Nature of Shear-Induced Primary Nuclei in iPP Melt

Although observations of molecular processes in the formation of primary nuclei prior to actual crystallization are beyond the detection limits of current instrumentation, we attempted to probe the nature of primary nuclei in sheared isotactic polypropylene (iPP) polymer melt. In situ rheo-SAXS (small-angle X-ray scattering) and -WAXD (wide angle X-ray diffraction) experiments using synchrotron radiation were carried out to evaluate the effects of an addition of a high molecular weight atactic polypropylene (aPP) (5 wt%), which is compatible with the iPP matrix but does not crystallize, on the evolution of oriented structures in the sheared iPP melt and its crystallization kinetics. It is unlikely that the aPP chain segments can be incorporated into iPP nuclei or crystal; hence, its addition effects, if any, would be seen only in the amorphous melt prior to crystallization. The results showed stonger orientation and improved crystallization kinetics in the iPP/aPP blend compared to pure iPP. Observations that the presence of long chains of an amorphous polymer aid in nucleation and crystallization kinetics of iPP, combined with our previous synchrotron results of sheared iPP melts at high temperature (165°C), lead us to conclude that primary nuclei in iPP most likely consist of liquid-crystalline or mesomorphic bundles of aligned chain segments prior to the formation of crystals.     

Laser Light and X-Ray Diffraction Studies of Oriented Isotactic Polypropylene (iPP) Prepared by Temperature Slope Crystallization

Isotactic polypropylene (iPP) film was melt-crystallized in a temperature gradient. The iPP film showed well oriented α- and β-crystalline textures along the gradient. The crystalline structure, phase transition boundary and lamellar twisting were examined by X-ray diffraction and laser light diffraction (LLD). On the α-β boundary, LLD shows a sharp streak perpendicular to the boundary, where the a-axis of the β-crystal is oriented perpendicular to the temperature gradient. Apart from the boundary, the a-axis of the β-crystal becomes parallel to the gradient. The β-crystal shows lamellar twisting with a pitch of 200 μm at room temperature. When heated the β-crystal, the lamellar distance of 295Å at room temperature decreases to 285Å at 80–100°C and then increases to more than 300Å above 120°C. During the heating, the value of the twist period increases from 200 to 210 μm at 90–100°C, and then to above 224 μm at 140°C. The increase of the twist period is related to the increasing crystalline thickness of the β-lamellae.     

Microstructural Evolution and Its Effect on Mechanical Properties of Isotactic Polypropylene by Shear Plastic Deformation at Elevated Temperatures

Isotactic polypropylene (iPP) was plastically shear deformed by equal channel angular extrusion (ECAE) at extrusion temperatures varied from 45 to 125°C (25 mm/min). The evolutions of morphology and crystal orientation were studied by reflected optical microscopy (ROM), scanning electron microscopy (SEM), and X-ray diffraction. It was found that the original spherulites were deformed into nearly ellipsoids with their long axis tilted at an angle away from the flow direction. Azimuthal scanning results revealed that two preferred crystal orientations were formed after ECAE. The crystal plasticity was activated by increasing the extrusion temperature, followed by fast rotation of crystallites toward the shear direction. The thermal mechanical analysis (TMA) indicated that low extrusion temperature was favorable to fix the molecular orientation. The iPP samples processed at the investigated temperatures displayed a significant increase in the impact strength, especially for those extruded at 45°C and 65°C. The tensile results revealed a greater elongation at break in the samples deformed at low temperatures (45°C and 65°C) but not in those deformed at high temperatures (85°C or above).     

A Comparison of the Effects of Calcium Glutarate and Pimelate on the Formation of β Crystalline Form in Isotactic Poly(propylene)

The effect of calcium glutarate (Cagt) and calcium pimelate (Capt) on the formation of β crystalline form in isotactic poly(propylene) in the crystallization temperature range of 110–130°C has been investigated. The content of β phase crystals increase with the addition of calcium glutarate. K (relative content of β crystalline form in the iPP sample) attains its maximum value for iPP doped with 0.3 wt.% Cagt isothermally crystallized at 110°C (26.71%) or 120°C (30.27%), and for iPP doped with 0.2 wt.% Cagt isothermally crystallized at 130°C (31.97%), respectively. Compared with the K values of iPP doped with 0.1 wt.% Capt (78.33–94.76%), the β nucleation ability of Cagt is inferior to that of Capt. The spherulite size of iPP doped with Capt is smaller than that of iPP doped with Cagt. The difference in the β nucleation ability between Cagt and Capt is explained by the difference between their crystal structure parameters and those of β‐iPP.     

