交联1,4—顺式聚丁二烯的取向结晶

用ＷＡＸＤ和ＳＡＸＳ研究交联１，４－顺式聚丁二烯的取向结晶。结果表明：该试样在拉伸状态时，形成折叠链片晶，而不是伸直链纤维晶。片晶之间断产生新的片晶，使长周期减小，并且片晶的横向尺寸不断增大，由此导致结晶度增大。     

聚乙烯串晶在单轴拉伸形变过程中的微结构变化和机理

本文采用电子显微镜和小角Ｘ－射线散射（ＳＡＸＳ）技术研究了含有串晶结构（Ｓｈｉｓｈ—ｋｅｂａｂ）的高密度聚乙烯（ＨＤＰＥ）／超高分子量聚乙烯（ＵＨＭＷＰＥ）共混物高取向膜在单轴拉伸过程中的微结构变化．深入探讨了拉伸温度对聚乙烯在形变过程中微结构变化的影响．室温拉伸时，聚乙烯串晶结构主要发生了解结晶过程；高温（１１５℃）形变时，主要表现为折叠链片晶直接转变为伸展链纤维晶的应变诱导结晶过程．     

热拉伸的超高分子量聚乙烯的晶体结构和力学性能

讨论了超高分子量聚乙烯（ＵＨＭＷ－ＰＥ）的熔融一次拉伸和二次拉伸的晶体结构和力学性能．利用ＷＡＸＤ和ＳＡＸＤ测定了拉伸片的晶体取向因子和极图，晶粒尺寸，晶体畸变，长周期等晶体结构．用ＤＳＣ和ＶＥＳ测定热性能和动态力学性能．应力－应变实验测定拉伸片的杨氏模量，断裂强度和伸长．这些实验结果说明ＵＨＭＷ－ＰＥ经二次拉伸能产生正交晶系的伸直链晶体．二次拉伸片由折叠链片晶和伸直链晶体两元结构组成．二次拉伸片的杨氏模量比一次拉伸片有大幅度提高．二次拉伸片的晶体结构和力学性能是在一次拉伸的基础上形成的．     

FRS-XRSA与SAXS研究硬弹性聚丙烯的结晶度、取向与超结构Ⅲ应变与回复

应用全倒易空间Ｘ 射线散射理论分析（ＦＲＳ ＸＲＳＡ）与ＳＡＸＳ研究了ＨＥＰＰ在应变（ε）与回复（Ｒ）过程中结晶、取向与超结构的变化．结果指出，ε可以诱发结晶，但当ε≥３０％后，结晶度（ＸＷＣ）趋于不变：ε可以导致晶粒破碎；ε与Ｒ对取向分布与平均取向基本上无影响，这符合片晶平行分离模型，而非叶簧弯曲模型；发现，在ε≤３０％时，层状片晶的分离为主要过程，而当ε＞３０％后，则分离的片晶会发生断层滑移；ε可以诱发微孔，类似地当ε＞２０％，微孔尺寸亦趋不变．从凝聚态结构阐明了ＨＥＰＰ在ε Ｒ过程中不同阶段的结构变化     

FRS—XRSA与SAXS研究硬弹性聚丙烯的结晶度,取向与超结构：Ⅲ.应变与回复

应用全倒易空间Ｘ－射线散射理论分析（ＦＲＳ－ＸＲＳＡ）与ＳＡＸＳ研究了ＨＥＰＰ在应变（ε）与回复（Ｒ）过程中结晶、取向与超结构的变化。结果指出，ε可以诱发结晶，但当ε≥３０％后，结晶度（ＸＣ＾Ｗ）趋于不变：ε可以导致晶粒破碎；ε与Ｒ对取向分布与平均取向基本上无影响，这符合片晶平行分离模型，而非叶簧弯曲模型；发现，在ε≤３０％时，层状片晶的分离为主要过程，而当ε〉３０％后，则分离的片晶会发生断层滑移     

刚性链芳香聚酰胺片晶结构

应用透射电子显微术直接观察了刚性链芳香聚酰胺结晶取向膜的结晶形态结构．结果表明了，在聚对苯二甲酰对苯二胺（ＰＰＴＡ）和聚对苯甲酰胺（ＰＢＡ）的结晶取向膜中均存在有片晶结构．片晶的厚度对ＰＰＴＡ为２０ｎｍ；而对ＰＢＡ为４０ｎｍ，其大小恰好分别与该高聚物分子链的相关长度相当．最后提出一伸直链构象的结构模型来描述这类刚性链高聚物形成片晶结构的分子链堆砌排列方式．     

