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Amorphous Phase (amorphous + phase)
Selected AbstractsLocal Viscosity of Si-O-C-N Nanoscale Amorphous Phases at Ceramic Grain BoundariesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 10 2001Giuseppe Pezzotti Internal friction characterization has been used to quantitatively assess the viscosity characteristics of Si-O-C-N glasses segregated to nanometer-sized grain boundaries of polycrystalline Si3N4 and SiC ceramics. A relaxation peak of internal friction, which arises with rising temperature from the viscous sliding of glassy grain boundaries, was systematically collected and analyzed with respect to its shift upon changing the oscillation frequency. As a result of such an analysis, both activation energy for viscous grain-boundary flow and inherent viscosity of the intergranular glass film could be quantitatively evaluated. Two main features are shown: (i) the presence of N and/or C greatly affects the viscosity characteristics of SiO2 phases at Si3N4 and SiC grain boundaries; and (ii) the internal friction method has potential as a unique experimental tool for understanding the local properties of nanoscale amorphous phases in new ceramic materials. [source] The Effect of Surface Area and Crystal Structure on the Catalytic Efficiency of Iron(III) Oxide Nanoparticles in Hydrogen Peroxide DecompositionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2010Cenek Gregor Abstract Iron(II) oxalate dihydrate has been used as a readily decomposable substance for the controlled synthesis of nanosized iron(III) oxides. The polymorphous composition, particle size and surface area of these iron oxide nanoparticles were controlled by varying the reaction temperature between 185 and 500 °C. As-prepared samples were characterized by XRD, low-temperature and in-field Mössbauer spectroscopy, BET surface area and the TEM technique. They were also tested as heterogeneous catalysts in hydrogen peroxide decomposition. At the selected temperatures, the formed nanomaterials did not contain any traces of amorphous phase, which is known to considerably reduce the catalytic efficiency of iron(III) oxide catalysts. As the thickness of the sample (, 2 mm) was above the critical value, a temporary temperature increase ("exo effect") was observed during all quasi-isothermal decompositions studied, irrespective of the reaction temperature. Increasing the reaction temperature resulted in a shift of the exo effect towards shorter times and an increased content of maghemite phase. The maghemite content decreases above 350 °C as a result of a thermally induced polymorphous transition into hematite. The catalytic data demonstrate that the crystal structure of iron(III) oxide (i.e. the relative contents of maghemite and hematite) does not influence the rate of hydrogen peroxide decomposition. However, the rate constant increases monotonously with increasing sample surface area (and decreasing thermolysis temperature), reaching a maximum of 27,×,10,3 min,1(g/L),1 for the sample with a surface area of 285 m2,g,1. This rate constant is currently the highest reported value of all known iron oxide catalytic systems and is even slightly higher than that observed for the most efficient catalyst reported to date, which has a significantly larger surface area of 337 m2,g,1. This surprisingly high catalytic activity at relatively low surface area can be ascribed to the absence of a amorphous phase in the samples prepared in this study. Taking into account these new findings, the contributions of the key factors highlighted above (surface area, particle size, crystal structure, crystallinity) to the overall activity of iron oxides forhydrogen peroxide decomposition are discussed. [source] Phase Diagrams and Glass Formation in Metallic Systems,ADVANCED ENGINEERING MATERIALS, Issue 6 2007M. Baricco Abstract The basic thermodynamic aspects of glass-formation in metallic systems are reviewed. In particular, the specific features of a phase diagram with respect to glass-formation are evidenced. On the basis of the regular solution model, the effect of various thermodynamic quantities on the free energy difference between undercooled liquid and crystal phases are outlined. In order to describe the amorphous phase, a specific heat difference between liquid and solid phases in the undercooling regime is introduced in the CALPHAD assessment of various binary systems. The glass-transition is described as a second order transition. Examples are given for different systems, including Fe-B and Cu-Mg. From the description of the free energy of various phases as a function of composition and temperature, the driving forces for nucleation of crystal phases and the T0 curves are estimated. [source] Time,Temperature,Transformation (TTT) Diagrams for Crystallization of Metal Oxide Thin FilmsADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Jennifer L. M. Rupp Abstract Time,temperature,transformation (TTT) diagrams are proposed for the crystallization of amorphous metal oxide thin films and their specific characteristics are discussed in