Preparation of a Novel Oriented Structure in Carbon Black Filled Isotactic Polypropylene Composites by Microwave Selective Heating

Microwave heating technology has numerous advantages compared with the traditional heating methods and has been widely used to process materials. However, most thermoplastics do not possess a sufficiently high dielectric property to be heated by microwaves. In this study, carbon black (CB) was utilized as the microwave absorber to improve the microwave heatability of isotactic polypropylene (iPP). Effects of CB contents on the microwave heatability of iPP/CB composites were studied. The temperature of iPP/CB composites with relatively low CB content (5% and 10%) increased slowly and tended to remain unchanged after 120 s of microwave exposure. In contrast, iPP/CB composites with relatively high CB content (15% and 20%) presented a much faster heating rate and the temperature of the sample kept increasing with the prolongation of exposure time. On the basis of the fact that iPP/CB composites with different CB contents have different microwave heatability, a novel oriented structure, in which the core layer has relatively high orientation and the surface layer has relatively low orientation, was prepared by selective microwave heating. Two-dimensional wide angle X-ray diffraction (2D-WAXD) analysis indicates that the orientation parameter calculated by the (040) plane of the surface layer (0.45) was lower than that of the core layer (0.83). The novel oriented structure is different from the common skin-core structure formed in the samples of semicrystalline polymers by traditional polymer processing methods, in which orientation of the skin layer is higher than that of the core layer. The novel oriented structure has not been reported before to our knowledge and its formation mechanism is also discussed in this paper.     

Study on Properties and Structure of Near Melt Point Extruded High‐Density Polyethylene

The effect of extrusion temperature on the mechanical properties of high‐density polyethylene (HDPE) was examined using solid‐state extrusion (SSE) and melt‐state extrusion (MSE) techniques. Differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) investigations were employed to provide evidence for explaining the relationship between mechanical properties and morphology of extrusion moldings. Extruded from a convergence‐divergence die, compared with samples obtained by MSE, the yield strength of samples obtained by SSE was enhanced in both longitudinal and transverse directions with a ductile failure. The yield strength decreased sharply with increasing extrusion temperature. The maximum longitudinal yield strength of samples extruded at 112°C was 181 MPa with an 87% elongation at break; the corresponding values were 28 MPa and 800% for samples extruded at 140°C (MSE); in the transverse direction the yield strength was 27 MPa with a 101% elongation at break for samples extruded at 140°C, while the maximum yield strength was 51 MPa with a 45% of elongation at break for samples extruded at 116°C. Compared with sheets extruded at 140°C, DSC data shows a 5.3°C increase in melting point, a 9.5°C decrease in melt point width, and a 7.1% decrease in crystallinity for sheets extruded at 112°C. SEM indicates that spherulites predominate in MSE samples, while a preferred orientation of the lamellae along the extrusion direction were mainly produced by SSE.     

Effect of quenching temperature on the structure of isotactic polypropylene films

Films of isotactic polypropylene (iPP) were quenched at different temperatures. Wide-angle x-ray diffractograms for these samples show the presence of the smectic form of iPP at low quenching temperatures and the appearance of mono-clinic form on increasing the thickness of the substrate and the quenching temperature. A quenching temperature higher than 80°C produces only the monoclinic form of iPP, whereas at intermediate temperatures we obtain three-phase amorphous-smectic-crystalline systems. Except for the two-phase amorphous-crystalline system obtained at high temperatures, density values alone do not allow us to obtain the three-phase fractions. We studied the transport properties, sorption, and diffusion of CH₂Cl₂ vapor in these systems to investigate the thermodynamic state of the amorphous component. The behavior of the amorphous component with respect to the diffusion of CH₂Cl₂, which proved identical in all the samples, led us to conclude that at low penetrant activity the smectic phase is not permeable, and therefore we were able to obtain the amorphous fraction in each sample. This value together with density values allowed the determination of the complete composition in terms of three phases for every sample. The crystalline fraction expressed as % mono-clinic form is very well correlated with the reciprocal of the half-height broadening of the (110) diffraction peak at about 2e = 14°.     

