Effects of Beta Irradiation,Copolymers, and Blends on the Transformation Rate of Polybutene-1

The beta irradiation of polybutene-1 (PB-1) and its random copolymers with ethylene results in sample degradation without chain cross-linking. The crystal structures of both homopolymer and ethylene copolymers were phase I (I), except that for samples of short time irradiation, after melting, where phase II (II) was also present. The sample crystallinity decreased from 64% to a low of 45% in the irradiated samples for the condition used. The crystal size/perfection of the transformed I was slightly lower than that of parent II. The beta irradiation increased the transformation rate of II → I but to a lower extent than did the amount of ethylene in the copolymers. IR analysis confirmed that electron irradiation resulted in chain scission and a decrease of ?CH₂? and ?CH₃ groups. The mechanical properties decreased with increasing ethylene content and irradiation dose.     

X-ray diffraction analysis for quasi-crystals under pressure

Abstract

X-ray diffration analysis under high pressure was performed on the icosahedral phase (I-phase) of an Al₈₀Mn₂₀ alloy and Al₆Li₃Cu alloy. The I-phase of an Al-Mn alloy was stable and there was no indication of phase transformations. In an Al-Li-Cu alloy, the I-phase underwent irreversible transformation successively to the amorphous state and the long-range ordered state. This is the first observation of the pressure-induced amorphization.     

X-ray diffraction,differential scanning calorimetric and spectroscopic studies of phase transitions in the bidimensional compound (C12H25NH3)2CdCl4

The existence of three main crystalline phases (called III, II and I) in (C₁₂H₂₅NH₃)₂CdCl₄ has been revealed by differential scanning calorimetry. X-ray diffraction and spectroscopic studies. The crystal- lographic evolution with increasing temperature appears to be monoclinic (III) → orthorhombic (II) → tetragonal (I). The low temperature phase III is the only ordered structure. The phase transition (III-II), which is of first order type, corresponds to an order-disorder mechanism involving the organic part of the structure (alkylammonium chains) whereas the phase transition (II-I), which is of second-order type, is related to the arrangement of the mineral matrix (octahedra of perovskite layers). An intermediate disordered form II', stable in a very narrow temperature range and structurally similar to the form II, has also been observed, so that the transformation (III-II) proceeds, in fact, in two steps (III-II'-II). The variation enthalpies observed at the transitions (III-II'-II) and analyzed through an order-disorder mechanism demonstrate the high disorder of the alkylammonium chains in form II, in agreement with spectroscopic results. No thermal anomaly or spectroscopic modification is observed for the high temperature transition (II-I).     

Synthesis of hafnium tungstate by a CO2 laser and its microstructure and Raman spectroscopic study

Densely packed hafnium tungstate blocks were synthesized by rapid solidification with a CO₂ laser. It is shown that the optimum synthesis conditions for HfW₂O₈ are around 700 W laser power and 1 mm/s scan speed. Scanning electron microscopy (SEM) observation shows that the blocks consist of oriented nano‐threads/rods that grew horizontally on the surface region and vertically in the interior. The orientations of the nanostructures are governed by the heat transfer directions on the surface and in the interior. Raman spectroscopic and X‐ray diffraction studies show that the samples solidified in the cubic structure with minor contents of the orthorhombic phase. This is explained by a compressive stress induced during the rapid solidification process due to a sudden drop of temperature of the molten pool to the ambient. The stress is estimated to be about 0.6 GPa by comparison with high‐pressure Raman study. Some specific Raman bands appear in the samples synthesized with the laser synthetic route but not in the sample by solid‐state reaction. Copyright © 2008 John Wiley & Sons, Ltd.     

Shape memory characteristics in the L1 0 -fcc order-disorder transformation of FePd

Shape recovery through L1 0 -fcc order-disorder transformation of FePd is examined. Under a uniaxial compressive stress, a reversible shape change associated with the order-disorder transformation is observed. Shape memory characteristics (transformation strain, time required for the transformation and temperature hysteresis) for single-crystal and polycrystal specimens are determined by a compression test under a constant stress. The transformation strain (4% for a single crystal) and time required for disordering (about 10 s for a single crystal) are comparable with those of conventional martensitic shape memory alloys. The alloys can be used as shape memory materials with relatively high transformation temperature.     

