Phase behavior in liquid crystallization for diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components

Phase behavior in liquid crystallization was studied for a series of liquid crystalline (LC) diblock copolymers consisting of rubbery amorphous and side-chain liquid crystalline components, poly(n-butyl acrylate) (PBA) and poly[11-(4′-cyanophenyl-4″-phenoxy)undecyl acrylate] (PLC), respectively, using a time-resolved small-angle X-ray scattering (SAXS) techniques, DSC and polarized optical microscopy (POM). The block copolymers used had three kinds of copolymer compositions, 44, 20 and 15 wt% of PLC compositions (BLC44, BLC20 and BLC15, respectively). BLC44 showed a smectic liquid crystalline structure. In the process of liquid crystallization for BLC44, the SAXS peak due to the microphase separation structure existing before liquid crystallization was changed continuously to be at a smaller angular side, and at almost the same time, a new peak appeared at a further smaller angular side and developed. The former peak disappeared with the development of liquid crystallization. The behavior of these SAXS peaks suggests that the microphase separation structure was changed discretely at the transition from isotropic to smectic and that two phases coexist in the early stage of the liquid crystallization. The coexistence of two peaks in the early stage of the liquid crystallization corresponded to the POM observation. In the isotropization process, coexistence of two phases was not observed. For BLC20 exhibiting a cylindrical structure in both isotropic and liquid crystalline states, the liquid crystalline structure was not smectic but probably nematic, and the spacing was changed continuously in liquid crystallization. No liquid crystallization was observed in SAXS, POM and DSC for BLC15. The orientation of smectic layers within lamellar domains was investigated using 2D-SAXS images. The smectic layer was aligned perpendicularly to the lamellar interface.     

有机羧酸钠盐对PET结晶和熔融行为的影响

采用差示扫描量热仪研究了5种具有不同取代基的苯甲酸钠盐作为结晶成核剂对聚对苯二甲酸乙二醇酯（HET）结晶和熔融行为的影响，并同滑石粉进行了对比。结果表明，成核剂的加入能明显改变PET的结晶和熔融行为。苯甲酸钠、对苯二甲酸甲酯单羧酸钠和对羟基苯甲酸钠提高既汀的熔融结晶温度（Tc）分别达22．93、21．7和19．37℃，但使PET降解严重；对苯酚钠甲酸钠能够提高Tc达17．75℃且对PET相对分子质量影响很小；对苯二甲酸二钠成核作用最差。低于滑石粉。此外，成核剂的成核能力越强，PET双熔融峰中的低温峰顶温度就越高。     

Structural properties of phosphorous-doped polycrystalline silicon

The structural properties and hydrogen bonding of undoped and phosphorous doped polycrystalline silicon produced by step-by-step laser dehydrogenation and crystallization technique were investigated using Raman spectroscopy and hydrogen effusion measurements. At low laser fluences, E_L, a two-layer system is created. This is accompanied by the change in hydrogen bonding. The intensity of the Si–H vibration mode at 2000 decreases faster than the one at 2100 cm⁻¹. This is even more pronounced in phosphorous-doped specimens. The laser crystallization results in an increase of the hydrogen binding energy by approximately 0.2–0.3 eV compared to the amorphous starting materials.     

新型超微晶软磁合金FePCCuMoSi微观结构缺陷的正电子湮没研究

用正电子湮没方法研究了新型超微晶软磁合金的微观结构缺陷，样品选用的是在不同温度下退火的Ｆｅ８１Ｐ１２Ｃ３Ｃｕ１Ｍｏ０．５Ｓｉ２．５合金，结果表明，合金的微观结构构陷大小，密度随退火温度有规律地变化，这种现象可能与非晶的晶化过程有关。     

Fe73.5Cu1Nb3Si13.5B9非晶合金的晶化动力学

用ＤＴＡ结合ＸＲＤ了Ｆｅ７３．５Ｃｕ１Ｎｂ３Ｓｉ１３．５Ｂ９晶合金的晶化动力学。表明，该事金在５００℃时析出α－Ｆｅ（Ｓｉ）相。晶化初期激活能最小为２４２ｋＪ／ｍｏｌ，它随晶化量的增加，在ＸＣ为０．４－０．８时，呈极大值为５２０ｋＪ／ｍｏｌ。在６２４℃时析出Ｆｅ２Ｂ相。     

