FTIR and X-ray study of polymorphs of nylon 11 and relation to ferroelectricity

Nylon-11 polymorphs have been studied by x-ray diffraction and by infrared spectroscopy. A γ or γ-like phase of Nylon-11 was produced by treating the metastable δ' phase with gaseous HCl or DCl and then exposing the resulting complex (amidonium salt) to 100% RH H₂O or D₂O vapor. An oriented form of the γ or γ-like phase results from treatment of the oriented δ' phase, but stretching of the unoriented γ or γ-like phase, obtained by treatment of the unoriented δ' phase, induces a transformation to the α phase stable at room temperature. The use of DCl and D₂O produced highly deuterated samples with Fermi resonances indicating the relative strengths of the hydrogen bonds are weakest in the α phase, intermediate in the δ' phase and strongest in the γ or γ-like phase. © 1994 John Wiley & Sons, Inc.     

Isothermal cross-section of phase equilibria diagram of Cr-Nb-Re system at 1375 K

An isothermal cross-section of phase equilibria diagram of Cr-Nb-Re system has been constructed at 1375 K using the method of equilibrium alloys and diffusion couples. The existence of four triphase equilibria has been established in the Cr-Nb-Re system at 1375 K, including σ + λ + β-Cr; χ + β-Nb; σ + χ + λ; and α-Re + χ + σ.     

The compounds and the phase diagram of MoO3-Rich Bi2O3MoO3 system

The equilibrium phase diagram between 0 and slightly above 50 mole% Bi₂O₃ in the Bi₂O₃MoO₃ system has been studied by differential thermogravimetric analysis (DTA) and X-ray diffraction measurements on fused mixtures and single crystals. The results confirm the existence of the four compounds α (Bi₂O₃·3MoO₃), β (Bi₂O₃·2MoO₃), γ (Bi₂O₃·MoO)₃ and ? (～1.3Bi₂O₃·MoO₃) in the system. However, the phase diagram as well as the nature of melting of the α and γ were found disagreed with previous results. The γ compound melts incongruently at 947°C, whereas the α compound melts congruently at 662°C. The crystal class and lattice parameters of the compounds were determined based on the single crystal as well as powder pattern techniques. The results show that all four compounds have the monoclinic structure. The unit cell parameter of the β, γ, and ? compounds were found to be quite different from previously reported data. The lattice parameters obtained from X-ray analysis were also verified by density measurements of the single crystals. The polymorphism of the compounds was also investigated with single crystal samples. No polymorphic transformations for the α, β, and γ phases were detected in the work.     

Phase equilibria in Al-Ni-Zr system at 1123 K

Phase equilibria in ternary Al-Ni-Zr system have been studied using X-ray phase and electron probe microanalyses at 1123 K in the content range of 0–45 at % Al. A fragment of the isothermal section of this system has been plotted. The existence of three-phase equilibria Zr₇Ni₁₀ + Zr₈Ni₂₁ + Zr₂Ni₇, τ₂-ZrNi₂Al + NiAl + Zr₂Ni₇, NiAl + Ni₃Al + Zr₂Ni₇, Zr₇Ni₁₀ + Zr₂Ni₇ + τ₂-ZrNi₂Al at 1123 K has been established for the first time. Phase based of binary compound Zr₂Ni₇ dissolves up to 13 at % aluminum. The crystalline structure of the τ₇-Zr₅Ni₄Al phase has been determined, including structure type U₃Si₂, spatial group P4/mbm (a = 7.1852(7) Å, c = 3.3019(5) Å).     

