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Molecular Orientation (molecular + orientation)
Selected AbstractsEffect of Molecular Orientation of Epitaxially Grown Platinum(II) Octaethyl Porphyrin Films on the Performance of Field-Effect Transistors,ADVANCED MATERIALS, Issue 9 2003Y.-Y. Noh The molecular alignment of platinum(II) octaethyl porphyrin (PtOEP) crystals evaporated on KBr (see atomic force microscopy image, Figure) can be readily changed from perpendicular to parallel by changing the substrate temperature. The field-effect mobility of transisitors prepared using epitaxially grown PtOEP films aligned perpendicularly to a substrate is 100 times higher than that of those of parallel alignment. [source] Phase Transition Behavior and Molecular Orientation of Oligo(9,9,-dioctylfluorene- alt -bithiophene)MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 17 2008Na Li Abstract A novel conjugated oligomer, oligo(9,9,-dioctylfluorene- alt -bithiophene) (OF8T2), was found to exhibit a unique phase transition between crystalline and liquid-crystalline states, and a liquid-crystalline glass was easily generated, offering better TFT device performance. In thin films, upon annealing the OF8T2 molecules oriented preferentially with their planes of conjugation being normal to the substrate, and both film thickness and annealing temperature were critical to the film morphology and the molecular orientation. When the OF8T2 film was deposited on a rubbed polyimide surface and annealed, the molecules aligned their long axes along the rubbing direction. [source] The Influence of Molecular Orientation on the Yield and Post-Yield Response of Injection-Molded PolycarbonateMACROMOLECULAR MATERIALS & ENGINEERING, Issue 12 2009Tom A. P. Engels Abstract The influence of the flow history experienced during injection molding on the mechanical properties of amorphous polymers is investigated. It is demonstrated that flow-induced molecular orientation only causes a small anisotropic effect on the yield stress, which can be regarded as insignificant with respect to its absolute value. Its influence on the post-yield strain-hardening response is also shown to be imperceptible, in contrast to a orientation which is applied during deformation below the glas transition. [source] Direct Correlation of Organic Semiconductor Film Structure to Field-Effect Mobility,ADVANCED MATERIALS, Issue 19 2005M. DeLongchamp Near-edge X-ray fine structure spectroscopy is used to measure simultaneous chemical conversion, molecular ordering, and defect formation in soluble oligothiophene precursor films. Film structure is correlated to OFET performance. Molecular orientation is determined by evaluating antibonding orbital overlap with the polarized electric field vector of incident soft X-rays (see Figure and cover). Upon conversion, the molecules become vertically oriented, allowing , overlap in the plane of hole transport. [source] Molecular orientation, crystallinity, and flexural modulus correlations in injection molded polypropylene/talc compositesPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 5 2010Marcia Cristina Branciforti Abstract In order to promote better understanding of the structure-mechanical properties relationships of filled thermoplastic compounds, the molecular orientation and the degree of crystallinity of injection molded talc-filled isotactic polypropylene (PP) composites were investigated by X-ray pole figures and wide-angle X-ray diffraction (WAXD). The usual orientation of the filler particles, where the plate planes of talc particles are oriented parallel to the surface of injection molding and influence the orientation of the , -PP crystallites was observed. The PP crystallites show bimodal orientation in which the c - and a*-axes are mixed oriented to the longitudinal direction (LD) and the b -axis is oriented to the normal direction (ND). It was found that the preferential b -axis orientation of PP crystallites increases significantly in the presence of talc particles up to 20,wt% in the composites and then levels-off at higher filler content. WAXD measurements of the degree of crystallinity through the thickness of injection molded PP/talc composites indicated an increasing gradient of PP matrix crystallinity content from the core to the skin layers of the molded plaques. Also, the bulk PP crystallinity content of the composites, as determined by DSC measurements, increased with talc filler concentration. The bulk crystallinity content of PP matrix and the orientation behavior of the matrix PP crystallites and that of the talc particles in composites are influenced by the presence of the filler content and these three composite's microstructure modification factors influence significantly the flexural moduli and the mechanical stiffness anisotropy data (ELD/ETD) of the analyzed PP/talc composites. Copyright © 2009 John Wiley & Sons, Ltd. [source] Orientation Control of Linear-Shaped Molecules in Vacuum-Deposited Organic Amorphous Films and Its Effect on Carrier MobilitiesADVANCED FUNCTIONAL MATERIALS, Issue 3 2010Daisuke Yokoyama Abstract The molecular orientation of linear-shaped molecules in organic amorphous films is