comparison to glass-based materials, such as glass-ceramics and metallic glasses. The films crystallize from amorphous to full crystallinity in the solid state. As an example the crystallization kinetics for a single-phase metal oxide, ceria, and its gadolinia solid solutions are reported made by the precipitation thin-film method spray pyrolysis. The crystallization of an amorphous metal oxide thin film generally follows the Lijschitz,Sletow,Wagner (LSW) Ostwald ripening theory: Below the percolation threshold of 20 vol% single grains crystallize in the amorphous phase and low crystallization rates are measured. In this state no impact of solute on crystallization is measurable. Once the grains form primary clusters above the threshold the solute slows down crystallization (and grain growth) thus shifting the TTT curves of the doped ceria films to longer times and higher temperatures in comparison to undoped ceria. Current views on crystallization of metal oxide thin films, the impact of solute dragging, and primary TTT diagrams are discussed. Finally, examples on how to use these TTT diagrams for better thermokinetic engineering of metal oxide thin films for MEMS are given, for example, for micro-Solid Oxide Fuel Cells and resistive sensors. In these examples the electrical properties depend on the degree of crystallinity and, thereby, on the TTT conditions. [source] Grayscale Photopatterning of an Amorphous Polymer Thin Film Prepared by Photopolymerization of a Bisanthracene-Functionalized Liquid-Crystalline MonomerADVANCED FUNCTIONAL MATERIALS, Issue 10 2010Hideyuki Kihara Abstract A method for grayscale photopatterning of an amorphous polymer film derived from a bisanthracene-functionalized liquid-crystalline monomer is developed. Solution photopolymerization of a monomer with two anthracene moieties, one at each end, affords an amorphous polymer. A combination of irradiation with patterned UV light and heating results in photopatterning on thin films prepared from the polymer. On non-irradiated areas of the film, the polymer reverts to the monomer owing to the thermal back-reaction of the anthracene photodimer, forming an ordered phase. On irradiated areas remaining in the amorphous phase, the thermal back-reaction is suppressed. This phenomenon results in a clear contrast and visual images on the film under polarized light. Grayscale photopatterning is also made possible for the solution-polymerized polymer by controlling the intensity of exposure. In addition, rewritable photopatterning can be achieved by melt photopolymerization of the monomer. The new photopatterning is essentially nondestructive because it needs neither image development nor anthracene-excitation light for reading. [source] Synthesis and Structure,Property Relations of a Series of Photochromic Molecular Glasses for Controlled and Efficient Formation of Surface Relief NanostructuresADVANCED FUNCTIONAL MATERIALS, Issue 16 2009Roland Walker Abstract This paper reports on the synthesis and properties of a new series of photochromic molecular glasses and their structure,property relations with respect to a controlled and efficient formation of surface relief nanostructures. The aim of the paper is to establish a correlation between molecular structure, optical susceptibility, and the achievable surface relief heights. The molecular glasses consist of a triphenylamine core and three azobenzene side groups attached via an ester linkage. Structural variations are performed with respect to the substitution at the azobenzene moiety in order to promote a formation of a stable amorphous phase and to tune absorption properties and molecular dynamics. Surface relief gratings (SRGs) and complex surface patterns can easily be inscribed via holographic techniques. The modulation heights are determined with an equation adapted from the theory for thin gratings, and the values are confirmed with AFM measurements. Temperature-dependent holographic measurements allow for monitoring of SRG build-up and decay and the stability at elevated temperatures, as well as determination of the glass transition temperature. SRG modulation heights of above 600,nm are achieved. These are the highest values reported for molecular glasses to date. The surface patterns of the molecular glasses are stable enough to be copied in a replica molding process. It is demonstrated that the replica can be used to transfer the surface pattern onto a common thermoplastic polymer. [source] Colloidal-Crystal-Assisted Patterning of Crystalline MaterialsADVANCED MATERIALS, Issue 13 2010Cheng Li Abstract Colloidal crystals have shown great potential as versatile templates for the fabrication of patterned micro- and nanostructures with complex architectures and novel properties. The patterning of functional crystalline materials in two and three dimensions is essential to the realization of their applications in many technologically important fields. This article highlights some recent progress in the fabrication of 2D and 3D patterned crystalline materials with the assistance of colloidal crystals. By combining a