Electrical conductivity and phase transitions of the solid electrolyte system (Cs1−yRby)Cu4Cl3(I2−xClx)

Results of electrical conductivity measurements, thermal analysis, and X-ray diffraction studies indicate the existence of four phases, between 295 K and the melting points, in the system (Cs_1?yRb_y)Cu₄Cl₃I₂. These phases are designated α, á β, γ in order of decreasing temperature. The α phase is isostructural with α-RbAg₄I₅; the á phase is also cubic and very likely belongs to space groupP2₁3, a subgroup ofP4₁32 andP4₃32 to which the α phase belongs. There is a high probability that the á → α transition is continuous. The á → α transition is not discernible in the conductivity measurements or thermal analysis; therefore the line of á-α transitions is presently unknown. The β phase transforms to the á and the γ phase transforms to the β phase wheny ≤ 0.36; the γ phase transforms to the α phase wheny ≥ 0.36. That is, there is a triple point aty = 0.36, T = 399K. The γ-β, β-α′, and γ-α transitions are all hysteretic and are therefore first order. The conductivities of the β phases are relatively low and the enthalpies of activation relatively high. The conductivity of the β phase decreases with increasingy. The β phase probably belongs to space groupR3, in which the Cu⁺ ions can be ordered. The α and á phases are the true solid electrolytes; the conductivities are high, >0.73 Ω^?1cm^?1 at 419 K, and the enthalpies of activation of motion of the Cu⁺ ions low, 0.11 eV.In the system CsCu₄Cl₃(I_2?xCl_x), 0 ≤ x ≤ 0.25, the Cl^? for I^? substitutions affect the transitions to only a small extent relative to the stoichiometric compound. The β phase occurs for allx and transforms to á.     

Phase formation of BICUVOX solid solutions

Phase formation of Bi₄(V_{1 ? x} Cu _x )₂O_{11 ? z} solid solutions (BICUVOX) with x = 0.00–0.20 and Δx = 0.02 was studied. The concentration stability ranges were determined for the α, β, and γ polymorphs of BICUVOX solid solutions at room temperature, and their unit cell parameters were revised. The following was found to occur as x rises: the α ai β phase transition temperature between the monoclinic and orthorhombic phases shifts down, the β ai γ phase transition temperature to the high-temperature tetragonal phase shifts down, and the order-disorder phase transition temperature between γ′ ai γ tetragonal phases shifts up.     

Isothermal section of phase-equilibria diagram of Cr-Ta-Re system at 1375 K

The isothermal section of the phase-equilibria diagram of the Cr-Ta-Re system at 1375 K has been constructed by means of equilibrium alloys and diffusion couples methods. Four three-phase equilibria have been established in the Cr-Ta-Re system at 1375 K, including α-Re + σ + χ, χ + σ + β-Ta, σ + β-Ta + β-Cr and β-Cr + β-Ta + λ.     

Zur Kenntnis einer modifizierten Form des β-CuNdW2O8-Typs: γ-CuTbW2O8

On a Modified Form of the β-CuNdW₂O₈ Type: γ-CuTbW₂O₈ Single crystals of γ-CuTbW₂O₈ were prepared by flux in closed copper tubes. X-ray investigations show triclinic symmetry, space group C-P1 , with a = 6.722, b = 9.831, c = 15.352 Å, α = 72.82, β = 88.53, γ = 71.76°, Z = 6. γ-CuTbW₂O₈ is closely related to β-CuNdW₂O₈. One significant difference can be seen in an alternate staggered location of Tb³⁺ ions along [110].     

Polymorphisme du sulfate de thallium(I), Tl2SO4

X-Ray and DTA techniques were employed to study the thermal and structural characteristics of thallium(I) sulfate. By means of heat treatment, it has been found to evolve successively from a γ-monoclinic phase, through four (β₁, β₂, β₃, β₄) orthorhombic phases to an α-trigonal phase. According to the preparation method at room temperature, this compound can be obtained in γ or β₁ or β₂ form or in a mixture of these three phases. The predominance of one of these three forms and the reversibility of some modifications are strongly influenced by crystal size.     