A Study of the Thermal Hysteresis in AgNO3

The reversible phase transformation of AgNO₃ is studied. Dielectric constant, d.c. resistivity, differential thermal analysis (DTA) and dilatometric measurements show the occurrence of a reversible phase transition II→I at 160°C with heat of transformation H = 0.78 kcal/mol. The thermal hysteresis in this reversible transformation is examined, the magnitude of the temperature hysteresis does not exceed 12°C. An acceptable agreement is observed between the measured values of the transition temperature obtained by three different experimental techniques. The dilatometric analysis shows that this transition is accompanied by thermal shrinkage with relative shrinkage coefficient 8 × 10^?4. Thermal analysis are also used to get thermodynamic and kinetic data of this phase transition. The temperature dependence of the dielectric constant and d.c. resistivity for single crystals as well as polycrystalline samples of AgNO₃ have clearly located and confirm the phase transitions II→I→II with a strong support to its thermal hysteresis character. The conduction mechanism is found to be activated by energy 0.12 eV for phase I and 0.36 eV for phase II. The observed thermal behaviour of the various measured parameters is attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for first time in AgNO₃.     

Solid energy calibration standards for P K‐edge XANES: electronic structure analysis of PPh4Br

P K‐edge X‐ray absorption near‐edge structure (XANES) spectroscopy is a powerful method for analyzing the electronic structure of organic and inorganic phosphorus compounds. Like all XANES experiments, P K‐edge XANES requires well defined and readily accessible calibration standards for energy referencing so that spectra collected at different beamlines or under different conditions can be compared. This is especially true for ligand K‐edge X‐ray absorption spectroscopy, which has well established energy calibration standards for Cl (Cs₂CuCl₄) and S (Na₂S₂O₃·5H₂O), but not neighboring P. This paper presents a review of common P K‐edge XANES energy calibration standards and analysis of PPh₄Br as a potential alternative. The P K‐edge XANES region of commercially available PPh₄Br revealed a single, highly resolved pre‐edge feature with a maximum at 2146.96 eV. PPh₄Br also showed no evidence of photodecomposition when repeatedly scanned over the course of several days. In contrast, we found that PPh₃ rapidly decomposes under identical conditions. Density functional theory calculations performed on PPh₃ and PPh₄⁺ revealed large differences in the molecular orbital energies that were ascribed to differences in the phosphorus oxidation state (III versus V) and molecular charge (neutral versus +1). Time‐dependent density functional theory calculations corroborated the experimental data and allowed the spectral features to be assigned. The first pre‐edge feature in the P K‐edge XANES spectrum of PPh₄Br was assigned to P 1s → P‐C π* transitions, whereas those at higher energy were P 1s → P‐C σ*. Overall, the analysis suggests that PPh₄Br is an excellent alternative to other solid energy calibration standards commonly used in P K‐edge XANES experiments.     

晶圆键合和激光剥离工艺对GaN基垂直结构发光二极管芯片残余应力的影响

GaN基发光二极管(LED)中的残余应力状态对器件的性能和稳定性有很大影响. 通过使用三种不同的键合衬底(Al₂O₃衬底, CuW衬底和Si衬底)以及改变键合温度(290 ℃, 320 ℃, 350 ℃和380 ℃), 并且使用不同的激光能量密度(875, 945和1015 mJ·cm^-2) 进行激光剥离, 制备了不同应力状态的GaN基LED器件. 对不同条件下GaN LED进行弯曲度、Raman 散射谱测试. 实验结果表明, 垂直结构LED中的残余应力的状态是键合衬底和键合金属共同作用的结果, 而键合温度影响着垂直结构LED中的残余应力的大小. 激光剥离过程中, 一定能量密度下激光剥离工艺一般不会对芯片中的残余应力造成影响, 但是如果该工艺对GaN 层造成了微裂缝, 则会在一定程度上起到释放残余应力的作用. 使用Si衬底键合后, 外延蓝宝石衬底翘曲变大, 对应制备的GaN基垂直结构 LED中的残余应力为张应力, 并且随着键合温度的上升而变大; 而Al₂O₃和CuW衬底制备的LED中的残余应力为压应力, 但使用Al₂O₃衬底键合制备的LED中压应力随键合温度上升而一定程度变大, CuW 衬底制备的LED中压应力随键合温度上升而下降.     

