Thermally- and solvent-induced crystallization kinetics of syndiotactic polystyrene viewed from time-resolved measurements of infrared spectra at the various temperatures (1) estimation of glass transition temperature shifted by solvent absorption

syndiotactic Polystyrene (sPS) glass crystallizes into the α form when it is heated above the glass transition temperature (T_g, about 100 °C). sPS can be crystallized also into the δ form in the solvent atmosphere at room temperature. In order to trace the structural evolution process, the time-resolved infrared spectral measurements have been performed in the isothermal crystallization from the glass to α form and in the solvent-induced crystallization from the glass to δ form at the various temperatures. Absorbance of crystallization-sensitive infrared bands was plotted against time, from which the crystallization kinetics were analyzed on the basis of Avrami equation: X(t)=1−exp[−(kt)ⁿ] where X is a normalized crystallinity, n is an index, k is a rate constant, and t is a time. The isothermal crystallization was investigated also by carrying out the temperature jump experiment of DSC thermograms, giving almost the same results as the infrared spectral measurements. The Avrami index n was 2-5 depending on the crystallization temperature (T_c). The k was also dependent on the T_c, about 10⁻¹-10⁻⁴ s⁻¹ and could be fitted reasonably by the equation of crystallization kinetics. An extrapolation of the k vs T_c plot to the negligibly small k value allowed us to predict the temperature at which no crystallization should occur, ca. 100 °C, in good agreement with the observed T_g value. On the other hand, the solvent-induced crystallization was investigated for the first time at the various temperatures from 50 to 9 °C by the time-resolved measurement of infrared spectra. Compared with the experiment at room temperature, the crystallization was highly accelerated at 40-50 °C, while the crystallization rate was reduced remarkably at such a low temperature as 9 °C. The time dependence of infrared absorbance was analyzed for the crystallization-sensitive bands on the basis of Avrami equation as the first approximation, although the crystallization mechanism was more complicated than the isothermal crystallization case. The logarithm of the k value was found to change almost linearly with temperature and an extrapolation to infinitesimally small k value gave a T_g of about −15 °C. That is to say, the glass transition temperature was estimated to shift remarkably from 100 to −15 °C by absorbing solvent molecules or by a plasticizing effect.     

X-ray diffraction technique to observe magnetostriction and magnetization at coextensive volumes of iron

We present a new technique for observing both magnetostriction and magnetization as a function of applied magnetic field strength. They are simultaneously measured by the same X-ray probes with a goniometer at exactly coextensive specimen volumes. The measurements yield experimental magnetostriction curves during a cyclic magnetization process in iron (100) single-crystal specimen at room temperature. The technique is a new tool to investigate magnetic properties within X-ray extinction depth from the surface.     

Preparation of hydroxyapatite/collagen injectable bone paste with an anti-washout property utilizing sodium alginate. Part 1: influences of excess supplementation of calcium compounds

The anti-washout property, viscosity, and cytocompatibility to an osteoblastic cell line, MG-63, of anti-washout pastes were investigated. Mixing a hydroxyapatite/collagen bone-like nanocomposite (HAp/Col), an aqueous solution of sodium alginate (Na-Alg), which is a paste hardening and lubricant agent, and supplementation of calcium carbonate or calcium citrate (Ca-Cit) as a calcium resource for the hardening reaction realized an injectable bone paste. Adding Ca-Cit at a concentration greater than eight times the Ca²⁺ ion concentration to Na-Alg improved the anti-washout property. Although the viscosity test indicated a gradual increase in the paste viscosity as the calcium compounds increased, pastes with excess supplementation of calcium compounds exhibited injectability through a syringe with a 1.8?mm inner diameter, realizing an injectable bone filler. Furthermore, the anti-washout pastes with Ca-Cit had almost the same cell proliferation rate as that of the HAp/Col dense body. Therefore, HAp/Col injectable anti-washout pastes composed of the HAp/Col, Na-Alg, and Ca-Cit are potential candidates for bioresorbable bone filler pastes.     

Osteoblast-like cell responses to silicate ions released from 45S5-type bioactive glass and siloxane-doped vaterite

Silicate ions released from bioactive glasses and ceramics have been reported to stimulate osteogenic cell functions. Here, we evaluated osteoblast-like cell reactions to silicate ions released from two different types of materials, 45S5 bioactive glass (BG) and siloxane-doped vaterite (SiV), to investigate the influence of the ionic structure of silicate ions on osteoblast-like cell properties. BG and SiV powders were prepared by using melt-quenching and carbonation methods, respectively. Aminopropyltriethoxysilane was used as a siloxane source of SiV. MC3T3-E1 and SaOS-2 cells were cultured in media containing dissolved BG or SiV ions (10–50 ppm of Si). Cell proliferation (metabolic activity), differentiation (alkaline phosphatase activity) and mineralisation (Ca deposition) were examined. ²⁹Si NMR spectra demonstrated that Q^0,1 species and T^0–3 species were released from BG and SiV, respectively. Proliferation and mineralisation of the two types of cells were influenced by silicate ions released from BG and SiV in a concentration-dependent manner. In particular, there were significant differences (P < 0.05) in the degree of proliferation and Ca deposition levels in SaOS-2 cells treated with dissolved BG and SiV ions. Furthermore, Ca deposition in SaOS-2 cells was influenced by both the presence of silicate ions and the duration of exposure of cells to them. The structure of silicate ions influenced the proliferation and mineralisation of SaOS-2 cells incubated for different time periods in culture media containing different Si concentrations. Understanding the effect of Si on bone cell behaviour will enable a design-led approach to further BG optimisation.     

