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.     

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     

Phase equilibria at 1375 K in three-component system of nickel-chromium-tantalum

The isothermal section of the phase equilibria diagram of the Ni-Cr-Ta system has been constructed at 1375 K by means of the method of equilibrium alloys and existence of six three-phase equilibria has been established, including γ-Ni + β-Cr + α; β-Cr + α + γ; α + γ + Ni₂Ta; γ + Ni₂Ta + μ; μ + γ + NiTa₂ and γ + NiTa₂ + β-Ta. It is shown that both cubic and hexagonal modifications are indicated in Laves binary phase.     

The mechanism of the heterogeneous catalysis of α and γ-cyclic six-membered aminoketones

On the basis of catalytic deuteration of cyclic α and γ -aminoketones in 1-2N DCl/D₂ or H₂, in the presence of PtO₂, it is assumed that the mechanism of heterogenous catalysis for both classes of compounds is ionic in character, and that the reaction takes place in the electrical double layer at the interface of solid and liquid. As a consequence of the reduction, two deuteriums (or hydrogens if HC1 is used) from the reduction medium are introduced into the molecule, the catalyst only facilitating and not participating in the reaction itself.     

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.     

A synchrotron diffraction study of two polymorphic forms of 2,5‐bis[2‐(4‐methoxyphenyl)ethenyl]pyrazine

Two polymorphs, α and γ, of the title compound, C₂₂H₂₀N₂O₂, have been characterized by means of single‐crystal synchrotron X‐ray diffraction. In the α form, the mol­ecules pack in a herring‐bone fashion, linked via weak C—H?N intermolecular interactions (H?N 2.58 Å). In the γ form, the mol­ecules are arranged in nearly planar sheets, which form a network held together by intermolecular hydrogen bonds of the type C—H?O (H?O 2.49 Å) and C—H?N (H?N 2.50 Å). The stacking distance between the sheets is 3.40 Å.     

Temperature dependence of the probabilities of VV energy exchange between H2 and DCl

The temperature dependence of the removal of the vibrational energy of H₂ by DCl in H₂(1) + DCl(0) has been investigated over the range of 300–3000 K. The energy transfer probability of H₂(1) + DCl(0) → H₂(0) + DCl(1), where the vibrational energy of H₂(1) is removed by both the vibrational and rotational motions of DCl(0), is found to be strongly temperature dependent and increases with temperature closely following the relation log P α T^1/3. Over the temperature range it changes by two orders of magnitude. The probability of the near-resonant process H₂ (1) + DCl(O) → H₂(0) + DCl(2) is very close to that of the former at 300 K, but it increases only slightly as the temperature is raised to 3000 K. The sum of the probabilities of these two processes at 300 K is 3.4 × 10^?5, which agrees with the experimental value of 3.95 × 10^?5.     

Structure of iodide ion arrays in iodinated nylon 6 and the chain orientation induced by iodine in nylon 6 films

Two species of iodide ions (I₃^? and I₅^?) are found in iodine—nylon 6 complexes. Orientation of I₅^? arrays (most likely I₂/I₃^? complex) along the polymer chain and I₃^? ions perpendicular to the chain axis in uniaxially drawn films and in films with planar orientation suggests that there is and intrinsic relation between the direction of iodide ion arrays and nylon 6 chains. When an unoriented film of nylon 6 in the amorphous or the α crystalline form is treated with an aqueous solution of iodine—potassium iodide, the I₃^? species in the resulting iodine—nylon complex lie in planes parallel to the surface of the film, and I₂/I₃^? units are oriented normal to the surface of the film. The γ form obtained by desorbing the iodine from this complex shows considerable uniaxial rientation with the nylon chains oriented perpendicular to the plane of the film; this orientation is maintained during the γ to α transition. It is proposed that the iodine-induced orientation of the nylon 6 chains is due to the nucleating effects of the iodide ion species as the iodine diffuses unidirectionally into the film.     

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.     

Relaxation behavior,intramolecular interactions,and local motions on monosubstituted esters of poly(itaconic acid)

The mechanical relaxation spectrum of poly(monocyclohexylmethylene itaconate) (PMCMI) exhibits two well-developed absorptions in the glassy state that in increasing temperature order are named γ and β absorptions. Owing to the restricted conformational versatility of the backbone, the polymer presents a weak glass-rubber relaxation whose intensity is significantly lower than that of the γ absorption. Comparison of the mechanical spectrum of this polymer with that of poly(dicyclohexylmethylene itaconate) (PDCMI) allows the conclusion that the β relaxation is produced by motions in which the ? COOCH₂C₆H₁₁ side groups are involved. The location of the mechanical γ peak suggests that this absorption is produced by flipping conformational transitions in the cyclohexyl residue. Three dielectric absorptions are observed in the glassy state of PMCMI which in increasing temperature order are called δ, γ, and β relaxations. Both the location and the activation energy of the dielectric and mechanical β absorptions suggest that both relaxations are caused by the same molecular motions. Dipolar interactions in the liquid and glassy state are calculated and the results compared with those experimentally evaluated. © 1994 John Wiley & Sons, Inc.     

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.     

Transition metal—Chalcogen systems,V.

