Characterizing the Effects of Washing by Different Detergents on the Wavelength-Scale Microstructures of Silk Samples Using Mueller Matrix Polarimetry

Silk fibers suffer from microstructural changes due to various external environmental conditions including daily washings. In this paper, we take the backscattering Mueller matrix images of silk samples for non-destructive and real-time quantitative characterization of the wavelength-scale microstructure and examination of the effects of washing by different detergents. The 2D images of the 16 Mueller matrix elements are reduced to the frequency distribution histograms (FDHs) whose central moments reveal the dominant structural features of the silk fibers. A group of new parameters are also proposed to characterize the wavelength-scale microstructural changes of the silk samples during the washing processes. Monte Carlo (MC) simulations are carried out to better understand how the Mueller matrix parameters are related to the wavelength-scale microstructure of silk fibers. The good agreement between experiments and simulations indicates that the Mueller matrix polarimetry and FDH based parameters can be used to quantitatively detect the wavelength-scale microstructural features of silk fibers. Mueller matrix polarimetry may be used as a powerful tool for non-destructive and in situ characterization of the wavelength-scale microstructures of silk based materials.     

Crystal size and distortion parameter of natural pure mysore silk fibers (Bombyx Mori)

Crystal size and lattice distortion parameters were determined experimentally by recording X-ray diffraction patterns of natural silk fiber (pure Mysore silk, Bombyx Mori) using Fourier cosine coefficients of the intensity profile of an X-ray (210) reflection. Also, the crystal size distribution along [210] direction is given.     

Properties of Recycled Polycarbonate/Waste Silk and Cotton Fiber Polymer Composites

Polymer-based composite structures have advantages over many other materials. The most important advantage is the higher mechanical properties obtained from the composites when supported by fiber reinforcement. The mechanical and thermal properties of fiber-reinforced composite structures are affected by the amount of fibers in the structures, orientation of the fibers and fiber length. Silk and cotton fibers are used in many fields but especially in clothing and textiles. However, there is not enough research on their usage as reinforcement fibers in composite structures. Silk fibers as a textile material have better physical and mechanical properties than other animal fibers. The improvement of the mechanical and physical properties of the composite structures allows them to be used in many areas. From economical, technological and environmental points of view, the improvement of mechanical and physical properties of polymeric materials are receiving much attention in recent studies.

In this study, different application areas were chosen to evaluate the waste silk and waste cotton rather than classic textile applications. Waste silk and cotton and recycled polycarbonate polymer were mixed and as a result composite structures were obtained. Silk and cotton waste fiber dimensions were in between 1 mm, 2.5 mm and 5 mm. The recycled PC/silk and cotton wastes were mixed in the rates of 97%/3%. Mixtures were prepared by twin-screw extruder. Tensile strength, % elongation, yield strength, elasticity modulus, Izod impact strength, melt flow index (MFI), heat deflection temperature (HDT) and Vicat softening temperature properties were determined. To determine the materials' thermal transition and microstructure properties, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used.     

Production of fine powder from silk by radiation

Silk fine powder was prepared directly from silk fibers irradiated with an accelerated electron beam (EB). Irradiated silk fibers were well pulverized only by physical crushing using a ball mill without any chemical pretreatment. Silk fibroin fibers were irradiated at ambient temperature in the dose range of 250–1 000 kGy. Although unirradiated silk fibers were not pulverized at all, irradiated fibers were easily pulverized and showed a high conversion efficiency from fiber to powder at high irradiation doses. The presence of oxygen in the irradiation atmosphere enhanced pulverization of the silk fibers. The electron microscopic observation showed that the minimum particle size of silk powder obtained from fibers irradiated at 1 000 kGy in oxygen was less than 10 μm. It was found that fibroin powder obtained in this work dissolved remarkably in water, thought unirradiated fibroin fibers were insoluble even in hot water. The soluble fraction was about 60% of fibroin powder for 1 000 kGy irradiation in oxygen.     