内应力对Mn2NiGa铁磁形状记忆合金的结构、相变和磁性能的影响

通过施加压应力的方法,在铁磁形状记忆合金Mn₂NiGa中引入残留内应力,研究了内应力对 Mn₂NiGa材料的结构、相变和磁性能的影响.研究发现,加压过程使材料发生了塑性形变,在材料内部引入了大量的位错缺陷.卸载后保留的位错缺陷在材料中造成了残留的内应力,导致了马氏体相变温度大幅度提高, 使原本室温下的母相转变成了马氏体相.测量到导致样品转变成马氏体的阈值压应力为1.0 GPa.加压形成的马氏体中的残留内应力将矫顽力从低于50 Oe提高到350 Oe.残留内应力在730 K的热处理中由于位错缺陷的消失而得以消除,样品实现了马氏体逆相变.如此高的逆相变温度使得 Mn₂NiGa马氏体的居里温度测量成为可能,获得了530K的数值.     

Phase Transitions in Isotactic Polybutene-1

The possibilities to influence the 4 major phase transitions of isotactic polybutene – 1 (iPB-1) and their transformation rate are described. The phase transformations result in new polymer structures with new physical and, in some cases, practically important properties. The transformation of phase II to I is spontaneous contrary to the phase transformation of III to I or II, which depends on the temperature (96?°C or higher). For the practically most important phase transition, II → I, there are 3 major transformation types (plus (P), neutral (N) and minus (M)) depending on the phase transition rate.     

(Pressure,temperature) phase diagram of the quasi-1D 3/4 filled organic salt (o-DMTTF)2Br

The family of quasi-one-dimensional organic salts (o-DMTTF)₂X, (X=Cl, Br, I) exhibits regular stacks and a high symmetry (tetragonal) structure which provides a perfect 3/4 band filling system with strong electronic correlations. We report transport measurements, resistivity and thermopower, performed as a function of pressure and/or temperature on (o-DMTTF)₂Br which presents all the characteristics of the family. Coupled with data obtained from X-rays diffraction and magnetic susceptibility experiments at ambient pressure, in order to identify the insulating ground states, our data allowed to establish the (pressure, temperature) phase diagram for (o-DMTTF)₂Br which differs significantly from those previously reported in other 3/4 filled systems.     

Mössbauer study of structural inhomogeneities formed upon the FCC–L10 transformation in equiatomic FePd alloy from different initial states

A comparative Mössbauer study of structural inhomogeneities that arise in the course of А1→ L1₀ phase transformation in nondeformed (as cast and quenched from 950°C and melt-spun from the ingot) and severely deformed samples of equiatomic FePd alloy upon ordering annealing at Т?=?450°С has been performed. According to the known experimental works, the chosen temperature of annealing is optimal for achieving the highest coercive force H_c in both quenched and deformed samples. It is shown that in the high-coercivity state both quenched and deformed samples FePd possess an inhomogeneous tetragonal structure, which is preserved even after quite a prolonged (40–100?h) annealing. All the samples contain, along with the configurations of the nearest neighbourhood that are assigned to the ordered L1₀ phase, significant volume fractions of configurations typical of nonequiatomic compositions. This conclusion is inconsistent with the commonly accepted concept on single-phase L1₀ type alloys with maximal values of H_c. An inference is made that the structural inhomogeneities detected in the samples under study result from the mismatch of the position of the point of congruent А1→ L1₀ transformation (≈58 at.% Pd) in the phase diagram of the FePd system to equiatomic composition.     

