Thermal Hysteresis Accompanying Incommensurate-Commensurate Phase Transition in Mixed Crystals (K1-xCsx)2ZnCl4

The mixed crystal (K_1-xCs_x)₂ZnCl₄ with x = 0, 0.001, 0.01, 0.1, and 0.2 with optical quality has been grown by the Czochralski method. Using the Atomic Absorption Spectroscopy (AAS) and Energy Dispersive Spectroscopy (EDS), we determined the amount of Cs ion included in the mixed crystal. By using of DTA and DSC, we observed the change of T_c and T_i. The thermal hysteresis in the dielectric constants show strong dependence on the thermal process and on the amount of impurity which are explained by the influence of the thermal process and impurity, respectively on the creation, annihilation, and growth of discommensuration (DC).     

Crystal growth of ferroelastic K2Cd2(SO4)3 and the K2SO4-CdSO4 phase diagram

Crystals of congruently melting K₂Cd₂(SO₄)₃ (having the langbeinite structure with a ferroelastic transition temperature of 156°C) were grown by the Bridgman and Czochralski techniques. The former yielded colorless crystals when using oxygen under pressure; the latter yielded tan crystals of slightly smaller unit cell volume and are assumed to be oxygen deficient. The ferroelastic transition was studied by thermal expansion measurements. Reexamination of the phase diagram showed the existence of a previously unreported phase K₆Cd(SO₄)₄ which is stable only between 520°C and the melting point of about 890°C.     

Growth and thermal studies on pure ADP,KDP and mixed K1‐x(NH4)xH2PO4 crystals

The investigations on the formation of mixed crystals of ammonium dihydrogen orthophosphate (ADP) and potassium dihydrogen orthophosphate (KDP) i.e. potassium ammonium dihydrogen phosphate, K_1‐x(NH₄)_xH₂PO₄ have been presented in this paper. Pure and mixed crystals of ADP and KDP have been grown by slow evaporation technique from the supersaturated solution at an ambient temperature 26±1 °C for ammonium concentration x in the range 0.0 ≤ x ≤ 1.0 in the case of mixed crystals. Crystal compositions were determined by flame atomic absorption spectroscopy and chemical analysis. The results of the X‐ray analysis of the grown crystals are also reported. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the kinetic process of dehydration and the high temperature phase behaviour. DTA showed the distinct thermal events attributed to dehydration of ADP, KDP and K_1‐x(NH₄)_xH₂PO₄. The results of thermal analysis and chemical analysis are consistent with each other. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dynamic and static orientational disorder in mixed K1 − x (NH4)xI crystals

Earlier, we have shown that, at low temperatures, the mixed K_{1 ? x} (NH₄)_xI crystals show two low-energy resonance modes in the dynamically orientationally disordered region of the α-phase and statically orientationally disordered phase of the orientational glass, absent in the orientationally ordered γ-phase. Below, we report the results of the experimental study of the low-energy resonance and local modes in K_{1 ? x} (NH₄)_xI crystals obtained by the method of inelastic incoherent neutron scattering (IINS) over the wide temperature range.     

Growth and Properties of Trigonal Aluminium Gallium Orthophosphate Single Crystals Al1-xGaxPO4

The new piezoelectric solid solution aluminium gallium orthophosphate single crystals have been successfully developed for the first time in our laboratory by hydrothermal method. It has been demonstrated that these crystals are homogeneous, and isomorphous with AIPO₄ and GaPO₄. The solid solution crystals Al_1-xGa_xPO₄ are easy to grown and have better optical quality than those of AlPO₄ crystals under the same conditions. A phase transition temperature T_α-β is 587 ± 3 °C for x = 0.12. Cell parameters, and elastic, piezoelectric, and dielectric constants are given.     

The Changes of Thermal,Dielectric, and Optical Properties at Insertion of Small Concentrations of Ammonium to K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> Crystals

The structure of (K_1–x(NH₄)_x)₃H(SO₄)₂ crystals with a low ammonium concentration and the behavior of their thermal, optical, and dielectric properties in a temperature range of 275–500 K have been investigated to clarify the influence of doping on the phase transition kinetics. An examination of unit-cell parameters of (K_{1 – x}(NH₄)_x)₃H(SO₄)₂ single crystals has confirmed the existence of a superprotonic phase transition at a temperature of ≈450K. The conducting properties of single-crystal and polycrystalline samples have been studied.     