辐照聚乙烯的熔融和重结晶

用差示扫描量热法（ＤＳＣ），小角Ｘ－射线散射（ＳＡＸＳ），广角Ｘ－射线衍（ＷＡＸＤ）等考察了辐照聚乙烯的熔融和重结晶，辐照破坏了聚乙烯结晶结构，使其熔融温度、结晶度均随辐照剂量的增加而降低，将辐聚乙烯熔融再结晶，其重结晶度、熔融温度随辐照剂量而下降的幅度较大，其原因被归结为片晶劈裂。     

超高分子量聚乙烯凝胶膜超高取向过程的几个不同阶段

通过Ｘ射线衍射、平板照相、扫描电镜等方法观测超高分子量聚乙烯凝胶／结晶膜取向过程中的结构形态变化，并根据ＰＥ片晶分子动力学模拟结果，提出ＵＨＭＷＰＥ凝胶膜在热拉伸取向过程中明显存在３个不同阶段，即：初期片晶转动或滑移，ｂ轴优先垂直于拉伸方向取向；随着拉伸比增大，片晶的ｃ轴平等于伸方向，同时，分子链的解折叠开始，部分非晶链也进入伸直链区取向，当拉伸比达到极限倍率时，分子链已经接近完全伸展成为比较刚直     

晶性3，4－聚异戊二烯的结构研究

采用ＷＡＸＤ、ＳＡＸＳ和Ｘ－射线平板照相法研究了不同聚合条件和拉伸倍数下的晶性３，４－聚异戊二烯的结构．结果发现，降低催化体系反应速度有利于产物结晶；不同的含氮类给电子试剂对聚合物的结晶结构影响较大．取向样品随着拉伸倍数的增加结晶度和长周期增大，微晶尺寸变小．ＳＡＸＳ的散射强度计算表明，该聚合物属多分散非均一粒子体系，微孔半径在３．５－１６．４ｎｍ间．     

晶性3，4－聚异戊二烯的结构研究

采用ＷＡＸＤ、ＳＡＸＳ和Ｘ－射线平板照相法研究了不同聚合条件和拉伸倍数下的晶性３，４－聚异戊二烯的结构，结果发现，降低催化体系反应速度有利于产物结晶；不同的含氮类给电子试剂对聚合物的结是昌结构影响较大，取向样品随着拉伸倍数的增加结晶度和长周期增大，微晶尺寸变小，ＳＡＸＳ的散射哟度计算表明，该聚合物属多分散非均一粒子体系，微孔半径在３．５－１６．４ｎｍ间。     

Self-assembly of spherical colloidal silica along the [100] direction of the FCC lattice and geometric control of crystallite formation

Opalescent starburst patterns were formed on a convex surface by sedimenting colloidal silica spheres with a low silica volume fraction. The opalescent starburst patterns were also formed by the radial expansion of the meniscus when sedimented samples were slowly dried. The dependence of starburst formation on the rate of sedimentation and drying was experimentally investigated. Self-assembled opals fabricated from colloidal silica spheres grew vertically along the [100] direction of the face-centered cubic lattice. Elongated single-crystal crystallites nearly 1 cm wide and a few centimeters long formed in the curve at the bottom of an ordinary laboratory beaker from sedimenting 200- and 290-nm colloidal silica spheres. The elongated crystallites appear to be the result of an increased sedimentation rate, which creates favorable growth conditions. This is caused by the presence of the curve in the beaker and the spheres' inability to expand into the interior of the beaker before being sedimented. A narrowing of crystallites is shown to result from the competition between neighboring crystallites and large crystallites are shown to result from a lack of competition during their formation.     

Molecular Oxygen as Mediator in the Metal Nanoparticles’ Electrosynthesis in <Emphasis Type="Italic">N,N</Emphasis>-Dimethylformamide

Ultra-fine gold (<2 nm), silver (5 ± 2 nm), and palladium (<1–2 nm) nanoparticles stabilized in polyvinylpyrrolidone shell were synthesized in N,N-dimethylformamide, using molecular oxygen dissolved in the electrolyte as mediator, by the reduction of the metals’ ions and complexes at the controlled potential of the oxygen reduction to its radical-anion. Pd-nanoparticles showed high catalytic activity in the reactions of p-nitrophenol reduction and Suzuki cross-coupling. Long-term ageing of spherical Ag-nanoparticles for 60 days in the post- electrolysis solution resulted in their consolidation (up to 17 ± 5 nm; the average size of crystallites 7.5 (3) nm). Upon similar exposure of Au-nanoparticles for 15 days, V-shaped nanoparticles were formed (length 112 ± 53 nm, width 58 ± 22 nm, crystallites 20(2)–31(1) nm); upon the isolation, dispersing into ethanol, and exposure for 48 h, hexagonal nanoparticles (105 ± 29 nm) and polygons (56 ± 25 nm, crystallites 24(2)–51(1) nm; upon dispersing into water and exposure for 8 h, spherical nanoparticles (13 ± 8 nm, crystallites 7(1)–13.4(5) nm). Thus obtained nanoparticles are characterized by methods of cyclic voltammetry, dynamic light scattering, scanning and high resolution transmission electron microscopy, and X-ray powder diffraction.     

