Glass transition and exclusion model in crystallization of polyether-polyester block copolymers with amide linkages

Polyether-polyester block copolymers having various polyetheramide contents were synthesized. Single glass transition intermediated in temperature between the glass transition temperatures of polyester and polyetheramide components was found for all of polyether-polyesters. The compositional variation of glass transition exhibited a similar trend to the predicted result of thermodynamic theory for compatible polymer blends. The incompatible pair of homopolyester and homopolyether was forced to be compatible after copolymerization. A modified theoretical prediction for the glass transition of copolymers based on the thermodynamic theory is proposed. Consistent results between theoretical prediction and experimental measurements were found. Unlike homopolyesters, the glass transition temperature of copolymer amorphous domains gradually decreases with crystallization time. An exclusion model for the crystallization of polyester segments in copolymers is proposed. The temperature width of the glass transition increases with crystallization time. The broadening towards the low temperature side in glass transition is interpreted as the evidence of crystallization-induced partial phase separation. Instead of forming macroscopic segregation, the excluded polyether segments resided in-between crystalline polyester lamellae and mix with amorphous polyesters to generate amorphous domains exhibiting concentration gradient along the lamellar basal surface normal. Further increasing the polyetheramide segment content brings the excluded polyetheramide segments to form domains among the crystallized polyester spherulites so as to inhibit the occurrence of spherulitic impingement.     

Properties and pervaporation separation of hydroxyl‐terminated polybutadiene‐based polyurethane/poly(methyl metharcylate) interpenetrating networks membranes

Hydroxyl‐terminated polybutadiene (HTPB), 4,4′‐dicyclohexyl methane diiscyanate (H₁₂MDI), and 1,4‐butane diol are used to synthesize polyurethane (PU) solutions by two‐stage process. Interpenetrating networks (IPNs) of HTPB‐based PU and poly(methyl methacrylate) (PMMA) with HTPB/MMA (wt/wt % ratio) = 2.0, 1.5, 1.0, 1.5, 0.8, and 0.6, which are designated as IPN1 to IPN5, respectively, are synthesized by sequential polymerization technique. Thermal properties, tensile strength, and contact angle of membranes increase with the increase of MMA content, while the elongation of membranes show the reverse trend. Characterization of membranes are investigated by C?C/C?O absorption ratio and infrared absorption frequency shiftment. These PU and IPN membranes are used for the separation of ethanol/water and isopropanol/water solution by pervaporation test. IPN3 membrane possesses the largest pervaporation permeability and the separation factor. The pervaporation results of ethanol/water feed has the same trend as that of isopropyl alcohol (IPA)/water solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

An EGF-pseudomonas exotoxin A recombinant protein with a deletion in toxin binding domain specifically kills EGF receptor bearing cells

We constructed two chimeric toxins; one composed of epidermalgrowth factor (EGF) and pseudomonas exotoxin A (PE), designatedEGF-PE and the other composed of EGF and PE with a deletionof the Ia domain (cell-binding domain), designated EGF-PE (Ia).Both chimeric toxins reacted with anti-EGF and anti-PE antibodies.The cell-killing experiments showed that EGF-PE, but not EGF-PE(Ia),was cytotoxic to the murine fibroblast cell line NR6, whichcarried the PE receptor, but not the EGF receptor. However,after NR6 was transfected with DNA for the expression of humanEGF receptor, the transfected cell line, designated NRHER5,overexpressed human EGF receptors and became sensitive to EGF-PE(IA).The cytotoxicity of EGF-PE(Ia), but not EGF-PE, to NRHER5 canbe completely blocked by an excess amount of EGF. To completelyreverse the cytotoxicity of EGF-PE on NRHER5, both the EGF receptorpathway and the PE receptor pathway need to be blocked. Theseresults suggest that EGF-PE exhibits both EGF and PE bindingactivities, while EGF-PE(IA) possesses only EGF binding activity.Thus, EGF-PE(Ia) may be a better chimeric toxin than EGF-PEin terms of target specificity to EGF receptor bearing cells.We, therefore, examined the cytotoxicity of EGF-PE(Ia) to varioushuman cancer cell lines. We find that human cancer cells containingmore EGF receptors are more sensitive to EGF-PE(Ia).     

Inclusion of third-person perspective in CAVE-like immersive 3D virtual reality role-playing games for social reciprocity training of children with an autism spectrum disorder

Universal Access in the Information Society - The present study aimed to improve the ability of children with autism to recognize emotions correctly. We used our third-person perspective...     

High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant

The flame retardant polypropylene containing the micro-envelope core-shell structure flame retardant, which encapsulated ammonium polyphosphate into melamine-formaldehyde resin and sodium silicate through in situ polymerization was prepared with polyamide 6, added as a carbon-forming agent. The composition of ammonium polyphosphate, encapsulated ammonium polyphosphate with melamine-formaldehyde resin and the micro-envelope core-shell structure flame retardant were characterized. The fire safety and thermal stability were investigated and showed an improvement including limiting oxygen index, thermogravimetric analysis, vertical burning tests, and microscale combustion calorimeter. The burned compounds were also studied to confirm the burning mechanism. The results showed the flame retardant performance had been greatly improved, while polyamide 6 had better char-forming effect. Besides, the water solubility of flame retardants and their influence on the mechanical properties of polypropylene were also investigated. The results on the effects of additives demonstrated a high efficiency flame retardant to polypropylene. A core-shell flame retardant that sodium silicate and melamine-formaldehyde resin-coated ammonium polyphosphate had been constructed. The effect of the built flame retardant system on the combustion performance of polypropylene was studied from the mechanism and performance. The LOI of the most flame retardant polypropylene reached 28.6%, and UL-94 reached the V-0 level.     