The iron—tellurium phase diagram was investigated by thermal, X-ray, and isopiestic measurements up to 1,100°C. Tetragonal β(≈FeTe_0.9) with a homogeneity range from 45.9 to 48.1 at % Te at 715°C is stable from room temperature to 844°C where it decomposes peritectoidally into Fe and rhombohedral high-temperature β′(≈FeTe_0.9). β′ decomposes at 914°C peritectically into Fe and liquid, and at 800°C by a eutectoid reaction into β and γ(≈FeTe_1.2). γ exists between 809° (γ→β′+δ) and 636°C (γ→β+δ). The monoclinically distorted NiAs-phase δ decomposes peritectically at 55.2 at % Te and 812°C into β′ and liquid and is stable down to the eutectoid δ?β+δ′ at 565±15°C and 58.8 at % Te. δ is separated from hexagonal NiAs-type δ′ by a narrow two-phase region. δ′ has a maximum range of homogeneity at 650°C from 59.2 to 65.1 at % Te and exists between the eutectoid δ′?β+ε at 519°C and the peritectic δ+L?δ′ at 766°C. Orthorhombic ε(≈FeTe_2.0) is stable from room temperature to the peritectic δ′+L=ε at 649°C. ε and Te form a degenerate eutectic at 446°C.     

Investigation of a Simple Pickup Method for Doping Molecules into Water Clusters

A capillary pickup method was investigated for doping molecules into water clusters, which were produced by supersonic expansion, and underwent a sticking collision with a crossed beam from the capillary. This method was applied to H₂O clusters in a beam with pickup of DCl, CH₃OH, NH₃, CO₂ and D₂O molecules, however, we found only molecule of DCl can be picked up by water clusters with the capillary configuration in those tested dopants. Meanwhile, two different distances between the capillary to the nozzle were investigated based on the collected mass spectra, and we found that the smaller distance can obtain the stronger mixed cluster intensity.     

Crystal morphology of the γ (triclinic) phase of isotactic polypropylene and its relation to the α phase

γ-phase crystals of isotactic polypropylene (iPP) obtained from low-molecular-weight extracts of pyrolyzed polymers are examined by electron microscopy and electron diffraction. γ-phase crystals differ from α-phase crystals in three important respects: (i) they are elongated along the b^* rather than the a^* axis, (ii) the chain axis is inclined at 50° to the lamellar surface (indexed as 101) rather than normal to it, and (iii) they show screw dislocations, while α crystals do not. γ crystals are nucleated on the lateral (010) faces of a α crystals; the b_α and b axes are parallel. Virtually no nucleation of the α phase takes place on the γ phase, which is therefore not involved in the repetitive lamellar branching leading to iPP quadrites. Crystallization of the γ phase appears to be favored by or linked to the absence of chain folds and may be involved in the macroscopic curvature of iPP branches.     

NMR.-Investigation of the Formaldehyde Addition and Oligomerisation Equilibria in the System Formaldehyde/Water/Acetic Acid/Hydrochloric Acid

An NMR. investigation of the state of formaldehyde in acidic solutions has been carried out. Solutions of DCl/D₂O/CD₃COOD containing two sources of formaldehyde, i.e. paraformaldehyde (I) and trioxane (II), were used for this purpose. In systems I and II the effect of various D₂O/CD₃COOD ratios, at a constant DCl concentration, was studied, while for II the effect of changing DCl concentration was also investigated. The results show that in aqueous solution, formaldehyde exists primarily as the monomeric and linear oligomeric forms of methylene glycol. Reducing the amount of D₂O (at constant DCl concentration), while increasing the CD₃COOD content, results in an increase in the polymeric species and in trioxane. In addition, substitution of water by acetic acid results in systems that are catalytically more active than aqueous solutions of the same hydrochloric acid concentration. Along with the usual polymer-monomer equilibria which exist in such solutions, side reactions of methylene glycol with the hydrochloric acid present also occur to a small extent, e.g. acetylation, substitution of OH by Cl and the Cannizzaro reaction. It is suggested that these findings will result in a better understanding of the formaldehyde crosslinking reactions in cotton cellulose.     

Electrophilic Reactions of Dithio-Substituted o-Methoxycinnamyllithium

The dithio-substituted o-methoxycinnamyllithium 3L reacted at the α-site with D₂O and most of carbonyl compounds in extents of 70–100 %. while it reacted with halides at either the α or γ-site, depending on the nature of respective halide.     

Tocochromanols composition in kernels recovered from different apricot varieties: RP-HPLC/FLD and RP-UPLC-ESI/MSn study

Composition of tocochromanols in kernels recovered from 16 different apricot varieties (Prunus armeniaca L.) was studied. Three tocopherol (T) homologues, namely α, γ and δ, were quantified in all tested samples by an RP-HPLC/FLD method. The γ-T was the main tocopherol homologue identified in apricot kernels and constituted approximately 93% of total detected tocopherols. The RP-UPLC-ESI/MSⁿ method detected trace amounts of two tocotrienol homologues α and γ in the apricot kernels. The concentration of individual tocopherol homologues in kernels of different apricots varieties, expressed in mg/100 g dwb, was in the following range: 1.38–4.41 (α-T), 42.48–73.27 (γ-T) and 0.77–2.09 (δ-T). Moreover, the ratio between individual tocopherol homologues α:γ:δ was nearly constant in all varieties and amounted to approximately 2:39:1.     

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.     

Polymorphism in copper pyrovanadate

Formation and stability temperatures were determined for the three polymorphs of copper pyrovanadate. The low-temperature β phase is formed at 500°C and is stable from room temperature to 610°C. The intermediate phase is stable within 610–705°C. The high-temperature γ phase is stable within 710–780°C. The rates of γ → α and α → β phase transitions upon cooling differ considerably. α-Cu₂V₂O₇ detected at room temperature upon cooling of a molten sample is metastable.