ESR研究非晶Ag￣＋导体的晶化

用电子自旋共振（ＥＳＲ）方法对非晶Ａｇ￣＋离子导体０．８５ＡｇＩ～０．１５Ａｇ＿４Ｐ＿２Ｏ＿７的热处理晶化过程进行研究，在样品中掺入微量（约１×１０￣（－３）ｇ／ｇ）的Ｍｎ￣（２＋）或Ｖ￣（４＋）离子作为自旋探针离子，它们的ＥＳＲ谱强度随升温线性减弱，当样品完全晶化时ＥＳＲ谱消失。这样测定的样品完全晶化的温度分别为９８℃（掺Ｍｎ的）和１０８℃（掺Ｖ的）．本文还对Ｍｎ￣（２＋）和Ｖ￣（４＋）的ＥＳＲ谱进行了分析。     

静高压下非晶（Fe0.09,Mo0.01）74Si9B13合金晶化过程的热力学研究

在６００－９３０Ｋ，常压到７ＧＰａ的范围内，对非晶（Ｆｅ０．９９，Ｍｏ０．０１）７８Ｓｉ９Ｂ１３合金等温等压退火３０ｍｉｎ。实验表明；其晶化产物α－Ｆｅ（Ｍｏ，Ｓｉ）Ｆｅ３Ｂ和Ｆｅ２Ｂ相的析出与所加压力密切相关。压力使非晶（Ｆｅ０．９９Ｍｏ０．０１）７８Ｓｉ９Ｂ１３合金的晶化温度和亚稳Ｆｅ３Ｂ相的析出温度下降，在一定的压力和温度下，亚稳Ｆｅ３Ｂ相半向稳定Ｆｅ２Ｂ相转变其转变温度随压力而变化。     

BiPbSbSrCaCuO非晶态及热处理对其影响

本工作用正电子湮没谱术（ＰＡＳ），Ｘ射线衍射谱（ＸＲＤ），示差热分析（ＤＴＡ），扫描电镜显微术（ＳＥＭ）和交流磁化率（Ｘａｃ）研究了Ｂｉ－Ｐｂ－Ｓｂ－Ｃａ－Ｃｕ－Ｏ非晶态和后续热处理的影响。结果表明：所研究的非晶态晶化温度Ｔｃ－４５０－４７０℃，当热处理温度Ｔａ＜Ｔｃ，非晶太经低温结构弛豫和高温弛豫。当Ｔａ＞Ｔｃ，在晶态多相体系中随温度升高发生低ｎ相向高ｎ相的转变，８５０℃退火可使超导转变温度...     

磷酸-氨水蒸沉γ晶型聚酰胺6的热行为研究

尼龙6是一种多晶型的半结晶高聚物。实验采用蒸沉法制备出尼龙6,首先通过XRD和FTIR的手段进行表征,与采用沸水处理的尼龙6样品表征结果对比,确定其为γ晶型,然后在130～211℃的温度范围内进行热处理,通过DSC研究其在低于熔点热处理时的整个热行为变化过程,并运用FTIR观察其在不同条件下热处理发生的晶型变化。发现蒸沉法制备的γ晶型尼龙6随着热处理温度的升高,整体结晶完善度以及晶片厚度随着处理温度的升高而增加。而且在这个过程中,样品厚度不同的晶片在不同温度下发生了γ晶型向α晶型的转化,最终在接近熔点(211℃)热处理时,样品变为以α晶型为主。     

一种新的非晶态超导合金Ti_80Pd_20

用悬浮熔炼液相高速淬火方法制备出了一种新的非晶态超导合金Ti_(80)Pd_20.热分析确定其晶化温度T_cr为976℃.玻璃转变温度T_g为550℃,低温测试表明其非晶相的超导转变温度T_c为2.1K。     

晶型转变对尼龙11分子链运动的影响

为进一步认识分子链运动与晶型之间的关系,用熔融、冰水淬火和退火等方法制备了α和δ′两种晶型的尼龙11薄膜试样.42Hz～5MHz的介电松弛谱显示了两种不同晶型试样的分子运动特征.不同频率下的介电温度谱显示α型结晶中代表分子链段运动的主松弛较δ′型结晶出现在更高温度,说明退火引起的δ′向α晶型转变使分子链段运动受到了限制.研究结果还显示,α和δ′型结晶中分子链局域松弛运动的活化能基本相同,但α型的松弛时间较δ′型的大,松弛强度则较δ′型的小,表明晶型转变使尼龙11的分子链局域松弛运动也受到了一定程度的抑制.     

