The preparation of poly[N(n-butoxymethyl) methacrylamide] grafted silk fibers by polymerization using a low pH system

The graft polymerizations of the N(n-butoxymethyl) methacrylamide (BMA) monomer onto silk fibers were effected after reducing the pH of the grafting system to 2.5 by the addition of a formic acid solution. We compared the grafting efficiencies, surface characteristics, and thermal behaviors, as well as the whiteness levels and the extent of reduction of the rate of yellowing following UV irradiation, with the equivalent features of poly(BMA)-grafted silk fibers, prepared under normal (pH 6) conditions. The grafting efficiency [as poly(BMA) weight gain] onto silk fiber that was attained was almost 100% through optimization of the pH environment in the polymerization system by the addition of formic acid. The stiffness of the silk fabrics observed, following the conventional grafting, was markedly higher than that of equivalent silks after the polymerization at pH 2.5. The rates of yellowness index increase, for these latter silk fabrics following UV irradiation were also reduced, specifically in the initial irradiation period (up to 60 h). The SEM of the grafted silk fabrics reveal the absence of granules on the surface of the grafted silk fiber, when the silk was grafted with poly(BMA), after reducing the pH of the grafting system to 2.5. These findings suggest that the BMA monomer was polymerized specifically within the silk fiber and not on the surface. It is suggested that the increase in the polymer weight gain, and the reduced adverse effect on the fabric handle, arise because of the modified polymer location. © 1993 John Wiley & Sons, Inc.     

Chemical modification of tussah silk fabrics with ethyleneglycol diglycidyl ether by a pad-batch method

Tussah silk fabrics have been chemically modified by pad-batch treatment with ethyleneglycol diglycidyl ether (EDGE). The maximum amount of weight gain attained was 5–6%. Epoxide adducts were formed with tyrosine and basic amino acid residues. The moisture regain of the fabric with 3% weight gain decreased slightly compared with that of the untreated sample. The crease recovery in the wet state improved significantly, while in dry state it remained unchanged. Mechanical and optical properties, and X-ray crystallinity did not exhibit noticeable changes. The position of the major DSC endothermic transition at 358d?C remained unchanged, regardless of the epoxide modification. Similar comments apply to the TMA contraction peak occurring at about 359d?C. The storage and loss modulus curves of EDGE-treated tussah silk fibres exhibited some changes, the most relevant consisting in a shift to higher temperature of the loss modulus peak.     

Grafting of methyl methacrylate onto silk fibers initiated by tri-n-butylborane

Structural characteristics of the methyl methacrylate (MMA)-grafted silk fibers using tri-n-butylborane as an initiator were analyzed by infrared spectroscopy and differential scanning calorimetry (DSC), and their refractive index and tensile properties were measured. Graft polymerization was promoted by FeCl₃ pretreatment of the silk. The graft yield reached a maximum by the immersion in 4% FeCl₃ solution for 1 min at 25°C. The infrared spectrum of poly(MMA)-grafted silk fibers showed overlapped absorption bands of silk fibroin with the β structure and of the grafted MMA polymer. A grafted silk fiber with graft yield of more than 140% exhibited two endothermic peaks at 321°C and 396°C on the DSC curve, attributed to the thermal decomposition of silk fibroin and grafted poly(MMA) chain, respectively. Refractive index measurements suggested that the molecular orientation and the crystallinity of the silk fiber decreased with increasing graft yield. Electron photomicrographs showed that silk was coated by grafted PMMA. The tensile strength of the grafted silk decreased rapidly by the grafting even at a lower level.     