Sintering of Mullite–Zirconia Composite Powder Prepared by Ultrasonic Spray Pyrolysis Technique

Sinterabilities of mullite (3Al₂O₃·2SiO₂–zirconia (ZrO₂)composite powders prepared by ultrasonic spray pyrolysis techniques (USPTs) were examined. Starting mullite powders containing 18.5 mol% (15.0 vol%) of zirconia (ZrO₂) were prepared by single-nozzle (SN) and double-nozzle (DN) USPT. In SN-USPT, the composite powder was prepared by spray pyrolysis of a water–ethanol solution in an Al(NO₃)₃–Si(OC₂H₅)₄–ZrOCl₂–YCl₃ system at 900°C, using one ultrasonic vibrator. In DN-USPT, the composite powder was prepared by simultaneous spray pyrolyses of a water–ethanol solution in an Al(NO₃)₃–Si(OC₂H₅)₄ system and one in a ZrOCl₂–YCl₃ system at 900°C, using two ultrasonic vibrators. When these composite compacts were fired at a temperature between 1400 and 1700°C for 5 h, the relative densities attained maxima, i.e., 87.2% (SN-USPT) and 95.5% (DN-USPT), at the firing temperature of 1500°C. Densification of the DN-USPT-derived powder compact proceeded more markedly than that of the SN-USPT-derived powder compact.     

The foundations of a theory-aware authoring tool for CSCL design

One of the most useful ways to enhance collaboration is to create scenarios where learners are able to interact more effectively. Nevertheless, the design of pedagogically sound and well-thought-out collaborative learning scenarios is a complex issue. This is due to the context of group learning where the synergy among learners’ interactions affects learning processes and, hence, the learning outcome. Although many advances have been made to support the designing of collaborative learning scenarios through technology, a more systematic approach is lacking. With the limitations of the current designing methods and tools, it is difficult to develop intelligent authoring systems that can guide users in order to produce more effective collaboration. One of the main difficulties with creating a more consistent (computer-understandable) approach to designing collaboration is the necessity of proposing better ways to formalize the group learning processes. In this paper, we present an innovative approach that uses ontologies and concepts from learning theories to create a framework that represents collaborative learning and its processes. Ontologies provide the necessary formalization to represent collaboration, while learning theories provide the concepts to justify and support the development of effective learning scenarios. Such an approach contributes to establish the foundations for the development of the next generation of intelligent authoring systems referred to as theory-aware systems. To verify the viability and usefulness of our proposed ontological framework in the context of systematic design, the development and use of an intelligent authoring tool for CSCL design is presented. This system is able to reason on ontologies to give suggestions that help users to create theory-compliant collaborative learning scenarios. We carried out several experiments with teachers in a geometry drawing course and the results indicate that the system helps teachers to create and interchange their scenarios more easily and facilitates the selection of important pedagogical strategies that influence positively the designing and effectiveness of group activities.     

The luminance resolution characteristics of multi‐primary‐color display

Abstract— In this paper, the resolution characteristics of multi‐primary‐color (MPC) display systems are analyzed. That four‐primary‐color (4PC) displays can increase the effective resolution for achromatic images in the luminance domain by a factor of two as compared to conventional RGB‐based displays with MPC‐specialized subpixel rendering, which is proposed in this paper, is demonstrated. Five‐ and six‐primary‐color (5PC and 6PC) display systems can reproduce denser luminance data than conventional RGB‐based display systems and solve a problem of MPC displays, viz. an increase of production costs and a decrease in the aperture ratio caused by increasing the number of subpixels in one pixel. This is an essential advantage of MPC display systems, which is related to the combination of the proposed color‐filter architecture and image processing. Thus, a completely new advantage of MPC display systems, in addition to their well‐known capabilities of color reproduction and power saving, is proposed.     

Oblique detonation wave stability around a spherical projectile by a high time resolution optical observation

Spherical projectiles were launched into detonable mixtures over a wide range of projectile velocities from near to about 1.8 times the Chapman–Jouguet (C–J) velocity. Oblique detonation waves (ODWs) and shock-induced combustions (SICs) stabilized around the projectiles were visualized with high time and high spatial resolutions using the Schlieren technique and a high-speed camera with a 1-μs frame speed. Unsteady wave structures called Straw Hat type structures consisting of a SIC region followed by a C–J ODW were observed near stabilizing criticalities of a C–J ODW, and they were divided into two propagation types, depending on whether the C–J ODW could be stabilized [11], [12], [14]. In the present study, we suggested wave structures of the Straw Hat types based on our examination of dozens of continuous images. Triple points were observed at the intersection of a bow shock, a C–J ODW and a transverse detonation or shock wave when projectile velocities were slightly higher than C–J velocities. Onsets of local explosions in the SIC region for stabilizing the ODW in the Straw Hat type structures have been reported [14]. We observed this stabilizing mechanism by visualizing onsets of periodical local explosions and their transition to spherical detonation waves when the projectile velocity was much higher than the C–J velocity. We also determined stabilizing criticalities using a stoichiometric acetylene-oxygen mixture diluted with argon or krypton in 50% or 75% volumetric fractions, respectively. We found that the stabilizing criticalities did not depend only on the ratio of the projectile diameter and the cell size of the mixture.     

Simple purification and selective enrichment of metallic SWCNTs produced using the arc-discharge method

Purified single-walled carbon nanotubes (SWCNTs) were produced using the arc-discharge method with a combination of air oxidation and dispersion–centrifugation processes in a tetrahydrofuran solution containing an amine as a dispersant. Subsequently, SWCNT samples were analyzed using thermo gravimetric analysis, vis-near infrared absorption spectroscopy, scanning electron microscopy, and Raman spectroscopy. Results revealed that metallic SWCNTs were enriched in a supernatant through the dispersion–centrifugation process.