Home About us Contact
|
Home About us Contact | ||
|
|
||
Crystalline Phase (crystalline + phase)
Kinds of Crystalline Phase Selected AbstractsDirect Preparation of Nanoscale Thin Films of Poly(vinylidene fluoride) Containing , -Crystalline Phase by Heat-Controlled Spin CoatingMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 24 2008Subramaniyan Ramasundaram Abstract Nanoscale thin films of PVDF containing the , -crystalline phase were directly prepared by heat-controlled spin coating without the influence of external stimuli either in the form of additives or post-treatments. Sample preparation was carried out at different temperatures, ranging from 10 to 70,°C. At elevated temperatures (40, 50, 60 and 70,°C), PVDF was crystallized into the , -phase, while at near-ambient conditions (20 and 30,°C) it was crystallized into the , -phase. Some samples exhibited a phase-segregated morphology, with varying particle sizes depending on the preparation temperature. The ferroelectric nature of a typical sample, prepared at 40,°C, was visualized by piezoresponse imaging studies. [source] Crystalline/Crystalline Phase Transitions in Polymer Systems Consisting of Finite-Size Crystals in Each Crystalline Phase: Generalized Gibbs-Thomson EquationMACROMOLECULAR THEORY AND SIMULATIONS, Issue 7 2010Matsuo Hirami Abstract For polymer systems of two crystalline phases of one polymer component, each phase being consisted of polymer crystals of a finite size, we derive the crystalline-crystalline phase transition relationship, i.e., generalized Gibbs-Thomson equation. Its application combined with the crystalline-liquid transition relationship (usual Gibbs-Thomson equation) to the phase behavior of PT phase diagram of polyethylene (PE) is investigated, where the orthorhombic-hexagonal phase transition of PE crystal under high pressure being involved. Comparison with experimental data leads to the estimates of the structural characteristics such as the ratios of (the end surface free energy of polymer crystal/crystal length) for the respective crystalline phases. [source] Direct Solid-State NMR Spectroscopic Evidence for the NH4AlF4 Crystalline Phase Derived from Zeolite HY Dealuminated with Ammonium HexafluorosilicateCHEMINFORM, Issue 48 2006Hsien-Ming Kao Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Synthesis and Characterization of Superconducting ,-Mo2N Crystalline Phase on a Si Substrate: An Application of Pulsed Laser Deposition to Nitride Chemistry.CHEMINFORM, Issue 8 2006Kei Inumaru Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access the actual ChemInform Abstract, please click on HTML or PDF. [source] Diastereoselectivity in [2, + 2,] Photocycloaddition of Cholesteryl Cinnamate to Methyl 9-Phenanthrenecarboxylate: Control of the Stereoselectivity in Liquid Crystalline Phase.CHEMINFORM, Issue 52 2004Hajime Maeda Abstract For Abstract see ChemInform Abstract in Full Text. [source] Electronic Structure and Bonding of All Crystalline Phases in the Silica,Yttria,Silicon Nitride Phase Equilibrium DiagramJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 11 2004Wai-Yim Ching This paper reviews the structures and properties of 10 binary, ternary, and quaternary crystals within the equilibrium phase diagram of the SiO2,Y2O3,Si3N4 system. They are binary compounds SiO2, Y2O3, Si3N4; ternary compounds Si2N2O, Y2Si2O7, and YSi2O5; and quaternary crystals Y2Si3N4O3 (M-melilite), Y4Si2O7N2, (N-YAM), YSiO2N (wallastonite), and Y10(SiO4)6N2 (N-apatite, N-APT). Although the binary compounds are well-known and extensively studied, the ternary and the quaternary crystals are not. Most of the ternary and the quaternary crystals simply have been referenced as secondary phases in the processing of nitrogen ceramics. Their crystal structures are complex and not precisely determined. In the quaternary crystals, there exists O/N disorder in that the exact atomic positions of the anions cannot be uniquely determined. It is envisioned that a variety of cation,anion bonding configurations exist in these complex crystals. The electronic structure and bonding in these crystals are, therefore, of great interest and are indispensable for a fundamental understanding of structural ceramics. We have used ab initio methods to study the structure and bonding properties of these 10 crystals. For crystals with unknown or incomplete structural information, we use an accurate total energy relaxation scheme to obtain the most likely atomic positions. Based on the theoretically modeled structures, the electronic structure and bonding in these crystals are investigated and related to various local cation,anion bonding configurations. These results are presented in the form of atom-resolved partial density of states, Mulliken effective charges, and bond order values. It is shown that Y,O and Y,N bonding are not negligible and should be a part of the discussion of the overall bonding schemes in these crystals. Spectroscopic properties in the form of complex, frequency-dependent