Phase transitions in LiKSO4: Low-temperature neutron diffraction results

Results of a detailed crystallographic study of the structural phase transitions in LiKSO₄, carried out using single crystal neutron diffraction at ambient and below-ambient temperatures (300–100 K), are presented. The study indicates two clear phase transitions at 205 K (from space group P6₃ to space group P31c), at 189 K (to space group Cc) and a third transition at about 130 K in the cooling cycle. The corresponding temperatures are 250 K, 200 K and 138 K in the heating cycle. The existence of twins, mixed phases, and extremely sluggish kinetics for the various phase transitions, as well as the structural details of the various phases in this mixed salt, can explain the apparent inconsistencies in the results of several experimental investigations reported in the literature.     

Powder neutron diffraction study of low temperature phase transition in LiKSO4

The salient features of the neutron diffraction measurements on polycrystalline sample of LiKSO₄ at 170 K and 104 K are reported. The sample undergoes a phase transformation to a single phase as against “mixed phases” reported in single crystal studies. These differences are discussed on the basis of the kinetics of nucleation and growth processes.     

Optical study of the phase transitions in LiKSO4

The birefringence of LiKSO₄ has been measured over the range 27–700°C. The change in birefringence with heating and cooling is seen to be very different. Observations have been made on domains in (001) and (100) plates near the phase transitions.     

Phase transitions in BaCeO3: neutron diffraction and Raman studies

Polycrystalline samples and small single crystals of the perovskite BaCeO₃ were studied by neutron diffraction and Raman spectrometry between 300 and 1200 K. The controversy about the phase transitions originally deduced from our previous Raman study and those observed since by neutron diffraction by Knight has stimulated this work. Pretransitional effects which are detected by Raman much before long-range ordering takes place can partly explain the above disagreement. A continuous monitoring of the structural changes by neutron diffraction and by Raman spectroscopy including polarization analysis has allowed discussion of the transition mechanisms: The first transition Pnma–Imma takes place at 573 K and is of second order. Although some modes soften when the temperature is raised as in many of these perovskite compounds the transition is likely partly displacive partly order–disorder. The Raman modes which disappear transform in modes at the X point of the Brillouin zone of the Imma phase. The second transition Imma–R c takes place at 673 K and is first order. The last transition R c–Pm3m occurs above 1200 K and the transition temperature which can be deduced by extrapolation to zero Raman intensity is in good agreement with neutron results. This second order transition is progressive and begins at about 400 K, the intermediate R c structure appearing as an attempt for slowing down the structural evolution toward the cubic perovskite form.     

Powder neutron diffraction study on TbPd3S4 and YbPd3S4

We report the results of low-temperature magnetic properties of newly synthesized samples of TbPd₃S₄ and YbPd₃S₄, which indicate that they merely exhibit antiferromagnetism below 2.9 and 1.8 K, respectively, without showing any other transitions above 0.4 K. From the powder neutron diffraction experiments, we determined the magnetic structure of these rare-earth palladium bronzes.     

EPR investigations of phase transitions in lithium potassium sulfate: LiKSO4

Single crystal EPR studies of NH⁺₃ doped in the K⁺ sites of lithium potassium sulfate (LKS) have been carried out from room temperature down to −150°C. The spin Hamiltonian parameters have been evaluated for the three phases which occur in this temperature range, P I (room temperature) (A_N)_XX = (A_N)_YY = 23.2 G and (A_N)_ZZ = 10.4 G; P II (below −69°C) (A_N)_XX = (A_N)_XX = 22.3 G and (A_N)_ZZ = 11.7 G; P III (below −83°C) (A_N)_XX = 8.9 G, (A_N)_YY = 20.8 G and (A_N)_ZZ = 25.9 G. The P I–P II transition at −69° C is rather sluggish and shows a mixed phase for 2.5–3 h. In P III the principal component (A_N)_ZZ moves out by an angle of 1.4° from the b-axis. The space group of this phase is most probably not Cmc2₁.     

