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.     

Study on prevention of angular distortion in fillet-welded T-joint by welding with a trailing reverse-side gas heating

Reduction or control of angular distortion without additional processes is demanded because it takes a lot of time and effort to correct the angular distortion of fillet-welded T-joints. In this study, the reduction or control of angular distortion of both sides of a fillet-welded T-joint by welding with trailing reverse-side gas heating was investigated through a welding experiment and its numerical simulation. First, the effect of gas heating position and intensity on the reduction in angular distortion was experimentally investigated using a gas burner. The results showed that angular distortion became smallest when reverse-side heating using the gas burner was located 50 mm backward of the welding torch. Also, the concentrated gas flame with increased propane and oxygen gas flow was effective for reducing angular distortion. It was clarified that the angular distortion could be controlled completely with an appropriate reverse-side gas heating condition. Next, the numerical simulation model of welding and gas heating was constructed based on comparison with the measured temperature histories and angular distortion. Through the numerical simulation of welding with a trailing reverse-side gas, more detailed understanding of the effect of gas heating condition on reduction in angular distortion was developed. In addition, it was confirmed that the gas heating position for the smallest angular distortion is dependent on the temperature distribution along the thickness of the flange plate.     

The correlation between the ionic degree of covalent bond comprising polymer main chain and the ionic yield due to mechanical fracture

The mechanical force to polymeric materials in vacuum at 77 K produces mechano radicals, mechano anions and mechano cations due to homogeneous and heterogeneous scissions of the covalent bonds comprising polymer main chain. The ionic degree of the covalent bond was estimated by calculating the “absolute ΔMulliken atomic charge,” which was defined as the difference between the Mulliken atomic charges of the two adjacent atoms comprising the covalent bond of the polymer main chain. The ionic yield of the covalent bond increased with increasing the absolute ΔMulliken atomic charge. The empirical formula for the ionic yield was obtained with the absolute ΔMulliken atomic charge, and indicates that the ionic yield could be estimated from its chemical structure.     

High tensile strength fiber of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] processed by two‐step drawing with intermediate annealing

High tensile strength fibers of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] [P(3HB‐co‐3HH)], a type of microbial polyesters, were processed by one‐step and two‐step cold‐drawn method with intermediate annealing. Thermal degradation behaviors were characterized by differential scanning calorimeter and gel permeation chromatography measurements. Thermal analyses were revealed that molecular weights decreased drastically within melting time at a few minute. One‐step cold‐drawn fiber with drawing ratio of 10 showed tensile strength of 281 MPa, while tensile strength of as‐spun fiber was 78 MPa. When two‐step drawing was applied for P(3HB‐co‐3HH) fibers, the tensile strength was led to 420 MPa. Furthermore, the optimization of intermediate annealing condition leads to enhance the tensile strength at 552 MPa of P(3HB‐co‐3HH) fiber. Wide‐angel X‐ray diffraction measurements of these fibers suggest that the fibers with high tensile strength include much amount of the planer‐zigzag conformation (β‐form) as molecular conformation together with 2₁ helix conformation (α‐form). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41258.     

Cytochemistry of gastric parietal cells with high-pressure freezing followed by freeze-substitution

Gastric parietal cells were examined for changes in their ultrastructure and distribution of the proton pump during feeding and fasting states in rats. The fundic glands from rats fed ad libitum or fasted with free access to water were cryofixed using high-pressure freezing followed by freeze-substitution in acetone containing osmium or acrolein and then embedded in Epon 812 or Lowicryl K4M resin, respectively. Excellent ultrastructural preservation was achieved. During the feeding state, intracellular canaliculi and numerous microvilli were well developed, while tubulovesicles were poorly developed. In contrast, during the fasting state, the microvilli in the narrowed space of the intracellular canaliculi were tightly packed and the tubulovesicles were enlarged. Ultrathin sections were immunostained with antibodies against the alpha- and beta-subunits of the proton pump, H+ x K(+)-ATPase, using the immunogold method. The labelling was strong and clearly localized in comparison with that obtained using the conventional chemical-fixation method. Each subunit was localized on the membrane of the microvilli, intracellular canaliculi and tubulovesicles. The distribution of subunit proteins varied between the two states. During ad libitum feeding, the immunolabelling was localized strongly on the membranes of the microvilli and intracellular canaliculi. In contrast, the labelling was strong on the tubulovesicle membrane in the fasting state. The results obtained with each anti-subunit antibody by H+ x K(+)-ATPase immunostaining revealed differences in distribution and labelling density between the feeding and fasting states.     

Electroreductive block copolymerization of dichlorosilanes in the presence of disilane additives

The electroreductive polymerization of dichloromethylphenylsilane in the presence of triphenylsilyl group‐containing disilanes such as hexaphenyldisilane followed by the electroreductive termination with chlorotriphenylsilane afforded triphenylsilyl group‐terminated polymethylphenylsilane in 15–32% yield. The isolated polymethylphenylsilane (M_n = 3350 g mol^?1, M_w/M_n = 1.4) was found to react as a macroinitiator to copolymerize with dibutyldichlorosilane under electroreductive conditions producing the corresponding block copolymer (M_n = 4730 g mol^?1, M_w/M_n = 1.2) in 38% yield. The ratio of monomer units (? MeSiPh? to? BuSiBu? ) of the copolymer was determined to be 75:25 using ¹H NMR analysis, which was in good agreement with the calculated ratio (74:26) on the assumption that molecular weight of the macroinitiator was not changed. The block structure of the resulting copolymer, poly(methylphenylsilane)‐block‐poly(dibutylsilane), was also confirmed by comparing its ¹H NMR and UV absorption spectra with those of polymethylphenylsilane, polydibutylsilane and a statistical copolymer prepared by electroreductive polymerization of dichloromethylphenylsilane with dibutyldichlorosilane. This method is applicable to the preparation of other types of macroinitiator such as triphenylsilyl group‐terminated polydibutylsilane, and polydibutylsilane‐block‐polymethylphenylsilane was also obtained using this macroinitiator. Copyright © 2011 Society of Chemical Industry     