Structural analysis of methacrylamide-grafted silk fibers

The structural changes and the thermal behavior of silk fibers grafted with methacrylamide (MAA) were investigated as a function of the weight gain. The refractive index parallel to the fiber axis decreased with increasing weight gain, whereas that perpendicular remained almost unchanged. Accordingly, birefringence decreased with a steeper slope in the weight gain range 0–80%, suggesting a lower degree of average molecular orientation. Only small changes in the isotropic refractive index were detected, suggesting that the crystallinity of the fibers remained essentially unaffected by MAA grafting, as confirmed by the X-ray diffraction data. The molecular orientation in the crystalline regions remained unchanged in the weight gain range 0–60%, then sharply decreased. The strength and the initial tensile resistance of grafted silk fibers decreased both in the dry and wet states, while elongation at break increased in the dry state and remained almost constant in the wet state. The results of the thermal behavior, investigated by differential scanning calorimetry, thermomechanical and thermogravimetric analysis, and dynamic mechanical measurements, were consistent with an increased thermal stability conferred on silk fibers by MAA grafting. The cross-sectional area of MAA-grafted silk fibers increased. Moreover, ion-etched cross sections of the grafted silk fiber showed the presence of fibrils with a diameter larger than that of the untreated control. © 1993 John Wiley & Sons, Inc.     

Chemical and property modification of silk with dibasic acid anhydrides

In an attempt to provide information for improving silk fiber and fabric properties including crease recovery and yellowing, silk modification has been studied by using succinic and glutaric anhydrides. Glutarylation has been found to protect silk fibers from yellowing caused by the high energy radiation and to be more effective on increasing the crease proofing. The silk fabrics did not reduce the tensile properties such as strength and elongation at break even after the chemical modification with dibasic acid anhydrides. Thermal properties of the fibers remained unchanged in spite of the succinylation or glutarylation. From all the considerations of the survey of dye uptake, it would seem that the ester crosslinks are easily formed much more by the glutarylation than by the succinylation. The recovery values and yellowness indices of the modified silk fabrics and the measuring results of thermal and thermomechanical properties are explicable, taking into account of the different reactivity of the functional groups induced by the chemical modification with the dibasic acid anhydrides.     

Chemical modification of tussah silk with acid anhydrides

Tussah silk fibroin was chemically modified by acylation with aliphatic, aromatic, and hydrophobic acid anhydrides. The tussah silk fibers were pretreated by immersing them in a lithium thiocyanate (LiSCN) solution and then acylated in dimethylformamide (DMF) at elevated temperatures. Using this method, acylated tussah silk fibers with weight gains of 8–22% could be obtained. The pretreatment with LiSCN was necessary to promote the acylation. Without it, the reaction did not proceed. The optimum temperature and reaction time of the pretreatment was 55°C and 60 min, respectively. When examining the physical properties and the thermal behavior of both pretreated and acylated tussah silk, it was found that the mechanical properties and the position of the major DSC endothermic peak remained unchanged, regardless of pretreatment and acylation. The moisture regain of the pretreated tussah silk increased slightly while the moisture regain of the acylated silk decreased linearly with increasing weight gain. The chemical modification allows for a wide control of the tussah silk fiber's properties, making it possible to use tussah silk for the development and production of novel textile and biomaterials. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 382–391, 2000     

Chemical modification of wool fibers with acid anhydrides

Wool fibers were chemically modified by reaction with succinic and glutaric anhydrides. The weight gain (and acyl content) increased with increasing the reaction temperature (65–80°C) and time (1–2 h), attaining 18.9% (158.9 mol/10⁵ g) and 23% (163.9 mol/10⁵ g) for succinylated and glutarylated wool, respectively. Changes in the amino acidic pattern of acylated wool, i.e., decrease of basic amino acid residues and formation of ornithine, were observed by acid hydrolysis. The X‐ray diffraction profiles of modified wool fibers remained essentially unchanged, suggesting that the crystalline structure was not affected by reaction with acid anhydrides. The degree of molecular orientation of acylated wool slightly decreased, especially at high weight gain. The viscoelastic response of wool modified with succinic and glutaric anhydrides was characterized by a shift to a lower temperature of both the drop of the storage modulus and the peak of the loss modulus. These features are indicative of a higher mobility of the keratin chians in the amorphous and crystalline domains. In fact, it is suggested that the chemical agent diffused into the accessible parts of α‐crystallites, reaching the available reactive sites. This did not cause changes in the crystalline pattern of wool, but resulted in a different thermal behavior of fibers. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1573–1579, 1999     