demonstrated to be controllable by the substrate temperature. It is also shown that the molecular orientation affects the charge-transport characteristics of the films. Although linear-shaped 4,4,-bis[(N -carbazole)styryl]biphenyl molecules deposited on substrates at room temperature are horizontally oriented in amorphous films, their orientation when deposited on heated substrates with smooth surfaces becomes more random as the substrate temperature increases, even at temperatures under the glass transition temperature. Another factor dominating the orientation of the molecules deposited on heated substrates is the surface roughness of the substrate. Lower carrier mobilities are observed in films composed of randomly oriented molecules, demonstrating the significant effect of a horizontal molecular orientation on the charge-transport characteristics of organic amorphous films. [source] Electronic Structure of Self-Assembled Monolayers on Au(111) Surfaces: The Impact of Backbone PolarizabilityADVANCED FUNCTIONAL MATERIALS, Issue 23 2009LinJun Wang Abstract Modifying metal electrodes with self-assembled monolayers (SAMs) has promising applications in organic and molecular electronics. The two key electronic parameters are the modification of the electrode work function because of SAM adsorption and the alignment of the SAM conducting states relative to the metal Fermi level. Through a comprehensive density-functional-theory study on a series of organic thiols self-assembled on Au(111), relationships between the electronic structure of the individual molecules (especially the backbone polarizability and its response to donor/acceptor substitutions) and the properties of the corresponding SAMs are described. The molecular backbone is found to significantly impacts the level alignment; for molecules with small ionization potentials, even Fermi-level pinning is observed. Nevertheless, independent of the backbone, polar head-group substitutions have no effect on the level alignment. For the work-function modification, the larger molecular dipole moments achieved when attaching donor/acceptor substituents to more polarizable backbones are largely compensated by increased depolarization in the SAMs. The main impact of the backbone on the work-function modification thus arises from its influence on the molecular orientation on the surface. This study provides a solid theoretical basis for the fundamental understanding of SAMs and significantly advances the understanding of structure,property relationships needed for the future development of functional organic interfaces. [source] Control of the Morphology and Structural Development of Solution-Processed Functionalized Acenes for High-Performance Organic TransistorsADVANCED FUNCTIONAL MATERIALS, Issue 10 2009Jung Ah Lim Abstract Solution-processable functionalized acenes have received special attention as promising organic semiconductors in recent years because of their superior intermolecular interactions and solution-processability, and provide useful benchmarks for organic field-effect transistors (OFETs). Charge-carrier transport in organic semiconductor thin films is governed by their morphologies and molecular orientation, so self-assembly of these functionalized acenes during solution processing is an important challenge. This article discusses the charge-carrier transport characteristics of solution-processed functionalized acene transistors and, in particular, focuses on the fine control of the films' morphologies and structural evolution during film-deposition processes such as inkjet printing and post-deposition annealing. We discuss strategies for controlling morphologies and crystalline microstructure of soluble acenes with a view to fabricating high-performance OFETs. [source] Room-Temperature Self-Organizing Characteristics of Soluble Acene Field-Effect Transistors,ADVANCED FUNCTIONAL MATERIALS, Issue 4 2008Wi Hyoung Lee We report on the room-temperature self-organizing characteristics of thin films of the organic small-molecule semiconductor triethylsilylethynyl-anthradithiophene (TES-ADT) and its effect on the electrical properties of TES-ADT-based field-effect transistors (FETs). The morphology of TES-ADT films changed dramatically with time, and the field-effect mobility of FETs based on these films increased about 100-fold after seven days as a result of the change in molecular orientation from a tilted structure in the as-prepared film to a well-oriented structure in the final film. We found that the molecular movement is large enough to induce a conformational change to an energetically stable state in spin-coated TES-ADT films, because TES-ADT has a low glass-transition temperature (around room temperature). Our findings demonstrate that organic small-molecule semiconductors that exhibit a low crystallinity immediately after spin-coating can be changed into highly crystalline structures by spontaneous self-organization of the molecules at room temperature, which results in improved electrical properties of FETs based on these semiconductors. [source] Surface-Transfer Doping of Organic Semiconductors Using Functionalized Self-Assembled Monolayers,ADVANCED FUNCTIONAL MATERIALS, Issue 