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Crystalline Domains (crystalline + domain)
Selected AbstractsSynthesis and Characteristics of a Nonaggregating Tris(tetrathiafulvaleno)dodecadehydro[18]annuleneCHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2006Asbjørn Sune Andersson Abstract A new tris(tetrathiafulvaleno)dodecadehydro[18]annulene with six peripheral n -hexyl substituents was prepared by oxidative Glaser,Hay cyclization of a corresponding diethynylated tetrathiafulvalene (TTF) precursor. The electronic properties of the neutral and oxidized species were studied by both UV/Vis absorption spectroscopy and electrochemistry. From these studies, it transpires that the strongly violet-colored macrocycle does not aggregate in solution to any significant degree, which was confirmed by 1H NMR spectroscopy. This reluctance towards aggregation contrasts that observed for related TTF,annulenes containing other peripheral substitutents. Oxidation of the TTF,annulene occurs in two three-electron steps as inferred from both the peak amplitudes and the spectroelectrochemical study. We find that the tris(TTF)-fused dehydro[18]annulene is more difficult to oxidize (by +0.20 V) than the silyl-protected diethynylated mono-TTF precursor. In contrast, the first vertical ionization energy calculated at the B3,LYP/6,311+G(2d,p) level for the parent tris(TTF)-fused dehydro[18]annulene devoid of peripheral hexyl substituents is in fact lower (by 0.44 eV). Moreover, the surface morphology of 1,d drop-cast on a mica substrate was investigated by atomic force microscopy (AFM). Crystalline domains with slightly different orientations were observed. The thickness of individual layers seen in the crystalline domains and the thickness of a monolayer obtained from a very dilute solution were determined to 1.8,1.9 nm. This thickness corresponds to the diameter of the macrocycle and the layers seen in the film are apparently formed when the molecules stack in the horizontal direction relative to the substrate. [source] Conformation analysis and molecular mobility of ethylene and tetrafluoroethylene copolymer using solid-state 19F MAS and 1H , 19F CP/MAS NMR spectroscopyMAGNETIC RESONANCE IN CHEMISTRY, Issue 7 2004Keitaro Aimi Abstract The changes in the conformation and molecular mobility accompanied by a phase transition in the crystalline domain were analyzed for ethylene (E) and tetrafluoroethylene (TFE) copolymer, ETFE, using variable-temperature (VT) solid-state 19F magic angle spinning (MAS) and 1H , 19F cross-polarization (CP)/MAS NMR spectroscopy. The shifts of the signals for fluorines in TFE units to higher frequency and the continuing decrease and increase in the T1,F values suggest that conformational exchange motions exist in the crystalline domain between 42 and 145 °C. Quantum chemical calculations of magnetic shielding constants showed that the high-frequency shift of TFE units should be induced by trans to gauche conformational changes at the CH2CF2 linkage in the E,TFE unit. Although the 19F signals of the crystalline domain are substantially overlapped with those of the amorphous domain at ambient probe temperature (68 °C), they were successfully distinguished by using the dipolar filter and spin-lock pulse sequences at 145 °C. The dipolar coupling constants for the crystalline domain, which can be estimated by fitting the dipolar oscillation behaviors in the 1H , 19F CP curve, showed a significant decrease with increasing temperature from 42 to 145 °C. This is due to the averaging of 1H19F dipolar interactions originating from the molecular motion in the crystalline domain. The increase in molecular mobility in the crystalline domain was clearly shown by VT T1,F and 1H , 19F CP measurements in the phase transition temperature range. Copyright © 2004 John Wiley & Sons, Ltd. [source] Ternary miscibility in blends of three polymers with balanced binary interactionsPOLYMER ENGINEERING & SCIENCE, Issue 3 2003E. M. Woo This study demonstrates and discusses ternary miscibility in a three-polymer blend system based on balanced binary interactions. A truly miscible ternary blend comprising poly(,-caprolactone) (PCL), poly(benzyl methacrylate) (PBzMA), and poly(vinyl methyl ether) (PVME), was discovered and reported. Miscibility with phase homogeneity (excluding the PCL crystalline domain) in a wide composition range has been demonstrated using criteria of thermal transition behavior, cloud point, and microscopy characterization. At ambient temperature, the three-polymer ternary system is completely miscible within the entire composition range (i.e., no immiscibility loop). However, at slightly elevated temperatures above the ambient. phase separation readily occurred in this originally miscible ternary blend. A quite low "lower critical solution temperature" (LCST) near 75°C was found for the ternary blend, which is much lower than any of those for the binary pairs. Balanced interactions with no offsetting ,, among the three binary pairs were a key factor leading to a ternary miscible system. [source] Determination of intermolecular distance for a model peptide of Bombyx mori silk fibroin, GAGAG, with rotational echo double resonanceBIOPOLYMERS, Issue 2 2002Tsunenori Kameda Abstract Rotational echo double resonance NMR spectroscopy is applied for the determination of the distance of intermolecular chains of pentapeptide, GAGAG (G: Gly, A: Ala), a model typical of the crystalline domain in Bombyx mori silk fibroin. 