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141.
The elastic constants of poly(L ‐lactic acid) (PLLA) crystals are reported on the basis of a commercial software package and the published crystal structure of the α form. A chain modulus of 36 GPa and a shear modulus of 3 GPa have been obtained for cylindrically symmetric aggregates of perfectly oriented crystals. The helical conformation of the PLLA molecule reduces the stiffness in the chain axis direction because bond rotation plays a significant role in the deformation. X‐ray crystal strain measurements suggest that shear of the α crystal parallel to the helix axis is the easiest mode of deformation, in agreement with the expectations obtained from the low shear modulus of 3 GPa obtained from the theoretical calculations. A combination of small‐ and wide‐angle X‐ray scattering, differential scanning calorimetry, dynamic mechanical thermal analysis, and shrinkage measurements has been used to characterize the structure that develops and the crystal transformation that occurs during fiber processing. The structure that develops during processing very much depends on the crystal transformation, and a structural model is proposed for fibers at different degrees of plastic deformation. The transformation of the α crystal into the β form and vice versa is governed primarily by shear along the helix axis because the chains must shear past each other during the crystal transformation, disrupting the lamellar packing. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 892–902, 2007 相似文献
142.
Ph. De Groote A. M. Jonas J. Devaux P. Godard 《Journal of Polymer Science.Polymer Physics》2001,39(17):2022-2034
The melt of polydodecamide (PA‐12) shows a significant viscosity decrease upon incorporation of benzenesulfonamide plasticizers (BSAs), this effect being maximum for a monofunctional BSA with a 12‐carbon‐atom‐long alkyl chain. Nonexhaustive X‐ray diffraction analysis developed on isothermally crystallized samples validated a two‐phase model for describing PA‐12 plasticized by N‐(n‐butyl)benzenesulfonamide (BBSA). The massive presence of BBSA between the lamellar crystals was established, and lamellar fragmentation was also observed. Further, a steady increase in PA‐12 crystallinity with an increasing BBSA content was evident (and confirmed by DSC) and is consistent with the plasticizer easing the mobility of polymer chains during crystallization. Large melting point depressions resulting from both polymer–plasticizer miscibility and lamellar fragmentation were observed with several mono‐ and bifunctional BSA plasticizers. Phase separation in PA‐12 solid state was only observed at 20 mol % of ?SO2NH2, alhough miscibility occurred in the melt. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2022–2034, 2001 相似文献
143.
David Grosso Cédric Boissière Lionel Nicole Clément Sanchez 《Journal of Sol-Gel Science and Technology》2006,40(2-3):141-154
The general approach to mesoporous ordered silica and crystalline metal oxide thin films, involving soft chemistry, liquid
deposition technique, surfactant templating and tuned annealing conditions, is presented. Highly ordered cubic mesoporous
structures, made of amorphous SiO2 xerogels or nanocrystalline particles such as anatase TiO2, γ-Al2O3, ilmenite CoTiO3, or perovskite SrTiO3 have been chosen to illustrate this article. In situ time resolved SAXS analyses, involving synchrotron high flux, were used to assess the various phenomena involved during deposition,
thermal treatment and crystallisation. It will be demonstrated that the self-assembly is not only critically dependant on
the structuring agent to inorganic volume fraction, but also on chemical and processing parameters such as the inorganic degree
of condensation and the atmosphere applied during the deposition. A general model of self-assembly, based on a Tunable Stated
State, is proposed. Concerning the crystallisation step, we will show that, depending on the heating regime, ordered mesoporous
nanocrystalline framework can be obtained through a rigorous control of nucleation, growth and diffusive sintering taking
successively place in the mineral matrix. Finally, the porosity and pore size distribution of these silica and non silica
layers were assessed using ellipsometry porosimetry. This novel and very efficient technique provides the full characteristics
of the layer porosity by measuring the variation of optical constant associated to the adsorption/desorption of a gas within
the porous network. 相似文献
144.
Weihua Wang Li Li Xuanji Yu Haoya Han Xuhong Guo 《Journal of polymer science. Part A, Polymer chemistry》2014,52(24):1681-1688
Magnetic nanoparticles (MNPs) with a size of about 2 nm are prepared in nanoreactors of spherical polyelectrolyte brushes (SPBs) consisting of a solid polystyrene (PS) core and a shell of linear poly(acrylic acid) (PAA) chains densely grafted onto the core by one end. The synthesized MNP are strongly adhered to PAA chains due to the intense interaction of chemical coordination with the carboxyl groups. The generation of MNP in SPB layer is legibly revealed by small-angle X-ray scattering (SAXS) due to the significant increase in electron density. The radial distribution of MNP in SPB is built by fitting SAXS data. Most of MNP are found to locate nearby the surface of PS core. Compared to dynamic light scattering and transmission electron microscopy, SAXS can observe the generation and distribution of MNP in SPB as well as the changes upon changing pH and salt concentration in real time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1681–1688 相似文献
145.