Structural characterisation and thermal stability of SnSe\GaSb stacked films

We have investigated the effect of thermal annealing on the structure of single and stacked phase change memory films based on SnSe and GaSb. Samples were prepared by pulsed laser deposition and investigated by X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) methods. Electrical resistance versus temperature investigations showed crystallisation temperatures of 292°C and 198°C for SnSe and GaSb single films, respectively. Above the transition temperature, GaSb crystallises into a face-centered cubic structure, whereas SnSe has an orthorhombic arrangement. Annealing at three temperatures (160°C, 250°C and 350°C) of the SnSe\GaSb stacked films promotes bond breaking, atom diffusion between the two layers and formation of new phases. At 160°C, GaSb films crystallise partially and no effect is observed on the crystallinity of SnSe films. After 250°C, rhombohedral SnSb emerges in addition to GaSb complete crystallisation. A major, completely new, body-centered orthorhombic unindexed quaternary Ga-Sn-Sb-Se phase formation was observed in the samples annealed at 350°C. The GaSb crystallites are fully dissolved and we have observed the formation of a minor hexagonal SnSe₂ phase. The analysis of EXAFS data, measured at Se and Ga K-edges, revealed changes in the local atomic environment as a function of the annealing temperature. A tetrahedral configuration is obtained for the Ga atoms in both as-deposited and annealed samples, whereas Se is mostly bivalent in the amorphous samples and has an octahedral arrangement in crystalline SnSe. Our results show that inter-layer diffusion should always be considered and evaluated when designing memory cells composed of stacked phase change chalcogenide films.     

KTN thin films prepared by pulsed laser deposition on transparent single crystal quartz(100)

Using the Sol-Gel method to produce the KTN ultrafine powder and the sintering technique with K2O atmosphere to prepare KTN ceramics as the targets instead of the KTN single crystal, highly oriented KTN thin films were produced on the transparent single crystal quartz (100) by the pulsed laser deposition (PLD). Since the thermal stress sustained by the quartz is relatively small, the limit temperature of the quartz substrates (300℃) is much lower than that of the P-Si substrates (560℃); the prepared thin film is at amorphous state. Increasing the pulsed laser energy density in the process incorporated with annealing the film after deposition at different temperatures converts the amorphous films into crystal. The optimal pulsed laser energy density and annealing temperature were 2.0 J/cm2 and 600℃, respectively. A discussion was made to understand the mechanism of film production at relatively low substrate temperature by PLD and effects of the annealing temperatures on the forming of the perovskite p     

CO2-induced Crystallization of Isotactic Polypropylene by Annealing Near Its Melting Temperature

CO₂-induced crystallization of isotactic polypropylene (iPP) by annealing had been studied using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). The iPP before annealed was in α-form and amorphous states. At lower temperatures by CO₂ isothermal treatments, iPP chains crystallized from the amorphous phase and only one crystal form, i.e., α-form, was observed. At higher temperatures by CO₂ isothermal treatments, both crystallization from the amorphous phase and thickening of existing crystal lamellae were observed. Moreover, light γ-form crystal appeared in the treated iPP. The crystalline lamellar thickness of iPP annealed at different CO₂ pressures had been determined. Using the Gibbs–Thomson plot method, the equilibrium melting temperature was found to be 187.6°C.     

Relaxation dynamics of poly(vinylidene fluoride) studied by dynamical mechanical measurements and dielectric spectroscopy

The aim of this study is to analyze the mobility of polymer chains in semicrystalline poly(vinylidene fluoride) (PVDF). PVDF crystallizes from the melt in the α crystalline phase. The transformation from the α phase to the electroactive β phase can be induced by stretching at temperatures in the range between 80 and 140 °C. The spherulitic structure of the crystalline phase is deformed during stretching to form fibrils oriented in the direction of the strain. The amorphous phase confined among the crystalline lamellae is distorted as well and some degree of orientation of the polymer chains is expected. Dynamic-mechanical and dielectric spectroscopy measurements were performed in PVDF films stretched to strain ratios up to 5 at temperatures between 80 and 140 °C. Dynamic-mechanical measurements were conducted between -60 °C and melting and in this temperature range the relaxation spectra show the main relaxation of the amorphous phase (called β-relaxation) and at higher temperatures a relaxation related to crystallites motions (α (c)-relaxation). Although the mean relaxation times of the β-relaxation are nearly equal in PVDF before and after crystal phase transformation, a significant change of shape of the relaxation spectrum proves the effect of chain distortion due to crystal reorganization. In stretched PVDF the elastic modulus of the polymer in the direction of deformation is significantly higher than in the transversal one, as expected by chain and crystals fibril orientation. The recovery of the deformation when the sample is heated is related with the appearance of the α (c)-relaxation. Dielectric spectroscopy spectrum shows the main relaxation of the amorphous phase and a secondary process (γ-relaxation) at lower temperatures. Stretching produces significant changes in the relaxation processes, mainly in the strength and shape of the main relaxation β. The Havriliak-Negami function has been applied to analyze the dielectric response.     

