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)     

Elastic and elasto‐optical properties of Rb1–x(NH4)xH2AsO4 mixed crystals studied by Brillouin spectroscopy

The elastic and elasto‐optical properties of Rb_1–x (NH₄)_x H₂AsO₄ mixed crystals were studied by Brillouin spectroscopy at room temperature. The measurements were made on single crystals obtained from the aqueous solution by slow evaporation. The behaviour of bulk phonons propagating in investigated crystals was studied for different polarisations of incident and scattered beam. The components of the tensors of elasto‐optical and elastic properties of the crystals studied were determined. (© 2010 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)     

Structural,optical and dielectric studies on K1‐x(NH4)xH2PO4 mixed crystals grown from z‐cut seeds

Mixed crystals of K_1‐x(NH₄)_xH₂PO₄(KADP) were grown from KDP (KH₂PO₄) dominated mixed solutions with varying molar proportion of ADP (NH₄H₂PO₄) addition. It was found that, as the increase of ADP molar concentration, the growth rate along z‐axis of KADP crystal decreased rapidly. The structure of KADP crystals was investigated by powder XRD and the lattice parameter was calculated. The results showed that the lattice parameter c of KADP crystal increased with the molar concentration of ADP. The optical homogeneity of grown KADP crystals was determined with a differential phase‐shifting interferometry. Frequency dependences of the dielectric constant and dielectric loss of KADP crystals were measured at room temperature (290 K). The dielectric constants of KADP crystals were almost invariant with the increase of frequency. In the region of 10²∼10⁴Hz, the values of the dielectric loss reduced with the increase of frequency. The piezo‐resonance coupling effect still exists in KADP crystals at room temperature, but shifted to low frequency band. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of undoped,Sr2+‐, and Mn2+‐doped ammonium tetrachlorozincate

Crystals of ammonium tetrachlorozincate (AZC) undoped and doped with Sr²⁺ or Mn²⁺ in different concentrations were grown by the slow evaporation method from an aqueous solution. The crystal morphology changed considerably by doping. The dopant concentration in the crystals was measured by the atomic absorption technique. Slight changes in the unit cell parameters of AZC after doping with Sr²⁺‐ or Mn²⁺ have been detected. Optical absorption measurements indicated strong influence of Sr²⁺ and Mn²⁺ doping. The optical energy gap at room temperature decreased continuously with increasing Sr²⁺ and Mn²⁺ concentration but with two different rates. The dc conductivity was also measured as a function of temperature for the undoped and two samples doped with 0.144 Sr²⁺ and 0.191 Mn²⁺ and the results were compared. Positions possibly occupied by Sr²⁺ and Mn²⁺ cations in AZC lattice have been identified. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Temperature dependence of the crystal-optics characteristics of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript>:Ni<Superscript>2+</Superscript> crystals with correlated motion of tetrahedral groups

The optical birefringence, optical indicatrix rotation, and residual intensity have been experimentally investigated in the parent and incommensurate phases of [N(CH₃)₄]₂ZnCl₄ crystals doped with Ni²⁺. The temperature dependences obtained are nonlinear in a wide temperature range (T _i − 360 K). It is shown that the nature of this nonlinearity is related to the presence of local spatial regions of the correlated motion of tetrahedral groups. It is established that the deformation of tetrahedral groups increases the temperature range of existence of these regions.     

Growth of Nd:Sr3Ga2Ge4O14 crystals by a modified Bridgman method

Bridgman growth of Nd:SGG (Sr₃Ga₂Ge₄O₁₄) crystals has been investigated for the first time. Pt crucible of ∅︁25mm×250mm with a seed well of ∅︁10mm×80 mm is used, and seed is SGG crystal of ∅︁10mm×50mm grown by Bridgman method in advance. The growth parameters are optimized as the furnace temperature is set to 1450∼1500°C, temperature gradient in the crystal‐melt interface is less than 25 K/cm and growth rate is less than 0.5mm/h. The Nd:SGG crystals with 25mm in diameter and 60mm in length are grown successfully from 1.5 to 8at% Nd³⁺ doped stoichiometric Sr₃Ga₂Ge₄O₁₄ melt. The distribution coefficient and concentration of Nd³⁺ in Nd:SGG crystals are obviously higher than those of Nd:YAG crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Self‐diffraction and edge enhanced effect in the photorefractive crystal (Ca0.28Ba0.72)0.75(Sr0.60Ba0.40)0.25Nb2O6