PC／PET共混物的非等温结晶动力学

采用等速变温ＤＳＣ法对ＰＣ／ＰＥＴ共混体系的非等温结晶动力学进行了研究，结果表明，从玻璃态结晶时，随着ＰＣ含量的增加，ＰＥＴ组分的结晶速率先增加后降低。耐从熔体结晶时，体系的结晶速率随着ＰＣ含量的增加而增加，讨论了ＰＣ对ＰＥＴ组分结晶过程的影响。     

Morphology and structure of poly(p-phenylene terephthalamide) crystallized from dilute organic solution

The high-temperature crystallization of poly(p-phenylene terephthalamide) (PPTA) from dilute organic solutions was achieved through the introduction of a non-solvent, or precipitating agent, at the desired crystallization temperature. The morphology and crystal structure were examined for crystals produced from PPTA polymer with two different molecular weights (M_w = 46000 and 3430 g mol⁻¹), using transmission electron microscopy. For the high-molecular-weight polymer, ribbon-like crystals were produced, while the low-molecular-weight polymer yielded small needles or platelets. In both cases, electron diffraction showed that the Northolt allomorph was obtained. For the high-molecular-weight polymer, the molecular axes were parallel to the ribbon axes in a chain-extended type structure. A hypothesis for the orientation of the low-molecular-weight PPTA in the small platelets, is also given.     

The effect of structural features on mechanical properties of loose optical fiber poly(butylene terephthalate) tubes

Results of a study on the modifying mechanical properties of loose optical‐fiber poly(butylene terephthalate) (PBT) tubes, produced during the standard industrial extrusion process, show that heat treatment make the structure of their material to change. The study comprised measurements of mechanical strengths properties of the tubes (tensile strength, compression strength, kinking) and determination of tube material structure [by differential thermal analysis (DTA), wide angle X‐ray scattering analysis (WAXD), and scanning electron microscopy (SEM)]. Results of the study allowed observation that the annealing at 70°C for 34 h of the tubes caused the crystalline α phase to increase in the tube material from ～28.5% to ～31.5% and the structure of the existing crystallites to become more perfect. This made the values of certain mechanical properties of the tubes to increase even by as much as 30%. The tubes following such thermal treatment could be used in cables exposed to heavy‐duty operation in arduous environments, where a larger margin from the standpoint of mechanical properties is required. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2130–2134, 2002     

Kinetic analysis of the crystallization of poly(p-phenylene sulphide)

Growth rates of spherulites were measured in poly(p-phenylene sulphide) crystallized from the melt and the quenched glass over the temperature range 100°C–280°C, possibly the most extensive overall range yet reported for any polymer and, as such, most propitious for study of régime III crystallization. For a medium M.wt. polymer, a régime II → III transition was obtained at 208°C using values of transport parameters common to many polymers ($\text{U1 = 1400}\text{cal mol}{}^{\mathrm{?1}}$, T_∞ ? T_g = 30°C) together with experimentally determined values of T⁰_m(315°C) and T_g(92°C). Under these conditions, the régime III/II slope ratio was found to be 2.07 (i.e. only 3.5% higher than predicted by régime theory), and reasonable estimates of surface free energies and of the work of chain folding were obtained. Other choices of the transport terms, including WLF and zero values, did not allow successful kinetic analyses. Although a régime I → II transition is predicted to occur at the high-temperature end of our growth-rate data, we found no experimental evidence for it. For a low M.wt. polymer, our analysis showed that régime III kinetics is obeyed at low temperatures, while at higher ones there is a continuous departure from that behaviour without, however, full attainment of régime II kinetics.     

Effect of pH on the Crystallization of Homogeneously Precipitated Nanosized PZT Powder

Nanosized lead zirconate titanate (PZT) powder with Zr:Ti ratio in the morphotropic phase boundary region was synthesized by homogeneous precipitation of metal ions. The powder precipitated at 90°C and at pH 6.7 resulted single-phase perovskite lead zirconate titanate powder when calcined at 550°C and above for 4 hours in air. The solution pH and the precipitation temperature strongly affect the composition of the calcined powder. The results obtained by structural characterization of homogeneously precipitated powder were compared with that obtained from the conventional precipitation method using ammonia in terms of crystallization, homogeneity, and microstructure. The homogeneously precipitated powder showed smaller particle size, minimum agglomeration and uniform shape on calcination and annealing. Powdered samples that precipitated by homogeneous precipitation crystallized directly to perovskite PZT, without any intermediate pyrochlore phase formation. In contrast, the NH₃ precipitated powder converted to perovskite PZT via metastable pyrochlore and it showed phase segregation upon annealing at higher temperatures. The reaction kinetics has been studied by X-ray diffraction, differential thermal analysis, and differential scanning calorimetry.