1:4 mixture of G[1- 13C]AGAG and GAG[15N]AG with antiparallel ,-sheet structure was used to determine the distance of intermolecular hydrogen bonding between adjacent molecules within pleated sheet and the 13C,15N interatomic distance was determined to be 4.3 Å. On the other hand, 1:4 mixture of GAG[1- 13C]AG and GAG[15N]AG gave information on the interpleated sheet arrangement. When we assumed the same distances between two interpleated sheets, the distance was calculated to be 5.3 Å and the angle 15N,13C,15N was 180°. © 2002 Wiley Periodicals, Inc. Biopolymers 64: 80,85, 2002 [source] Solid-State Supramolecular Organization of Polythiophene Chains Containing Thienothiophene UnitsADVANCED MATERIALS, Issue 10-11 2009Patrick Brocorens Abstract We use molecular modeling and the simulation of X-ray diffraction patterns to determine the molecular packing of a thiophene-based polymer showing exceptionally high field-effect mobilities (up to 1,cm2,V,1,s,1). We focus on the organization of the polymer chains in lamellae and the orientation of these crystalline domains with respect to the substrate in thin films. The analysis is supported by XRD and NEXAFS experiments and is complemented by calculating intermolecular transfer integrals, which govern the charge mobility. [source] Achieving Perpendicular Alignment of Rigid Polythiophene Backbones to the Substrate by Using Solvent-Vapor Treatment,ADVANCED MATERIALS, Issue 21 2007H. Lu The rigid backbone of the poly(3-butylthiophene) molecule adopts a perpendicular orientation with respect to the substrate by using a solvent-vapor treatment (see figure). Small and closely contacting spherulites instead of conventional whisker-like crystals are achieved. This could be utilized to improve charge-carrier mobility particularly in the direction normal to the film plane by designing and constructing thick crystalline domains in the functional layer. [source] Crystallization effects on autoclave foaming of polycarbonate using supercritical carbon dioxideADVANCES IN POLYMER TECHNOLOGY, Issue 4 2006L. Mascia Abstract In this study, the conditions leading to the formation of cells and to the onset of crystallization of polycarbonate were examined with the use of supercritical carbon dioxide for the production of foams from preforms. Small plaques cut from extruded sheets were treated with supercritical carbon dioxide in an autoclave at temperatures varying from 60 to 200°C and from 4.5 to 30 MPa pressure. Visual observations and stereoscan electron microscopy examination revealed that penetration of supercritical carbon dioxide takes place via the advancing layer mechanism and that, for the particular grade of polycarbonate used in this study, the nucleation of the cells can take place at temperatures as low as 60°C. It requires, however, long treatment times and high pressures, and the growth of foam cells is severely restricted. Nucleation and growth of cells occurred much more readily at somewhat higher temperatures. With treatments at around 80°C, the onset of crystallization started to impose considerable hindrance to the formation of uniform and evenly distributed cells. This becomes increasingly evident at higher temperatures, between 100 and 180°C, owing to the formation of large spherulitic crystalline domains. A very effective nucleation and growth mechanism for the formation of cells was obtained, on the other hand, with treatments at 200°C due to the absence of crystallization phenomena. The degree of crystallinity increased with increasing treatment temperature, and the resulting morphology gave rise to two broad melting peaks. These are displaced to higher temperatures and become closer, merging into one peak with a low-temperature shoulder. These events were monitored by thermal analysis and wide-angle X-ray diffraction examinations. © 2007 Wiley Periodicals, Inc. Adv Polym Techn 25:225,235, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20075 [source] Structure and mechanical properties of cellulose derivatives/soy protein isolate blendsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008Ziyan Zhou Abstract Biodegradable and biocompatible composites based on soy protein isolate (SPI) and various cellulose derivatives have been prepared, and