聚苯硫醚熔体的压致凝固行为

采用施加压力的方法将聚苯硫醚熔体凝固,凝固后获得的聚苯硫醚样品经过降温和卸压后在常温常压下回收. X射线衍射和差示扫描量热分析表明:约20 ms时间的快速压缩过程可以抑制熔体结晶,制备出非晶态聚苯硫醚块材,样品的表面及中心都是非晶态.非晶态聚苯硫醚的玻璃化转变温度和晶化温度分别为318和362 K.常压下的退火实验表明,非晶态聚苯硫醚在425 K等温结晶的产物为正交相晶型.压致凝固法中熔体的凝固不是靠温度变化,而是靠压力变化,样品表面和内部处在一致的温度下同时受压凝固,避免了热传导对非晶尺寸的影响,因此非常有利于获得结构均匀的大尺寸非晶态材料.     

与Al发生扩散反应的非晶(Fe0.99Mo0.01)78Si9B13晶化

高压下与Ａｌ发生扩散反应的非晶（Ｆｅ０．９９Ｍｏ０．０１）７８Ｓｉ９Ｂ１３（ＦＭＳＢ）的不同。与Ａｌ反应的ＦＭＳＢ非晶在３．０￣５．０ＧＰａ,７８０￣９００Ｋ热处理时,晶化为α－Ｆｅ（Ａｌ）和次亚稳非晶合金;在这一压力范围以外,７２０￣９００Ｋ热处理时,晶化为α－Ｆｅ（Ｓｉ）,Ｆｅ３Ｂ或Ｆｅ２Ｂ。与Ａｌ发生反应的ＦＭＳＢ非晶可能通过与Ａｌ的扩散反应在Ａｌ／ＦＭＳＢ界面开始晶化。压力和温度对晶化过程     

用拉曼光谱研究溶胶－凝胶法制TiO_2的析晶过程

本文报道了用拉曼光谱研究溶胶一凝胶（Ｓｏｌ一Ｇｅｌ）法制备ＴｉＯ＿２粉末的析晶过程。结果发现在４００～５００℃时析出锐钛型晶体，在６００℃前锐钛型开始向金红石型晶体转变，６００～７００℃析出的是锐钛型与金红石型的混合晶体，到８００～９００℃时完全转变成金红石晶体析出。析晶温度和转化温度比一般工业法制ＴｉＯ＿２粉末的相应温度要低得多。其原因初步用溶胶一凝胶法本身的反应机制和凝胶的多孔网络特性加以阐明。     

块体非晶合金的黏度与玻璃形成能力的关系

基于经典结晶理论讨论了非晶合金的晶化动力学因素和晶化热力学因素对玻璃形成能力（GFA）的影响.分析表明,合金的等温转变（TTT）曲线“鼻尖”温度T_n对应的黏度与晶化阻力因子成正比;重新加热时晶化开始温度T_x对应的黏度与晶化驱动力因子成反比.由此得到了新的GFA参数ω₀=（T_g-T₀）/（T_x-T₀）-（T_g-T₀）/（T_n-T₀）,其中T_g为玻璃转变温度,T₀为理想玻璃转变温度.统计结果显示,ω₀与临界冷却速率具有较高的相关性,R²高达09626.进一步分析表明：新提出的ω₀参数可以合理地解释过冷熔体的黏度、脆性、液相稳定性、热稳定性以及T_rg、ΔT_x、γ、γ_m、ΔT_rg、α、β、δ和φ等参数与GFA的关系. 关键词： 块体非晶合金 黏度 脆性 玻璃形成能力     

Structure and properties of polybutylene crystallized from the glassy state. I. X-ray scattering,DSC, and torsion pendulum