dielectric functions, X-ray absorption near-edge structure (XANES), and the electron energy-loss near-edge structure (ELNES) spectra in these crystals also are calculated and compared. These results are discussed in the context of specific bonding configurations between cations (silicon and yttrium) and anions (oxygen and nitrogen) and their implications on intergranular thin films in polycrystalline Si3N4 containing rare-earth elements. [source] High-Temperature Crystalline Phases in Nylon 6/Clay NanocompositesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 13 2005Xiaohui Liu Abstract Summary: Nylon 6/clay nanocomposites (N6CN) with different cooling histories were investigated by differential scanning calorimetry (DSC) and variable-temperature X-ray diffraction (XRD). Above the melting temperature, new endothermic peaks appeared in the DSC trace for N6CN. All the neat nylon 6 samples presented amorphous XRD patterns when heated up to the melting range. However, for N6CN samples, undefined crystalline structures remained in the substantially molten polymer matrix up to 300,°C. XRD patterns of a quenched nylon 6 sample annealed at 210,°C and N6CN samples annealed at 210, 230, and 300,°C, respectively. [source] ChemInform Abstract: X-Ray Investigation of Metastable Crystalline Phases in Co-Deposited Fe,Cr Alloy Nanometer Films.CHEMINFORM, Issue 18 2002A. A. Levin Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Electric-Field Triggered Controlled Release of Bioactive Volatiles from Imine-Based Liquid Crystalline PhasesCHEMISTRY - A EUROPEAN JOURNAL, Issue 1 2009Andreas Herrmann Dr. Abstract Application of an electric field to liquid crystalline film forming imines with negative dielectric anisotropy, such as N -(4-methoxybenzylidene)-4-butylaniline (MBBA, 1), results in the expulsion of compounds that do not participate in the formation of the liquid crystalline phase. Furthermore, amines and aromatic aldehydes undergo component exchange with the imine by generating constitutional dynamic libraries. The strength of the electric field and the duration of its application to the liquid crystalline film influence the release rate of the expelled compounds and, at the same time, modulate the equilibration of the dynamic libraries. The controlled release of volatile organic molecules with different chemical functionalities from the film was quantified by dynamic headspace analysis. In all cases, higher headspace concentrations were detected in the presence of an electric field. These results point to the possibility of using imine-based liquid crystalline films to build devices for the controlled release of a broad variety of bioactive volatiles as a direct response to an external electric signal. [source] Distinct Columnar and Lamellar Liquid Crystalline Phases Formed by New Bolaamphiphiles with Linear and Branched Lateral Hydrocarbon ChainsCHEMISTRY - A EUROPEAN JOURNAL, Issue 21 2008Marko Prehm Dr. Abstract A universal building block for the convergent synthesis of a wide variety of different T-shaped ternary amphiphiles was developed and used for the synthesis of a series of new liquid-crystalline materials composed of a rigid biphenyl core with polar glycerol groups at both ends and linear or branched alkyl chains in a lateral position. In addition, compounds with bulky achiral (2,4,6-trimethylphenoxy, adamantane-1-carboxylate, benzoate) or chiral (menthyl or cholesteryl) substituents attached to the end of the lateral alkyl chain were also investigated. In all cases the lateral chains were connected to the aromatic core by an ether linkage. The effect of the ether linking unit on mesophase stability and mesophase type is discussed with respect to conformational effects. The liquid-crystalline phases were investigated by polarizing microscopy, calorimetry, and X-ray diffraction of surface aligned samples. Upon enlarging the lateral chains a series of different polygonal cylinder phases was observed, which were replaced by lamellar phases and a non-cylinder hexagonal columnar phase by further increasing the size of these substituents. Remarkably, only pentagonal, hexagonal, and giant hexagonal cylinder phases could be observed, whereas mesophases composed of cylinders with a smaller number of sides are missing. No distinct chirality effects were observed for the menthyl- and cholesteryl-substituted compounds. However, the rodlike shape of the polycyclic cholesteryl core leads to a unique phase structure combining an organization of the alicyclic cholesteryl cores perpendicular to the layer planes and the aromatic biphenyl cores parallel to the layer planes. [source] Effect of Core Twisting on Self-Assembly and Optical Properties of Perylene Bisimide Dyes in Solution and Columnar Liquid Crystalline PhasesCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2007Zhijian Chen Abstract A series of highly soluble and fluorescent core-twisted perylene bisimide dyes (PBIs) 3,a,f with different substituents at the bay area (1,6,7,12 positions of