Methane hydrate formation and decomposition: structural studies via neutron diffraction and empirical potential structure refinement

Neutron diffraction studies with hydrogen/deuterium isotope substitution measurements are performed to investigate the water structure at the early, medium, and late periods of methane clathrate hydrate formation and decomposition. These measurements are coupled with simultaneous gas consumption measurements to track the formation of methane hydrate from a gas/water mixture, and then the complete decomposition of hydrate. Empirical potential structure refinement computer simulations are used to analyze the neutron diffraction data and extract from the data the water structure in the bulk methane hydrate solution. The results highlight the significant changes in the water structure of the remaining liquid at various stages of hydrate formation and decomposition, and give further insight into the way in which hydrates form. The results also have important implications on the memory effect, suggesting that the water structure in the presence of hydrate crystallites is significantly different at equivalent stages of forming compared to decomposing. These results are in sharp contrast to the previously reported cases when all remaining hydrate crystallites are absent from the solution. For these systems there is no detectable change in the water structure or the methane hydration shell before hydrate formation and after decomposition. Based on the new results presented in this paper, it is clear that the local water structure is affected by the presence of hydrate crystallites, which may in turn be responsible for the "history" or "memory" effect where the production of hydrate from a solution of formed and then subsequently melted hydrate is reportedly much quicker than producing hydrate from a fresh water/gas mixture.     

An overview of studies on the highly dispersed uranium oxide species occluded within mesoporous MCM-41 and MCM-48 host materials

In this article we have consolidated our recent studies on anchoring of uranyl groups and encapsulation of highly dispersed nano-particles of -U₃O₈ in mesoporous MCM samples. The size of uranium oxide crystallites and the binding of uranyl groups at framework sites of host matrix depended on the preparation method, viz. wet impregnation, exchange of template cations, and the hydrothermal route. These uranium species contributed individually to the catalytic oxidation of organic molecules, such as methanol, toluene and benzyl alcohol; the uranyl groups playing a more important role at lower reaction temperatures. Also, the size and the lattice oxygen of uranium oxide crystallites played a vital role, not only in the lowering of reaction onset temperature but also in deciding the nature and the reactivity of the transient surface species formed during the oxidation of above mentioned organics. For instance, the results of in situ IR spectroscopy experiments have shown that while larger-size U₃O₈ crystallites help in the growth of certain oxymethylene (–OCH₂) and polymerized oxymethylene (–OCH₂)_n species, adsorption of methanol on smaller size particles helped in the additional formation of formate-type complexes. Thus, a relationship was found between the size of uranium oxide crystallites, the nature of the transient species formed and the catalytic conversion of methanol to form CO₂, CO and methane. In addition, the uranyl ions anchored within the pore system of host matrix are found to serve as efficient heterogeneous photocatalysts for the sunlight-assisted deep oxidation of organic molecules in the vapor phase and at room temperature. The reaction mechanisms, accounting for the catalytic properties of occluded UO_x species without and in the presence of radiation, are discussed in the light of the above mentioned results.     

A crystallite packing model for pseudoboehmite formed during the hydrolysis of trisecbutoxyaluminium to explain the peptizability

A model for pseudoboehmite crystallite packing formed during the hydrolysis of trisecbutoxyaluminium is postulated. The model describes platelike crystallites of pseudoboehmite stacked in a sharing edges only configuration. With this type of stacking, the pore sizes detected are approximately equal to the crystallite sizes of the hydrolysates. The hydrolysates age via a dissolution re-precipitation reaction. This increases the size of the crystallite size of the pseudoboehmite formed, speeding peptization by allowing nitrate ions to enter pores and access the surfaces of the crystallites. This type of model also allows an explanation for the peptization kinetics of systems containing sec-butanol formed during the hydrolysis of trisecbutoxyaluminium.     