Effect of thermomechanical processing on microstructural evolution and deformation behaviour of polycrystalline magnesium under quasi-static and high strain rate conditions

Abstract

The effect of thermomechanical processing on microstructure evolution and room temperature flow behaviour of polycrystalline magnesium in compression at strain rates of ~10^?2 and ~10³ s^?1 was investigated. Different initial microstructures were produced by optimising rolling and annealing cycles. Prior to annealing for 1 h at 350 °C, Mg samples were processed by two different treatments such as (i) hot rolling at 350 °C and (ii) hot rolling at 350 °C plus cold rolling at room temperature. Introduction of cold working step led to an increased fraction of hard oriented grains with a marginal grain size difference in post-annealed samples. A profound effect of thermomechanical processing on strain hardening rate as well as rate-sensitive flow behaviour of Mg was observed. The influence of prior processing history and strain rate on flow behaviour of Mg was clearly reflected in terms of texture strengthening/weakening phenomena and formation of microstructural deformation bands.     

Mechanical behavior of poly(ethyleoe terephthalate) at cryogenic temperatures

The mechanical behavior of poly(ethylene terephthalate) (PET) was studied at temperatures from 4 to 300°K with a free oscillating torsion pendulum and an Instron tester.

Torsion pendulum data show the presence of relaxation maxima below 80°K. Noncrystalline specimens show a small peak at 48°K (δ) and a shoulder at 8-12° K (?). A peak at 20° K is observed in crystalline samples, both oriented and unoriented. In addition drawn specimens show a pronounced peak at 48° K and the assymmetric maximum in the 100-240° K region is split into two peaks. The logarithmic decrement in the β-loss region decreases with increasing crystallinity and orientation, while the cryogenic loss peaks increase in intensity.

Tensile tests with biaxially oriented and heat-set films show a twofold increase in elastic modulus and a tenfold increase in toughness at cryogenic temperatures when compared with “amorphous” PET.     

Crystallization Behavior of Amorphous Poly(l-Lactide)

Amorphous poly(l-lactide) (PLLA) was annealed in two different ways: amorphous samples were heated at a given temperature to induce crystallization (one-step annealing); and amorphous samples were first crystallized at a low temperature and subsequently annealed at a higher temperature than the crystallization temperature. Samples thus prepared were measured by DSC. The original amorphous sample exhibited an exothermic peak at about 100°C (exothermic peak I), an exothermic peak just below the melting point (exothermic peak II), and an endothermic peak when it was melted. Exothermic peak I was caused by cold crystallization. When the melting points of PLLA samples, heat-treated in various ways, were plotted as a function of annealing temperature, there was discontinuity at about 120°C. From analyses of wide-angle X-ray diffraction patterns, it was found that when amorphous PLLA was crystallized at a temperature below 120°C, crystallites of the β-form formed, and when annealed at a temperature above 120°C, crystallites of the α-form grew. Thus, exothermic peak I was attributed to cold crystallization of the β-form, and peak II was caused by the phase transition of the β-form to a more stable form.     

A correlation between structural and optical properties of cobalt oxide nanoparticles for various annealing conditions

Two stable phases of cobalt oxide nanoparticles of controlled sizes have been synthesized using environmentally friendly inorganic precursor. Structural characterization using X-ray diffraction (XRD) shows a single-phase spinal Co₃O₄ structure up to annealing temperature of 800 °C and a mixed phase of Co₃O₄ and CoO particles for T>900 °C. Single-phase CoO nanoparticles are also obtained by annealing the particles at a temperature >900 °C and cooling in inert atmosphere. Average macro- and micro-strain were estimated using XRD data. Macrostrain was found to be the minimum for particles annealed at 600 °C, whereas microstrain was found to decrease with increasing annealing temperature up to 900 °C. A correlation between the density of localized states (DOS) in the band gap and strain is expected because the origin of both strain and DOS are defects and bond length distortions. Sub-gap absorption measurement and model calculations have been used for the determination of DOS. For cobalt oxide nanoparticle samples we find a correlation between estimated strain and density of states in the band gap.     

Surface characterization and H2S-sensing potential of iron molybdate particles produced by supercritical solvothermal method and subsequent oxidation

The mostly crystalline polymorph β-FeMoO₄ was prepared by solvothermal synthesis from organic precursors, followed by high temperature supercritical drying in an autoclave. Crystallization of the synthesized particles occurred during subsequent heat treatment at 350 °C, confirmed by X-ray diffraction pattern analysis. The presence of Fe³⁺ ions in the powder, both well-crystallized and amorphous after heat treatment at 500 °C, was confirmed by room temperature Mössbauer spectrum. Thick-film gas sensors were prepared by conventional hand coating of a paste, the Fe₂(MoO₄)₃ powder mixed with an α-terpineol-based solvent, over the Au electrodes. The response of the prepared sensors to H₂S gas in the low concentration range 1–10 ppm in air was investigated. Moderately fast response and recovery times were observed. The iron molybdate, produced at low temperature, may be successfully used in the preparation of a H₂S gas sensor.     