Dyeing of silk cloth with colloidal gold

Silk cloth was dyed successfully by dipping it in a gold hydrosol which was prepared in the presence of a cationic surfactant, stearyltrimethylammonium chloride (SC). The color of thus dyed silk cloths is due to colloidal gold particles adsorbed on silk fibers and varies from reddish purple to dark purple according to the periods of dipping time and the amounts of SC in the gold hydrosol used. The mechanism for the adsorption of colloidal gold on the silk fibers is proposed.     

Effects on behavior ofApanteles melanoscelus females caused by modifications in extraction,storage, and presentation of Gypsy moth silk kairomone

Choice experiments were performed to investigate details of femaleApanteles melanoscelus (Ratzeburg) behavior when exposed to gypsy moth silk kairomone [Lymantria dispar (L.)] and to host larvae when kairomone is present. Female parasites only responded to the kairomone when it had been placed on thin strands such as cotton fibers. Both gypsy moth silk and silk glands contain the same or similar kairomones. Silk gland extracts were more active than head, alimentary canal, or hemolymph extracts of host larvae. Female responses decreased when low concentrations of silk gland extract or small numbers of treated fibers were presented to them. Silk gland extract was stable when frozen for 2 weeks, heated to 100 °C for 0.5 hr, freeze dried, or treated with 95% ethanol. The active component was nondialyzable. Silk deposited on the substrate increased host contacts and oviposition attempts, more so if wider areas were covered with silk, and even if the areas having silk were separated from the host. A theory of host selection inA. melanoscelus is proposed.Hymenoptera, Braconidae. Lymantria dispar L. (Lepidoptera: Lymantriidae).     

Preparation and heat-insulating property of the bio-inspired ZrO2 fibers based on the silk template

Natural silk fibers were used as the template to prepare biomorphic ZrO₂ fibers. Silk fibers were first immersed into a Zr(NO₃)₄ solution and then sintered in air at high temperatures to produce the final ZrO₂ fibers. Their microstructures, phases, synthesis process, infrared absorption spectra and thermal conductivity were analyzed. The results show that these synthesized fibers retained the morphologies of silk faithfully. These ZrO₂ fibers also obtained the ability of absorbing infrared from the silk, so that they possessed better heat-insulating property than the traditional ZrO₂ fibers.     

Preparation of water‐repellent silks by a reaction with octadecenylsuccinic anhydride

Silk fibers and membranes were acylated with octadecenylsuccinic anhydride (ODSA) at 75°C for different times. Swelling [N,N‐dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)] and nonswelling (xylene) solvent media were used for the reaction. Silk membranes that reacted in DMF or DMSO displayed faster reaction kinetics and attained higher weight‐gain values than fibers. The effect of the solvent on the reaction yield was in the following order: DMSO > DMF ? xylene. The Fourier transform infrared spectra of acylated silk samples showed the characteristic absorption bands of the anhydride at 2990, 2852, 1780–1700, and 1170 cm^?1. The intensity of the latter band, which increased linearly with the weight gain, was used as a marker for evaluating the reaction kinetics of the samples acylated in the nonswelling medium. The moisture regain and water retention of silk fibers acylated with ODSA decreased significantly, regardless of the solvent system used. Accordingly, the water repellency increased. Acylation induced an increase in the thermal stability of the silk fibers and membranes. Fine particles adhering to the surfaces of the silk fibers acylated in xylene were detected by scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 324–332, 2003     

Investigation of Properties of Polymer/Textile Fiber Composites

Polymer-based composite structures have advantages over other materials. The most important advantage is the higher mechanical properties obtained from the composites when supported by fiber reinforcement. The mechanical and thermal properties of fiber-reinforced composite structures are affected by the amount of fibers in the structures, orientation of the fiber and fiber length. Silk and cotton fibers are used in many fields but especially in clothing and textiles. However, there is not enough research on their usage as reinforcement fibers in composite structures. Silk fibers as a textile material have better physical and mechanic properties than other animal fibers. It is very important that the improvement of the mechanical and physical properties of the composite structures allows them to be used in many areas. From economical, technological and environmental points of view, the improved the mechanical and physical properties of polymeric materials are receiving much attention in the recent studies.