8 2007W. Chen Abstract Controlling charge doping in organic semiconductors represents one of the key challenges in organic electronics that needs to be solved in order to optimize charge transport in organic devices. Charge transfer or charge separation at the molecule/substrate interface can be used to dope the semiconductor (substrate) surface or the active molecular layers close to the interface, and this process is referred to as surface-transfer doping. By modifying the Au(111) substrate with self-assembled monolayers (SAMs) of aromatic thiols with strong electron-withdrawing trifluoromethyl (CF3) functional groups, significant electron transfer from the active organic layers (copper(II) phthalocyanine; CuPc) to the underlying CF3 -SAM near the interface is clearly observed by synchrotron photoemission spectroscopy. The electron transfer at the CuPc/CF3 -SAM interface leads to an electron accumulation layer in CF3 -SAM and a depletion layer in CuPc, thereby achieving p-type doping of the CuPc layers close to the interface. In contrast, methyl (CH3)-terminated SAMs do not display significant electron transfer behavior at the CuPc/CH3 -SAM interface, suggesting that these effects can be generalized to other organic-SAM interfaces. Angular-dependent near-edge X-ray absorption fine structure (NEXAFS) measurements reveal that CuPc molecules adopt a standing-up configuration on both SAMs, suggesting that interface charge transfer has a negligible effect on the molecular orientation of CuPc on various SAMs. [source] Adsorption-Induced Magnetization of PbS Self-Assembled Nanoparticles on GaAs,ADVANCED MATERIALS, Issue 13 2008Alexander Zakrassov PbS nanoparticles attached to a GaAs substrate via organic molecules have magnetic properties. When the organic molecules are aligned parallel or at some angle relative to the surface normal, the magnetic anisotropy vector K coincides with the molecular orientation. [source] Rheological properties of LDPE processed by conventional processing machinesADVANCES IN POLYMER TECHNOLOGY, Issue 3 2003Masayuki Yamaguchi Abstract The impact of applied processing history and the postprocessing annealing on the rheological properties of low-density polyethylene (LDPE) have been studied employing various kinds of conventional processing machines. Processing by a corotating twin-screw extruder (Co-TSE) and an internal batch mixer depressed the drawdown force, one of the elastic properties of a melt, to a great extent, even though molecular weight and the polydispersity did not change. On the other hand, the sample processed by a two-roll mill exhibited the drawdown force as high as the original pellets, which is owing to the intermittent stress history instead of the relentless one in the Co-TSE and the internal batch mixer. Furthermore, the effect of screw configuration in the Co-TSE has also been investigated. It was found that the processing by conveying screws depressed the drawdown force and melt fracture more than that by kneading blocks as long as the torque and the residence time are the same. The large, abrupt, and frequent change in flow direction in the Co-TSE with kneading blocks prohibits the molecular orientation, which leads to disentanglement associated with long-chain branches. © 2003 Wiley Periodicals, Inc. Adv Polym Techn 22: 179,187, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.10047 [source] Amorphous orientation and its relationship to processing stages of blended polypropylene/polyethylene fibersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Amy M. Trottier Abstract Changes in the molecular orientation, melting behavior, and percent crystallinity of the individual components in a fibrous blend of isotactic polypropylene (iPP) and high-density polyethylene (HDPE) that occur during the melt extrusion process were examined using wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The crystalline orientation of each component was found using Wilchinsky's treatment of uniaxial orientation and described by the Hermans,Stein orientation parameter. The amorphous orientation was found by resolving the X-ray diffraction pattern in steps of the azimuthal angle into its iPP and HDPE crystalline and amorphous reflections. The utility of DSC and WAXD analyses to capture the effects of small differences in processing, and the use of these results as fingerprints of a particular manufacturing process were demonstrated. Major increases in the melting temperatures, percent crystallinities, and molecular orientations of the iPP and HDPE components occurred during the main stretching stage of the melt extrusion process. The annealing stage was found to have little to no effect on the melting behavior and molecular orientation of these components. