Thermoanalytical investigation of crystalline layered hafnium salts

Transition metal containing hafnium phosphates forms has layered monoclinic structure. In general these materials have similar route of thermal decomposition; i.e. they loss their crystal water first then at a higher temperature their structural one. At least the result HfP₂O₇ goes through phase change at about 1000 K. In detail among their thermal decomposition some differences occur. The Mn and Zn containing samples have similar behaviour as pure hafnium phosphate. The Cu and Ni containing materials have an additional exo-process connected with the transition metal oxide forms. In case of Co containing sample similar to that of Zn containing one (but very weak) processes were observed.     

The Polymorphism of Glycine. Thermochemical and structural aspects

X-ray, DSC and solution calorimetric investigations were carried out for α-, β- and γ-modifications of glycine. Particular attention was paid to kinetic and thermochemical aspects of γ- → α-phase transition. The temperature of this phase transition turned out to be sensitive to a) conditions under which the crystals of the γ-modification were grown, b) tempering of crystals c) form (geometry) of crystals. Kinetics of this phase transition of single crystals of γ-phase in rhomboedric form can be described by the equation for two-dimension nuclei growth, whereas for crystals of triangle geometry the equation for three dimension growth is valid. On the basis of energy parameters describing growth of α-form in γ- →α-phase transition, the kind of structure defects, which are responsible for this phase transition, was estimated. Taking into account the Δ_sol H _m, the absolute values of the lattice energies of the investigated polymorphs indescending order are follows: γ->α->β-modification. The obtained results are discussed with respect to the peculiarity of the crystal lattice structures, particularly the network of hydrogen bonds. The β-modification of glycine is monotropically related to the other forms, whereas γ-and α-polymorphs are enantiotropically-related phases. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal change of Alq3, tris(8-hydroxyquinolinato) aluminum(III) studied by TG and XRD-DSC

The thermal change of the tris(8-hydroxyquinolinato)aluminum (Alq₃) is currently investigated by XRD-DSC and TG. The phase transition of Alq₃ from α-phase to γ-phase takes place at 643–669 K. A very sharp peak with the peak temperature at approx. 709 K is ascribed to the melting of the Alq₃. The decomposition of the Alq₃ was observed accompanied with the melting and evaporation at >703K. The effect of the atmospheres on the mass loss procedure was studied by TG. It was found that thermal process of Alq₃ was strongly influenced by the partial pressure of water vapor in the atmosphere instead of oxygen.     

The mechanism of α-γ transition of poly- (vinylidene fluoride) in the miscible blends

The simultaneous DSC-FTIR was used for the observation of crystallization and melting of poly(vinylidene fluoride) (PVDF) and its blends with poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The isothermal crystallization was carried out under the condition of both α-form and γ-form crystallized competitively. The crystal growth rate of α -form and γ -form were evaluated from the absorbance changes at 795 cm^-1 (α -form, CH₂ rocking) and 810 cm^-1 (γ -form, CH₂ rocking) obtained by the DSC-FTIR. The crystal growth rate of γ -form decreased at the same crystallization temperature in the order of PVDF/syn-PMMA, PVDF/PEMA and PVDF/at-PMMA, which was corresponding to the order of interaction parameter. The mechanism of α -g transition of PVDF in the miscible blends with at-PMMA, syn-PMMA and PEMA was evaluated from the relationship between the decrease of α -form and the increase of γ -form. The critical crystallization temperature, at which the transformation from α -form to γ -form proceeded only in the solid state, shifted to higher temperature side in the order of interaction parameter. This revised version was published online in August 2006 with corrections to the Cover Date.     

β Phase transformations in the Cu–11mass%Al alloy with Ag additions

In the Cu–Al system, due to the sluggishness of the β ↔ (α + γ₁) eutectoid reaction, the β phase can be retained metastably. During quenching, metastable β alloys undergo a martensitic transformation to a β′ phase at Al low content. The ordering reaction β ↔ β₁ precedes the martensitic transformation. The influence of Ag additions on the reactions containing the β phase in the Cu–11mass%Al alloy was studied using differential scanning calorimetry and in situ X-ray diffractometry. The results indicated that, on cooling, two reactions are occurring in the same temperature range, the β → (α + γ₁) decomposition reaction and the β → β₁ reaction, with different reaction mechanisms (diffusive for the former and ordering for the latter) and, consequently, with different reaction rates. For lower cooling rates, the dominant is the decomposition reaction and for higher cooling rates the ordering reaction prevails. On heating, the (α + γ₁) → β reverse eutectoid reaction occurs with a resulting β phase saturated with α. The increase of Ag concentration retards the β → (α + γ₁) decomposition reaction and the β → β₁ ordering reaction, which occurs in the same temperature range, becomes the predominant process.     