Crystallite orientation during melting of oriented ultra-high-molecular-weight polyethylene

The changes in crystallite orientation during melting of oriented ultra-high-molecular-weight polyethylene (UHMW PE) were investigated by means of wide-angle X-ray scattering. The orientation distribution of crystallites in drawn UHMW PE is composed of two components differing in width. The narrow and broad components revealed in this study indicate the existence of two classes of crystallites with different orientability. Some of the crystallites are oriented almost perfectly even at low-draw ratios, while the others do not orient so effectively. The analysis of melting behaviour of such a texture composed of orthorhombic crystals indicates that highly oriented crystallites are formed by taut molecules and transform first to the hexagonal phase, while the molecules constituting low-oriented crystallites melt directly to the typical amorphous phase. The increase in orientation of highly oriented crystallites during their partial melting, observed in the samples kept at constant length and even those allowed to shrink under constant load, can be explained by the kinetic factor proposed by Ziabicki. Received: 11 September 1998 Accepted in revised form: 18 February 1999     

Structure of ethylene sulphide crystallites in block copolymers

Block copolymers, having the configuration ethylene sulphide-isoprene-styrene or ethylene sulphide-isoprene-ethylene sulphide, have been characterized to define the structure of the ethylene sulphide moiety. It is concluded that ethylene sulphide-isoprene-styrene block copolymers exist in solution and in bulk (above the styrene softening point) as radial aggregates held together by polyethylene sulphide crystallites. During polymerization, these crystallites are formed with a linear extended chain morphology which is retained in bulk in ethylene sulphide-isoprene-styrene copolymers: in the copolymers which require processing above the melting point of the ethylene sulphide crystallites, the linear morphology is destroyed during moulding.     

Large single crystals of colloidal silica spheres appearing in deionized and diluted suspension

Close-up color photographs are taken for crystallites (single crystals surrounded by the grain boundaries) in the colloidal crystals of monodisperse silica spheres (diameter: 110 nm±4.5 nm (standard deviation)). Very large crystallites (34 mm) are observed with the naked eye (for the first time) for the completely deionized and diluted suspensions. Deionization is carefully made with the mixed beds of ion-exchange resins more than 2 weeks old. Size of the crystallites increases sharply as the concentration of spheres decreases, and becomes small at the concentrations slightly higher than the critical concentration of melting toward liquid-like structure. Shape of the crystallites, i.e., mixture of triangle, cubic, pentagonal, hexagonal, cone-like, etc., is recognized in the photographs.     

A Preparation Method for Well‐Defined Crystallites of Mgcl2‐Supported Ziegler‐Natta Catalysts and their Observation by AFM and SEM

A method for the preparation of well‐defined crystallites of MgCl₂‐supported Ziegler‐Natta catalysts on Si wafers has been developed. This has been achieved by the spin‐coating of a MgCl₂ solution onto a flat Si wafer, followed by controlled crystal growth to give well‐defined MgCl₂ · nEtOH crystallites. The growth of the crystallites on the flat silica facilitates their characterization using electron and scanning probe microscopy. The relative proportions of 120° and 90° edge angles indicate the preference for the formation of a particular crystallite face for the MgCl₂. Polyethylene has been identified to be formed on the lateral faces of the crystallite.

     

Hydrogen-bonded monolayers and interdigitated multilayers at the air-water interface

Crystalline monolayers of octadecylsulfonate amphiphiles (C18S) separated by hydrophilic guanidinium (G) spacer molecules were formed at the air-water interface at a surface coverage that was consistent with that expected for a fully condensed monolayer self-assembled by hydrogen bonding between the G ions and the sulfonate groups. The surface pressure-area isotherms reflected reinforcement of this monolayer by hydrogen bonding between the G ions and the sulfonate groups, and grazing incidence X-ray diffraction (GIXD) measurements, performed in-situ at the air-water interface, revealed substantial tilt of the alkyl hydrophobes (t = 49 degrees with respect to the surface normal), which allowed the close packing of the C18 chains needed for a stable crystalline monolayer. This property contrasts with behavior observed previously for monolayers of hexadecylbiphenylsulfonate (C16BPS) and G, which only formed crystallites upon compression, accompanied by ejection of the G ions from the air-water interface. Upon compression to higher surface pressures, GIXD revealed that the highly tilted (G)C18S monolayer crystallites transformed to a self-interdigitated (G)C18S crystalline multilayer accompanied by a new crystalline monolayer phase with slightly tilted alkyl chains and disordered sulfonate headgroups. This transformation was dependent on the rate of compression, suggesting kinetic limitations for the "zipper-like" transformation from the crystalline monolayer to the self-interdigitated (G)C18S crystalline multilayer.