Characteristic features of the change of domain structure in mixed [(NH4)1?xRbx]3H(SO4)2 crystals in the vicinity of superprotonic phase transition

X-ray diffraction measurements of mixed [(NH₄)_1−x Rb_x]₃H(SO₄)₂ crystals of different compositions are performed. The characteristics of the change of the domain structure in the vicinity of the supeprotonic-ferroelastic phase transition in crystals of different compositions are studied and compared with the variations of the crystal structure in the course of gradual substitution of ammonium by rubidium. This phase transition is theoretically described based on the phenomenological theory of a high-temperature phase transition. __________ Translated from Kristallografiya, Vol. 50, No. 1, 2005, pp. 115–121. Original Russian Text Copyright ? 2005 by Kirpichnikova, Polomska, Pietraszko, Shakhmatov, Hilczer.     

Elements of the Phase Diagram of YbInCu4

To clearify how the valence transition temperature of YbInCu₄ is connected with the composition of the grown crystals, we investigated the phase diagram. Since elements of the liquidus curve of the system Yb-In-Cu were already known we focused on the solidus curve in the surrounding of the valence changing YbInCu₄. Bridgman-technique for crystal growth was used. The composition of the solidified crystals was determined by means of wavelength-dispersive X-ray analysis. The valence transition temperature is measured via the lattice constant by low temperature X-ray diffraction. Results are, that the assumed exchange of Yb and In, which is indicated in the formula Yb_xIn_2-xCu₄ seems to be not correct. Not the quasi-binary section for constant Copper content should be used, but one for constant Ytterbium content. Starting compositions with an excess of Ytterbium lead to the substitution of Indium by Copper. The valence transition temperature of these crystals is shifted from 40K to 70K.     

Optical properties of non‐centrosymmetric mixed crystals K2(La1‐x Cex)(NO3)5 · 2 H2O (x = 0.0 – 1.0)

Large single crystals of optical quality of the non‐centrosymmetric orthorhombic potassium rare earth nitrate mixed crystals K₂(La_1–x Ce_x)(NO₃)₅ · 2 H₂O were grown at 38 °C from diluted HNO₃. For crystals with x = 0.0, 0.19, 0.38 and 0.66 refractive indices and their dispersion were determined with an error less than 1 · 10^–4 in the wavelength range 0.404 – 1.083 μm by the prism method. Phase matching conditions for collinear SHG frequency conversion were analysed in detail, including calculation of the effective nonlinear optical susceptibility. By an appropriate choice of the fraction x of cerium the mixed crystals K₂(La_1–x Ce_x)(NO₃)₅ · 2 H₂O allow an adjustment of non‐critical type I phase matching conditions to a desired wavelength of the fundamental wave within the range 1.055(4) – 1.107(6) μm. Non‐critical type II phase matching can be tuned in the wavelength range 0.949(2) – 0.931(2) μm. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of x‐irradiation on indentation size effect and formation of cracks for [Ky(NH4)1‐y]2ZnCl4 mixed crystals

The effects of x‐beam irradiation with different doses on microhardness and its related physical constants on [K_y(NH₄)_1‐y]₂ZnCl₄ mixed crystals with concentrations, y equals 0.000, 0.232, 0.644, 0.859 or 1.000 has been studied. The tests were performed for x‐doses from 0.2 kGy up to 1.6 kGy for loads from 20 to 160 g. The variation of hardness on (010) faces of orthorhombic [K_y(NH₄)_1‐y]₂ZnCl₄ mixed crystals with load were studied. The experimental results showed that, the hardness decreased as the x‐doses increased. Variation of the microhardness follows the normal ISE trend for low x‐doses and un‐irradiated crystals, then follows the reverse ISE trend for high x‐doses. Analysis of the experimental results revealed that: the radial cracks length, indentation size and applied indentation load are mutually related, and these dependences related with fracture mechanics are the basis of Meyer's empirical law. Indentation size effect (ISE) can be explained satisfactory by Hays‐Kendall's approach and proportional specimen resistance model. Brittleness of two cracks system are applicable for characterizing cracks around indentation impression (i.e. radial cracks) and another is (lateral cracks) for [K_y(NH₄)_1‐y]₂ZnCl₄ mixed crystals, crystals in the load range 60 – 160 g. It is shown that indentation induced microhardness decreases, whereas the length of radial cracks induced on indentation increases with the increase of x‐doses. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects induced by chemical non‐stoichiometry and γ‐irradiation on the habit and unit cell parameters of ammonium tetrachlorozincate