Structural and magnetic phase transitions in TbPO4 studied by neutron diffraction

Neutron diffraction experiments on TbPO₄ single crystals have been performed in the temperature range from 1.35 to 294 K. We observe two phase transitions: the onset of antiferromagnetic ordering along the tetragonalc-axis at 2.28 K and tilting of the moments away from thec-axis below 2.15 K. The analysis of the measured reflection profiles shows that the tilting is connected with a distortion of the tetragonal zircon structure.     

Low-temperature neutron diffraction study of the crystal and magnetic phase transitions in DyCrO4

The crystal and magnetic structures of DyCrO₄ were studied using neutron powder diffraction. Complete diffraction data at 3.6, 17, 27, and 40 K show that a crystal structural phase transition from tetragonal I4₁/amd to orthorhombic Imma symmetry is found to take place between 27 and 40 K. This transition does not involve a significant change in the unit cell volume. Strong ferromagnetic reflections are observed at 3.6 and 17 K, and can be fit well using the magnetic model of space group Im'ma', with the moments of both Dy³⁺ and Cr⁵⁺ ions aligning along the y-axis. Detailed temperature dependent magnetic intensities of 101/011 and 211/121 peaks reveal a Curie temperature of T_c=22.35(15) K.     

High-pressure neutron diffraction studies of KH2PO4-type phase transitions

Abstract

High-pressure neutron-diffraction studies have been carried out on KH₂PO₄, KD₂PO₄, H₂C₄O₄ and PbHPO₄, using single-crystal samples. The results show that changes in the H-ordering temperature, T_C, with pressure (or deuteration) in these systems can be largely attributed to the variation of the H-site separation, δ, with pressure (or deuteration).     

Kinetics of phase transitions in modulated ferroelectrics: Time-resolved neutron diffraction from Rb2ZnCl4

The kinetics of the ferroelectric phase transition between modulated phases in Rb₂ZnCl₄ at about 190K has been investigated by time-resolved neutron scattering. Observing the time dependence of satellite spectra, it is found that the structural changes associated with the field-induced transformation proceed on a millisecond time scale. Under the influence of fast cycling strong electric fields unusual non-equilibrium states are obtained which are modulated in space as well as in time and characterised by the presence of internal mechanical strains.     

Low-temperature phase transitions in LiKSO4: A neutron study

A single crystal neutron diffraction study of the low temperature structural phase transitions in LiKSO₄ has been carried out. Detailed temperature dependence of the Bragg peak profiles and integrated intensities for a group of about 20 reflections has been investigated upon cooling and heating in the temperature range 300 K to 96 K. The crystal undergoes three clear phase transitions at 205 K (from sp. gr. P6₃ to sp. gr. P31c), at 189 K and at about 135 K on cooling. The corresponding temperatures are 250 K, 190 K and 138 K on the heating cycle. These transitions are extremely sluggish, the kinetics depending on the thermal treatment of the crystal.     

Phase transitions and crystalline structures in neutron star cores

The mixed phase of a fully equilibrated nuclear system that is asymmetric in isospin (i.e. in charge) will develop a geometrical structure of the rarer phase immersed in the dominant one. This happens because the isospin asymmetry energy will exploit the degree of freedom available to a system of more than one independent component (or conserved charge) by rearranging the proportion of charge to baryon number between the two equilibrium phases so as to lower the energy; that is, to effectively reduce the isospin asymmetry in the normal nuclear phase. Consequently, the two phases will have opposite charge; competition between Coulomb and surface energy will be resolved by formation of a Coulomb lattice of the rarer phase situated at sites in the dominant phase. The geometric form, size, and spacing of the phase occupying the lattice sites will depend on the pressure or density of matter. Thus, a neutron star containing a mixed phase region of whatever kind, will have a varying geometric structure of one phase embedded in the other. This is expected to effect transport properties of the star as well as to effect the glitch behavior of pulsars that contain a mixed phase region. We study in particular, the quark deconfinement and kaon condensation phase transitions as examples of this general phenomenon.     