Synthesis and characterization of dextrin derivatives by heterogeneous esterification

A series of fully-acylated dextrin esters (DS = 3) with varying side-chain lengths (C2–12) were synthesized by heterogeneous esterification using trifluoroacetic anhydride/carboxylic acid. The influence of side-chain lengths on structure and properties of dextrin esters were investigated by structural, thermal, mechanical and hydrophobic analysis. The thermal stability of dextrin was enhanced by esterification, presenting ca. 40–60 °C higher decomposition temperatures than that of neat-dextrin. The transition temperatures of melting and crystallization were not observed for all dextrin esters because they were amorphous polymers. The glass transition temperature (T_g) was not observed in dextrin but was observed in dextrin esters. As increasing side-chain length, T_gs of dextrin esters decreased ranged from 162.2 °C (C2) to 49.2 °C (C12). Colorless and transparent dextrin ester films were prepared to measure the film properties. Tensile strength of dextrin ester films tended to decrease with increasing side-chain lengths, whereas the elongation at break increased. And, dextrin ester films showed significantly increased hydrophobicity with a contact angle of up to 102° (C12).     

Synthesis of polyamides from sugar derived d-glucaric acid and xylylenediamines

d -Glucaric acid (GA) is the one of aldaric acids and is an important bio-based building block for polymers. In this study, poly(m-xylylene-acetyl glucaramide) and poly(p-xylylene-acetyl glucaramide) were synthesized from GA acetate and two kind of aromatic diamines by solution polymerization. The chemical structures of the polyamides were analyzed by nuclear magnetic resonance spectroscopy. The weight-average molecular weights ranged from 3.3 × 10³ to 1.15 × 10⁴ with a polydispersity of 1.6–1.9, depending on monomer ratio or monomer concentration in solution. The 10% decomposition temperature of the polymers was about 210 °C. Differential scanning calorimetry revealed that the polyamides exhibited no peaks attributed to crystallization or melting point, which indicated that the polyamides were amorphous. No crystalline pattern was observed in the X-ray diffractograms, supporting this result. Polarized optical microscopy observation revealed that the polyamides exhibited melting-like behavior at above 150 °C, which was attributed to glass-transition behavior. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47255.     

Enhanced crystallization of poly(lactide) stereocomplex by xylan propionate

The effect of xylan propionate (XylPr) as a novel biomass‐derived nucleating agent on the poly(lactide) sterecomplex was investigated. Addition of XylPr to an enantiomeric blend of poly(l ‐lactide) (PLLA) and poly(d ‐lactide) (PDLA) was performed in either the solution state or molten state. The solution blend of PLLA/PDLA with XylPr was prepared by mixing equal volumes of 1 wt% XylPr/PLLA and 1 wt% XylPr/PDLA solutions in chloroform and precipitating in methanol. The solution blend with XylPr showed shorter half‐time crystallization than the solution blend without XylPr in isothermal crystallization between 80 and 140 °C, although homocrystallization occurred. Enhanced stereocomplex crystallization in the solution blend with XylPr was observed at 180 °C, where no crystallization occurred in the solution blend without XylPr. Addition of XylPr to PLLA/PDLA blend in the molten state was performed at 240 °C. Thereafter, the melt blend of PLLA/PDLA with or without XylPr was either quenched in iced water or isothermally crystallized directly from the melt. Isothermal crystallization of the melt‐quenched blend with XylPr gave a similar result to the solution blend with XylPr. In contrast, the melt‐crystallized blend with XylPr formed only stereocomplex crystals after crystallization above 140 °C. Furthermore, the melt‐crystallized blend with XylPr showed a higher crystallinity index and melting temperature than the melt‐crystallized blend without XylPr. This shows that XylPr promotes stereocomplex crystallization only when the blend of PLLA/PDLA with XylPr is directly crystallized from the molten state just after blending. © 2016 Society of Chemical Industry     

Morphological study on thermal treatment and degradation behaviors of solution-grown poly(l-lactide) single crystals

Morphological changes of solution-grown crystals (SGCs) of poly(l-lactide) (PLLA) following thermal treatment and enzymatic degradation were investigated using atomic force microscopy in terms of defects in the crystals. PLLA SGCs were grown from a dilute solution of acetonitrile at 5 °C. The obtained solution-grown monolamellar crystals have a lozenge-shaped morphology containing unique dimensions, with one side measuring 12 μm. To investigate enzymatic degradation behavior, PLLA SGCs were incubated in buffered solution with proteinase-K at 37 °C. The initial stage of enzymatic degradation of PLLA SGCs with proteinase-K occurs in loosely folding chains at the surface of the crystal. Thermally treated PLLA SGCs below the melting temperature showed an increase of the lamellar thickness of the SGCs at the treated temperature and partial surface erosion following enzyme exposure. These results indicate that less ordered chains exist throughout the lamellae and their thermal-induced chain extension makes them more susceptible to enzyme attack.