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] A new method for the gradient-based optimization of molecular complexesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 9 2009Jan Fuhrmann Abstract We present a novel method for the local optimization of molecular complexes. This new approach is especially suited for usage in molecular docking. In molecular modeling, molecules are often described employing a compact representation to reduce the number of degrees of freedom. This compact representation is realized by fixing bond lengths and angles while permitting changes in translation, orientation, and selected dihedral angles. Gradient-based energy minimization of molecular complexes using this representation suffers from well-known singularities arising during the optimization process. We suggest an approach new in the field of structure optimization that allows to employ gradient-based optimization algorithms for such a compact representation. We propose to use exponential mapping to define the molecular orientation which facilitates calculating the orientational gradient. To avoid singularities of this parametrization, the local minimization algorithm is modified to change efficiently the orientational parameters while preserving the molecular orientation, i.e. we perform well-defined jumps on the objective function. Our approach is applicable to continuous, but not necessarily differentiable objective functions. We evaluated our new method by optimizing several ligands with an increasing number of internal degrees of freedom in the presence of large receptors. In comparison to the method of Solis and Wets in the challenging case of a non-differentiable scoring function, our proposed method leads to substantially improved results in all test cases, i.e. we obtain better scores in fewer steps for all complexes. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] Polyamide-imide nanofiltration hollow fiber membranes with elongation-induced nano-pore evolutionAICHE JOURNAL, Issue 6 2010Shi Peng Sun Abstract The molecular design of nanoporous membranes with desired morphology and selectivity has attracted significant interest over the past few decades. A major problem in their applications is the trade-off between sieving property and permeability. Here, we report the discovery of elongation-induced nano-pore evolution during the external stretching of a novel polyamide-imide nanofiltration hollow fiber membrane in a dry-jet wet-spinning process that simultaneously leads to a decreased pore size but increased pure water permeability. The molecular weight cutoff, pore size, and pore size distribution were finely tuned using this approach. AFM and polarized FTIR verified the nano-pore morphological evolution and an enhanced molecular orientation in the surface skin layer. The resultant nanofiltration membranes exhibit highly effective fractionation of the monovalent and divalent ions of NaCl/Na2SO4 binary salt solutions. More than 99.5% glutathione can be rejected by the nanofiltration membranes at neutral pH, offering the feasibility of recovering this tripeptide. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Absolute enantioselective separation: Optical activity ex machinaJOURNAL OF SEPARATION SCIENCE, JSS, Issue 17 2005Roman Bielski Abstract The paper describes methodology of using three independent macroscopic factors affecting molecular orientation to accomplish separation of a racemic mixture without the presence of any other chiral compounds, i. e., absolute enantioselective separation (AES) which is an extension of a concept of applying these factors to absolute asymmetric synthesis. The three factors may be applied simultaneously or, if their effects can be retained, consecutively. The resulting three mutually orthogonal or near orthogonal directors constitute a true chiral influence and their scalar triple product is the measure of the chirality of the system. AES can be executed in a chromatography-like microfluidic process in the presence of an electric field. It may be carried out on a chemically modified flat surface, a monolithic polymer column made of a mesoporous material, each having imparted directional properties. Separation parameters were estimated for these media and possible implications for the natural homochirality are discussed. [source] Raman spectroscopic evaluation of molecular orientation in polysulfoneLASER PHYSICS LETTERS, Issue 7 2004S. J. Shilton Abstract In this paper, we present for the first time a Raman spectroscopic method for the determination of molecular orientation in uniaxially oriented polysulfone (PSU). (© 2004 by ASTRO, Ltd. Published exclusively by WILEY-VCH Verlag GmbH & Co. KGaA) [source] Phase Transition Behavior and Molecular Orientation of Oligo(9,9,-dioctylfluorene- alt -bithiophene)MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 17 2008Na Li Abstract A novel conjugated oligomer, oligo(9,9,-dioctylfluorene- alt -bithiophene) (OF8T2), was found to exhibit a unique phase transition between crystalline and liquid-crystalline states, and a liquid-crystalline glass was easily generated, offering better TFT device performance. In thin films, upon annealing the OF8T2 molecules oriented preferentially with their planes of conjugation being normal to the substrate, and both film thickness and annealing temperature were critical to the film morphology and the molecular orientation. When the OF8T2 film was deposited on a rubbed polyimide surface and annealed, the molecules aligned their long axes along the rubbing direction. [source] Enhanced Mechanical Performance of Self-Bundled Electrospun Fiber Yarns