Comparison of carbon-doped MgB2 bulks fabricated from pre-synthesized Mg/CNT and Mg/amorphous carbon composites

MgB₂ samples containing 2.5 wt% multi-walled carbon nanotubes (CNTs) and amorphous carbon (nano-C) were sintered at 800 °C. The doped samples were prepared from Mg/CNT and Mg/nano-C composites, which were previously synthesized from coarse Mg and fine Mg by chemical vapor deposition, respectively. We made comparisons between the two samples on the C-doping level, the MgO contents, and the effects of the carbon source on critical current density (J _c) by investigating the phase composition, microstructure, and magnetic properties. Compared with pure MgB₂ (coarse Mg), the J _c performance at high field was improved in the CNT-doped sample (coarse Mg) due to the high C substitution level induced lattice defects as pinning centers. However, J _c values of the amorphous C-doped sample with sufficient C doping decreased over the entire field in contrast with the pure sample (fine Mg), which exhibited the highest J _c performance among the samples. This is attributed to the much more MgO impurities, mostly generated during the preparation of Mg/C composites, than the CNT-doped sample.     

Low-Temperature (<100°C) Poly-Si Thin Film Fabrication on Glass

Polycrystalline silicon (poly-Si) thin-film is fabricated on Al-coated planar glass substrates at the temperature below 100°C, using aluminium-induced crystallized (AIC) amorphous silicon (a-Si) deposited by dc-magnetron sputtering under an electric field. The properties of NA poly-Si films (AIC of dc-magnetron sputtered silicon non-annealing) are characterized by Raman spectroscopy and x-ray diffraction (XRD) spectroscopy. A narrow and symmetrical Raman peak at a wave number of about 521cm^-1 is observed for samples, showing that the films are fully crystallized. XRD spectra reveal that the films are preferentially (111) oriented. Furthermore, the XRD spectrum of the sample prepared without electric field does not show any XRD peaks for poly-Si, which only appears at about 38°for Al (111) orientation. It is indicated that the electric field plays an important role in crystallization of poly-Si during the dc-magnetron sputtering. Thus, high quality poly-Si film can be obtained at low temperature and separate post-deposition step of AIC of a-silicon can be avoided.     

A high pressure,high temperature study of 1,1-diamino-2,2-dinitro ethylene

We report a synchrotron energy-dispersive X-ray diffraction study of the novel high explosive 1,1-diamino-2,2-dinitroethylene at high pressures and high temperatures. Pressure was generated using a Paris–Edinburgh cell to employ larger sample volumes. High temperatures were created using a resistive graphite cylinder surrounding the sample. The PT phase diagram was explored in the 3.3 GPa pressure range and in the ～ 400°C temperature range. We believe that the sample commenced in the α-phase and then ended up in an amorphous phase when the temperature increased beyond 280°C near 2 GPa, which we believe to be the γ-phase. Further pressure and temperature cycling suggests that the sample transformed reversibly into and out of the amorphous phase near the phase line.     

Effect of annealing temperature on optical and electrochemical properties of chitosan–ZnO nanostructure

Chitosan–ZnO nanostructures were prepared by chemical precipitation method using different concentration of zinc chloride and sodium hydroxide solutions. Nanorod-shaped grains with hexagonal structure for samples annealed at 300 °C and porous structure with amorphous morphology for samples annealed at 600 °C were revealed in SEM analysis. X-ray diffraction patterns confirmed the hexagonal phase ZnO with crystallite size found to be in the range of ~24.15–34.83 nm. Blue shift of UV–Vis absorption shows formation of nanocrystals/nanorods of ZnO with marginal increase in band gap. Photoluminescence spectra show that blue–green emission band at 380–580 nm. The chitosan–ZnO nanostructures used on surface of a glassy carbon electrode gives the oxidation peak potential at ~0.6 V. The electrical conductivity of chitosan–ZnO composites were observed at 2.1?×?10^?5 to 2.85?×?10^?5?S/m. The nanorods with high surface area and nontoxicity nature of chitosan–ZnO nanostructures observed in samples annealed at 300 °C were suitable as a potential material for biosensing.