the dependence of structures and mechanical properties on the content and species of cellulose derivatives for the composites were investigated by X-ray diffraction, differential scanning calorimetry, scanning electron microscope, and tensile test. The selected cellulose derivatives, such as methyl cellulose (MC), hydroxyethyl cellulose (HEC), and hydroxypropyl cellulose, were miscible with SPI when the content of cellulose derivatives was low, and then the isolated crystalline domains, shown as the structures of network and great aggregate, formed with an increase of cellulose derivative content. The miscible blends could produce the higher strength, and even result in the simultaneous enhancement of strength and elongation for the HEC/SPI and MC/SPI blends. Meanwhile, the moderate content of great MC domains also reinforced the materials. However, the damage of original ordered structure in SPI gave the decreased modulus. Since all the components, i.e., cellulose derivatives and soy protein, are biocompatible, the resultant composites are not only used as environment-friendly material, but the biomedical application can be expected, especially for the tissue engineering scaffold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Synthesis and properties of gradient copolymers based on 2-phenyl-2-oxazoline and 2-nonyl-2-oxazolineJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2009Hanneke M. L. Lambermont-Thijs Abstract In this study, the structure,property relationships for a series of statistical 2-nonyl-2-oxazoline (NonOx) and 2-phenyl-2-oxazoline (PhOx) copolymers were investigated for the first time. The copolymerization kinetics were studied and the reactivity ratios were calculated to be rNonOx = 7.1 ± 1.4 and rPhOx = 0.02 ± 0.1 revealing the formation of gradient copolymers. The synthesis of a systematical series of NonOx,PhOx copolymers is described, whereby the amount of NonOx was increased in steps of 10 mol %. The thermal and surface properties were investigated for this series of well-defined copolymers. The thermal properties revealed a linear decrease in glass transition temperature for copolymers containing up to 39 wt % NonOx. Furthermore, the melting temperature of the copolymers containing 0 to 55 wt % PhOx linearly decreased most likely due to disturbance of the NonOx crystalline domains by incorporation of PhOx in the NonOx part of the copolymer. The surface energies of spincoated polymer films revealed a strong decrease in surface energy upon incorporation of NonOx in the copolymers due to strong phase separation between NonOx and PhOx allowing the NonOx chains to orient to the surface. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6433,6440, 2009 [source] Synthesis and liquid crystalline properties of new amide-modified poly(1,4-cyclohexanedimethylene terephthalate),JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 1 2006P. Deepa Abstract New series of cycloaliphatic poly(ester-amide)s, poly(1,4-cyclohexanedimethyleneterephthalate- co -1,3-cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4-cyclohexanedimethanol and 1,3-cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester-amides). The thermal analysis indicate that the new poly(ester-amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester-amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory,Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42,52, 2006 [source] Physical Hydrogels of Poly(vinyl alcohol) with Different Syndiotacticity Prepared in the Presence of Lactosilated Chitosan DerivativesMACROMOLECULAR BIOSCIENCE, Issue 9 2003Giancarlo Masci Abstract Poly(vinyl alcohol) (PVA) physical hydrogels were prepared by repeated freeze,thawing cycles using aqueous solutions of two PVA samples having different degrees of syndiotacticity, a-PVA and s-PVA with 55% and 61% of syndiotactic diads, respectively. The hydrogels were prepared in the presence of different amounts of lactosilated chitosan derivatives (LC) of different molecular weight. The PVA stereoregularity was found to have a dramatic effect on the amount of PVA incorporated into the hydrogels, leading to remarkable differences in the swelling degree and porosity of a-PVA and s-PVA hydrogels. A significant amount of LC was retained in the hydrogels after equilibrium swelling. The swelling of the a-PVA hydrogels was found to increase significantly by increasing the amount of LC while it was only slightly increased in the case of s-PVA hydrogels. The amount of LC released after equilibrium swelling was lower when chitosan derivatives with higher molecular weights were used. Increased initial concentrations of LC resulted in much higher porosity of the hydrogels. TGA and DSC studies showed that LC is stabilized by the incorporation in the PVA hydrogels. The melting temperature of the crystalline regions of PVA was not significantly influenced