Effect of substrate temperature on the magnetic properties and internal stresses of CoPt/AlN multilayer deposited by dc magnetron sputtering

Magnetic properties and internal stresses of AlN(20 nm)/[CoPt(2 nm)/AlN(20 nm)]₅ multilayer structure deposited at different substrate temperatures by dc magnetron sputtering have been studied. It is found that with increasing the substrate temperature from room temperature to 400 °C, in-plane magnetic anisotropy field of the film becomes smaller, and the out-of-plane magnetization becomes stronger. Especially when the film is deposited at substrate temperature of 400 °C, the out-of-plane magnetization becomes as strong as the in-plane magnetization. On the other hand, the total in-plane residual stress of the film changes gradually from compressive to tensile. The compressive intrinsic stress is generated during deposition process and decreases with increasing the substrate temperature. After annealing at high temperatures, the films show strong perpendicular magnetic anisotropy. With increasing the annealing temperature, the in-plane thermal stress also increases and becomes dominant, which is considered to result in the perpendicular magnetic anisotropy of the films.     

铸锭凝固组织对相应非晶合金晶化过程中二十面体准晶相形成动力学的影响

通过在真空电弧熔炼炉内对合金铸锭进行反复熔炼处理，获得到了凝固组织不同的Zr₆₅Al_7.5Cu_12.5Ni₁₀Ag₅合金铸锭.在相同的制备条件下，由凝固组织不同的合金铸锭通过吸铸法制备得到了薄片非晶合金.利用差示扫描量热法(DSC)对非晶合金的晶化动力学进行了分析.x射线衍射谱表明，在Zr₆₅Al_7.5Cu_12.5Ni₁₀Ag₅非晶合金晶化过程中，二十面体准晶相(I相)作为初生相析出.Kissinger分析结果表明，合金铸锭的凝固组织细化，相对应的非晶合金发生晶化时，I相形成与分解的有效激活能都增大，说明非晶合金及析出的I相的热稳定性都提高.从结构的遗传性角度就合金铸锭凝固组织对相应非晶合金晶化过程中二十面体准晶相的形成动力学的影响进行了讨论. 关键词： 二十面体准晶相 晶化动力学 凝固组织     

Feasibility study of laser cooling of InF molecule

By employing ab initio quantum chemistry method, we investigate the feasibility of laser cooling InF molecule. Four low-lying electronic states (X¹Σ⁺, C¹Π, ³Π and 2³Π) of InF have been calculated using the multi-reference configuration interaction (MRCI) method. The spin-orbit coupling effects are also taken into account in the electronic structure computation at the MRCI level. The highly diagonal Franck-Condon factors for C¹Π → X¹Σ⁺ transitions are estimated. The radiative lifetime of the C¹Π (v′ = 0) state is about 2.22 ns, which is found to be enough short for rapid laser cooling. Though the cooling wavelength of InF is located in the short-wavelength ultraviolet light (UVC), a frequency quadrupled Ti: sapphire laser (189–235 nm) could be capable of generating laser transition wavelength of InF. Furthermore, the C¹Π → X¹Σ⁺ transitions perhaps can be followed by the B³Π₁ → X¹Σ⁺_0⁺ transitions to attain a lower Doppler temperature. Meanwhile, for achieving quasi-closed transition cycle of InF molecule, we investigate the hyperfine structure of the lowest state X¹Σ⁺. Overall, the present results indicate the possibility of laser cooling InF molecules.     

Raman spectroscopic investigations of structural aspects of the different phases of lithium sodium and potassium nitrate

Raman spectra have been obtained for LiNO₃, NaNO₃ and KNO₃ as oriented single crystals and polycrystalline solids over a wide range of temperatures up to the melting points. The anomalous component previously observed in the symmetric stretching region and attributed to a disordered nitrate group has been studied as a function of temperature. The results suggest that the peak may have a hot band origin such that transitions 0001 → 1001 and 0100→ 1100 may occur in addition to the ground state transition, 0000→ 1000 of nitrate. In the symmetric stretching region the shift of the hot band is sufficiently large to ensure that the modes of this origin are not coupled to the ground state lattice in the usual way. Hot bands with an external mode origin could not be detected. KNO₃(II), KNO₃(III), NaNO₃(II) and LiNO₃, have ordered structures with small amounts of disorder of a hot band origin. KNO₃(I) and NaNO₃(I) have similarly disordered structures but exhibit minor differences due to different relative populations and symmetries of the disordered sites. Raman studies of the disordered phases suggest that the crystal symmetry is lower than the “average” structure deduced from X-ray diffraction methods. A number of bands previously reported have not been detected while several bands were reassigned on the basis of ¹⁵N substitution.     