via Post-TreatmentsMACROMOLECULAR RAPID COMMUNICATIONS, Issue 10 2008Xuefen Wang Abstract A new route to high-performance electrospun polymer fibers was developed using a self-bundling electrospinning technique combined with post-treatments such as stretching and annealing under conditions similar to those used for conventional fibers. Self-bundled electrospun PAN fiber yarns were characterized by SEM, mechanical tests, polarized FT-IR spectroscopy and WAXD. The obtained results revealed that the PAN nanofiber yarns possessed enhanced alignment, a higher degree of crystallinity and higher molecular orientation after treatments, resulting in a remarkable improvement in mechanical performance, approaching the strength value of the corresponding conventional fibers. [source] Fiber orientation control of short-fiber reinforced thermoplastics by ram extrusionPOLYMER COMPOSITES, Issue 5 2003Yukio Sanomura In this study we examine the fiber orientation distribution, fiber length and Young's modulus of extruded short-fiber reinforced thermoplastics such as polypropylene. Axial orientation distributions are presented to illustrate the influence of extrusion ratio on the orientation state of the fibrous phase. Fibers are markedly aligned parallel to the extrusion direction with increasing extrusion ratio. The orientation state of extruded fiber-reinforced thermoplastics (FRTP) is almost uniform throughout the section. The control of fiber orientation can be easily achieved by means of ram extrusion. Experimental results are also presented for Young's modulus of extruded FRTP in the extrusion direction. Young's modulus follows a linear trend with increasing extrusion ratio because the degree of the molecular orientation and the fiber orientation increases. The model proposed by Cox, and Fukuda and Kawada describes the effect of fiber length and orientation on Young's modulus. The value of the orientation coefficient is calculated by assuming a rectangular orientation distribution and calculating the fiber distribution limit angle given by orientation parameters. By comparing the predicted Young's modulus with experimental results, the validity of the model is elucidated. The mean fiber length linearly decreases with increasing extrusion ratio because of fiber breakage due to plastic deformation. There is a small effect on Young's modulus due to fiber breakage by ram extrusion. [source] Properties and strain hardening character of polyethylene terephthalate containing IsosorbidePOLYMER ENGINEERING & SCIENCE, Issue 3 2009Ramesh M. Gohil Polyethylene terephthalate containing Isosorbide (PEIT) polymers made from renewable corn-derived Isosorbide monomer exhibit a wide range of glass transition temperatures (80,180°C) and are therefore able to be used in many applications. Stress,strain curves for high Isosorbide content copolymers show strain softening, which impairs the molecular orientation during orientation of films and bottles. It is therefore necessary to find ways to modify deformation behavior of PEIT copolymers. Deformation characteristics of PEIT and other polyesters have been evaluated to define stretching parameters and necessary composition for making oriented bottles for hot fill applications. In the presence of polymeric nucleating agents, (polymeric ionomers or polyesters containing sodium ions), strain-hardening parameters become almost temperature- independent below solid state deformation temperature of 125°C. We developed a methodology to achieve molecular orientation comparable with films and articles made by conventional processing of poly(ethylene terephthalate), PET. Polyesters containing sodium ions are efficient nucleating agents for PEIT, and their required concentration is dependent on deformation temperature. Both strain hardening and stress at 250% strain depend on the concentration of nucleating agents and deformation temperatures. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers [source] Effect of orientation and crystallinity on the photodegradation of poly(ethylene terephthalate) fibersPOLYMER ENGINEERING & SCIENCE, Issue 5 2008H. Fashandi In this research, photodegradation of poly(ethylene terephthalate) (PET) fibers was investigated with emphasis on the morphological state of yarns. Two kinds of yarns, FDY (Fully Drawn Yarn) and POY (Partially Oriented Yarn), with different molecular orientation and crystallinity were applied in this research. FDY is spun in the same way as POY and subsequently drawn at high speed and then entangled before winding up. This sample has higher molecular orientation and crystallinity than the POY sample. Several analytical methods were applied in this study: viscometry, X-ray diffraction, FTIR spectroscopy, UV,Visible spectrophotometry, and mechanical testing. Viscometry was used to determine molecular weight as a monitoring factor for degradation. X-ray diagrams showed higher crystallinity for FDY samples during weathering process by irradiation. Results of mechanical testing indicated that the tenacity of the FDY fibers had less deterioration in comparison with the POY ones. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers [source] Anisotropy in the electrical behavior of immiscible polypropylene/nylon/carbon black blends processed slightly below the melting temperature of the nylonPOLYMER ENGINEERING & SCIENCE, Issue 9 2006J. Zoldan Carbon black (CB) containing polypropylene/nylon (PP/Ny) blends, processed slightly below the melting temperature (Tm) of the dispersed Ny phase, leads to formation of fibrillar Ny phase and electrically anisotropic systems. CB containing PP/Ny blends were compounded (twin screw extruder) and processed (injection molding) slightly below the Tm of dispersed Ny phase at different blending sequences. To establish structure,property relationships scanning electron microscopy, high resolution scanning electron microscopy, differential scanning calorimeter were used and electrical properties were also studied. Addition of CB to binary PP/Ny blends, processed below the Ny Tm, altered the Ny fibrillation process forming an irregular continuous phase, containing the CB particles, rather than the fibrils formed in the PP/Ny blends. Yet, upon changing the processing sequence, i.e., compounding PP and CB and then adding Ny in the injection molding stage, Ny fibrils were attained, maintaining phase continuity, oriented in the flow direction and CB particles preferentially located on their surfaces. Blends exhibiting a fibrillar Ny network covered by CB particles exhibited electrical anisotropy. The Ny fibrils exhibited an additional higher crystalline melting peak and molecular orientation. The composites are conductive in the Ny fibril direction, while insulating in the perpendicular direction. Once the CB is located within both, the Ny and the PP matrix the electrical behavior is isotropic. POLYM. ENG. SCI., 46:1250,1262, 2006. © 2006 Society of Plastics Engineers [source] Theoretical and experimental studies of anisotropic shrinkage in injection moldings of semicrystalline polymersPOLYMER ENGINEERING & SCIENCE, Issue 6 2006Keehae Kwon A novel approach to predict anisotropic shrinkage of semicrystalline polymers in injection moldings was proposed using flow-induced crystallization, frozen-in molecular orientation, elastic recovery, and PVT equation of state. The anisotropic thermal expansion and compressibility affected by the frozen-in orientation function and the elastic recovery that was not frozen during moldings were introduced to obtain the in-plane anisotropic shrinkages. The frozen-in orientation function was calculated from amorphous and crystalline contributions. The amorphous contribution was based on the frozen-in and intrinsic amorphous birefringence, whereas the crystalline contribution was based on the crystalline orientation function, which was determined from the elastic recovery and intrinsic crystalline birefringence. To model the elastic recovery and frozen-in stresses related to birefringence during molding process, a nonlinear viscoelastic constitutive equation was used with temperature- and crystallinity-dependent viscosity and relaxation time. Occurrence of the flow-induced crystallization was introduced through the elevation of melting temperature affected by entropy production during flow of the viscoelastic melt. Kinetics of the crystallization was modeled using Nakamura and Hoffman-Lauritzen equations with the rate constant affected by the elevated melting temperature. Numerous injection molding runs on polypropylene of various molecular weights were carried out by varying the packing time, flow rate, melt temperature, and mold temperature. The anisotropic shrinkage of the moldings was measured. Comparison of the experimental and simulated results indicated a good predictive capability of the proposed approach. POLYM. ENG. SCI., 46:712,728, 2006. © 2006 Society of Plastics Engineers [source] Evaluation of mechanical properties of adjacent flow weldlinePOLYMER ENGINEERING & SCIENCE, Issue 8 2005Koji Yamada Weldlines occur at the interface of two adjacent flows of material behind an obstructive pin in a cavity in injection molding (meldline or hot weldline). Tensile strength of such "adjacent flow weldline" in injection molded polystyrene plates was evaluated by a mechanical step-by-step milling technique. The strength when the milling depth was 1/5 of the thickness from each surface was about the same and independent of the distance from the pin. In contrast, the strength without milling decreased once and then increased along the flow direction. This demonstrates that the strength of a weldline is predominantly dependent on the properties of the surface layer of the weldline. The depth of the surface layer was defined as the depth of the weld, Dw. Dw reduced monotonously along the flow direction and faded away with the V-notch, resulting in an increase of strength along the direction. On the other hand, it was considered that the farther from the pin, the flow-induced molecular orientation in the surface layer is greater. It caused a decrease of the strength along the flow direction. The sequence of decrease and increase in tensile strength of adjacent flow weldline is due to the complex effect of these two contradictory factors. POLYM. ENG. SCI., 45:1180,1186, 2005. © 2005 Society of Plastics Engineers [source] Effect of vibration extrusion on the