the perylene core) were synthesized and fully characterized by 1H,NMR, UV/Vis spectroscopy, MS spectrometry, and elemental analysis. The ,,, aggregation properties of these new functional dyes were investigated in detail both in solution and in condensed phase by UV/Vis and fluorescence spectroscopy, vapor pressure osmometry (VPO), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X-ray diffraction. Concentration-dependent UV/Vis measurements and VPO analysis revealed that these core-twisted ,-conjugated systems show distinct self-dimerization equilibria in apolar solvent methylcyclohexane (MCH) with dimerization constants between 1.3×104 and 30,M,1. The photoluminescence spectra of the dimers of PBIs 3,a,f exhibit bathochromic shifts of quite different magnitude which could be attributed to different longitudinal or rotational offsets between the dyes as well as differences in the respective ,,, stacking distance. In condensed state, quite a few of these PBIs form luminescent rectangular or hexagonal columnar liquid crystalline phases with low isotropization temperatures. The effects of the distortion of the , systems on their ,,, stacking and the optical properties of the resultant stacks in solution and in LC phases have been explored in detail. In one case (3,a) a particularly interesting phase change from crystalline into liquid crystalline could be observed upon annealing that was accompanied by a transformation from non-fluorescent H -type into strongly fluorescent J -type packing of the dyes. [source] Microstructural Characteristics of an AZ91 Matrix-Glassy Carbon Particle Composite,ADVANCED ENGINEERING MATERIALS, Issue 7 2010Anita Olszówka-Myalska This paper presents the results of a microstructural investigation of a new type of ultralight glassy carbon particles (Cp)-AZ91 magnesium alloy matrix composite manufactured by the powder metallurgy method. Glassy Cp with unmodified surfaces and surfaces modified with SiO2 amorphous nanocoating were used in the experiment. The composite microstructure, with an emphasis given on the interface, was characterized by scanning electron microscope (SEM), TEM, and HRTEM microscopy. Uniform distribution of the particles in the matrix and their good bonding with the metal matrix were observed. A continuous very thin MgO oxide layer containing needle-like Al2MgO4 phase was detected at the glassy carbon,AZ91 interface. An increase of aluminum concentration at the interface as a result of Mg and Al diffusion into the SiO2 nanolayer was observed in the case of particles modified with SiO2. Crystalline phases containing carbon were not detected at the interface. [source] Synthesis and Dielectric Properties of Niobia Coating on BaTiO3INTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY, Issue 6 2009Jia-Jia Gan Different from conventional powder mixing, this study demonstrates a method of homogeneous coating for niobia (Nb2O5) on ferroelectric barium titanate (BaTiO3) powders. The precipitation of Nb coating with pH has been determined quantitatively by the inductance-coupled plasma method. Crystalline phases were determined by X-ray diffractometry, and the formation of a "core-shell" structure with a Nb concentration gradient was observed by a transmission electron microscope with X-ray energy-dispersive spectroscopy. The dielectric constant (K) of the samples prepared by the nanocoating method showed a more stable temperature coefficient of capacitance and well satisfied the requirements of X7R. [source] Devitrification Kinetics and Mechanism of K2O,CaO,SrO,BaO,B2O3,SiO2 Glass-CeramicJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 6 2001Jau-Ho Jean The devitrification kinetics and mechanism of a low-dielectric, low-temperature, cofirable K2O,CaO,SrO,BaO,B2O3,SiO2 glass-ceramic have been investigated. Crystalline phases including cristobalite (SiO2) and pseudowollastonite ((Ca,Ba,Sr) SiO3) are formed during firing. Activation energy analysis shows that the nucleation of the crystalline phases is controlled by phase separation of the glass. The crystallization kinetics of both cristobalite and pseudowollastonite obey Avrami-like behavior, and the results show an apparent activation energy close to that of the diffusion of alkaline and alkali ions in the glass, suggesting that diffusion is rate limiting. The above conclusion is further supported by analysis of measured growth rates. [source] Phase transition behavior and structure of the thermotropic liquid crystal 6-{[(4,-{[(undecyl)carbonyl]oxy}biphenyl-4yl)carbonyl]oxy}-1-hexyneCRYSTAL RESEARCH AND TECHNOLOGY, Issue 9 2006Leijing Liu Abstract The phase transition behaviors and corresponding structures of 6-{[(4,-{[(undecyl)carbonyl]oxy}biphenyl-4yl)carbonyl]oxy}-1-hexyne (A4EE11) were investigated using differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and wide angle X-ray diffraction (WAXD). In comparison with the published homologues, 5-{[(4,-heptoxy-biphenyl-4-yl)carbonyl]oxy}-1-pentyne (A3EO7) which shows a monotropic smectic