bioinspired synthetic strategy based on a transient amorphous phase with a colloidal-crystal templating method, unique 3D ordered macroporous (3DOM) calcite single crystals can be created. Moreover, patterned arrays of regular ZnO nanopillars with controlled size, shape, and orientation can be fabricated via a facile wet chemical approach by using masks derived from monolayer colloidal crystals (MCC). [source] Experimental Study of the Aging and Self-Healing of the Glass/Ceramic Sealant Used in SOFCsINTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY, Issue 1 2010Wenning N. Liu High operating temperatures of solid oxide fuel cells (SOFCs) require that the sealant must function at a high temperature between 600°C and 900°C and in the oxidizing and reducing environments of fuel and air. This paper describes tests to investigate the temporal evolution of the volume fraction of ceramic phases, the evolution of micro-damage, and the self-healing behavior of the glass,ceramic sealant used in SOFCs. It was found that after the initial sintering process, further crystallization of the glass,ceramic sealant does not stop, but slows down and reduces the residual glass content while boosting the ceramic crystalline content. Under a long-term operating environment, distinct fibrous and needle-like crystals in the amorphous phase disappeared, and smeared/diffused phase boundaries between the glass phase and ceramic phase were observed. Meanwhile, the micro-damage was induced by the cooling down process from the operating temperature to room temperature, which can potentially degrade the mechanical properties of the glass/ceramic sealant. The glass/ceramic sealant exhibited self-healing upon reheating to the SOFC operating temperature, which can restore the mechanical performance of the glass/ceramic sealant. [source] A comparative in situ Rietveld refinement study: thermal decomposition and transformation of CoAl and CoZnAl layered double hydroxidesJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 6 2008Rune E. Johnsen Rietveld refinement based on in situ X-ray powder diffraction (XRPD) data was combined with thermogravimetric analysis (TGA) and mass spectrometry (MS) to study and compare the phase transformations, thermal stability, microstructural and structural changes of two cobalt-containing nitrate-based layered double hydroxides (LDHs) upon heating in a controlled inert atmosphere of nitrogen. The XRPD data were collected, using synchrotron X-ray radiation, with a time resolution of 107,s, which made it possible to carry out detailed structural studies of the initial layered double hydroxides as well as their decomposition products: spinel for a CoAl,NO3 LDH and spinel/zincite for a CoZnAl,NO3 LDH. Correlating these data with those from the TGA,MS analyses gives us information about the transformation mechanisms. Rietveld refinements of the two spinel phases reveal remarkable differences. The a axis of the spinel formed by decomposition of the CoAl,NO3 LDH increases almost linearly from approximately 598 to 1163,K, mainly due to the dominating thermal expansion, whereas the a axis of the spinel formed by decomposition of the CoZnAl,NO3 shows a more complex temperature dependency. Between approximately 698 and 1073,K, the a axis is almost constant due to pronounced chemical interaction with an additional amorphous phase and the zincite phase, whereas from 1073 up to 1163,K it increases linearly. Calculations, based on the results of the Rietveld refinements, of the size of the octahedral and tetrahedral coordination polyhedra in the spinel show that the octahedra shrink and the tetrahedra expand with increasing temperature. The unusual thermal behaviour of the octahedra is discussed and attributed to the low formation temperature of the cobalt aluminium spinel phase. Finally, the intensity of a low-angle scattering (LAS) signal observed in the XRPD patterns was correlated with the decomposition of the LDH, and determination of the specific surface areas gave the temperature-dependent BET surface areas. [source] Effect of chain architecture on biaxial orientation and oxygen permeability of polypropylene filmJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008P. Dias Abstract Films of two isotactic propylene homopolymers prepared with different catalysts and a propylene/ethylene copolymer were biaxially oriented under conditions of temperature and strain rate that were similar to those encountered in a commercial film process. The draw temperature was varied in the range between the onset of melting and the peak melting temperature. It was found that the stress response during stretching depended on the residual crystallinity in the same way for all three polymers. Biaxial orientation reduced the oxygen permeability of the oriented films, however, the reduction did not correlate with the amount of orientation as measured by birefringence, with the fraction of amorphous phase as determined by density, or with free volume hole size as determined by PALS. Rather, the decrease in permeability was attributed to reduced mobility of amorphous tie