by LC. Conversely, the extension of the crystalline domains increased in the presence of LC. The retention of a chitosan derivative bearing , - D -galactose side chain residues makes these hydrogels potentially useful as scaffolds for hepatocytes culture. Scanning electron micrographs of PVA-LC hydrogels: (a) a-PVA; (b) a-PVA/LC150 80:20; (c) a-PVA/LC150 50:50. [source] Nanostructured thermoelectric oxides with low thermal conductivityPHYSICA STATUS SOLIDI - RAPID RESEARCH LETTERS, Issue 6 2007A. Weidenkaff Abstract Complex metal oxides, such as e.g. perovskite-type phases are developed as potential functional materials to improve the efficiency of thermoelectric converters. Among those, cobaltates with p-type conductivity and n-type manganates are considered for the realisation of a ceramic thermoelectric converter. Sintered pellets with the composition AMO3,, (A = Ln, RE; M = Co, Mn, Ni, Ti) and "Ca3Co4O9 derivates" were synthesized and characterised concerning their thermoelectric properties in a broad temperature range. It was found that the Seebeck coefficient and the electrical conductivity do not depend on the dimensions of the crystallites, while the heat conductivity can be substantially lowered by decreasing the size of the crystalline domains in these systems. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Thermal and morphological properties of high-density polyethylene/ethylene,vinyl acetate copolymer composites with polyhedral oligomeric silsesquioxane nanostructurePOLYMER INTERNATIONAL, Issue 2 2010Patrícia Scapini Abstract The demand for improved properties of common polymers keeps increasing, and several new approaches have been investigated. In the study reported here, composites with a polymer matrix comprising a blend of high-density polyethylene with ethylene,vinyl acetate copolymer (EVA), and with polyhedral oligomeric silsesquioxane (POSS) as a nanostructure, were processed and characterized in terms of their thermal and morphological properties. For the preparation of the composites, the concentrations of the blend components (0, 50 and 100 wt%) and of the POSS (0, 1 and 5 wt%) were varied. X-ray diffraction results indicated that the presence of EVA in the composites led to the appearance of crystalline domains at lower POSS concentrations. Transmission and scanning electron microscopy showed that samples with 1 wt% of POSS had a homogeneous distribution in the polymer matrix with average dimensions of ca 150 nm. However, the formation of aggregates occurred in samples with 5 wt% of POSS. Differential scanning calorimetry and thermogravimetic analyses indicated that the POSS did not affect the melt and degradation temperatures of the polymer matrix. POSS underwent aggregation at higher concentrations during the composite processing, indicating a solubility limit of around 1 wt%. The presence of EVA in the composite favors POSS aggregation due to an increase in the polarity of the polymer matrix. Copyright © 2009 Society of Chemical Industry [source] Morphology and micromechanical properties of ethylene/1-octene copolymers and their blends with high density polyethylene,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 2-3 2005R. Adhikari Abstract The relationship between morphology and deformation behavior of selected ethylene/1-octene copolymers (EOCs) and their blends with high density polyethylene (HDPE) was investigated. The copolymers showed, depending on the 1-octene content, different morphologies ranging from lamellar to worm-like crystalline domains. The binary HDPE/EOC blends studied, which showed well phase-separated structures consistent with individual melting and crystallization behavior of the blend components, were characterized by a wide range of mechanical and micromechanical properties. The study of strain induced structural changes in an HDPE/EOC blend revealed that at large strains, the extensive stretching of the soft EOC phase is accompanied by rotation of lamellar stack along the strain axis and subsequent fragmentation of the crystals forming beaded-string-like structures. A significant depression in microhardness was observed in the copolymers. In their blends with HDPE, a deviation in microhardness behavior from the additivity law was observed. Copyright © 2005 John Wiley & Sons, Ltd. [source] Reciprocal-space mapping of epitaxic thin films with crystallite size and shape polydispersityACTA CRYSTALLOGRAPHICA SECTION A, Issue 1 2006A. Boulle A development is presented that allows the simulation of reciprocal-space maps (RSMs) of epitaxic thin films exhibiting fluctuations in the size and shape of the crystalline domains over which diffraction is coherent (crystallites). Three different crystallite shapes are studied, namely parallelepipeds, trigonal prisms and hexagonal prisms. For each shape, two cases are considered. Firstly, the overall size