Effect of poly(butylene succinate) on the morphology evolution of poly(vinylidene fluoride) in their blends

The effect of PBS on the morphological features of PVDF has been investigated by optical and atomic force microscopies under various conditions.It was found that neat PVDF forms largeγform spherulites with extraordinarily weak birefringence at 170℃.Adding 30%PBS makes PVDF exhibit intrigued flower-like spherulitic morphology.The growth mechanism was explained by the decrease of the supercooling and the materials dissipation.Increasing the PBS content to 70%favors the formation of ring banded spherulites.Temperature dependent experiments verify theα→γphase transition occurs from the junction sites of theαandγcrystals,while starts from the centers ofαspherulites in the blends.Ring banded structures could be observed in neat PVDF,70/30 blend and 30/70 blend when crystallized at 155℃,withoutγcrystals.The band period of PVDFαspherulites increases with crystallization temperature as well as the amount of PBS content.At 140℃,spherulites in neat PVDF lose their ring banded feature,while coarse spherulites consisting of evident lamellar bundles could be found in 30/70 blend.     

Thermal And Structural Characterization of Commercial α-, β-, and γ-Cyclodextrins

α-, β-, and γ-cyclodextrins (CDs) marketed by five different companies were characterized from the thermal and structural point of view. Three αCD samples showed two-step DSC dehydration profiles and their XRD patterns were characteristic for αCD⋅6H₂O form I, whereas one brand with an apparent three-step DSC dehydration behaviour was a mixture of αCD⋅6H₂O form I and anhydrous αCD. The differences in the DSC profiles after dehydration and EGA onset decomposition temperatures recorded for the five βCD brands were attributed to different manufacturing and purification processes. The five γCDs brands showed a common thermal behaviour and very similar XRD patterns. The patterns did not match the idealized pattern of γCD⋅14.1H₂O, indicating the occurrence of two different hydrated crystal structures. This revised version was published online in August 2006 with corrections to the Cover Date.     

γ-Zirconium and γ-Titanium Phosphates Platinum Intercalation Compound Preparation, characterization and thermal behaviour

Inorganic ion-exchangers with a layered structure such as γ-zirconium and γ-titanium phosphates, intercalated with organic diamines, are able to exchange Pt²⁺ ions to give new intercalation compounds that can be utilized in heterogeneous catalysis. The experiments performed at different temperatures (25 and 45°C), show different ion uptakes, greater at 45°C and for the materials derived from γ-zirconium phosphate. After platinum exchange, all the materials show an amorphization in the XRD if compared with their precursors. The thermal behaviour of the platinum materials is specific, depending on the exchanger used and the ligand inside the exchanger. Pt²⁺ ion has a catalytic effect on ligand elimination in the γ-zirconium phosphate platinum compounds, but not in those derived from γ-titanium. All the obtained yellow materials show a small step in the TG curves and simultaneously we have the Pt²⁺→Pt⁰ reduction: this is confirmed by XRD registered at the temperatures of the thermal effect, showing peaks at d_hkl=2.27 and 1.95 Å. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis and thermal decomposition of lanthanide hexacyanochromate(iii) complexes,Ln[Cr(CN)6]·nH2O (Ln=La-Lu; n=3, 4)

New solid complex of nitrilotriacetic acid and bismuth trichloride was synthesized by a solid phase reaction of nitrilotriacetic acid and bismuth trichloride at room temperature. The composition of the sample is BiCl₃[N(CH₂COOH)₃]_2.5. The crystal structure of the complex belongs to triclinic system with the lattice parameters: α=0.7849 nm, β=0.9821 nm, χ=2.0021 nm, α=96.50°, β=98.76° and γ=90.49°. The far-infrared spectra show the bonding between the Bi ion and N atom of nitrilotriacetic acid. The thermal analysis also demonstrates the complex formation between the bismuth ion and nitrilotriacetic acid. The gaseous pyrolysis product and the final residue in the thermal decomposition process are determined to check the thermal decomposition reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase transition in LAMOX type compounds

La₂Mo₂O₉ (LMO) was synthesized at lower temperature 973 K (LT-phase) by ceramic route. Differential thermal analysis (DTA) scan of LT-phase of LMO showed α→β transition at 843 K during heating and β→α conversion via a metastable γ-phase during cooling. This was also confirmed by thermo-dilatometry and impedance spectroscopy. La₂Mo_1.95V_0.05O_9-δ (LMVO), La_1.96Sr_0.04Mo₂O_9-δ (LSMO) and La_1.96Sr_0.04Mo_1.95V_0.05O_9-δ (LSMVO) were prepared in a similar way. These compounds exhibited α→β transition on heating with shift in transition temperature, but the existence of γ-phase during cooling disappeared. Substitution increased the ionic conductivity of α-phase and reduced that of β-phase.     