Phase transitions and diffraction of kinked vicinal surfaces

Several aspects related to kinked vicinal surfaces are studied here. First, a symmetry classification of ordered kinked crystal surfaces is given. Possible second order (continuous) phase transitions are identified within the context of Landau-Lifshitz theory. In addition to the Ising and the X - Y model (with cubic anisotropy) universality classes, we obtain a special case in which transitions are in the Potts universality class. Transitions in the latter class do not occur on the stepped vicinal surfaces. Secondly, an expression for the diffraction intensity of the ordered kinked surface is derived. The Bragg peaks for the kinked surface are predicted to split into quadruplets and are calculated for a specific surface. Finally, an exact expression is obtained for the atomic pair correlation function. In the appropriate limits these expressions reduce to the corresponding formulae for the vicinal stepped surfaces.     

A neutron diffraction study of ferroelectric PbHAsO4 at room temperature

A single-crystal neutron-diffraction structural study of PbHAsO₄ in its ferroelectric phase at room temperature (24°C) is presented as part of an investigation of a family of monetites. The crystal structure of PbHAsO₄, and its phase transition mechanism are discussed. Comparison of the crystal structures of PbHPO₄ and PbHAsO₄ reveals that these two ferroelectrics are isomorphous. The role of protons in structural phase transition of PbHAsO₄ is also discussed.     

Magnetic octupole order in : A polarized neutron diffraction study

Recently, in phase IV of Ce_xLa_1-xB₆, weak but distinct superlattice reflections from the order parameter of phase IV have been detected by our unpolarized neutron scattering experiment [K. Kuwahara, K. Iwasa, M. Kohgi, N. Aso, M. Sera, F. Iga, J. Phys. Soc. Japan 76 (2007) 093702]. The scattering vector dependence of the intensity of superlattice reflections is quite unusual; the intensity is stronger for high scattering vectors. This result strongly indicates that the order parameter of phase IV is the magnetic octupole. However, the possibility that the observed superlattice reflections are due to lattice distortions could not be completely ruled out only on the basis of the unpolarized neutron scattering experiment. To confirm that the superlattice reflections are magnetic, therefore, we have performed a single crystal polarized neutron diffraction experiment on Ce_0.7La_0.3B₆. The obtained result has clearly shown that the time reversal symmetry is broken by the order parameter of phase IV. This is further evidence for the magnetic octupole order in Ce_xLa_1-xB₆.     

Phase transitions in DyVO4 and DyAsO4

This paper reports on optical, magnetic, and specific heat experiments at low temperatures on DyVO₄ and DyAsO₄, including a summary of previous works on these two substances. The crystallographic phase transition in DyVO₄ is second order, whereas in DyAsO₄ there is a latent heat at the distortion temperature. In contrast to the results of neutron diffraction experiments, no evidence for a canted antiferromagnetic structure in DyAsO₄ below the magnetic transition temperature was found. Magnetically, DyAsO₄ behaves almost identically to DyVO₄.Dedicated to Prof. Dr. W. Buckel on the occasion of his 60th birthdayThis work is a somewhat shortened translation of the Habilitationsschrift submitted to the Fakultät für Physik der Universität Karlsruhe     

Cu-Zn disorder in Cu2ZnGeSe4: A complementary neutron diffraction and Raman spectroscopy study

The crystal structure of the quaternary compound semiconductor Cu₂ZnGeSe₄ (CZGSe) was investigated by the complementary use of neutron diffraction, and Raman spectroscopy. The powder sample, which resulting from wavelength dispersive X-ray spectroscopy (WDX) turned out to be single phase Cu-rich CZGSe, was synthesized by solid state reaction of the pure elements in an evacuated silica tube at 700 °C. Raman spectroscopy confirmed the homogeneity and phase purity of the sample, in addition, the kesterite type structure was suggested. Rietveld analysis of the neutron diffraction data confirmed that the compound crystallizes in the tetragonal kesterite type structure. The refined site occupancy factors were used to determine the average neutron scattering lengths of the cation sites, giving insights into cation distribution and finally point defect types. Thus it has been shown, that additional to the Cu_Zn-Zn_Cu anti-site defects in the lattice planes at z=¼ and ¾ (Cu-Zn disorder) also the off-stoichiometry type related point defects like Cu_i and Cu_Zn occur in Cu-rich CZGSe.