A (SmA) phase and a metastable monotropic smectic C (SmC) phase; 5-{[(4,-heptoxy-biphenyl-4-yl)oxy]carbonyl}- 1-pentyne (A3E'O7) that exhibits three enantiotropic stable liquid crystalline (LC) phases, SmA phase, SmC phase and smectic X (SmX) phase; 5-{[(4,-heptoxy-biphenyl-4-yl)carbonyl]oxy}-1-undecyne (A9EO7) which has a monotropic SmA phase and a metastable crystal phase, A4EE11 integrates the enantiotropy, monotropy and metastability of the LC phases of those three compounds. Upon cooling from isotropic state to room temperature, in the temperature range of 62.0 to 58.5°C, A4EE11 shows an enantiotropic smectic A (SmA) phase with a layer spacing d=32.69Å. Further lowering the temperature, it enters into a metastable monotropic smectic B (SmB) phase with a longer layer spacing d=34.22Å which has a tendency towards crystallization. The metastability of the liquid crystalline phase may associate to the linkage order of the ester bridge between the mesogenic core and the flexible spacer. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Synthesis and Characterization of a New Guanidine,Borane Complex and a Dinuclear Boron(II) Hydride with Bridging Guanidinate LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2007Oxana Ciobanu Abstract We report the synthesis and structural characterization of the new monomeric borane complex H3B·hppH (hppH = 1,3,4,6,7,8-hexahydro-2H -pyrimido[1,2- a]pyrimidine), which represents the first example of a structurally characterized 1:1 complex between hppH and a group 13 element hydride. Significant intramolecular and, in the crystalline phase, intermolecular H···H contacts are established in this complex. It is shown that the complex can be used as a precursor to new dinuclear boron(II) compounds featuring a B,B single bond. Thus H2 elimination followed by dimerization of H3B·hppH leads to [(hpp)BH]2 with two bridging hpp units. The structural details derived from X-ray diffraction measurements are reported.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Nanocomposite Hard Coatings: Deposition Issues and Validation of their Mechanical Properties,ADVANCED ENGINEERING MATERIALS, Issue 5 2005P. Schwaller Abstract The limitations of conventional coatings due to inferior hardness or poor oxidation stability can be overcome by nanocomposite hard coatings such as nc-TiN/a-SiNx, which consists of nanocrystalline TiN and a non-crystalline tissue phase of SiNx which are mutually immiscible. The properties of nanocomposite coatings, especially their increased hardness, can be explained by their nanostructure, which leads to a maximum hardness at typically 80 atomic percent of the crystalline phase. We show that enhanced hardness can only be attained when the silicon nitride phase is sufficiently nitrided. The accurate and reliable measurement of the hardness and elastic modulus requires the use of appropriate nanoindentation equipment and a careful tip correction with periodical validation. It is shown that for a correct hardness determination of a few microns thick nanocomposite coatings, an indentation depth of 100,nm is sufficient. The maximum hardness of our nc-TiN/a-SiNx coatings deposited by a hybrid UBM/arc-PVD process is about 40,GPa. This value represents a global hardness value, due to the nanocomposite structure there may be a local hardness variation of about ±10,%. [source] The Quest for Nanoscale Magnets: The example of [Mn12] Single Molecule MagnetsADVANCED MATERIALS, Issue 43 2009Guillaume Rogez Abstract Recent advances on the organization and characterization of [Mn12] single molecule magnets (SMMs) on a surface or in 3D are reviewed. By using nonconventional techniques such as X-ray magnetic circular dichroism (XMCD) and scanning tunneling microscopy (STM), it is shown that [Mn12]-based SMMs deposited on a surface lose their SMM behavior, even though the molecules seem to be structurally undamaged. A new approach is reported to get high-density information-storage devices, based on the 3D assembling of SMMs in a liquid crystalline phase. The 3D nanostructure exhibits the anisotropic character of the SMMs, thus opening the way to address micrometric volumes by two photon absorption using the pump-probe technique. We present recent developments such as µ-SQUID, magneto-optical Kerr effect (MOKE), or magneto-optical circular dichroism (MOCD), which enable the characterization of SMM nanostructures with exceptional sensitivity. Further, the spin-polarized version of the STM under ultrahigh vacuum is shown to be the key tool for addressing not only single molecule magnets, but also magnetic nano-objects. [source] Sol,Gel Synthesis of PZT,Glass Nanocomposites Using a Simple System and CharacterizationINTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY, Issue 5 2006V. Kumar A simple inorganic system has been developed for the sol,gel synthesis of piezoelectric PZT,glass nanocomposites. Nanocrystalline PZT are nucleated from the amorphous xerogel through controlled heat treatment at 600°C. The