Crystallization behavior of a propylene-1-butene random copolymer in its α and γ modifications

A random propylene-based copolymer containing 1.0 mol% 1-butene as co-unit, synthesized with Ziegler-Natta catalyst and then fractionated to make the sample having a uniform in molecular microstructure, was investigated by differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXD), and atomic force microscopy (AFM). In the DSC curves, one can see clearly the endothermic peaks corresponding to the melting of α-iPP crystals and a group of broad endothermic peaks associated to the melting of the γ-iPP crystals. Wide-angle X-ray diffraction results indicate that both the α and γ modifications can be formed in the copolymer in a wide temperature range. The γ fraction increases first with increasing the crystallization temperature at the expense of its α component, which has been explained according to crystalline structures of iPP in its α and γ forms, and then decreases with increasing crystallization temperature as the crystallization of iPP in its γ phase has been suppressed at high temperatures. The γ-iPP content in the copolymer reaches maximum at the temperature of 130 °C. The in situ X-ray diffraction characterization on the isothermal crystallization process at 130 °C indicates that, as long as the γ-iPP can be detected, it takes always ca. 25% of the overall crystallinity. This leads to the conclusion that α- and γ-iPP crystals grow simultaneously during the crystallization process. The fact that the α and γ phases cannot be distinguished by morphological observation leads to the conclusion that they may intermix within one spherulite.     

XRD and thermal studies of AgI confined in nm-size pores by forming porous silica-AgI composites

To investigate the nm-size dependence of structural and thermal properties for AgI, the formation of composites between AgI and porous silica with controlled pore diameters of 10, 15, 30, and 50 nm was examined. The introduction of AgI within the micropores of the porous silica was performed successfully by a salt-bridge precipitation method with using AgNO₃ and KI aqueous solutions. The AgI formed within the micropores was identified to be β/γ-AgI, independent of the pore size of 10-50 nm, by powder X-ray diffractometry. In differential scanning calorimetry, the composites showed thermal anomaly at around 150°C on heating due to the phase transition from β/γ -AgI to α -AgI as in the case of bulk crystalline AgI (T _trs=147°C). However, the transition temperature from α-AgI to β/γ -AgI on cooling decreased remarkably with the decrease of the pore size from 50 to 10 nm. The result indicates the possibility for AgI particles with diameter less than 10 nm to exist as α -AgI even below 100°C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Low-temperature heat capacity of α and γ polymorphs of glycine

Low-temperature heat capacity of two polymorphs of glycine (α and γ) was measured from 5.5 to 304 K and thermodynamic functions were calculated. Difference in heat capacity between polymorphs ranges from +26% at 10 K to -3% at 300 K. The difference indicates the contribution into the heat capacity of piezoelectric γ polymorph, probably connected with phase transition and ferroelectricity. Thermodynamic evaluations show that at ambient conditions γ polymorph is stable and α polymorph is metastable. This revised version was published online in August 2006 with corrections to the Cover Date.     

Isothermal crystallization of propylene-1-decene copolymers

The isothermal crystallization and subsequent melting behavior of one propylene homopolymer and three propylene-1-decene copolymers with different comonomer contents prepared by metallocene catalyst were studied using differential scanning calorimetry (DSC). It is found that the Avrami exponent of the propylene copolymers decreases gradually with the increase of comonomer content, from 3.0 for the propylene homopolymer to 1.4 for the copolymer with 7.83 mol% 1-decene units. Higher comonomer content also weakens the dependence of crystallization rate constant and crystallization halftime on temperature. Double melting peaks, which correspond to α and γ crystal phases, respectively, are observed for all copolymers under isothermal crystallization. The result shows that higher crystallization temperature is favorable to the segregation of α and γ crystal phases, resulting in higher proportion of γ crystal phase. This revised version was published online in July 2006 with corrections to the Cover Date.     