The site preference and doping effect on mechanical properties of Ni3Al-based γ′ phase in superalloys by combing first-principles calculations and thermodynamic model

The fundamental aspects of site preference of alloying elements on sublattice of the strengthen γ′ phase with L1₂ structure have not been well understood, which hinders the optimized design of advanced Ni-based high-temperature alloys. In this contribution, the temperature- and composition-dependent site occupying preferences of the binary, ternary, and quaternary of Ni₃Al-based γ′ phase alloyed with M_i where M_i represents the additional transitional metals Co, Cr, Cu, Fe, Mn, Mo, Re, Ta, Ti, V, or W atoms (arranged in alphabetical order) chosen frequently, were studied using a two-sublattice thermodynamic model (Ni, Al, M_i)_1a(Ni, Al, M_i)_3c. The site occupying fractions (SOFs) were calculated based on a thermodynamic database established in this work, where the thermodynamic data of the end-members involved were obtained using first-principles calculations and phonon spectrum calculations. The calculated SOFs results show that there is an obvious site preference for stoichiometry binary Ni₃Al, and its site configuration changes from (Al)_1a(Ni)_3c at room temperature to (Al_0.9984Ni_0.0015)_1a (Al₀Ni_0.9994)_3c at 1273 K. For the γ′ phase with the composition 78Ni-26Al-4M_i (atom ratio and x_Ni/x_Al = 3:1), Mo atoms always preferred to occupy the 1a sublattice (Al site), Co, Mn, and Ti atoms always prefer the 3c sublattice (Ni site) in the whole temperature range, while the site preference of Cr, Cu, Fe, Re, Ta, V, or W atom is affected by temperature. For example, when the heat treatment temperature is lower than 700 K, Cr, Cu, Fe, Ta, V, and W atoms occupy the 1a and 3c sublattice randomly, and Re atoms prefer to 3c sublattice, while when the heat treatment temperature is higher than 1273 K, Cr, Cu, and W atoms prefer 3c sublattice, Fe and Ta atoms prefer to 1a sublattice, while all Re atoms occupy the 3c sublattice exclusively, and all V atoms occupy the 1a sublattice exclusively, respectively. Likewise, the site preference of the quaternary system with selective compositions 78Ni-26Al-2 M₁-2 M₂ was also predicted. Based on calculated SOFs results, the mechanical and thermodynamic properties were studied at the ground state. It has been revealed that Cr, Re, and V doping can improve the microhardness of Ni₃Al alloys; in particular, the effect of Cr is extraordinary; and all elements, except Mn, Mo, and Ti, would enhance the bulk modulus of Ni₃Al-based γ′ phase, in which Mn have the greatest influence on reducing the bulk and shear modulus, respectively. Furthermore, all the B/G ratios of the computed Ni₃Al-based γ′ phase are >1.75, showing inherent ductility. Only Cr doping significantly enhances the Debye temperature of the Ni₃Al-based γ′ phase.     

Electronic structure and chemical bonding in oxygen conductors β-Bi4V2O11 and γ-Bi4V2O11

Ab initio calculations of the electron density are fulfilled for bismuth vanadate polymorphs: β-Bi₄V₂O₁₁ and γ-Bi₄V₂O₁₁. A semiconductor-type spectrum is obtained for both phases. The calculated bandgap value decreases in the direction from the β to γ phase. Chemical bond analysis shows an increase in the strength of covalent interactions in the series of Bi-V, Bi-O, and V-O bonds. The V-O bond strength in β-Bi₄V₂O₁₁ is appreciably higher than in the γ phase. The relatively weak binding of oxygen in the tetragonal structure of γ-Bi₄V₂O₁₁ confirms the possibility of easier oxygen transport in the γ phase than in the β phase. The stability of the bismuth vanadate polymorphs and the oxygen-disorder features in the γ-Bi₄V₂O₁₁ structure are discussed using the results of calculation of the total energies of the phases. Bond overlap population analysis explains the existence of the homogeneous range and the feasibility of doping β-Bi₄V₂O₁₁ and γ-Bi₄V₂O₁₁. The possibility of using four-and five-charged d cations as stabilizers of the crystal structure of bismuth vanadates is discussed.     