Structure and physical properties of silk fibroin/polyacrylamide blend films

This article deals with the characterization of blend films obtained by mixing silk fibroin (SF) and polyacrylamide (PAAm). The DSC curves of SF/PAAm blend films showed overlapping of the main thermal transitions characteristic of the individual polymers. The exothermic peak at 218°C, assigned to the β‐sheet crystallization of silk fibroin, slightly shifted to a lower temperature by blending. The weight‐retention properties (TG) of the blend films were intermediate between those of the two constituents. The TMA response was indicative of a higher thermal stability of the blend films, even at low PAAm content (≤25%), the final breaking occurring at about 300°C (100°C higher than pure SF film). The peak of dynamic loss modulus of silk fibroin at 193°C gradually shifted to lower temperature in the blend films, suggesting an enhancement of the molecular motion of the fibroin chains induced by the presence of PAAm. Changes in the NH stretching region of silk fibroin were detected by FTIR analysis of blend films. These are attributable to disturbance of the hydrogen bond pattern of silk fibroin and formation of new hydrogen bonds with PAAm. The values of strength and elongation at break of blend films slightly improved at 20–25% PAAm content. A sea–island structure was observed by examining the air surface of the blend films by scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1563–1571, 1999     

Analysis of precursors for crystal growth of YBaCuO thin films in magnetron sputtering deposition

We correlated the crystallinity of YBaCuO films prepared by magnetron sputtering deposition using Ar/O₂ mixture gas with the atomic and molecular composition in the gas phase. YBaCuO films were deposited on MgO substrates at 670 °C. Two-dimensional distributions of Y, Ba, Cu, YO, BaO, and CuO densities and one-dimensional distribution of O density were measured by laser-induced fluorescence spectroscopy. The Y and Ba densities decreased significantly with the increase of the O₂ partial pressure, and they were below the detection limit at an O₂ flow ratio of 10% and a total gas pressure of 53 Pa. The decrease in the Y and Ba densities was compensated by an increase in the YO and BaO densities. The decrease in the Cu density with the increase of the O₂ partial pressure was less significant, while the CuO density was below the detection limit at all the discharge conditions. The O density was evaluated to be 10¹²-10¹³ cm^− 3, which was much higher than the Cu density. On the other hand, YBaCuO films with high crystallinity were obtained at total gas pressures of 53-80 Pa and O₂ flow ratios of 50-70%. Therefore, it is concluded that the precursors for the deposition of YBaCuO films with high crystallinity are Cu, YO, BaO, and O.     

Introduction of Cu(II) complex into transparent synthetic resin and optical function of the resin as a near-infrared ray cutoff filter

A mole ratio method was conducted to determine a necessary condition to solubilize Cu(II) ion into an organic solvent. Copper benzoate anhydrous (CB) and acetone was used as a Cu(II) ion supplier and a solvent, respectively. Methacryloyloxy-ethyl phosphate (PMOE) and di(2-ethylhexyl) phosphate (DIEHP) were used asligands for solubilization. Cu(II) ion was solubilized with only two PMOE molecules, although six molecules were needed for DIEHP. PMOE formed an intermediate layer which surrounded the Cu(II) ion with two molecules between the ion and solvent and made it possible to solubilize Cu(II) ion into the organic solvent. In the case of DIEHP, however, six molecules were needed to form such a layer for solubilization. Furthermore, Cu(II) ion was introduced homogeneously into poly(methyl methacrylate) (PMMA) by copolymerization of PMOE with MMA, although the polymer was opaque in the case of DIEHP. The ligand having a methacryloyl group was considered to participate in the polymerization process, which avoided exclusion of the Cu(II) complex from polymer phase. The intermediate zone formed by PMOE was considered to keep compatibility of Cu(II) ion with the polymer matrix even after polymerization. The near-infrared ray cutting-off filter made of resin was realized by introducing Cu(II) ion at higher concentration through complexation with the proper ligand. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:903–912, 1998