Isotactic polybutene (PB) can be quenched into a completely glassy state by quenching molten films into a solid-liquid mixture of isopentane, Freon, or ethanol. The crystallization of PB from the glass form was studied by x-ray scattering, differential scanning calorimetry (DSC), and dynamic mechanical spectroscopy (torsion pendulum). As for crystallization from the melt, PB crystallizes from the glass into a tetragonal crystal structure (Form II) at ca. 0°C, depending on sample thickness, and then transforms to the twinned hexagonal structure (Form I) upon aging at room temperature. In the presence of isopentane, PB crystallizes partially from the glass into the untwinned hexagonal (Form 1′) structure at ca. -70°C; the rest of the sample starts to transform to tetragonal structure at ca. -30°C and nearly completes crystallization at ca. 0°C. The exact temperatures of both transformations depend on the amount of isopentane present and sample thickness. Upon aging at room temperature the tetragonal structure converts to the twinned hexagonal structure even faster than in the absence of isopentane. Dynamic mechanical experiments show the presence of two relaxation-like peaks for the ultraquenched samples: T_r (L) = -27°C and T_r (U) = -15°C. X-ray diffraction, DSC, and torsion pendulum experiments show that PB crystallizes from the glass at T_r (U).     

压力对非晶铜形成影响的分子动力学模拟

用分子动力学模拟法研究了Cu熔体在冷却过程中形成非晶的能力. 结果表明，压力使Cu熔体在冷却过程中形成晶体的倾向增加. 高压下冷却形成的Cu非晶中含有较多的晶态原子团，有序度较高.     

In situ ultrasonic diagnostic of zeolite X crystallization with novel (hierarchical) morphology from coal fly ash

In this paper the applicability of an in situ ultrasonic diagnostic technique in understanding the formation process of zeolite X with a novel morphology was demonstrated. The complexity of the starting fly ash feedstock demands independent studies of the formation process for each type of zeolite since it is not known whether the crystallization mechanism will always follow the expected reaction pathway. The hierarchical zeolite X was noted to follow a solution phase-mediated crystallization mechanism which differs from earlier studies of the zeolite A formation process from unaged, clear solution extracted from fused fly ash. The use of the in situ ultrasonic monitoring system provided sufficient data points which enabled closer estimation of the time of transition from the nucleation to the crystal growth step. In order to evaluate the effect of temperature on the resulting in situ attenuation signal, synthesis at three higher temperatures (80, 90 and 94 °C) was investigated. It was shown, by the shift of the US-attenuation signal, that faster crystallization occurred when higher temperatures were applied. The novel hierarchical zeolite X was comprised of intergrown disc-like platelets. It was further observed that there was preferential growth of the disc-shaped platelets of zeolite X crystals in one dimension as the synthesis temperature was increased, allowing tailoring of the hierarchical morphology.     

New Insights into the Effects of Physical Aging on Glass Transition of Polystyrene by FTIR

A new method to detect the glass transition was used to investigate the effects of physical aging on the glass transition of polystyrene by Fourier transform infrared (FTIR) spectroscopy. The results showed that the onset point of the glass transition shifted to higher temperature with aging, but the end point didn't change. It was demonstrated that this method was of great use in determining the glass transition temperature of aged polymeric samples. For each aged sample, the four bands assigned to the vibrational modes of the main chain groups and the side groups of polystyrene showed the same transition regions, indicating that the main chain and the side groups were aging synchronously. The rates of increase of the relative peak areas for the four investigated bands during the glass transition decreased with aging with the increased rates of the relative peak areas for the two bands assigned to side group decreasing less than those of main chain, which seemed to indicate the dominance of the side group in aging process.     

Two-stage crystallization on the surface of smectic nanofilms

The influence of the surface and finite size on crystallization in nanofilms of a smectic C liquid crystal with thicknesses between two and several tens of molecular layers has been studied. Transitions in a single surface molecular layer have been detected by optical methods. It has been found that transitions on the film surface take place at a temperature 8°C higher than the crystallization temperature in a bulk sample. Two-stage crystallization has been detected in surface layers where the surface induces a transition to an intermediate structure different from the structure of the phases of the bulk sample.     