molecules. A single one-to-one correlation between the oxygen permeability and the intensity of the dynamic mechanical ,-relaxation was demonstrated for all the polymers used in the study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Effect of sequence distribution of PES/PEES random, block, and alternative copolymers on excimer formation in solutionJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Xiao-Ming Zhou Abstract Three copolymers of poly(ether sulfone) and poly(ether ether sulfone) with the same composition but different sequence distribution were synthesized by three kinds of methods. Their molecular aggregation in dichloromethane was studied by fluorescence spectrophotometer and electron microscope. The experimental results revealed that the formation of intermolecular excimers in alternative copolymer (A50) dichloromethane solution were observed at a A50 concentration about 1.6 × 10,2 g/mL by the fluorescence analysis, but the formation of intermolecular excimers in dichloromethane were not found for random copolymer (R50) and block copolymer (B50). The electron micrograph of three copolymer films, heat-treated at 200°C for 7 days, presented a diffraction micrograph, which suggest that three copolymer molecular aggregation is changed from a randomly coiled amorphous phase to an ordered one, and the order structure of alternative copolymer (A50) was the most distinct in three copolymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [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] The contribution of coating microstructure to degradation and particle release in hydroxyapatite coated prosthesesJOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2002K. A. Gross Abstract Plasma-sprayed coatings of hydroxyapatite powder are widely used on hip replacements. Commercially, they are supplied by a large number of companies and thus offer different coating design philosophies. This study focuses on a retrieved prosthetic stem that exhibited coating loss on the femoral stem occurring concurrently with third-body wear. The purpose of the research was to establish possible links between the coating microstructure and the clinical findings. A coated stem and cup were sectioned and the cross section was prepared to reveal the coating microstructure. Characterization included X-ray diffraction, FTIR spectroscopy, and crystalline particle quantification within the coating. It was found that the coating has a high amorphous content that provides fast resorption. The amount of crystalline particles increased on the distal location of the stem, the threads of the acetabular shell, and was generally higher on the cup. Accelerated degradation illustrated how the coating may be a particle-generating source by preferential dissolution of the amorphous phase, possibly allowing liberation of crystalline areas and other particulates at the substrate-coating interface. Such particles mainly include the less soluble hydroxyapatide formed from unmelted particles in the plasma or recrystallisation in the coating, but may also include entrapped grit lodged in the substrate during the roughening process. This study accents the importance of coating microstructure in understanding coating resorption. © 2002 Wiley Periodicals, Inc. J Biomed Mater Res (Appl Biomater) 63: 106,114, 2002; DOI 10.1002/jbm.10090 [source] Polymorph transitions of bicalutamide: A remarkable example of mechanical activationJOURNAL OF PHARMACEUTICAL SCIENCES, Issue 8 2008Zoltán Német Abstract Bicalutamide, an active pharmaceutical ingredient possessing antiandrogenic activity, is known to exhibit polymorphism. The higher melting Form I relates monotropically to the lower melting Form II. The amorphous form can be easily produced by quench cooling the melt, but it is known to crystallize spontaneously to Form II at room temperature within days. Our results show that crystallization of amorphous bicalutamide is greatly influenced by experimental conditions and sample treatment. The effect of mechanical activation on the polymorph transitions is investigated in detail. Seeds of Form I can be formed in the amorphous phase even due to gentle mechanical treatment, which results in crystallization to the more stable structure at elevated temperature. The crystalline Form II may as well be transformed to the stable modification through mechanical activation at elevated temperature. © 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 97: 3222,3232, 2008 [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] Preparation and characterization of poly(butylene terephthalate)/poly(ethylene terephthalate) copolymers via solid-state and melt polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2007M. A. G. Jansen Abstract To increase the Tg in combination with a retained crystallization rate, bis(2-hydroxyethyl)terephthalate (BHET) was incorporated into poly(butylene terephthalate) (PBT) via solid-state copolymerization (SSP). The incorporated BHET fraction depends on the miscibility of BHET in the amorphous phase of PBT prior to SSP. DSC measurements showed that BHET is only partially miscible. During SSP, the miscible BHET fraction reacts via transesterification reactions with the mobile amorphous PBT segments. The immiscible BHET fraction reacts by self-condensation, resulting in the formation of poly(ethylene terephthalate) (PET) homopolymer. 