The optical properties based on Self‐diffraction phenomena and the edge enhanced of optical correlation pattern effect with a Ca²⁺‐doped (Ca_0.28Ba_0.72)_0.75(Sr_0.60Ba_0.40)_0.25Nb₂O₆ (CSBN₇₅) crystals and a He‐Ne laser at 632.8 nm are studied in this paper. The experimental results show that its practical application as photorefractive material is worth further investigation. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth kinetics and micromorphology of NH4Cl:Mn2+ crystals formed in the NH4Cl-MnCl2-H2O-CONH3 system

The growth kinetics and elementary growth processes on the surface of NH₄Cl:Mn²⁺ heterogeneous crystals formed in the NH₄Cl-MnCl₂-H₂O-CONH₃ system are experimentally studied. It is found that a change in the composition of complexes in an NH₄Cl crystal from Mn(NH₄)₂Cl₄ · 2H₂O to MnCl₂ · 2CONH₃ leads to the occurrence of a local maximum in the kinetic curve and a change in the shape of dislocation growth centers from flat to conical. The growth kinetics of {100} faces of heterogeneous NH₄Cl:Mn²⁺ crystals is described within the Bliznakov model using the Fowler-Guggenheim adsorption isotherm, which takes into account the lateral interaction of adsorbed particles.     

Crystal structure of the binary complex of cobalt and zinc chlorides with carbamide [Co(OCN<Subscript>2</Subscript>H<Subscript>4</Subscript>)<Subscript>5</Subscript>(H<Subscript>2</Subscript>O)][ZnCl<Subscript>4</Subscript>]

Mixed single crystals of [Co(OCN₂H₄)₅(H₂O)][ZnCl₄] were grown by the isothermal evaporation of an aqueous solution. The crystal structure of this complex was established by X-ray diffraction (R = 0.052 based on 7003 reflections). The crystals consist of [Co(OCN₂H₄)₅(H₂O)]²⁺ cations containing Co atoms in an octahedral coordination and [ZnCl₄]²⁻] anions containing Zn atoms in a tetrahedral coordination. The carbamide molecules are involved in both intramolecular and interionic hydrogen bonds. The H₂O molecule forms hydrogen bonds with the anions.     

Transport Properties of (NH4)2 CuCl4.2H2O Low Dimensional Single Crystals

The X‐ray diffraction and Infrared (IR) spectral studies of (NH₄)₂ CuCl₄.2H₂O single crystals reveals that these crystals contains tetragonal crystal structure with the unit cell dimensions of a = 7.58Å, c = 7.95Å, z= 2, β =90° and two water molecules in the unit cell. The temperature dependence of thermally stimulated depolarization current (TSDC) and dc electrical conductivity (σ) studies of this two‐dimensional (NH₄)₂ CuCl₄.2H₂O single crystal have been carried out in 77K–300K temperature region. The TSDC thermograph shows only one sharp peak at 248K with a peak current of 130nA, which is attributed to the Maxwell‐Wagner peak. The activation energy (U), relaxation time (τ) are calculated as 0.78eV and 3.44×10^‐15 s respectively. Dc electrical conductivity studies of these crystals show a first order phase transition at about 248K.     

Stable and transient color centers in Gd3Ga5O12 crystals

The work is devoted to investigation of stable color centers (CC) that are created in Gd₃Ga₅O₁₂ (GGG) crystals under irradiation with γ-quanta (E = 1.25 MeV, D = 10⁵ Gy ) as well as transient CC created in the crystals under irradiation with pulsed electron beam (E = 0.25 MeV, pulse duration 10 ns, fluence 10¹² cm^-2, time interval of registration 0-500 ns). On the basis of the performed study of optical absorption spectra of the as-grown and irradiated crystals it was established the correlation between a defect subsystem of as-grown crystals and a type of CC induced by radiation in the crystals. The role of Ca²⁺ dopant ions in the processes of CC formation is examined. Models of the stable and transient CC are proposed. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical and experimental study on the conoscopic interference in uniaxial crystal (Ca0.28Ba0.72)x(Sr0.60Ba0.40)1‐xNb2O6

