge density waves (ICDW) at T_CDW = 33 K atP = 1 bar and 26 K at P = 21 kbar. Below T_CDW, the lineshapes of the (m → m ? 1) transitions agree with a local distribution of Knight shift and electric field gradients respecting the symmetry of a triple ICDW, while above T_CDW, pre-transitional broadening is observed. The product T₁T = 500 ± 100 msk was found constant in the temperature range 4.2–77 K and pressure independant.     

Pressure and field dependence of the magnetic transition in GdBa2Cu3O7-x

The influence of hydrostatic pressure and of magnetic field strenght is presented for the low temperature antiferromagnetic ordering temperature (T_N=2.3 K) of GdBa₂Cu₃O_7-x. Data are presented for both superconducting and normal samples, the superconducting sample having a sharp 95 K transition and the oxygen-depleted normal sample being a semiconductor. For both systems the Néel temperatures, extrapolated to zero measuring field, are identical: T_N = (2.33±0.03) K. The effect of pressure is to raise the transition temperature slightly for both samples, dT_N/dP=+0.03 K/kbar for the superconducting sample and +0.04 K/kbar for the normal sample. The temperature dependence of the heat capacity made in several fixed external magnetic fields and the isothermal magnetization for T<T_N provide a measure of the antiferromagnetic-paramagnetic phase boundary, which shows T_N approaching T=0 K at about 2.5 T.     

Phase diagram of YBa2Cu3O7−y at T<T c according to transverse nuclear relaxation data for Cu(2)

Two peaks are observed at T=35 and 47 K in the transverse relaxation rate for Cu(2) nuclei in YBa₂Cu₃O_7?y . A comparison of the relaxation rates for isotopes ⁶³Cu(2) and ⁶⁵Cu(2) at T=47 K indicates the magnetic nature of relaxation. The enhancement of local magnetic field fluctuations perpendicular to CuO₂ planes at T=47 K is associated with critical fluctuations of orbital currents. The peak at T=35 K is attributed to the emergence of an inhomogeneous superconducting phase. The obtained experimental results and the available data from the literature made it possible to propose a qualitatively new phase diagram of the superconducting state.     

Studies of the heat capacity and thermal expansion of the Na0.95K0.05NbO3 solid solution

The heat capacity and thermal expansion of ceramic samples of the Na_0.95K_0.05NbO₃ solid solution have been investigated over a wide temperature range of 100–750 K. The observed anomalies in the heat capacity and thermal expansion at T ₄ = 297 K, T ₃ = 535 K, T ₂ = 665 K, and T ₁ ≈ 710 K correspond to the sequences of phase transitions N → Q → G → S → T1. It has been shown that, as a result of the phase transitions, the unit cell volume at T ₄ and T ₂ decreases, and at T ₃ and T ₁, increases with increasing temperature. The directions of the shift of the phase transition temperatures induced by hydrostatic pressure have been determined. It has been established that all structural transformations are accompanied by relatively small variations in the entropy. Different mechanisms of the structural distortions have been discussed.     

Magnetism and superconductivity in R1.5Ce0.5MSr2Cu2O10‐δ (M=Ru and Fe) compounds

It is shown here, that the superconducting (SC) R_1.5Ce_0.5RuSr₂Cu₂O_10-δ (RCeRuSCO, R= Eu and Gd) materials (T_c ～ 32 and 42 K) are also antiferromagnetically (AFM) ordered at T _N(Ru) ～ 122 and 180 K, respectively, thus, T_N ? T_c, a trend which is contrary to that obtained in “magnetic‐SC” intermetallic systems. Mössbauer spectroscopy (MS) on 0.5% ⁵⁷Fe doped samples shows that all Fe ions reside in the Ru site which is magnetically ordered, whereas SC is confined to the CuO₂ planes. On the other hand, for Y_1.5Ce_0.5FeSr₂Cu₂O₉ (YCeFSCO) no SC is found and the Cu–O planes order AFM at T _N(Cu)=31 K. MS studies reveal two in equivalent Fe sites, and that Fe resides predominantly (60%) in the Cu(1) site. In both sites, the Fe does not order magnetically, and the low T _N(Cu) obtained is due to frustration of the Cu moments by the presence of Fe. T _N is sensitive to oxygen concentration and shifts toward 260 K when oxygen is depleted.     

Mössbauer study of the intermetallic compound Nd2Fe14B. II. Temperature dependence and spin reorientation

The ⁵⁷Fe Mössbauer effects of Nd₂Fe₁₄B were measured in a temperature range of 4.2−300 K. Below the spin reorientation transition temperature T_sc = 148 K, the spectra were satisfactorily analyzed with twelve Zeeman sextuplets due to splitting of six crystallographic Fe-sites into twelve non-equivalent sites. It was shown that the magnetic moments of the Fe and the Nd atoms are non-collinearly coupled in the magnetic structure with canted moments below T_sc. The directions of the moments at 4.2 K are inclined at 27° for Fe and at 58° for Nd from the c-axis to the [110] direction. The average moments are 2.27μ_B for Fe and 3.3μ_B for Nd at 4.2 K. The increase of the average hyperfine field with decreasing temperature is suppressed below T_sc, and its value at 4.2 K is reduced by 1% from the value of 337 kOe which is observed in Y₂Fe₁₄B and also estimated for Nd₂Fe₁₄B by extrapolating the values above T_sc. On the other hand, the Nd moment increases abruptly around T_sc as the temperature decreases. The directions of the principal axes of electric field gradients on the six distinct Fe-sites were also obtained. The anomalous temperature dependence of quadrupole splittings and isomer shifts was observed around T_sc. They were discussed in a framework of the changes in the band structure and the lattice parameters incidental to the spin reorientation transition.