In this study, various lengths (1 mm–2.5 mm and 5 mm) of waste silk and waste cotton fibers were added to high-density polyethylene (HDPE) and polypropylene (PP) polymer in the mixing ratios of (polymer:fiber) 100%:0%, 97%:3%, and 94%:6% to produce composite structures. On the other hand, known lengths (1–2.5–5 mm) of waste silk and waste cotton fibers were added to recycled polyamide-6 (PA₆) and polycarbonate (PC) polymers in mixing quantities of 100%-0%, 97%-3%. A twin-screw extruder was employed for the production of composites. Tensile strength, % elongation, yield strength, elasticity modulus, Izod impact strength, melt flow index (MFI), heat deflection temperature (HDT), and Vicat softening temperature properties were determined. In order to determine the materials' thermal transition and microstructure properties, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used. Results have shown that cotton and silk fibers behave differently than in the composite structure. Waste silk fiber composites give better mechanical properties than waste cotton fiber.     

Optothermal properties of fibers. IX. Study changes of optical parameters by multiple-beam technique due to thermal annealing for natural silk fibers

Multiple-beam Fizeau fringes were used for studying the effect of the annealing process on the refractive indices and birefringence of natural silk fibers (best yellow Italian silk, Ford & Co. Ltd). Silk fibers were annealed at a constant time of 2 h with different annealing temperatures ranging from 60 to 160 ± 1°C. A scanning electron microscope was used for measuring the cross-sectional shape and a longitudinal view of the natural silk fibers. The Becke-line method was used for measuring the skin refractive indices and the birefringence of the natural silk fibers. The thermal coefficient of the refractive index, Cauchy dispersion constants, dispersive power, dielectric constant at infinity, polarizability per unit volume, isotropic polarizability, and isotropic refractive index were determined interferometrically. Microinterferograms and curves are given for illustration. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1495–1504, 1998     

Synthesis and Thermal Conductivities of the Biomorphic Al2O3 Fibers Derived from Silk Template

Silk was used as the template to prepare biomorphic Al₂O₃ fibers. Silk fibers were first immersed into an AlCl₃ solution and then sintered at high temperatures to produce the final Al₂O₃ fibers. Their microstructures, phases, synthesis process, infrared absorption spectra, and thermal conductivity were analyzed. The results show that these Al₂O₃ fibers retained the morphologies of silk. Different from the traditional Al₂O₃ fibers, these biomorphic fibers exhibit hollow and possess a good ability of absorbing infrared got from the silk, so that they possessed better heat‐insulating property than the traditional Al₂O₃ fibers.     

Mechanical properties of silk fibers treated with methacrylamide

Silk fibers were treated with methacrylamide (MAA), and changes in the mechanical properties of the silk fibers were investigated. The breaking load of the silk fibers was almost unchanged, whereas rigidity was markedly increased by the methylmethacrylate (MAA) treatment. Elongation at break of the silk fibers decreased significantly when the fibers were treated with MAA up to polymer add-on (ca. 300%). The cross-sectional area of the MAA-treated silk fiber was given by the addition of the cross-sectional area of the original silk fiber and that of the MAA polymer. The Young's modulus of MAA-treated silk fibers increased linearly with increasing volume fractions of fiber in MAA-grafted silk fibers. The Young's modulus of the MAA polymer in the MAA-treated silk fibers was estimated by extrapolating the relation between Young's moduli and volume fractions of fiber to the zero volume fraction of fiber. The Young's modulus of the MAA polymer in the MAA-treated silk fibers was larger than the sonic modulus measured for an MAA polymer plate. © 1996 John Wiley & Sons, Inc.     