1H-NMR sequence distribution analysis showed that self-condensation of BHET proceeded faster than the transesterification with PBT. SAXS measurements showed an increase in the long period with increasing fraction BHET present in the mixtures used for SSP followed by a decrease due to the formation of small PET crystals. DSC confirmed the presence of separate PET crystals. Furthermore, the incorporation of BHET via SSP resulted in PBT-PET copolymers with an increased Tg compared to PBT. However, these copolymers showed a poorer crystallization behavior. The modified copolymer chain segments are apparently fully miscible with the unmodified PBT chains in the molten state. Consequently, the crystal growth process is retarded resulting in a decreased crystallization rate and crystallinity. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 882,899, 2007. [source] Superplasticity of a Fine-Grained TZ3Y Material Involving Dynamic Grain Growth and Dislocation MotionJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 3 2010Guillaume Bernard-Granger Superplastic deformation of a fully dense TZ3Y material, having a starting grain size around 135,145 nm and depleted of any amorphous phase at grain boundaries, has been investigated using compressive creep tests in air in the temperature range of 1100°,1300°C and the real stress range of 50,100 MPa. The key parameters of the creep law have been determined by performing temperature changes at a fixed stress and stress jumps at a fixed temperature. From such experiments, an average value for the apparent stress exponent of around 3 is obtained when the applied stress varied from 50 to 100 MPa and the temperature was kept constant in the range of 1100°,1300°C. The apparent activation energy of the mechanism controlling the creep deformation is evaluated at 577±75 kJ/mol in the temperature range of 1200°,1300°C, for a real stress of 70 MPa. The values of the apparent grain size exponent can be calculated from the initial grain size in the as-sintered samples and the grain size in the crept samples. In all cases, it was determined to be around 2. Observation of the microstructure of the crept samples, using scanning electron microscopy, reveals grain growth but does not show any significant elongation of the elemental grains. Transmission electron microscopy of a sample crept under 100 MPa at 1300°C reveals clear intragranular dislocation activity. This dislocation activity seems to be mainly confined in folds emitted at triple points. Because the creep parameters (experimental and calculated using a simple geometric model) and the microstructure observed are in good agreement, we propose that the creep mechanism involved is grain boundary sliding accommodated by dynamic grain growth and the formation of triple-point folds. [source] Combined Effect of Salt Water and High-Temperature Exposure on the Strength Retention of NextelÔ720 Fibers and NextelÔ720-Aluminosilicate CompositesJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 4 2006Triplicane A. Parthasarathy The relative contribution of fiber strength loss to reported degradation in the mechanical behavior of NextelÔ720-aluminosilicate composites after exposure to salt fog (ASTM B117) was explored. Single filament tension tests were performed on NextelÔ720 (3M, Inc., Minneapolis, MN) fibers after immersion in NaCl solutions followed by high-temperature exposure in air. The results were compared with the behavior of control specimens which received high-temperature exposure but were not immersed in NaCl solution. There was no degradation in fiber strengths for NaCl solutions below 1 wt%. However, significant degradation was observed at 5 wt% NaCl upon exposure to temperatures between 900° and 1150°C, while no degradation was observed upon an exposure to 1200°C. The relative contribution of fiber strength loss to composite degradation was estimated as nearly 50%, indicating that both fibers and matrix/interface degrade from exposure to salt water. X-ray diffraction and transmission electron microscopy of the exposed fibers and composites were conducted to help rationalize the observations. Microstructure of degraded fibers showed presence of Na at grain boundaries near the surface, without any evidence of a crystalline phase, indicating weakening from segregation or formation of an amorphous phase. The degraded composites showed that matrix and fiber/matrix interfaces had Na rich regions/phases. [source] Preparation of Highly Dispersed Ultrafine Barium Titanate Powder by Using Microbial-Derived SurfactantJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 12 2003Hidehiro Kamiya To uniformly disperse ultrafine BaTiO3 particles with a stoichiometric composition and several tens of nanometers in diameter to primary particles during the sol,gel synthesis process, a new aqueous