structure and properties of high-density polyethylene pipesPOLYMER INTERNATIONAL, Issue 2 2009Chen Kaiyuan Abstract BACKGROUND: The axial strength of a plastic pipe is much higher than its circumferential strength due to the macromolecular orientation during extrusion. In this work, a custom-made electromagnetic dynamic plasticating extruder was adopted to extrude high-density polyethylene (HDPE) pipes. A vibration force field was introduced into the whole plasticating and extrusion process by axial vibration of the screw. The aim of superimposing a vibration force field was to change the crystalline structure of HDPE and improve the molecular orientation in the circumferential direction to obtain high-circumferential-strength pipes. RESULTS: Through vibration extrusion, the circumferential strength of HDPE pipes increased significantly, and biaxial self-reinforcement pipes could be obtained. The maximum increase of bursting pressure and tensile yield strength was 34.2 and 5.3%, respectively. According to differential scanning calorimetry and wide-angle X-ray diffraction measurements, the HDPE pipes prepared by vibration extrusion had higher crystallinity, higher melting temperature, larger crystal sizes and more perfect crystals. CONCLUSION: Vibration extrusion can effectively enhance the mechanical properties of HDPE pipes, especially the circumferential strength. The improvement of mechanical properties of HDPE pipes obtained by vibration extrusion can be attributed to the higher degree of crystallinity and the improvement of the molecular orientation and of the crystalline morphology. Copyright © 2008 Society of Chemical Industry [source] Molecular orientation, crystallinity, and flexural modulus correlations in injection molded polypropylene/talc compositesPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 5 2010Marcia Cristina Branciforti Abstract In order to promote better understanding of the structure-mechanical properties relationships of filled thermoplastic compounds, the molecular orientation and the degree of crystallinity of injection molded talc-filled isotactic polypropylene (PP) composites were investigated by X-ray pole figures and wide-angle X-ray diffraction (WAXD). The usual orientation of the filler particles, where the plate planes of talc particles are oriented parallel to the surface of injection molding and influence the orientation of the , -PP crystallites was observed. The PP crystallites show bimodal orientation in which the c - and a*-axes are mixed oriented to the longitudinal direction (LD) and the b -axis is oriented to the normal direction (ND). It was found that the preferential b -axis orientation of PP crystallites increases significantly in the presence of talc particles up to 20,wt% in the composites and then levels-off at higher filler content. WAXD measurements of the degree of crystallinity through the thickness of injection molded PP/talc composites indicated an increasing gradient of PP matrix crystallinity content from the core to the skin layers of the molded plaques. Also, the bulk PP crystallinity content of the composites, as determined by DSC measurements, increased with talc filler concentration. The bulk crystallinity content of PP matrix and the orientation behavior of the matrix PP crystallites and that of the talc particles in composites are influenced by the presence of the filler content and these three composite's microstructure modification factors influence significantly the flexural moduli and the mechanical stiffness anisotropy data (ELD/ETD) of the analyzed PP/talc composites. Copyright © 2009 John Wiley & Sons, Ltd. [source] Control of orientation for carbazole group in comb copolymers arranged by method of organized molecular filmsPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 5 2007Hiroko Hoshizawa Abstract We investigated the molecular orientation of organized molecular films with regard to solid-state structures for newly synthesized comb copolymers with N -vinylcarbazole (NVCz) by in-plane and out-of plane X-ray diffraction (XRD), differential scanning calorimetry (DSC), and atomic force microscopy (AFM). In the bulk state, hydrogenated and fluorinated comb copolymers form side-chain crystals for a two-dimensional lattice spacing of 4.2 and 5.0,Å, respectively. The findings suggest that the carbazole rings in the main-chain are arranged in opposition to each other. From the results of the DSC measurement, sharp-shaped melting peaks appear on the relatively lower temperature side of the thermograms. This result supports the formation of side-chain crystals in the synthesized comb copolymers. These monolayers of the copolymers on the water surface were extremely condensed, except for the fluorocarbon:NVCz,=,1:1 copolymer. From the in-plane XRD measurement of multilayers on solids, the changes in the two-dimensional lattice structure of fluorinated comb copolymer films containing NVCz units, as opposed to their bulk state, were confirmed. It seems that these structural changes are caused by the stronger ,,, interaction between the carbazole rings rather than the van der Waals interaction between fluorocarbons. Copyright © 2007 John Wiley & Sons, Ltd. [source] Structural consequences of hen egg-white lysozyme orthorhombic crystal growth in a high magnetic field: validation of X-ray diffraction intensity, conformational energy searching and quantitative analysis of B factors and mosaicityACTA CRYSTALLOGRAPHICA SECTION D, Issue 3 2005Shinya Saijo A novel method has been developed to improve protein-crystal perfection during crystallization in a high magnetic field and structural studies have been undertaken. The three-dimensional structure of orthorhombic hen egg-white (HEW) lysozyme crystals grown in a homogeneous and static magnetic field of 10,T has been determined and refined to a resolution of 1.13,Å and an R factor of 17.0%. The 10,T crystals belonged to space group P212121, with unit-cell parameters a = 56.54,(3), b = 73.86,(6), c = 30.50,(2),Å and one molecule per asymmetric unit. A comparison of the structures of the 0,T and 10,T crystals has been carried out. The magnitude of the structural changes, with a root-mean-square deviation value of 0.75,Å for the positions of all protein atoms, is similar to that observed when an identical protein structure is resolved in two different crystalline lattices. The structures remain similar, with the exception of a few residues e.g. Arg68, Arg73, Arg128 and Gln121. The shifts of the arginine residues result in very significant structural fluctuations, which can have large effects on a protein's crystallization properties. The high magnetic field contributed to an improvement in diffraction intensity by (i) the displacement of the charged side chains of Arg68 and Arg73 in the flexible loop and of Arg128 at the C-terminus and (ii) the removal of the alternate conformations of the charged side chains of Arg21, Lys97 or Arg114. The improvement in crystal perfection might arise from the magnetic effect on molecular orientation without structural change and differences in molecular interactions. X-ray diffraction and molecular-modelling studies of lysozyme crystals grown in a 10,T field have indicated that the field contributes to the stability of the dihedral angle. The average difference in conformational energy has a value of ,578,kJ,mol,1 per charged residue in favour of the crystal grown in the magnetic field. For most protein atoms, the average B factor in the 10,T crystal shows an improvement of 1.8,Å2 over that for the 0,T control; subsequently, the difference in diffraction intensity between the 10,T and 0,T crystals corresponds to an increase of 22.6% at the resolution limit. The mosaicity of the 10,T crystal was better than that of the 0,T crystal. More highly isotropic values of 0.0065, 0.0049 and 0.0048° were recorded along the a, b and c axes, respectively. Anisotropic mosaicity analysis indicated that crystal growth is most perfect in the direction that corresponds to the favoured growth direction of the crystal, and that the crystal grown in the magnetic field had domains that were three times the volume of those of the control crystal. Overall, the magnetic field has improved the quality of these crystals and the diffracted intensity has increased significantly with the magnetic field, leading to a higher resolution. [source] Modification of Supramolecular Binding Motifs Induced By Substrate Registry: Formation of Self-Assembled Macrocycles and Chain-Like PatternsCHEMISTRY - A EUROPEAN JOURNAL, Issue 42 2009Leslie-Anne Fendt Abstract The self-assembly properties of two ZnII porphyrin isomers on Cu(111) are studied at different coverage by means of scanning tunneling microscopy (STM). Both isomers are substituted in their meso -positions by two voluminous 3,5-di(tert -butyl)phenyl and two rod-like 4,-cyanobiphenyl groups, respectively. In the trans -isomer, the two 4,-cyanobiphenyl groups are opposite to each other, whereas they are located at right angle in the cis -isomer. For coverage up to one monolayer, the cis- substituted porphyrins self-assemble to form oligomeric macrocycles held together by antiparallel CN,,,CN dipolar interactions and CN,,,H-C(sp2) hydrogen bonding. Cyclic trimers and tetramers occur most frequently but everything from cyclic dimers to hexamers can be observed. Upon annealing of the samples at temperatures >150,°C, dimeric macrocyclic structures are observed, in which the two porphyrins are bridged by Cu atoms, originating from the surface, under formation of two CN,,,Cu,,,NC coordination bonds. The trans -isomer builds up linear chains on Cu(111) at low coverage, whereas for higher coverage the molecules assemble in a periodic, densely packed structure. Both cis - and trans -bis(4,-cyanobiphenyl)-substituted ZnII porphyrins behave very differently on Cu(111) compared to similar porphyrins in literature on less reactive surfaces such as Au(111) and Ag(111). On the latter surfaces, there is no signal visible between molecular orientation and the crystal directions of the substrate, whereas on Cu(111), very strong adsorbate,substrate interactions have a dominating influence on all observed structures. This strong porphyrin,substrate interaction enables a much broader variety of structures, including also less favorable intermolecular bonding motifs and geometries. [source] | |||||||||||||||||||||||||