Chemical,Thermal, Time,and Enzymatic Stability of Silk Materials with Silk I Structure

The crystalline structure of silk fibroin Silk I is generally considered to be a metastable structure; however, there is no definite conclusion under what circumstances this crystalline structure is stable or the crystal form will change. In this study, silk fibroin solution was prepared from B. Mori silkworm cocoons, and a combined method of freeze-crystallization and freeze-drying at different temperatures was used to obtain stable Silk I crystalline material and uncrystallized silk material, respectively. Different concentrations of methanol and ethanol were used to soak the two materials with different time periods to investigate the effect of immersion treatments on the crystalline structure of silk fibroin materials. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman scattering spectroscopy (Raman), Scanning electron microscope (SEM), and Thermogravimetric analysis (TGA) were used to characterize the structure of silk fibroin before and after the treatments. The results showed that, after immersion treatments, uncrystallized silk fibroin material with random coil structure was transformed into Silk II crystal structure, while the silk material with dominated Silk I crystal structure showed good long-term stability without obvious transition to Silk II crystal structure. α-chymotrypsin biodegradation study showed that the crystalline structure of silk fibroin Silk I materials is enzymatically degradable with a much lower rate compared to uncrystallized silk materials. The crystalline structure of Silk I materials demonstrate a good long-term stability, endurance to alcohol sterilization without structural changes, and can be applied to many emerging fields, such as biomedical materials, sustainable materials, and biosensors.     

Microstructural parameters in electron‐irradiated hydroxypropyl methylcellulose films using X‐ray line profile analysis

The changes in microstructural parameters in hydroxypropyl methylcellulose (HPMC) polymer films irradiated with 8 MeV electron beam have been studied using wide‐angle X‐ray scattering (WAXS) method. The crystal imperfection parameters such as crystal size <N>, lattice strain (g in %), and enthalpy (α^*) have been determined by line profile analysis (LPA) using Fourier method of Warren. Exponential, Lognormal, and Reinhold functions for the column length distributions have been used for the determination of these parameters. The goodness of the fit and the consistency of these results suggest that the exponential distribution gives much better results, even though lognormal distribution has been widely used to estimate the similar stacking faults in metal oxide compounds. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Silk I structure formation through silk fibroin self-assembly

Regenerated silk fibroin films are normally produced by increasing the Silk II structure (β-sheet content). In the present study, silk fibroin films were prepared by controlling the environmental temperature and humidity, resulting in the formation of silk films with a predominant Silk I structure instead of Silk II structure. Wide angle X-ray diffraction indicated that when the relative humidity was 55%, the silk films prepared were mainly composed of Silk I structure, whereas silk films formed on other relative humidity had a higher Silk II structure. Fourier transform infrared analysis (FTIR) results also conformed that the secondary structure of silk fibroin can be controlled by changing the humidity of the films formed process. Thermal analysis results revealed Silk I structure was a stable crystal, and the degradation peak increased to 320°C, indicating a greater thermal stability of these films formed under the 55% relative humidity conditions. Atomic force microscopy (AFM) results depicted silk fibroin in the fresh solution had many nanospheres existing with 20–50 nm diameters and mainly maintained a random coil structure without specific nanostructures. At the same time, it also illustrated the self-assembly process of silk fibroin in the aqueous solution without any human intervention. In addition, this present study also provided additional support for self-assembly mechanism of silk fibroin films formation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on secondary structural transition of nano‐TiO2 modified silk fibroin composite films by two‐dimensional Raman correlation spectroscopy and solid‐state 13C‐NMR spectroscopy

By a sol–gel processing, the nano‐TiO₂/silk fibroin (SF) composite films were prepared. One‐dimensional (1D) Raman, two‐dimensional (2D) correlation Raman spectroscopy, and ¹³C cross‐polarization magic‐angle‐spinning nuclear magnetic resonance (¹³C CP‐MAS NMR) were used to characterize the structural evolution of SF as the nano‐TiO₂ content increased from 0 to 0.4 wt%. The experimental data demonstrated that the secondary structures in the pure SF film and nano‐TiO₂/silk fibroin (SF) composite films were random coil, α‐helix and β‐sheet structures. The nano‐TiO₂ particles formed in the SF films might induce partial structural transitions from random coil and Silk I (α‐helix) to Silk II (β‐sheet). The transition identified by 2D‐Raman correlation spectra was the following order: silk I‐like structure, silk I (α‐helical structure), Silk II‐like structure, and Silk II (β‐sheet structure). POLYM. COMPOS., 36:121–127, 2015. © 2014 Society of Plastics Engineers     