Conoscopic interference of polarized light for the white‐light and LPS‐7,5Volts direct current semiconductor laser (Green light) with wavelength at 532 nm in (Ca_0.28Ba_0.72)_x(Sr_0.60Ba_0.40)_1‐xNb₂O₆ crystals were observed with the beams transmitting along optical‐axes and deflection optical‐axes from 0 to 140°. Endo‐exo variation from looseness to tightness of conoscopic interference patterns were analyzed in theory. A hyperbolic black cross of interference patterns were observed as well as its formation process was proposed in this paper. Also, the inferences of the birefringence with different Ca²⁺‐doped were obtained in this investigation. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Crystallization of PbxSr1‐x(NO3)2 Solid Solutions from Aqueous Solutions

A series of Pb_xSr_1‐x(NO₃)₂ crystals have been grown from aqueous solutions and characterized by X‐ray powder diffraction. All diffraction data were well indexed according to the simple cubic structure. The variation of lattice constants with the concentrations of Pb²⁺ in the crystals accorded quite well to the Vegard's Law. The composition of the Sr(NO₃)₂ crystal doped with Pb²⁺ was studied by electron microprobe and it was found that Pb²⁺ was enriched in the 111 sectors. Equilibrium behavior in the Pb(NO₃)₂‐Sr(NO₃)₂‐H₂O system was analyzed by Lippmann's phase diagram and the equilibrium distribution coefficient D_Pb=133.6. This large value of D indicates that Pb²⁺ ion is preferentially distributed to the solid phase.     

Contribution to the study of elastic properties of KGd(WO4)2:Er3+ single crystals by Brillouin spectroscopy

In this paper we present the study of the acoustic phonons propagating in Er³⁺‐doped KGd(WO₄)₂ single crystals by Brillouin spectroscopy. For the investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101] and [110] have been determined. Moreover, the values of the elastic constants: C₂₂, C₄₄ and C₆₆ of Er³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Er³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% does not influence their elastic properties. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Elastic properties of KGd(WO4)2:Ho3+ single crystals studied by Brillouin spectroscopy

The analysis some of the acoustic phonons propagating in pure and Ho³⁺‐doped KGd(WO₄)₂ single crystals in the GHz frequency range by Brillouin scattering method has been presented. For investigated crystals the velocities of the longitudinal and transverse acoustic phonons [100], [010], [001], [101], [101] and [110] have been determined. Moreover, the value of elastic constants C₂₂, C₄₄ and C₆₆ of pure and Ho³⁺‐doped KGd(WO₄)₂ single crystals have been estimated. It was revealed that the presence of the Ho³⁺‐ions in KGd(WO₄)₂ crystals, for the used doping concentration 1 at% and 8 at%, does not influence their elastic properties. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Internal stress in doped NH<Subscript>4</Subscript>Cl:Mn<Superscript>2+</Superscript> crystals

The relationship of the effect of impurity on crystal growth and morphology, along with the internal stress and anomalous birefringence arising upon impurity trapping by a growing crystal, is considered. The NH₄Cl-MnCl₂-H₂O-CONH₃ model system and the heterostructural NH₄Cl:Mn²⁺ crystals formed in it are experimentally studied. It is found that up to 6.63 wt % Mn²⁺ impurity is effectively captured by growing NH₄Cl crystals at an impurity trapping coefficient only slightly below unity. The effect of Mn impurity stabilizes the full-face growth of NH₄Cl crystals with a rhombododecahedral habit in aqueous solutions and a cubic habit in water-formamide solutions. The trapping of manganese impurity by ammonium chloride crystals causes high internal stress (up to 4 GPa) in them, which manifests itself in the form of anomalous birefringence and leads to splitting, twinning, and cracking in NH₄Cl crystals.     

Spectroscopic and Transport Properties of (NH4)2CuCl4 · 2 H2O Single Crystal

Electron paramagnetic resonance (EPR), Optical absorption and Transport properties of (NH₄)₂CuCl₄ 2 H₂O single crystals have been studied. An anisotropic g tensor was observed with gl = 2.241 and g∥ = 2.081 by EPR method. The spin orbit coupling constant is found to be 540 cm⁻¹. The optical absorption in UV region are characterized by charge transfer band, in the visible and near infrared region at 13,333, 4,480, 4,336, and 3,998 cm⁻¹ attributed to the transitions between the (d-d) stark energy levels of the copper (II) ion in an extended octahedral crystal field. Dc electrical conductivity measurements with temperature reveal an anisotropic characteristic of a two-dimensional layered structure, and exhibits two first order structural phase transitions at about 383 K and 413 K. These transitions are attributed to loss of the two water inolecules of hydration and free rotation of NH⁺₄ ion from a state of torsional oscillation.     

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)