Determination of the long term corrosion behavior of coated steel with A.C. impedance measurements

A previous study of the a.c. impedance of thin polymer films on aluminum alloys, steel, and phosphated steel, determined over a wide frequency range, has resulted in a general model for the electrochemical impedance across the coated surfaces. According to this model, penetration of the coating by the electrolyte results in an impedance behavior which is typical of a dielectric film short-circuited by conducting electrolytic paths perpendicular and parallel to the polymer/metal interface. Comparison of the time dependence of the impedance of coated steel substrates with the impedance across a free film has demonstrated that the corrosion of the substrate enhances the development of parallel paths of ionic conduction in the coating. A.c. impedance measurements carried out on polybutadiene-coated steels pretreated by different procedures determine quantitatively the resistance R_p of the conducting paths. The time dependence of R_p for the coated substrates has been determined for exposure periods of up to three weeks. Visual observation of the corroded and delaminated areas according to ASTM D610 has been carried out simultaneously, and correlations have been established with R_p. The results are discussed in terms of the possibility to predict the corrosion behavior of a coated metal, based on the measurement of R_p.     

Microstructures and Properties of Laser-Glazed Plasma-Sprayed ZrO2-YO1.5/Ni-22Cr-10AI-1Y Thermal Barrier Coatings

Thermal barrier coatings (TBCs) consisting of two layers with various yttria contents (ZrO ₂- YO_1.5/Ni-22Cr-10Al- lY) were plasma sprayed, and parts of the various specimens were glazed by using a pulsed CO₂ laser. All the specimens were then subjected to furnace thermal cycling tests at 1100 °C; the effect of laser glazing on the durability and failure mechanism of the TBCs was then evaluated. From these results, two models were developed to show the failure mechanism of as- sprayed and laser- glazed TBCs: model A, which is thermal-stress dominant, and model V, which is oxidation-stress dominant. For top coats containing cubic phase, cubic and monoclinic phases, or tetragonal and a relatively larger amount of monoclinic phases, whose degradation is thermal- stress dominant, laser glazing improved the durability of TBCs by a factor of about two to six. Segmented cracks that occurred during glazing proved beneficial for accommodating thermal stress and raising the tolerance to oxidation, which resulted in a higher durability. Thermal barrier coatings with top coats containing tetragonal phase had the highest durability. Degradation of such TBCs resulted mainly from oxidation of the bond coats. For top coats with a greater amount of monoclinic phase, thermal mismatch stress occurred during cooling and detrimentally affected durability.     

Examination of wire electrical discharge machining of Al2O3p/6061Al composites

Alumina particle reinforced 6061 aluminum matrix composites (Al₂O₃p/6061Al) have excellent physical and chemical properties than those of a traditional metal; however, their poor machinability lead to worse surface quality and serious cutting tool wear. In this study, wire electrical discharge machining (WEDM) is adopted in machining Al₂O₃p/6061Al composite. In the experiments, machining parameters of pulse-on time were changed to explore their effects on machining performance, including the cutting speed, the width of slit and surface roughness. Moreover, the wire electrode is easily broken during the machining Al₂O₃p/6061Al composite, so this work comprehensively investigates into the locations of the broken wire and the reason of wire breaking.The experimental results indicate that the cutting speed (material removal rate), the surface roughness and the width of the slit of cutting test material significantly depend on volume fraction of reinforcement (Al₂O₃ particles). Furthermore, bands on the machined surface for cutting 20 vol.% Al₂O₃p/6061Al composite are easily formed, basically due to some embedded reinforcing Al₂O₃ particles on the surface of 6061 aluminum matrix, interrupt the machining process. Test results reveal that in machining Al₂O₃p/6061Al composites a very low wire tension, a high flushing rate and a high wire speed are required to prevent wire breakage; an appropriate servo voltage, a short pulse-on time, and a short pulse-off time, which are normally associated with a high cutting speed, have little effect on the surface roughness.     

Simulation of ultrasonic-vibration drawing using the finite element method (FEM)

In ultrasonic-vibration drawing, wires are drawn while ultrasonic vibration is applied to a drawing die. Prior studies provide experimental proof that ultrasonic-vibration drawing reduces drawing resistance, improves lubrication and prevents wire breakage. In the future, ultrasonic-vibration drawing is expected to contribute to the drawing of difficult-to-draw materials and operations, such as shaped wires, ultrafine wires, and the wire drawing operation in semidry or dry condition. However, a detailed analysis and understanding of the mechanism of improvement is not possible on the basis of conventional experimental observations because the ultrasonic-vibration processing phenomenon occurs at high speed. Therefore, we attempted to understand the processing mechanism of ultrasonic-vibration drawing using the finite element method (FEM). ABAQUS was used for the FEM. Drawing force and stress–strain distributions in drawn wires were analyzed. From these studies, we quantitatively clarified the mechanism of improved drawing characteristics, such as decreased drawing force.     

Screen‐based color vision test for digital quantification of deutan color defects using a color‐calibrated monitor

Display technologies are used in various industries. However, few studies on color vision testing using self‐luminous displays are reported. In this study, a screen‐based color vision test, termed the digital color vision test (DCVT), is developed on a color‐calibrated monitor. A control bar is adjusted by the observer to build just noticeable chromatic difference ellipses in CIE u′v′ chromaticity diagram, which indicate the capabilities of subjects' color visions. Ten color‐normal observers and 13 deutan observers participated in the psychophysical experiments. The observers also performed the other two typical diagnostic tests (D‐15 and anomaloscope). Results from the experiment using the adjustment psychophysical method for digital quantification of deutan color vision defects are presented. It is found that the diagnosis accuracy of the DCVT is approximately equivalent to those of D‐15 and anomaloscope tests.