is allowed to vary but with a fixed thickness/width ratio. Secondly, the thickness and width are allowed to vary independently. The calculations are performed assuming three different size probability density functions: the normal distribution, the lognormal distribution and a general histogram distribution. In all cases considered, the computation of the RSM only requires a two-dimensional Fourier integral and the integrand has a simple analytical expression, i.e. there is no significant increase in computing times by taking size and shape fluctuations into account. The approach presented is compatible with most lattice disorder models (dislocations, inclusions, mosaicity, ,) and allows a straightforward account of the instrumental resolution. The applicability of the model is illustrated with the case of an yttria-stabilized zirconia film grown on sapphire. [source] Structure and hydration of the amylopectin trisaccharide building blocks,Synthesis, NMR, and molecular dynamicsBIOPOLYMERS, Issue 12 2008Peter I. Hansen Abstract To gain insight into the molecular details and hydration of amylopectin, the five constituting trisaccharides have been chemically synthesized as their methyl ,-glycosides. All five trisaccharides were subjected to 950 MHz NMR spectroscopy for complete assignment and nanosecond molecular dynamics trajectories were calculated to study the structure and dynamics of the trisaccharides in aqueous solution. Systematic analysis of the simulation data revealed several examples of bridging water molecules playing an important role in the stabilization of specific amylopectin conformations, which was also supported by the experimental NMR data such as interresidue NOE's and heteronuclear scalar couplings between nuclei from neighboring residues. Although ,-maltotriose, ,-iso-maltotriose, ,-panose and ,-isopanose are relatively well characterized structures, the study also includes one less characterized trisaccharide with the structure ,Glcp(1,4),Glcp(1,6),Glcp. This trisaccharide, tentatively labelled ,-forkose, is located at the branch point of amylopectin, forking the amylopectin into two strands that align into double-helical segments. The results show that the conformation of ,-forkose takes a natural bend form which fits well into the structure of the double-helical segment of amylopectin. As the only trisaccharide in this study the structure of ,-forkose is not significantly influenced by the hydration. In contrast, ,-isopanose takes a restricted, but rather extended form due to an exceptionally strong localized water density. The two homo-linkage oligomers, ,-maltotriose and ,-iso-maltotriose, showed to be the most extended and the most flexible trimers, respectively, providing regular structure for crystalline domains and maximum linker flexibility for amorphous domains. © 2008 Wiley Periodicals, Inc. Biopolymers 89: 1179,1193, 2008. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] Synthesis and Characteristics of a Nonaggregating Tris(tetrathiafulvaleno)dodecadehydro[18]annuleneCHEMISTRY - A EUROPEAN JOURNAL, Issue 33 2006Asbjørn Sune Andersson Abstract A new tris(tetrathiafulvaleno)dodecadehydro[18]annulene with six peripheral n -hexyl substituents was prepared by oxidative Glaser,Hay cyclization of a corresponding diethynylated tetrathiafulvalene (TTF) precursor. The electronic properties of the neutral and oxidized species were studied by both UV/Vis absorption spectroscopy and electrochemistry. From these studies, it transpires that the strongly violet-colored macrocycle does not aggregate in solution to any significant degree, which was confirmed by 1H NMR spectroscopy. This reluctance towards aggregation contrasts that observed for related TTF,annulenes containing other peripheral substitutents. Oxidation of the TTF,annulene occurs in two three-electron steps as inferred from both the peak amplitudes and the spectroelectrochemical study. We find that the tris(TTF)-fused dehydro[18]annulene is more difficult to oxidize (by +0.20 V) than the silyl-protected diethynylated mono-TTF precursor. In contrast, the first vertical ionization energy calculated at the B3,LYP/6,311+G(2d,p) level for the parent tris(TTF)-fused dehydro[18]annulene devoid of peripheral hexyl substituents is in fact lower (by 0.44 eV). Moreover, the surface morphology of 1,d drop-cast on a mica substrate was investigated by atomic force microscopy (AFM). Crystalline domains with slightly different orientations were observed. The thickness of individual layers seen in the crystalline domains and the thickness of a monolayer obtained from a very dilute solution were determined to 1.8,1.9 nm. This thickness corresponds to the diameter of the macrocycle and the layers seen in the film are apparently formed when the molecules stack in the horizontal direction relative to the substrate. [source] | |||||||||||||