surfactant with a high hydrophilic group density and special cis-structure was prepared from a microbial product and added to solution before the sol,gel synthesis reaction. Because of the rapid formation of large and porous aggregates which were 30,50 ,m in diameter in suspension without addition of this unique structural surfactant, the prepared ultrafine BaTiO3 particles caused rapid sedimentation in suspension. The addition of the surfactant in the range of 7.1 wt% for the synthesized BaTiO3 particles made it possible to decrease the size of the aggregates in suspension as well as the sedimentation velocity while maintaining the stoichiometric composition. The optimum additive content to obtain the minimum aggregate size of about 100,200 nm in diameter and the highest dispersion stability in suspension while maintaining the stoichiometric composition of prepared ultrafine BaTiO3 particles without other phases was determined at about 7.1 wt%. Because the excess addition of this surfactant at more than 8.5 wt% inhibited the uniform synthesis of BaTiO3 particles, an amorphous phase with a highly specific surface area and a BaCO3 phase formed in the synthesized particles. [source] Analytical Electron Microscopy Study of Green Ceramics Formed from Aqueous Suspensions Using the Hydrolysis-Assisted Solidification ProcessJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 1 2002a Novak During the hydrolysis-assisted solidification (HAS) of aqueous ceramic suspensions, aluminum hydroxides are formed that bind the ceramic particles into a stiff wet body. Transmission electron microscopy investigations of HAS-processed Al2O3 and ZrO2 green parts after drying revealed that the secondary phase is amorphous and distributed uniformly around the host ceramic particles. The estimated thickness of this layer was 3,5 nm. Moreover, areas of a few tens of nanometers in size were found at three-particle junctions that contained an amorphous phase and individual nanocrystals of boehmite. [source] Bioinspired Mineralization of Inorganics from Aqueous Media Controlled by Synthetic PolymersMACROMOLECULAR BIOSCIENCE, Issue 2 2007Katarzyna Gorna Abstract The formation of inorganic structures in nature is commonly controlled by biogenic macromolecules. The understanding of mineralization phenomena and the nucleation and growth mechanisms involved is still a challenge in science but also of great industrial interest. This article focuses on the formation and mineralization of two archetypical inorganic materials: zinc oxide and amorphous calcium carbonate (ACC). Zinc oxide is selected as a model compound to investigate the role that polymers play in mineralization. Most of the effort has been devoted to the investigation of the effects of double-hydrophilic block and graft copolymers. Recent work has demonstrated that latex particles synthesized by miniemulsion polymerization, properly functionalized by various chemical groups, have similar effects to conventional block copolymers and are excellently suited for morphology control of ZnO crystals. Latex particles might serve as analogues of natural proteins in biomineralization. The second example presented, ACC, addresses the issue of whether this amorphous phase is an intermediate in the biomineralization of calcite, vaterite, or aragonite. Conditions under which amorphous calcium carbonate can be obtained as nanometer-sized spheres as a consequence of a liquid,liquid phase segregation are presented. Addition of specific block copolymers allows control of the particle size from the micrometer to the submicrometer length scale. The physical properties of novel materials synthesized from concentrated solution and their potential applications as a filler of polymers are also discussed. [source] Miscibility in Blends of Isotactic/Syndiotactic Polystyrenes at Melt or Quenched Amorphous Solid StateMACROMOLECULAR MATERIALS & ENGINEERING, Issue 11 2006Shu Hsien Li Abstract Summary: Miscibility in amorphous phase and behavior in a crystalline phase of blends of two semicrystalline and isomeric polymers, isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), was probed. Optical and scanning electron microscopy results indicate no discernible heterogeneity in iPS/sPS blends in either melt state or rapidly quenched amorphous super-cooled state, while the Tg behavior of the quenched amorphous blends shows an intimately mixed state of two polymer chains. The crystal forms of the blends were further analyzed to provide additional evidence of miscibility in the amorphous domain. The sPS in the iPS/sPS blends upon melt crystallization was found to predominantly exist as the more stable , -form (rather than mixed , -form and , -form in neat sPS), which also suggests evidence of miscibility in the iPS/sPS blends. The melting behavior of semicrystalline sPS in the iPS/sPS mixtures was analyzed using the Flory-Huggins approach for estimation of interactions. By measuring the equilibrium melting point of the higher-melting sPS species in the sPS/iPS blends, a small negative value, for the interaction parameter (,,,,,0.11) was