Studying the crystallization behavior of the Se85S10Sb5 chalcogenide semiconducting glass by DSC and X-ray diffraction

Crystallization kinetics of the Se₈₅S₁₀Sb₅ chalcogenide glassy alloy is studied by differential scanning calorimeter (DSC) non-isothermally. The glassy state of the as-prepared sample and the crystalline phases of the heat treated sample are characterized using X-ray diffraction. The glass transition activation energy E_g is found to be 65.2±0.8 kJ/mol and the crystallization activation energies for the first and the second crystallization peaks (E_c1 and E_c2) are found to be 70±0.8 and 85.2±0.8 kJ/mol, respectively. The determined kinetic parameters have made it possible to postulate the type of crystal growth exhibited in the crystallization process. The phases at which the alloy crystallizes after the thermal process have been identified by X-ray diffraction. The diffractogram of the transformed material indicates the presence of nanocrystallites of Sb₂Se₃, Se-S and Se, with a remaining additional amorphous matrix.     

Studies on crystalline forms of Nylon 6. III. Crystallization from the glassy state

The relative amounts of the α- and γ-crystalline forms of nylon 6 obtained from the glassy state under different crystallization conditions have been studied by the X-ray diffraction procedure described in the previous paper. The weight fraction of the γ-form decreases with increasing crystallization temperature above 160°C and that of the α-form increases. Growth of the γ-form is predominant in crystallization at 100°C and of the α-form at 200°C. Differential scanning calorimetry and density data are presented. A large amount of a thermally unstable form is included in the γ-form crystallized from the glassy state at lower crystallization temperatures and is transformed into the a-form with annealing at 200γC. Thermal stability of the γ-form obtained from the glassy state was quantitatively investigated and discussed.     

环丁醇温致相变的原位拉曼光谱研究

采用拉曼光谱和红外光谱解析了常温条件下环丁醇的各个振动模式及其与分子构象间的关联,结果表明液态环丁醇以赤道–反式构象为主,并含有少量的赤道间扭式构象。在此基础上结合差示扫描量热技术和变温拉曼光谱,原位研究了环丁醇的温致相变过程和分子构象随温度的变化。结果表明,冷却至140 K的过程中,环丁醇并未结晶固化,而是保持亚稳定的无序液体状态,即出现过冷现象,继续降温至138 K出现玻璃化转变。升温过程中,在170 K时出现放热峰,同时有新的拉曼峰出现,并且拉曼峰的半高宽和强度发生明显的突变,表明环丁醇由无序结构转变为有序的结晶相。因此,我们获得了环丁醇的温致相变序列： 液态→过冷液体→玻璃态→结晶态→液态。通过对环丁醇不同分子构象的拉曼特征峰的定量分析,证实环丁醇在降温过程中,反式构象和间扭式构象的比例未发生明显改变,即没有发生构象变化。然而升温时,伴随170 K时结晶态的转变,反式构象特征峰的相对强度减小,表明部分分子由赤道–反式构象转变为赤道–间扭式构象。该研究结果对进一步理解和研究其他有机小分子的温致相变和构象变化具有指导意义。     

Physical and water aging of glass fiber-reinforced plastic pipes

Physical and water aging of glass/epoxy composite — GFRE — pipes used for oil transport were investigated with special emphasis on their effect on the flexural and impact behavior. Different aging conditions were selected in order to simulate in-service environments trying to obtain reliable results from accelerated laboratory tests. In water uptake experiments at 80°C, the mass increases continuously, suggesting that an irreversible process occurs. In addition, samples aged in air at 80°C exhibit a DSC endothermic peak that can be related to physical aging. The calorimetric curve for specimens water aged at 80°C shows combined effects of water absorption and physical aging. On the other hand, while the independent effect of temperature and water aging on the composites mechanical response is only moderate, their combined effect seems to be dramatic. This result is mostly attributed to the weakening of the fiber–matrix interface induced by the water ging at high temperature, which consequently affects flexural and impact properties. SEM observations confirm the irreversible damage observed in water uptake experiments. Good interfacial adhesion between fiber glass and epoxy resin is observed for unaged specimens, whereas completely clean fibers are seen for specimens water aged at 80°C, indicating that the fiber–matrix interface is completely removed as a result of this aging condition.     

Storage of laser-induced holographic gratings in discotic liquid crystals

We demonstrate that low molar mass discotic liquid crystals can be used for holographic storage. Grating structures are optically induced and stored in the glassy state of the investigated liquid crystal. The material is suitable for multiple storage processes since the stored information can be erased by heating the sample above the glass transition temperature.