In situ Fourier transform IR spectroscopy and variable-temperature wide-angle X-ray diffraction studies on the crystalline transformation of melt-crystallized nylon 12 12

 The crystalline transformation in nylon 12 12 was monitored by variable-temperature wide-angle X-ray diffraction during heating, isothermal and cooling processes. It could be found that the α phase of the sample transforms into a γ phase at about 130 °C if the sample is heated from room temperature to a high temperature, which is the so-called Brill transition temperature. In addition, nylon 12 12 was found to crystallize into the γ phase when isothermally crystallized at high temperature from the melt. Upon further cooling from the crystallization temperature to room temperature, the reverse transition from the γ phase to the α phase can be detected. Furthermore, in situ Fourier transform IR spectroscopy was also used to study the Brill transition of nylon 12 12 samples on both heating and cooling. It is interesting that the hydrogen-bond strength in nylons decreases dramatically and that some Brill bands of nylon 12 12 disappear abruptly during the Brill transition on heating. Received: 3 April 2001 Accepted: 28 July 2001     

Structural and spectroscopic characterization of Al2−x Cr x O3 powders obtained by polymeric precursor method

Al₂O₃ and Al_2−x Cr _x O₃ (x = 0.01, 0.02 and 0.04) powders have been synthesized by the polymeric precursors method. A study of the structural evolution of crystalline phases corresponding to the obtained powders was accomplished through X-Ray Diffraction and UV-vis spectroscopy (reflectance spectra and CIEL^*a^*b^* color data). The obtained results allow to identify the γ-Al₂O₃ to α-Al₂O₃ phase transition. The single-phase α-Al₂O₃ powder was obtained after heat treatment at 1050 °C for 2 h. The results show that the green to red color transition and ruby luminescence lines observed for the powders of Al_2−x Cr _x O₃ are related to the γ to α-Al₂O₃ phase transition and the temperature and time range for such transition depends on the chromium content.     

Thermal behavior of the Cu–22.55 at.%Al alloy with small Ag additions

In this study the effect of Ag additions on the thermal behavior of the Cu–22.55 at.%Al alloy was studied using electrical resistivity measurements, in situ X-ray diffractometry, differential scanning calorimetry, and optical microscopy. The results indicated that Ag additions do not change the phase transformations sequence in the studied alloys, but modify its critical temperatures due to a change on entropy of system. It was verified that at the cooling rate of 10 K/min the decomposition of β phase into (α + γ₁) is incomplete, but for lower cooling rates than 1.0 K/min this reaction is completed.     

Phase Relations in the Ni–Mn–Ga Ternary System and Aging Effect on Shape Memory Properties of Ferromagnetic Ni<Subscript>2</Subscript>MnGa Sputtered Films

Summary. Isothermal sections of the Ni–Mn–Ga ternary phase diagram at 1073 and 1273 K were investigated over a wide range of alloy compositions. The range of the β-Ni₂MnGa phase, its equilibria with the γ-(Mn, Ni), α′-Ni₃Ga, and γ-Ni₃Ga₂ phases, and the liquidus and solidus lines were determined experimentally. The aging effect on the shape memory effect (SME) of Ni₂MnGa sputtered films was also investigated. The two-way SME of the constraint-aged films was confirmed by the temperature change.     

Phase Relations in the Ni–Mn–Ga Ternary System and Aging Effect on Shape Memory Properties of Ferromagnetic Ni2MnGa Sputtered Films

Isothermal sections of the Ni–Mn–Ga ternary phase diagram at 1073 and 1273 K were investigated over a wide range of alloy compositions. The range of the β-Ni₂MnGa phase, its equilibria with the γ-(Mn, Ni), α′-Ni₃Ga, and γ-Ni₃Ga₂ phases, and the liquidus and solidus lines were determined experimentally. The aging effect on the shape memory effect (SME) of Ni₂MnGa sputtered films was also investigated. The two-way SME of the constraint-aged films was confirmed by the temperature change.     

咪唑-氰基合铁(Ⅲ)氢键型超分子晶体的合成、相变及介电性质

通过溶剂蒸发法,咪唑、18-冠醚-6和铁氰酸在甲醇溶液内反应,获得了氰基合铁配合物氢键型笼状超分子晶体材料(C3H5N2)3[Fe(CN)6]·2(18-crown-6)·2H2O(1)。通过变温X射线单晶衍射、红外光谱、元素分析、热重分析(TG)、差示扫描量热法(DSC)和变温-介电常数测试等对该晶体进行了结构、热能及电性能分析。该晶体的空间群为P21/c,属于单斜晶系,结构显示氰基合铁阳离子、水分子和咪唑阳离子在空间内通过氢键的相互作用形成以铁原子为顶点的三维笼状结构。温度变化触发笼状结构突变,同时引起[Fe(CN)6]3-框架内超分子发生动态摆动,从而引起晶体结构发生相变,该结构相变温度区间伴随介电物理特性阶梯状变化,从220到280 K,介电常数由38变为43,且可逆。温度在270 K之后的介电突然跃升是水汽影响导致。