formation of the crystalline phase, particle size, morphology, kinetics, and mechanism of crystallization of PZT in the glass matrix have been studied using X-ray diffraction, scanning electron microscopy, and differential thermal analysis. The piezoelectric characteristics of the PZT,glass compositions have been determined, and are correlated with the microstructure and the crystalline phase of PZT. [source] Formation of Lipid Emulsions and Clear Gels by Liquid Crystal EmulsificationINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 1 2007T. Suzuki Recently developed emulsion technologies for the formation of fine emulsions, lipid emulsions and clear gels by liquid crystal emulsification were reviewed. As a basic information on liquid crystal emulsification, the structures and characteristic behaviours of lyotropic liquid crystals were summarized. Formation of a liquid crystalline phase was often seen in emulsions and biological systems. The significance of liquid crystal formation during emulsification was analysed by comparing the states and stabilities of emulsions prepared by different processes. Then uses of liquid crystals for formation of the characteristic emulsions and gels were also discussed. In liquid crystal emulsification, an oil phase is dispersed directly into the lamellar liquid-crystalline phase composed of surfactant, glycerol and water to prepare a gel-like oil-in-liquid crystal emulsion. This is followed by dilution with the remaining water to produce an emulsion. From the phase behaviour during emulsification and analysis of the local motion of the liquid crystal membrane by fluorometry, it was confirmed that the interaction between surfactant and a polyol molecule such as glycerol promotes hydrogen bonding and enhances the strength of the lamellar liquid crystal membranes, which results in the formation of oil-in-liquid crystal emulsions. The interaction between the liquid crystal and oil was analysed from the changes in molecular motion of the membrane at the oil-liquid crystal interface using the spin label technique of electron spin resonance (ESR). The fluidity of the liquid crystal membrane did not change when oil was added, and therefore oil-in-liquid crystal emulsions of various oils were prepared by the identical process. This lack of dependence of the liquid crystal membrane on oil results in the unique properties of liquid crystal emulsification, which can be used for oils of various polarity and different molecular constituents. When a self-organizing artificial stratum corneum lipid containing pseudo-ceramide was used as a principal component of the oil, a multilamellar emulsion of concentric lamellar structure was formed. The multilamellar emulsion supplements the physiological function of stratum corneum by the identical mechanism as natural intercellular lipids. High-pressure treatment of the lipid emulsion produced a gel-like emulsion crystal, in which the homogeneous nanoemulsion droplets were arranged in a hexagonal array. This review paper was presented at the Conference of the Asian Societies of Cosmetic Scientists 2005 in Bangkok. [source] Abinitio structure determination of m -toluidine by powder X-ray diffractionJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 3 2004Mwaffak Rukiah The powder X-ray diffraction pattern of the crystalline phase of m -toluidine has been recorded with a sensitive curved detector (CPS120) at 150,K. The structure has been solved by real-space methods (simulated annealing) followed by Rietveld refinements with phenyl rings as rigid bodies and with soft constraints on bond lengths for peripheral atoms. The cell is monoclinic with space group P21/c and Z = 8. Equivalent molecules form chains along c. The crystalline cohesion is achieved by N,H,N hydrogen bonds between neighbouring chains of non-equivalent molecules and by van der Waals interactions of neighbouring chains of equivalent molecules. The hydrogen-bonding network has been confirmed by lattice-energy minimization. Anisotropic strain effects of the cell have been calculated. The directions of the minimal strains correspond to the directions of the hydrogen bonds. An explanation of the difficulty to crystallize the metastable phase is given. [source] Effect of cavitation on the plastic deformation and failure of isotactic polypropyleneJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007Bing Na Abstract To clarify the effect of cavitation, which is mostly induced by crystalline phase, on the plastic deformation and failure of isotactic polypropylene, solid-state annealing at 160°C for 1.5 h is adopted to change the crystalline phase only while the amorphous phase keeps nearly intact. With aid of a special video setup, the relation of true stress and strain as well as the evolution of volume strain with axial strain has been derived. Enhancing crystalline phase due to annealing increases the yield stress and volume strain simultaneously. Moreover, the strain corresponding to steep increasing of volume strain is comparable with that related to yield, indicating that cavitation at early stage is accompanied with process of yield. With knowledge of toughness derived from impact tensile stretching and essential work of fracture (EWF), respectively, the relationship between cavitation and toughness has been correlated to some degree. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 [source] Effect of flow history on poly(vinylidine fluoride) crystalline phase transformationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2007Hadi Sobhani Abstract This study was devoted to the effect of extensional flow during film extrusion on the formation of the ,-crystalline phase and on the piezoelectric properties of the extruded poly(vinylidine fluoride) (PVDF) films after cold drawing. The PVDF films were extruded at different draw ratios with two different dies, a conventional slit die and a two-channel die, of which the latter was capable of applying high extensional flow to the PVDF melt. The PVDF films prepared with the two-channel die were drawn at different temperatures, strain rates, and strains. The optimum stretching conditions for the achievement of the maximum ,-phase content were determined as follows: temperature = 90°C, strain = 500%, and strain rate = 0.083 s,1. The samples prepared from the dies were then drawn under optimum stretching conditions, and their ,-phase content and piezoelectric strain coefficient (d33) values were compared at equal draw ratios. Measured by the Fourier transform infrared technique, a maximum of 82% ,-phase content was obtained for the samples prepared with the two-channel die, which was 7% higher than that of the samples prepared by the slit die. The d33 value of the two-channel die was 35 pC/N, which was also 5 pC/N higher than that of the samples prepared with the slit die. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source] An investigation into the mechanism of dissolution rate enhancement of poorly water-soluble drugs from spray chilled gelucire 50/13 microspheresJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 1 2010Sheng Qi Abstract The production and physicochemical characterisation of spray chilled Gelucire 50/13 microspheres is described with a view to improving the dissolution of a poorly water-soluble drug, piroxicam, and understanding the fundamental mechanisms associated with the improved drug release. Thermorheological testing was developed as a fast screening method for predicting the processability of dispersions for spray chilling preparation. Spray chilled piroxicam loaded microspheres were spherical in shape with a median diameter of circa 150,µm. DSC indicated no interaction between piroxicam and lipid matrix, while HSM studies performed in polarized light mode indicated that the spheres contained distinct drug crystals. Polarising light microscopy and small-angle XRD investigations on the hydration behaviour of the lipid and the spray chilled microspheres revealed the formation of liquid crystalline phases depending on the degree of hydration. The dissolution behaviour of the piroxicam loaded microspheres showed significant improvements compared to drug alone. The particle size, drug loading and aging of the microspheres were all found to have an influence on the release behaviour. It was proposed that Gelucire 50/13 microspheres release the entrapped piroxicam via formation of a lyotropic liquid crystalline phase, which allows dissolution of the drug particles in a finely divided, high surface area and well-wetted state. © 2009 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:262,274, 2010 [source] Crystallization pathways and kinetics of carbamazepine,nicotinamide cocrystals from the amorphous state by in situ thermomicroscopy, spectroscopy, and calorimetry studiesJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 5 2007K. Seefeldt Abstract The work presented here was motivated by the premise that the amorphous state serves as a medium to study cocrystal formation. The molecular mobility inherent to amorphous phases can lead to molecular associations between different components such that a single crystalline phase of multiple components or cocrystal is formed. Cocrystallization pathways and kinetics were investigated from amorphous equimolar phases of carbamazepine and nicotinamide using hot-stage polarized microscopy (HSPM), hot-stage Raman microscopy (HSRM), differential scanning calorimetry (DSC), and X-ray powder diffraction (XRPD). Nonisothermal studies revealed that amorphous phases generate cocrystals and that thermal history affects crystallization pathways in significant ways. Two different pathways to cocrystal formation from the amorphous phase were identified: (1) at low heating rates (3°C/min) a metastable cocrystalline phase initially nucleates and transforms to the more stable cocrystalline phase of CBZ,NCT, and (2) at higher heating rates (10°C/min) individual components crystallize, then melt and the stable cocrystalline phase nucleates and grows from the melt. Isothermal studies above the Tg of the amorphous equimolar phase also confirm the nucleation of a metastable cocrystalline phase from the amorphous state followed by a solid phase mediated transformation to the stable cocrystalline phase. Cocrystallization kinetics were measured by image analysis and by thermal analysis from small samples and are described by the Avrami,Erofeev model. These findings have important implications for the use of amorphous phases in the discovery of cocrystals and to determine the propensity of cocrystallization from process-induced amorphization. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 96: 1147,1158, 2007 [source] Solid-state properties of warfarin sodium 2-propanol solvateJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 11 2004Agam R. Sheth Abstract The goal of the present work was to understand the effect of relative humidity (RH) and temperature on the molecular structure, crystal structure, and physical properties of warfarin sodium 2-propanol solvate (W). After previous determination of the crystal structure of W, which corresponds to a 1:1 2-propanol solvate, the present work shows that W has a critical RH (60%,<,RH0,,,68%), below which minimal uptake of water occurs, due to surface adsorption, but above which gradual and continuous uptake of water occurs, due to deliquescence. Deliquescence begins at the surface and proceeds inward into the bulk of the crystal. Single crystal X-ray diffractometry indicates no change in the crystal and molecular structure of W during the initial stages of deliquescence. Studies of the unit cell and volume computations of W show that water can neither find space to enter the crystal lattice, nor can replace 2-propanol. Thus, water does not exchange with 2-propanol within the lattice, contrary to previous reports. Storage of single crystals of W at 120°C for 23 h produces shrinkage cracks along the needle (b) axis, which are interpreted as a reduction in d -spacing of the 00l planes. Thus, under thermal stress, W crystals undergo amorphization with concurrent loss of 2-propanol, which may proceed via an intermediate crystalline phase. The phase changes of W, which depend on RH and temperature, are explained at the molecular level. © 2004 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 93:2669,2680, 2004 [source] DIATOM SILICA BIOMINERALIZATION: AT NANOSCALE LEVEL A CHEMICALLY UNIFORM PROCESSJOURNAL OF PHYCOLOGY, Issue 2000E. G. Vrieling Using a high-brilliance synchrotron X-ray source, combined small- and wide-angle X-ray scattering (SAXS and WAXS) was applied to study nanoscale characteristics, in particular pore size in the range of 3 to 65 nm, of a variety of unialgal cultures of centric and pennate diatoms, and of mixed diatom populations sampled in the field. Results of scattering analysis were compared with details of pore size, structure and orientation visible at the electron microscopic level. WAXS patterns did not reveal any crystalline phase or features of microcrystallinity (resolution 0.07 to 0.51 nm), which implies a totally amorphous character of the SiO2 matrix of the frustule material. SAXS data (resolution 3 to 65 nm) provided information on geometry, size, and distribution of pores in the silica. Overall, two pore regions were recognized that were common to the silica of all samples: the smallest (d less than 10 nm) regularly spaced and shaped spherically, the larger (up to 65 nm) being cylinders or slits. Apparently, at a nanoscale level diatomaceous silica is quite homologous among species, in agreement with the chemical principles of silica polymerization under the conditions of pH and precursor concentrations inside the silicon deposition vesicle. The final frustule "macro"-morphology is of course species-specific, being determined genetically. Synthetically-derived MCM-type silicas have a similarly organized pore distribution in an amorphous silica matrix as we found in all diatom species studied. We therefore suggest that organic molecules of a kind used as structure-directing agents to produce these artificial silicas play a role in the nucleation of the silica polymerization reaction and the shaping of pore morphology inside the silicon deposition vesicle of diatoms. Structure-directing molecules now await isolation from the SDV, followed by identification and characterisation by molecular techniques. [source] Nanoscale uniformity of pore architecture in diatomaceous silica: a combined small and wide angle x-ray scattering studyJOURNAL OF PHYCOLOGY, Issue 1 2000Engel G. Vrieling Combined small and wide angle X-ray scattering (SAXS and WAXS) analysis was applied to purified biogenic silica of cultured diatom frustules and of natural populations sampled on marine tidal flats. The overall WAXS patterns did not reveal crystalline phases (WAXS domain between 0.07 to 0.5 nm) in this biogenic silica, which is in line with previous reports on the amorphous character of the SiO2 matrix of diatom frustules. One exception