Makoto Yamaguchi Takeshi Terao Akihiro Ohira Naoki Hasegawa Kazuhiko Shinohara 《Journal of Polymer Science.Polymer Physics》2019,57(13):813-818
Perfluorosulfonic acid ionomers have been widely used as proton‐conducting materials in polymer‐electrolyte membrane fuel cells and their dispersions in polar solvents are used to prepare proton‐conducting membranes as well as catalyst layers. While it has been known that the dispersed particles become monodisperse after heating to 230 °C or above, their size and shape have not been fully characterized yet. Cryogenic transmission electron microscopy images and small‐angle X‐ray scattering profiles of the dilute aqueous dispersions before and after heating to 240 °C have clearly shown that rod‐like particles became significantly shorter cylinders without changing their radii. Particle length distributions were lognormal and average molar mass and dispersity after heating to 240 °C were consistent with the values from size exclusion chromatography. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 813–818 相似文献
146.
Sebastián Tognana Leonel Silva Walter Salgueiro 《Journal of Polymer Science.Polymer Physics》2014,52(13):882-886
Real‐time experiments using small‐angle X‐ray scattering and differential scanning calorimetry on blends of the semicrystalline polyester poly(3‐hydroxybutyrate) (PHB) and amorphous monomer epoxy DGEBA (diglycidyl ether of bisphenol A) were performed. Differences in the processes of melting and re‐crystallization were observed in blends relative to pure PHB. The results obtained in this study indicated that re‐crystallization is more important in blends with 50% DGEBA than in pure PHB. Moreover, segregation toward the interfibrillar region would facilitate re‐crystallization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 882–886 相似文献
147.
The multiple melting behavior of poly(ε‐caprolactone) (PCL) was investigated by real‐time small angle X‐ray scattering (SAXS) and wide angle X‐ray scattering (WAXS) measurements coupling with differential scanning calorimetry (DSC). Semicrystalline specimens prepared by a continuous cooling process showed lengthening of the Bragg period during the progress of double melting. A model of variable thickness of lamella was proposed to fit to the SAXS patterns and revealed that both the crystalline lamella and the amorphous layer contributed to the increase in Bragg period while the later dominated the contribution. The model of variable thickness although satisfied the SAXS data was unable to compromise the data from other probing tools. A modification of the model proposed that each lamella piling up to construct the stacks in the crystallites was itself nonuniform in thickness. The modification with the parallel occurrence of the mechanism of surface melting and crystallization successfully compromised the observations from SAXS, DSC, and optical microscopy and provided a new perspective for the explanation to lengthening of the Bragg period related to multiple melting behavior. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1777–1785, 2010 相似文献
148.
149.
Small-angle X-ray scattering, wide-angle X-ray diffraction and differential scanning calorimetry analysis were carried out to evaluate the evolution of the supermolecular structure of poly(ethylene terephthalate) (PET) during isothermal crystallization and annealing process. PET was crystallized from the melt by isothermal treatments at 226 °C. Partially crystallized samples were prepared interrupting the crystallization by quenching, while prolonged treatments were performed to prepare annealed samples. The adopted crystallization procedures allowed to form crystals which developed during primary and secondary crystallization, and the annealing process. On the basis of X-ray data, the lamellar and amorphous phases were unambiguously attributed. The lamellar thickness and the crystallinity progressively enhance with increasing the time of thermal treatment; on the contrary, the long period decreases and this effect is mainly due to the contraction of the amorphous phase. The melting behaviour of the annealed samples indicates that the heating-induced crystal reorganization phenomena are inconsistent. The interdependency between the melting temperature and the crystal thickness allowed to extrapolate the equilibrium melting temperature. 相似文献
150.
Xilian Wei Shizhou Fu Baolin Yin Qing Sang Dezhi Sun Jiali Dou Zhongni Wang Lusheng Chen 《Fluid Phase Equilibria》2010
Phase diagrams for ternary system of the Gemini cationic surfactants, N,N-long chain alkyl-2-hydroxyl-N,N,N,N-tetramethyl diammonium dichloride (GnCl2) with butanol and water have been drawn based on experimental data at 25 °C. The phase diagrams show that L phase and different liquid crystalline phases are existent in the ternary system at different components. Electric conductivity of the L phase has been studied. Small-angle X-ray scattering (SAXS), 2H (deuterium) quadrupolar splitting (2H NMR) and the polarizing-light microscope were employed to confirm the characteristic texture structures and the microstructure of three different liquid crystalline phases. 相似文献