found. Further, by introducing a third polymer, poly(2,6-dimethyl- p -phenylene oxide) (PPO), a ternary iPS/sPS/PPO blend system was also proven miscible, which constituted a further test for stable phase miscibility in the iPS/sPS blend. General nature of miscibility in blends composed of two crystalline isomeric polymers is discussed. Issues in dealing with blends of polymers of the same chemical repeat unit but different tacticities were addressed. X-ray diffractograms for neat sPS and iPS/sPS blends, each having been isothermally crystallized at 245,°C for 4 h. [source] Cu/Ti base multicomponent amorphous Cu47Ti33Zr11Ni8Si1 and nanocrystalline silver compositesPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 5 2010Jan Dutkiewicz Abstract An easy glass-forming alloy based on Cu,Ti of composition Cu47Ti33Zr11Ni8Si1 was ball milled for 40,h to obtain amorphous powder. X-ray diffraction and differential scanning calorimetry (DSC) measurements confirmed the dominant presence of the amorphous phase after ball milling. However, transmission electron microscopy from powders allowed identification of Si particles and intermetallic phases a few nanometre in diameter, often of CuNi2Ti or Cu,Ti structures. The powder was then hot pressed in vacuum at temperature of 460,°C between the glass transition and the crystallization point to form bulk amorphous samples. Composites were prepared in the same way from mixed milled amorphous powders and nanocrystalline silver powder prepared by ball milling. Various ratios of amorphous to silver powder were applied with a maximum of 60% of nanocrystalline silver The microhardness of the amorphous phase component was near 1100,HV, much higher than the 90,HV of silver. Composites containing 20% of nanosilver have shown a much higher compression strength of 850,MPa, as compared to the 450,MPa of the composite containing 60% of silver, however, the latter has better ductility, near 5%, before fracture. [source] Influence of Nb substituted for Fe on the microstructure and magnetic properties of Fe-based nanocomposite alloyPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 12 2007N. Q. Hoa Abstract The influence of Nb substituted for Fe on the microstructure and magnetic properties including the magnetoimpedance effect of a Fe-based have been investigated. The nanocomposite structure composed of ultra-fine Fe(Si) grains embedded in an amorphous matrix was obtained by annealing the Fe-based amorphous alloy prepared by rapidly-quenched method. The measurements of thermomagnetic curves indicated that the Curie temperature of the amorphous phase of the samples decreases with increasing Nb content. The optimal heat treatment was performed at Ta = 480 °C for 30 min and showed that the ultrasoft magnetic properties of nanocomposite materials were obtained. The magnetoimpedance (MI) of these samples has been studied in range frequency from 1MHz to 5 MHz and varying a dc magnetic field within 300 Oe. The correlation between the MI effect and the soft magnetic properties is discussed. The incremental permeability ratio (PR) showed the drastic changes of soft magnetic properties as a function of annealing temperatures. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Dispersing silicon nanoparticles in a stirred media mill , investigating the evolution of morphology, structure and oxide formationPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 7 2007A. Reindl Abstract Silicon nanoparticles were dispersed for 24 hours in 1-butanol using a stirred media mill. Via this process intrinsically stable suspensions (in regard to aggregation) of Si nanoparticles were produced after 6 hours of dispersing. The evolution of morphology, particle size and structure was investigated by dynamic light scattering, X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy as a function of dispersing time. The average crystallite size decreased from about 18 nm down to about 10 nm within 24 hours of milling as determined by X-ray diffraction and Raman scattering measurements. In addition careful analysis of the Raman spectra revealed a decrease of the crystalline volume fraction from 75% down to 24% and a corresponding increase of the amorphous phase. The microstructural development with varying crystallite size and crystalline volume fraction was directly confirmed by transmission electron microscopy measurements. Elemental analysis showed an increase of oxygen content that was directly proportional to the increase in specific surface area of the silicon nanoparticles during the dispersing process. The surface chemistry of the Si nanoparticles was analyzed by diffuse reflectance infrared Fourier transform spectroscopy that indicated vibrational bands of HSi,Si3,xOx, SiOx, and residual 1-butanol. The final product of the dispersing process seems to be a two-phase mixture of amorphous Si and Si nanocrystallites covered with SiOx on the surface. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Magnetic study of Hitperm alloys (Fe0.5Co0.5)1,x ,y ,zMxByCuz (M = Hf, Zr, Nb)PHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 7 2006Abstract A family of the Hitperm alloys (Fe0.5Co0.5)1,x ,y ,zMxByCuz (M = Hf, Zr, Nb) produced in an argon atmosphere as amorphous ribbons with 0.025 mm thickness are investigated up to 1200 K. The partial replacement of Fe by Co with optimal Fe0.5Co0.5 ratio increases the Curie temperature of the amorphous phase and the magnetic moment per formula unit. The early stages of crystallization can be observed by magnetization measurements. Alloys subjected to the first controlled crystallization stage are built of bcc-(Fe,Co) nanocrystals that are homegeneously embedded in the amorphous matrix. Mean grain sizes are about 11 nm. These two-phase alloys exhibit good soft magnetic properties with the relatively low coercive fields up to 50 A/m. Hafnium and hafnium/zirconium mixture are found to be the best inhibitors of the nanograin growth resulting in the best soft magnetic parameters. Alloys with niobium exhibit lower thermal stability and higher coercive fields. The correlation between the structure evolution and the magnetic properties is analysed and discussed. Conditions for optimum heat treatment are also determined. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Thermomagnetic monitoring of nanocomposite formation in mechanically alloyed Nd,Fe,B alloysPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 8 2004H. W. Kwon Abstract A mechanical alloying technique was applied to NdxFe94,xB6 (x = 5.5,11.0) alloys for preparing an exchange-coupled nanocomposite. The structural development during the nanocomposite formation was monitored by thermomagnetic means. The mechanically alloyed NdxFe94,xB6 alloys in the as-milled condition consisted of an amorphous Nd,Fe,B phase and ,-Fe nanocrystallites. The crystallisation temperature of the amorphous phase was independent of the milling time. The amorphous phase in the as-milled NdxFe94,xB6 alloys with higher Nd content had a lower crystallisation temperature. The NdxFe94,xB6 (x = 8.5) alloy milled for longer than 30 h consisted of a two-phase structure containing ,-Fe and Nd2Fe14B phases after being isothermally annealed at 600 °C for 20 min. This annealed powder showed a smooth demagnetisation curve, indicating an intergranular exchange coupling between the hard Nd2Fe14B and soft magnetic ,-Fe grains. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] The electronic and electrochemical properties of the TiFe1,xNix alloysPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 1 2003A. Szajek Abstract Mechanical alloying (MA) process was introduced to produce nanocrystalline TiFe1,xNix alloys (0 , x , 1). XRD analysis showed that, firstly, after 25 h of milling, the starting mixture of the elements had decomposed into an amorphous phase and, secondly, the annealing in high purity argon at 750 °C for 0.5 h led to formation of the CsCl-type (B2) structures with a crystallite sizes of about 30 nm. These materials, used as negative electrodes for Ni,MH batteries, showed an increase in discharge capacity with a maximum for x = 3/4. The band structure has been studied by the Tight Binding version of the Linear Muffin-Tin method in the Atomic Sphere Approximation (TB LMTO ASA). Increasing content of Ni atoms intensified charge transfer from Ti atoms, extended valence bands and increased the values of the densities of electronic states at the Fermi level. [source] X-ray diffraction study of amorphous phase of BaSi2 under high pressurePHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 1 2007T. Nishii Abstract A high-pressure synchrotron X-ray diffraction study of zintl phase BaSi2 semiconductor has been performed up to 45 GPa. The pressure-induced amorphization occurred at 13 GPa. In the amorphous phase, the Ba,Si bond distance decreased with increasing pressure, while the Ba,Ba bond distances were almost unchanged. The Rietveld refinement revealed that these distances in the crystal phase decreased with increasing pressure. By combining these results, the Ba,Si bond compressibility in both phases is almost identical. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Thin film formation by rf sputtering with EuGa2S4 target and photoluminescence of the prepared filmsPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 8 2006M. Dohi Abstract Thin films were deposited on Si and fused quartz substrates by rf sputtering with EuGa2S4 target. The deposited films were annealed in the mixed atmosphere of S and He, which led crystallization of the film from amorphous phase. Photoluminescence of the annealed films, characteristic to the Eu2+ ion, was observed with room temperature quantum efficiency of 17%. Decay time constants at room temperature and liquid nitrogen temperature were measured to be 140 ns, and 430 ns, respectively. The latter value is close to the reported radiative lifetime of the EuGa2S4 crystal. Construction possibility of a surface-emitting laser is discussed with data on behaviour of excitation intensity dependent time-resolved spectra under pulsed laser excitation and on surface roughness of the film. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] | ||||||||||||||||||||||||||||||||||