was the silica of the pennate species Cylindrotheca fusiformis Reimann et Lewin, which revealed wide peaks in the WAXS spectra. These peaks either indicate the presence of a yet unknown crystalline phase with a repetitive distance (d -value ,0.06 nm) or are caused by the ordering of the fibrous silica fragments; numerous girdle bands. The SAXS spectra revealed the size range of pores (diameter d between 3.0 and 65 nm), the presence of distinct pores (slope transitions), and structure factors (oscillation of the spectra). All slopes varied in the range of ,4.0 to ,2.5, with two clear common regions among species: d < 10 nm (slopes ,4, denoted as region I and also called the Porod region), and 10.0 < d < 40.0 nm (slopes ,2.9 to ,3.8, denoted as region II). The existence of these common regions suggests the presence of comparable form (region I) and structure (region II) factors, respectively the shape of the primary building units of the silica and the geometry of the pores. Contrast variation experiments using dibromomethane to fill pores in the SiO2 matrix showed that scattering was caused by pores rather than silica particles. Electron microscopic analysis confirmed the presence of circular, elliptical, and rectangular pores ranging in size from 3 to 65 nm, determining the structure factor. The fine architecture (length/width ratio of pore diameters) and distribution of the pores, however, seemed to be influenced by environmental factors, such as the salinity of and additions of AlCl3 to the growth medium. The results indicate that diatoms deposit silica with pores <50 nm in size and are highly homologous with respect to geometry. Consequently, it is suggested that in diatoms, whether pennate or centric, the formation of silica at a nanoscale level is a uniform process. [source] Liquid crystalline conjugated polymers and their applications in organic electronicsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2009Sheng-Hsiung Yang Abstract This article describes the syntheses and electro-optical applications of liquid crystalline (LC) conjugated polymers, for example, poly(p -phenylenevinylene), polyfluorene, polythiophene, and other conjugated polymers. The polymerization involves several mechanisms: the Gilch route, Heck coupling, or Knoevenagel condensation for poly(p -phenylenevinylene)s, the Suzuki- or Yamamoto-coupling reaction for polyfluorenes, and miscellaneous coupling reactions for other conjugated polymers. These LC conjugated polymers are classified into two types: conjugated main chain polymers with long alkyl side chains, namely main-chain type LC polymers, and conjugated polymers grafting with mesogenic side groups, namely side-chain type LC conjugated polymers. In general, the former shows higher transition temperature and only nematic phase; the latter possesses lower transition temperature and more mesophases, for example, smectic and nematic phases, depending on the structure of mesogenic side chains. The fully conjugated main chain promises them as good candidates for polarized electroluminescent or field-effect devices. The polarized emission can be obtained by surface rubbing or thermal annealing in liquid crystalline phase, with maximum dichroic ratio more than 20. In addition, conjugated oligomers with LC properties are also included and discussed in this article. Several oligo-fluorene derivatives show outstanding polarized emission properties and potential use in LCD backlight application. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2713,2733, 2009 [source] Phase behavior and photo-responsive studies of photoactive liquid crystalline hyperbranched polyethers containing benzylidene moietyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2009V. Srinivasa Rao Abstract Two sets of hyperbranched polyether epoxies were synthesized to study the effect of substituent, rigidity, and nature of photoactive unit on the thermal and photoresponsive properties. Each set was comprised of one molecule with an acyclic moiety in the repeating unit, and two molecules with a cyclic moiety of varying rigidity (cycle size) in the repeating unit. Two substituents on aromatic rings in the repeating unit were present in one set, and other set was without a substituent. The mesogenic and photoresponsive properties were studied and correlated to the varied structural parameters. The effects of varied molecular structural parameters on phase behavior and photoresponsive properties were very prominent. Out of six monomeric diols, only four have exhibited liquid crystalline phase while the polymers corresponding to all monomeric diols revealed mesophase. The findings in photoresponsive properties were further supported by molecular modeling studies. The changes in refractive index, photoviscosity, and fluorescence intensity with irradiation time substantiated the spectral pattern observed in UV-Vis spectroscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2774,2786, 2009 [source] | |||||||||||||||||||||||||||||||||||||||||||