Comparative study of dielectric,mechanical, and nuclear magnetic relaxations of linear polyethylene. I. Broad-line NMR investigation of the fine structure of the α and γ loss bands observed by dielectric and mechanical measurements

Detailed investigation of the linewidth, second moment, and mobile fraction by straightline decomposition of NMR spectra of linear polyethylene from ca. ?160 to ca. 100°C reveals five molecular processes denoted γ₁, γ₂, β, α′, and α. Relaxation maps show that the γ₁, γ₂, and β processes correspond to the dielectric and mechanical relaxations given the same names, while the α and α′ processes correspond respectively to the mechanical α₂ process due to molecular motion in the interior of crystals and to the dielectric α process. Close relations are found between the mass fractions of protons for the γ₁ and β processes and also between those for the γ₂ and α′ processes. From the effects of diluent on these processes and the annealing-time dependence of mass fractions of protons, the γ₁, and β processes are attributed to two modes of molecular motion in an interlamellar amorphous region, while the γ₂ and α′ processes are attributed to motions in the lamellar surface layers. The surface-layer thickness obtained by applying the two-phase model for the data on mobile fraction agrees quite well with that reported in the literature. The Bergmann–Nawotki three-component analysis of NMR spectra and symmetric-line decomposition for determining mobile fraction are shown to be unsuitable for studying the fine structure of the α and γ loss bands.     

Thermal analysis and X‐ray scattering study of metallocene isotactic polypropylene prepared by partial melting

In this study, we examine the effects of heating, nucleation, cooling, and reheating on the thermal properties and structure of metallocene isotactic polypropylene (m‐iPP) that had been prepared initially in a standard state containing nearly equal amounts of the crystallographic α and γ phases. Heat treatment was achieved through partial melting and annealing by the heating of samples to self‐nucleation temperatures (T_n's) that spanned and exceeded the entire range of melting of the standard state, from 122 to 160 °C. The relative amounts of α and γ crystals are determined from the area under the unique wide‐angle X‐ray reflections. The lower and upper endotherms are caused by the melting of γ and α crystals, respectively. Four distinct regions of T_n were identified on the basis of the thermal and structural parameters of m‐iPP. In region I, T_n is below the peak melting temperature of the γ phase. Here, γ crystals are annealed and α crystals are barely affected by T_n. In region II, T_n is above the peak of the lower endotherm but below the peak of the upper endotherm. γ crystals melt, and α crystals anneal. In both regions I and II, the portion of the sample melted at T_n recrystallizes epitaxially with existing parent α lamellae as the substrates, and the amount of α always exceeds the amount of γ. In region III, T_n is above the peak of the upper endotherm, and all γ crystals and some or all α crystals are melted at T_n. The number of α‐crystal nuclei steadily decreases as T_n increases, causing systematic depression of the crystallization and melting temperatures seen during cooling. Finally, in region IV, T_n exceeds the upper endotherm, and only small self‐nuclei or heterogeneous nuclei remain. Recrystallization is now suppressed to lower temperatures. For regions III and IV, a crossover behavior in the relative amounts of α and γ is observed during cooling from T_n. Because of the effective nucleating ability of α toward γ, as the temperature drops, the amount of γ increases and then exceeds the amount of α. With subsequent reheating, the reverse crossover occurs because of the lower melting point of γ. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1644–1660, 2002     

On the existence of pyrophosphates of tetravalent metals having a layered structure

After an accurate investigation of the thermal behaviour (TG and DTA curves) of several samples of α-Zr(HPO₄)₂·H₂O and α-Ti(HPO₄)₂·H₂O, prepared both by the refluxing and HF procedures, γ-Zr(HPO₄)₂·2 H₂O and γ-Ti(HPO₄)₂·2 H₂O, new pyrophosphate phases of tetravalent metals have been isolated.The structure of these compounds, deduced from X-ray diffraction data, density measurements and considerations of bond length and angles, arises from the packing of layers of α and γ type, identical to those present in the starting materials and held together by POP bridges.These layered M(IV)P₂O₇ are obtained after the condensation process of the HPO₄ groups present in α and γ-M(IV)(HPO₄)₂ and are stable until the transition to the respective cubic pyrophosphates takes place.The range of stability of these phases changes on going from the α to the γ phase and in part depends on the degree of crystallinity and/or the crystal size of the starting layered exchanger. The chemical implications of α- and γ-L-M(IV)P₂O₇ are examined and discussed.     