The effect of chemical non‐stoichiometry and γ‐irradiation on the unit cell parameters of ammonium tetrachlorozincate (NH₄)₂ZnCl₄ (A₂ZC₄) has been studied. The unit cell parameters of crystal grown from solution with NH₄Cl/ZnCl₂ molar ratio 1:1, apparently non‐stoichiometrric, are nearly the same as those given for ammonium tetrachlorozincate in the literature. The 2:1 ratio is actually ‘pseudo‐stoichiometric’ due to the hygroscopic nature of ZnCl₂. The unit cell parameters of crystal grown from solution with molar ratio 2:1 match those of the structure (NH₄)₃ZnCl₅ (A₃ZC₅). The habit of the crystal grown in the former case, from solution with excess ZnCl₂, was different from that of the crystal grown in the later case, from solution with excess (NH₄)Cl. Between these two limits, a set of four samples were prepared from solutions with an excess of ZnCl₂ of 20, 30, 60 and 80 wt% in order to detect exact stoichiometric composition to grow A₂ZC₄. Analysis by X‐ray diffraction shows that the first two crystals out of this set are mixed from A₂ZC₄ and A₃ZC₅ The third and fourth crystals still contain traces of A₃ZC₅. Analysis of the X‐ray diffraction was then confirmed by DTA study. Irradiating A₂ZC₄ with γ‐dose of 250 kGy slightly increased the unit cell volume due to imperfections created by irradiation. Two computer programs were used to calculate the lattice constants and the results were compared. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric constant,loss factor and ac conductivity of Ni2+‐doped K2ZnCl4 crystals in the ferroelectric‐commensurate,incommensurate and normal phases

The dielectric constant (ϵ), dielectric loss (tanδ) and ac conductivity (σ_ac) of virgin and thermally cycled undoped and Ni²⁺‐doped K₂ZnCl₄ (KZC) crystals in the ferroelectric‐commensurate (FC), incommensurate (IC) and normal phases (N) have been studied. Anomalous behaviour at the two‐phase transition points was observed while measuring ϵ along the polar a‐axis for the undoped sample. With increasing Ni²⁺concentration a systematic shift of the phase transition temperature towards lower values and a continuous inhibition of the peak height were detected. ϵ changed linearly with lnf up to f =10⁵ Hz. tanδ along the a‐axis declared the phase transitions by peak changes. After Ni²⁺‐doping this behaviour was preserved at the FC‐IC phase transition point while the IC‐N phase transition was manifested by a change in the slope of the straight line representing the tanδ‐T dependence. The ac conductivity changed lineally with frequency according to a relation of the form σ_ac = σ_o f ^β where 0>β>1.9. σ_ac increased monotonically with increasing temperature and doping concentration in the low‐temperature phases tending to merge in one straight‐line with high activation energy that might be due to superionic dc conduction in the high temperature N‐phase. Doping with Ni²⁺ pinned stripples, decreased the soliton‐soliton interaction, weakened discommensuration effects, shortened the IC‐phase and strongly affected the ‘chaotic' behaviour at the T_C‐IC. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation of the structure and properties of (K x (NH4)1 − x )3H(SO4)2 single crystals

The influence of isomorphous replacement in the cation sublattice on the kinetics of the phase transition in single crystals of the solid solutions (K _x (NH₄)_{1 ? x} ) _m H _n (SO₄)_{(m + n)/2} · yH₂O belonging to the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O salt system was studied. Superproton phase transitions for the end compositions of this system have been found earlier. The optical and thermal properties of crystals with the composition (K,NH₄)₃H(SO₄)₂ in the temperature range from 295 to 500 K were investigated, and the crystal structure was determined at 295 K. The results of the study and the comparison with the literature data show that the replacement of potassium atoms with ammonia leads to a fundamental change in the kinetics of the phase transition, the phase-transition temperature remaining virtually unchanged.     

Growth and properties of mixed K2Ni x Co1−x (SO4)2 · 6H2O crystals

Optically homogeneous mixed K₂Ni _x Co_{(1 ? x)}(SO₄)₂ · 6H₂O crystals are grown from solutions of different compositions by the temperature-reduction technique in static and dynamic regimes. The optical characteristics of the grown crystals are measured: transmittance reaches 80% in the wavelength range of 240–290 nm and no more than 9% in the visible spectral range. The thermal stability of the crystals is studied. It is established that the thermal stability of mixed K₂Ni _x Co_{1 ? x} (SO₄)₂ · 6H₂O crystals is higher than that of K₂Co(SO₄)₂ · 6H₂O crystal. The defects of the mixed crystals grown in static and dynamic regimes are investigated by X-ray topography.     

Physical Properties of K2ZnCl4

Large single crystals of orthorhombic K₂ZnCl₄ with optical quality have been grown by the Czochralski method. The elastic constants and their temperature and pressure derivatives have been determined from ultrasonic resonance frequencies of thick plates of different orientation and the shift of these frequencies induced by temperature and pressure changes, respectively. K₂ZnCl₄ shows a small elastic anisotropy. Measurement of the dielectric constant was made along the ferroelectric axis ε_a in the temperature from 303 K to 573 K. ε_a of K₂ZnCI₄ grown by the Czochralski-method shows a smaller thermal hysteresis at the incommensurate-commensurate transition point (403 K) than that of crystals grown from an aqueous solution. It explains that crystals grown by the Czochralski-method are more purified, the pinning effect is weakened. The thermal hysteresis occurs with the same width at 10 KHz, 100KHz, 1 MHz and 10 MHz.     

