Supramolecular morphology of two-step melt-spun poly(dioxanone) fibers

Structure of poly(dioxanone) (PPDX) fibers produced through a two-step melt-spinning process with an additional short-period annealing above the melting temperature of PPDX was investigated and the effect of annealing on the degradation behavior was discussed. The morphological study carried out by etching the fibers using a phosphate or permanganate solution suggested that the fibers take a skin–core structure, and both the skin layer and the core region consist of a bundle of microfibrils. The micro-beam X-ray diffraction analysis revealed that the short-period annealing in the production process only slightly promotes the crystallization in the skin layer but contributes to increasing the packing of amorphous chains near the skin, which seems to be the controlling factor of the hydrolytic degradation behavior of the fibers.     

Dummy humanoid robot simulating several trunk postures and abdominal shapes – Report of element technologies

Development of clothing in consideration of the shape and body function of a person with spinal cord injury is an important task. Then, a dummy robot with a deformation mechanism was developed in this study for evaluating the comfortable level of clothings. Specifically, a trunk joint mechanism and an abdominal mechanism that can realize various deformations of the abdominal area and various trunk poses were developed. The trunk joint mechanism was implemented in order to simulate the seated posture of persons with spinal cord injury. The abdominal deformation mechanism was implemented using linear actuators and rotating servomotors in order to simulate abdominal obesity of persons with spinal cord injury. Further, a tactile sensor system was developed for measuring the clothing pressure on the abdominal area and evaluating the comfort or discomfort of clothing.     

Phosphorus flame retardants in indoor dust and their relation to asthma and allergies of inhabitants

Organophosphate esters are used as additives in flame retardants and plasticizers, and they are ubiquitous in the indoor environment. Phosphorus flame retardants (PFRs) are present in residential dust, but few epidemiological studies have assessed their impact on human health. We measured the levels of 11 PFRs in indoor floor dust and multi‐surface dust in 182 single‐family dwellings in Japan. We evaluated their correlations with asthma and allergies of the inhabitants. Tris(2‐butoxyethyl) phosphate was detected in all samples (median value: 580 μg/g in floor dust, 111 μg/g in multi‐surface dust). Tris(2‐chloro‐iso‐propyl) phosphate (TCIPP) was detected at 8.69 μg/g in floor dust and 25.8 μg/g in multi‐surface dust. After adjustment for potential confounders, significant associations were found between the prevalence of atopic dermatitis and the presence of TCIPP and tris(1,3‐dichloro‐2‐propyl) phosphate in floor dust [per log₁₀‐unit, odds ratio (OR): 2.43 and 1.84, respectively]. Tributyl phosphate was significantly associated with the prevalence of asthma (OR: 2.85 in floor dust, 5.34 in multi‐surface dust) and allergic rhinitis (OR: 2.55 in multi‐surface dust). PFR levels in Japan were high compared with values reported previously for Europe, Asia‐Pacific, and the USA. Higher levels of PFRs in house dust were related to the inhabitants' health status.     

Selective hydrogenation of 4-isobutylacetophenone over a sodium-promoted Pd/C catalyst

The effect of sodium promotion on the selective hydrogenation of 4-isobutylacetophenone, 4-IBAP, was investigated over a Pd/C catalyst. A precipitation and deposition method was used to prepare the catalyst, and sodium was promoted on the Pd/C catalyst via post-impregnation while varying the sodium content. The sodium-promoted Pd/C catalyst resulted in a significantly improved yield greater than 96% of the desired product, 1-(4-isobutylphenyl) ethanol (4-IBPE), compared with the non-patented literature results under a mild hydrogenation condition. A detailed hydrogenation network over the Pd/C catalyst was suggested. The reaction mechanism for the yield and selectivity enhancement of 4-IBPE induced-by the promoted Pd/C was elucidated in relation to the geometric and electronic effects of reactant molecules in the microporous support depending on the reaction steps.     

Effects of supercritical carbon dioxide treatment on the morphology of poly(l‐lactide)

Synthetic l ‐lactide random copolymers can be employed as controlled release materials when prepared using supercritical carbon dioxide (scCO₂), since they are biodegradable via hydrolysis. To determine the effects of thermal properties on polymer performance following scCO₂ processing, three types of poly(l ‐lactide) having different properties were assessed. The T_m of one poly(l ‐lactide) sample (H‐100) was found to be approximately 170 °C over the processing pressure range from 8 to 18 MPa, while a second sample (H‐440) also showed a constant value of approximately 152 °C. In contrast, the poly(l ‐lactide) REVODE exhibited a T_m of 146 °C prior to processing but a higher value of 147 °C following treatment at 8 MPa. Unlike the H‐100 and H‐440, the T_m value of the REVODE tended to decrease with increasing pressure. The T_g values increased greatly under mild conditions of 8 MPa pressure and a temperature of 40 °C. In particular, the T_g values for the H‐440 and REVODE increased by 4 °C and 5 °C, respectively. All T_g values were lowest at 12 MPa and increased with increasing processing pressure, although the effect of processing temperature was minimal. The Χ_{c DSC} of the H‐100 was 18% initially but increased to 20% upon scCO₂ processing at 40 °C and 14 MPa, and showed further increases at higher processing temperatures. Although the relationship between processing temperature and Χ_{c DSC} values for the H‐440 showed the same trend as observed with the H‐100, a different trend was seen for the REVODE. The Χ_{c XRD} values obtained from the XRD analyses differed from the values generated by DSC analysis, and showed a maximum degree of crystallinity following processing at 80 °C both with and without scCO₂ treatment. ATR FT‐IR analyses identified peaks due to semicrystalline regions in poly(l ‐lactide) samples treated with scCO₂, even when applying low temperatures. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44006.     

