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.     

Psychological separation, attachment security, vocational self-concept crystallization, and career indecision: A structural equation analysis.

Structural equation modeling was used to test theoretically based models in which psychological separation and attachment security variables were related to career indecision and those relations were mediated through vocational self-concept crystallization. In contrast to previous studies, which have found either weak or no support for a relation between separation or attachment security variables and career indecision, results based on a sample of 350 college students indicated that some components of separation and attachment security did relate to career indecision in a theoretically supportable direction. Results also revealed that regardless of whether global or component career indecision measures were used, separation and attachment security effects on indecision were at least partially mediated through vocational self-concept crystallization. The strongest mediated relations were observed for the effects of attachment anxiety and maternal separation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Criteria and methodology for the evaluation of conservation interventions on treated porous stone susceptible to salt decay

Susceptibility of stone to salt decay is directly related to its microstructural and mechanical characteristics. In the present work, a porous stone from a quarry in Cyprus was examined. Samples of this stone were consolidated and protected with certain conservation materials. The modification of microstructural characteristics of the stone was evaluated by mercury intrusion porosimetry, while its mechanical characteristics were measured by compressive and bending strength tests. From these data, the susceptibility of Cyprus stone to salt (NaCl) decay was estimated. The values of crystallization pressure of NaCl were calculated and compared to the experimentally measured compressive and tensile strength of the stone, in order to examine the probability of stone disruption due to salt crystallization. The development of the phenomenon after coarse pores’ filling with crystals, i.e. crystallization of salts in capillaries or mechanical failure of the stone, was determined by thermodynamic analysis. Additionally, artificial weathering tests of marine salt spray were performed for the evaluation of stone’s durability after the conservation. The treated stone proved to be resistant to salt decay, as it presented ameliorated microstructural and mechanical characteristics, concerning decay due to soluble salt crystallization. The most possible thermodynamic scenario was small pores repletion with crystals, avoiding mechanical failure of the stone.     

含两种不同共聚组分改性聚酯的结晶速率

添加己二酸、间苯二甲酸,聚乙二醇对PET进行改性,合成样品。用DSC法研究合成共聚物的等温结晶动力学。结果表明,在所选择的温度范围内,共聚物很好的符合Avrami方程。随温度的升高,共聚物的结晶速度常数K和Avrami指数n逐渐减小,结晶速度G逐渐降低。含2种柔性组分的共聚酯随着一种柔性组分含量的增加,结晶速率G上升;含一种刚性一种柔性组分的共聚酯随刚性组分含量的增加,结晶速率G下降。     

Crystallization of Polymer-Derived Silicon Carbonitride at 1873 K under Nitrogen Overpressure

The chemical stability of an amorphous silicon carbonitride ceramic, having the composition 0.57SiC·0.43Si₃N₄·0.49C is studied as a function of nitrogen overpressure at 1873 K. The ceramic suffers a weight loss at p _N2 < 3.5 bar (1 bar = 100 kPa), does not show a weight change from 3.5 to 11 bar, and gains weight above 11 bar. The structure of the ceramic changes with pressure: it is crystalline from 1 to 6 bar, amorphous at ∼10 bar, and is crystalline above ∼10 bar. The weight-loss transition, at 3.5 bar, is in excellent agreement with the prediction from thermodynamic analysis when the activities of carbon, SiC, and Si₃N₄ are set equal to those of the crystalline forms; this implies that the material crystallizes before decomposition. The amorphous to crystalline transition that occurs at ∼10 bar, and which is accompanied by weight gain, is likely to have taken place by a different mechanism. A nucleation and growth reaction with the atmospheric nitrogen is proposed as the likely mechanism. The supersaturation required to nucleate α-Si₃N₄ crystals is calculated to be 30 kJ/mol.     

氮对纳米硅氮薄膜品化的影响

在电容式耦合等离子体化学气相沉积系统中，用高氢稀释硅烷和氮气为反应气氛制备纳米硅氮（ｎｃ－ＳｉＮｘ：Ｈ）薄膜结果表明：当Ｎ＿２／ＳｉＨ＿４气体流量比（Ｘｎ）从１增加为４时，薄膜的晶态年从５８％降至１４％，晶粒尺寸从１０ｎｍ降至５ｕｍ，Ｎ／Ｓｉ含量比从０．０３增至０．１２．当Ｘｎ≥５，则生成非晶硅氮（ａ－ＳｉＮｘ：Ｈ）薄膜．当Ｘｎ从１增加为１０时，薄膜暗电导率从１０￣（－５）（Ωｃｍ）￣（－１）降至１０￣（－１１）（Ωｃｍ）￣（－１），具有逾渗行为，这与薄膜的晶态率紧密相关．