Interaction between Cr2Se3 and Cu2GeSe3

The interaction along the Cu₂GeSe₃-Cr₂Se₃ join has been investigated using differential thermal and X-ray powder diffraction analyses. It has been found that the join is quasi-binary with a degenerate eutectic based on the Cu₂GeSe₃ compound. Two new quaternary compounds have been found along the join, namely, Cu₂GeCr₆Se₁₂ and the γ phase. The phase is formed at 915°C by the peritectic reaction L + β-Cr₂Se₃ = γ and has the primary crystallization region up to 9 mol % Cr₂Se₃ in the temperature range 758–915°C. The room-temperature homogeneity range of the γ phase is 65–70 mol % Cr₂Se₃. The Cu₂GeCr₆Se₁₂ compound is formed by the peritectoid reaction γ + β-Cr₂Se₃=Cu₂GeCr₆Se₁₂ at 880°C, and its homogeneity range is 73–79 mol %. The X-ray reflections of the γ phase are indexed for the tetragonal crystal system with the unit cell parameters a = 12.043 Å and c = 9.180 Å. Samples with ferromagnetic properties are found in the homogeneity regions of both compounds.     

Study of the molecular mobility of collagen

The dielectric relaxations of a biopolymer, collagen, have been studied by means of the thermally stimulated current (TSC) technique. To investigate effects of water on TSC spectra, complementary measurements by differential scanning calorimetry (DSC) have been performed. In dehydrated collagen, three spectral bands were recorded in the temperature range of -180-60°C, labelled α, β₁, and γ in the order of decreasing temperature. The TSC spectrum of hydrated collagen exhibits a supplementary band labelled β₂. By using the fractional polarization method, the γ and β₁ modes have been attributed to localized movements of nonpolar (apolar) sequences and polar sequences, respectively. The α mode has been associated with delocalized movements of the collagen macromolecules. Finally the β₂ mode has been attributed to reorientations of bound water molecules inside the collagen fibers. © 1995 John Wiley & Sons, Inc.     

Electrical properties of the α, β, γ, and δ phases of bismuth sesquioxide

Conductivity measurements have been performed on compressed powder specimens of Bi₂O₃ in the temperature region 300–800°C. The conductivity in the β, γ, and δ phases is predominantly ionic. Oxide ions are the mobile charge carriers. The disorder in these phases is intrinsic even when the samples are contaminated with Au or Pt. The conductivity in the α phase is predominantly p type. The disorder in the α phase is extrinsic up to the α → δ transition at 729°C. From 650 to 729°C a rapidly increasing contribution of oxygen vacancies to the conductivity is apparent.     

About SnF2 stannous fluoride. IV. Kinetics of the α → γ and β, γ → α transitions

The kinetics of the reconstructive first order phase transitions α → γ (upon heating) and β, γ → α (upon cooling) of SnF₂ were studied by quantitative X-ray powder diffraction. The main feature of the kinetics is that these transformations are incomplete over a wide temperature range. Consequently it is not possible to fit the experimental data using the usual solid state rate expressions. Although these transitions are not reversible (large hysteresis) the empirical use of a kinetic model of a reversible transformation provides a good fit. The α → γ transformation was also investigated by D.T.A.; this transition was found to be greatly influenced by particle size: the transition temperature increases with grain size, and its enthalpy decreases. The X-ray investigation revealed that the process of the α → γ transformation involves an intermediate noncrystalline phase named the “transition phase.” It is suggested that the transition proceeds through a process of fragmentation-reconstruction.     

Structural and thermal characterization of the γ″ polymorph of Bi2MoO6

Among the different polymorphic phases of the Bi₂MoO₆ system, the intermediate γ″ compound has been characterized within a metastable state by high temperature X-ray diffraction and Raman spectroscopy. The transition γ ? γ″ is found to be partially displacive and partially reconstructive. In the context of the ferroelectricity of γ, the nature of the paraelectric phase is discussed with the help of space group considerations and Buerger's theory of phase transitions.