Hot drawing of partially miscible blends of polycarbonate and poly(butylene terephthalate)

Samples of PC-PBT blends over the entire composition range were drawn at 160°C to high extensions, 2.1–5.8, to study the mechanical reinforcement and the molecular structure development upon deformation. Elastic modulus E' increases with extension ratio for all compositions and temperatures. Blends with 25 and 40 wt% of PC show higher E' at low temperature than pure PBT blends do. Crystallinity increases with extension ratio and is relatively smaller with increasing PC content. The influence of the reversible α to β crystal form transformation was also studied. The second moment of the orientation function f for both crystal forms increases to high values > 0.9 at relatively low extensions. f decreases with PC content for α crystals but decreases for β crystals. The α fraction is high for PBT and decreases with PC content and extension ratio in the blends. Strain recovery experiments show that the α to β transformation is also elastic in nature at high extension ratios and that the reinforcing effect in high PBT content blends is not due to the α/β ratio. © 1996 John Wiley & Sons, Inc.     

Thermal behavior,morphology, and mechanical properties of blend strands consisting of poly(ethylene terephthalate) and semiaromatic liquid crystalline polymer

Polymer blends of poly(ethylene terephthalate) (PET) and a liquid crystalline polymer (LCP) [random copolymers of the poly(ethylene telephthalate) and poly (hydroxybenzoic acid)] were prepared by using a twin-screw extruder. Strands were extruded from a capillary die. Extruded stands were stretched in an oven at 80°C. DSC and SEM were employed to investigate the structural properties of the strands. Mechanical properties of the strands were evaluated by a sonic propagation method. DSC investigation suggested that LCP phases may act as a nucleating agent of PET and the orientation-induced crystallization of PET was accelerated by the presence of LCP. An SEM micrograph shows that the LCP phases formed finely spherical domains with a diameter of 0.1–1.0 μm in the PET matrix and large parts of LCP spherical droplets were deformed to fibrils. In the case of unstretched strands, sonic moduli increased linearly with increasing LCP content, because PET was reinforced by LCP fibrils as in the case of glass fiber-reinforced PET. The degree of crys-tallization of PET also increased with increasing LCP contents. In the case of stretched strands, sonic moduli increased with an increasing stretching ratio due to the orientation-induced crystallization of PET. A larger increasing of the sonic modulus was shown in LCP-containing strands in the regions of a low stretching ratio (1–5), since the orientation-induced crystallization of PET was accelerated by the presence of LCP phases. © 1996 John Wiley & Sons. Inc.     

Tribochemical behaviour and lubrication characteristics of aromatic compounds

Radical scavenger, radical anion scavenger, and peroxide decomposer were added to aromatic hydrocarbons and phosphates in aromatic rings with and without side chain, and the effect of these inhibitors on tribopolymerisation and the lubrication characteristics of the aromatic compounds were investigated, in various atmospheres, in order to clarify the reaction mechanism. The aromatics of both hydrocarbons and phosphates with a methyl group in aromatic rings react readily at the rubbing surfaces to form polymer or polymer-like products, improving the lubricating characteristics. The tribochemical reactions of alkylaromatic compounds is shown to differ from those of trialkyl or triarylphosphates. It was concluded that the reaction proceeds through the radical or radicalanion and via peroxide to cause polymerisation.     

Synthesis,properties, and biodegradability of three-branched copolyamide (4/6)

Previous studies on polyamide 4, excellent properties, functionalities, and biodegradation in natural condition have been shown. In this study, three-branched (star-shaped) copolyamides constituted of polyamide 4 and polyamide 6 constitutional unit were synthesized by anionic ring-opening copolymerization of 2-pyrrolidone with ε-caprolactam. The thermal and mechanical properties and the biodegradability of the obtained copolyamides have been systematically investigated. The weight-average molecular weight of the copolyamides was as high as tens of thousands (M_w 10–80 × 10³ g/mol). The composition of the copolyamides was approximately in accord with the monomer feed ratio, thereby being controllable. The thermal and mechanical properties changed readily as the composition was varied (T_m 146–266°C, ΔH_m 10–70 J/g, T_d 278–369°C, tensile strength 28–64 MPa, elongation at break 80–750%). The copolyamide having 2-pyrrolidone unit of 96–51 mol% exhibited biodegradability by an activated sludge. The biodegradation of the copolyamide proceeded uniformly without disproportion in constitutional unit.