Investigation of the structural conditionality for changes in physical properties of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

With the aim of elucidating the nature of anomalies in the physical properties of K₃H(SO₄)₂ crystals that arise as the temperature grows, the dielectric and optical properties of the crystals are studied, an X-ray diffraction analysis of single-crystal and polycrystalline specimens are performed, and the morphology and chemical composition are studied by scanning electron microscopy and energy-dispersive X-ray spectroscopy. As a result of the studies performed, a phase transition from the phase with the monoclinic symmetry (space group C2/c) to the phase with the trigonal symmetry (space group R $ \bar 3 $ \bar 3 m) is found in a number of K₃H(SO₄)₂ specimens at a temperature of ≈457 K, the responsibility of the dynamically disordered hydrogen-bond system for the rise of high proton conductivity in the high-temperature phases of the crystals of this family is confirmed, and data on the solid-phase reactions proceeding at high temperatures are obtained.     

Preparation and studies of new crystals in the K3H(SO4)2-(NH4)3H(SO4)2-H2O system

To elucidate the effect of isomorphic substitution on the kinetics of phase transitions, single crystals of (K _x (NH₄)_1?x ) _m H _n (SO₄)_{(m + n)/2} · yH₂O solid solutions are grown from the K₃H(SO₄)₂-(NH₄)₃H(SO₄)₂-H₂O system, whose end members are known to undergo superprotonic phase transitions of fundamentally different kinetics. The chemical composition of the single crystals grown is determined by energy dispersive X-ray microanalysis. The thermal and optical behavior of (K,NH₄)₉H₇(SO₄)₈ · H₂O single crystals is studied in the temperature range 295–420 K and the crystal structure at 295 K is determined. A comparison of the results of the studies with data for crystal K₉H₇(SO₄)₈ · H₂O published earlier shows that the substitution of ammonium for potassium atoms lowers the temperature of the structural phase transition by 8 K.     

Synthesis and properties of zirconium-doped RbTiOPO<Subscript>4</Subscript> single crystals

Single crystals of the solid solutions RbTi_{1 ? x} Zr _x OPO₄ (0.015 < x < 0.034) were grown and their physical properties were studied. In the presence of zirconium in the crystals with the maximum content x = 0.034, the ferroelectric phase transition and the high-temperature transition from the orthorhombic to the cubic phase are shifted to lower temperatures by 100 and 50°C, respectively. In the temperature range from 700°C to room temperature, the conductivity of doped crystals decreases compared to that of the undoped crystals. It is of particular interest that the intensity of the second-harmonic generation of the doped crystals is substantially higher than that of RbTiOPO₄.     

Neutron studies of the structure and dynamics of Rb1 − x (NH4)xI mixed crystals

The structural and dynamical properties of the x-T phase diagram of the system of Rb_{1 ? x} (NH₄)_xI mixed crystals is of great interest, because such solid solutions are almost free of internal stresses due to almost equal ionic radii of ammonium and rubidium. The x-T phase diagram of Rb_{1 ? x} (NH₄)_xI is studied on samples with ammonium concentration ranging from 0.01 to 0.73 over the temperature range from 15 to 300 K by the methods of powder neutron diffraction and inelastic incoherent neutron scattering. The results obtained by powder neutron diffraction show that the α-β phase transition at low temperature is rather extended and occurs at the ammonium concentrations x = 0.50 and 0.66. The region of orientational state glass is determined by inelastic incoherent neutron scattering at the concentrations x = 0.29 and 0.40 at the temperature T = 20 K.     

Synthesis,properties, and structure of potassium titanyl phosphate single crystals doped with hafnium

Single crystals of potassium titanyl phosphate doped with hafnium are grown by spontaneous flux crystallization. Their physical properties are studied, and the structure of three KTi_{1 − x} Hf _x OPO₄ crystals (x = 0.01, 0.03, and 0.12) is determined. In the crystals studied, hafnium mostly occupies the second titanium position. The doping of KTP crystals with hafnium results in an elongation of K-O bonds in the potassium polyhedra and, as a consequence, in a considerable (by approximately 180°C) decrease in the temperature of ferroelectric phase transition. The magnitude of anomalous permittivity substantially decreases. The electrical conduction in the specimens studied decreases by approximately half an order of magnitude in the low-temperature region but remains almost unchanged in the high-temperature region. Even at minor concentrations, the presence of a hafnium additive in the specimens considerably (by 35%) enhances the intensity of the second harmonic generation of laser radiation.