Diffusion-controlled transformation plasticity of steel under externally applied stress

The transformation plasticity of steel during phase transformation under external stress was modelled on a migrating interface diffusion mechanism. Atomic diffusion along the migrating phase interface is assumed to cause transformation plasticity by an accelerated Coble creep. A creep equation on transformation plasticity is derived as a function of transformation rate, temperature and externally applied stress. Predictions are compared with dilatometric measurements during the austenite-to-ferrite and ferrite-to-austenite transformation of steel under various levels of uniaxial compressive stress. Good agreement was found between the calculated and experimental transformation strain. The model proposed also successfully describes the thermally activated behaviour of the transformation strain. The evaluated effective diffusion coefficients on the migrating interface are three to four orders of magnitude larger than those reported for stationary boundaries.     

Investigation of the reconstructive phase transition between metastable (α) and stable (β) modifications of the NH<Subscript>4</Subscript>LiSO<Subscript>4</Subscript> crystal

Crystals of ammonium lithium sulfate NH₄LiSO₄ in α and β modifications are studied, and conditions of their nucleation and growth are determined. The α modification of NH₄LiSO₄ and α → β phase transitions are investigated using polarized light microscopy, x-ray diffraction, and differential scanning calorimetry in the temperature range 80–530 K. It is found that, depending on the conditions of growth and storage, there exist two temperature ranges (T_{α → β} ≈ 340–350 and ≈440–450 K) in which the crystals can undergo an α → β reconstructive phase transition. The enthalpy of this transformation depends on the symmetry of the final phase. In the former case (340–350 K), the reconstructive phase transition leads to rapid destruction of the sample. In the latter case (440–450 K), the crystal structure undergoes a slow transformation (recrystallization) without noticeable distortions. The results obtained indicate that no structural phase transition occurs in the α modification of NH₄LiSO₄ at 250 K.     

Crystallographic texture and microstructure evolution during hot compression of Ti–6Al–4V–0.1B alloy in the (α + β)-regime

Microstructure and texture are known to undergo drastic modifications due to trace hypoeutectic boron addition (~0.1 wt.%) for various titanium alloys e.g. Ti–6Al–4V. The deformation behaviour of such an alloy Ti–6Al–4V–0.1B is investigated in the (α?+?β) phase field and compared against that of the base alloy Ti–6Al–4V studied under selfsame conditions. The deformation microstructures for the two alloys display bending and kinking of α lamellae in near α and softening via globularization of α lamella in near β phase regimes, respectively. The transition temperature at which pure slip based deformation changes to softening is lower for the boron added alloy. The presence of TiB particles is largely held attributable for the early softening of Ti–6Al–4V–0.1B alloy. The compression texture of both the alloys carry signature of pure α phase defamation at lower temperature and α→β→α phase transformation near the β transus temperature. Texture is influenced by a complex interplay of the deformation and transformation processes in the intermediate temperature range. The contribution from phase transformation is prominent for Ti–6Al–4V–0.1B alloy at comparatively lower temperature.     

Effect of alloying on the structure and phase transformations in Ni-Mn alloys alloyed by titanium

The crystal structure of NiMn alloy alloyed by titanium in a wide range of temperatures and compositions has been investigated using resistivity measurements, transmission electron microscopy, electron diffraction, and X ray diffraction. It is found that alloying by titanium not only decreases the martensitic transformation temperature but also changes the martensite crystal structure. The martensitic transformation temperatures are determined and the diagram of martensitic transformations for Ni₅₀Mn_{50 ? x} Ti _x alloys is constructed.