Chemical modification of silk with aromatic acid anhydrides

Bombyx mori silk fibers were chemically modified by acylation with aromatic acid anhydrides, such as phthalic and o-sulfobenzoic anhydrides. We examined the reactivity of these modifying agents toward silk fibers, the physical and thermal properties, and the dyeing behavior with acid and cationic dyes. The o-sulfobenzoic anhydride was more reactive toward silk fibroin than phthalic anhydride. The amount of both basic and acidic amino acid residues decreased after modification with aromatic acid anhydrides. The moisture regain of silk treated with phthalic anhydride remained almost unchanged, while that of the samples modified with o-sulfobenzoic anhydride increased linearly as the weight gain increased. Chemically modified silk fabrics showed improved crease recovery behavior, even though phthalic anhydride seemed more effective at comparatively low weight gain. The modification of silk with o-sulfobenzoic anhydride caused a drastic a reduction of acid dye uptake and enhanced the affinity of silk for cationic dye. Silk fibers did not show any significant change in thermal behavior, regardless of the modification with o-sulfobenzoic anhydride. Silk fibers modified with phthalic anhydride showed on differential scanning calorimetry (DSC) curves a minor and broad endothermic peak at around 210°C, attributed probably to the breaking of the crosslinks formed between adjacent fibroin molecules.     

Structure–property relation in varieties of silk fibers

Crystallite shape ellipsoid in different varieties of silk fibers namely (i) Chinese (ii) Indian, and (iii) Japanese, has been computed using wide‐angle X‐ray data and Hosemann's one‐dimensional paracrystalline model. The estimated microcrystalline parameters are correlated with the observed physical property of the silk fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1979–1985, 2001     

Structure and properties of bombyx mori silk fibers grafted with methacrylamide (MAA) and 2-hydroxyethyl methacrylate (HEMA)

Silk fibers were graft-copolymerized with methacrylamide (MAA) and 2-hydroxyethyl methacrylate (HEMA) in aqueous media, using a chemical redox system as an initiator. High weight gains (300%) were obtained with both monomers, the weight gain being linearly related to the amount of monomer contained in the reaction system. The reaction efficiency attained 95–100%. The extent of homopolymerization was negligible for the MAA grafting system, while large amounts of poly-HEMA covered the surface of silk fibers beyond 70% weight gain. The fiber size increased linearly with the weight gain. The moisture content of MAA-grafted silk fibers was highly enhanced by grafting. The severe grafting conditions caused a partial degradation of the tensile properties of silk fibers, as well as of the degree of fiber whiteness. Following grafting, the breaking load slightly increased, while elongation at break and energy decreased. The decomposition temperature of grafted silk fibers shifted upwards. The Raman spectra of untreated silk fibers showed strong lines at 1667 (amide I), 1451, 1227 (amide III), 1172 and 1083 cm⁻¹. Overlapping of the lines characteristic of both silk fibroin and grafted polymer was observed in the spectra of grafted silk samples. The vibrational mode of the amide III lines of silk fibroin was significantly modified by grafting. © 1996 John Wiley & Sons, Inc.     

Molecular weight distribution of the methyl methacrylate (MMA) polymer separated from the MMA-grafted silk fiber

The molecular weight distribution of poly-methyl methacrylate (poly-MMA) chains separated from MMA-grafted silk fibers obtained by using potassium persulfate (KPS) and tri-n-butylborane (TBB) as initiator of the graft-copolymerization reaction have been examined by gel permeation chromatography (GPC). GPC elution pattern of poly-MMA chains shows a bimodal molecular weight distribution. The two peaks have been identified as heavy and light component. The average molecular weight of the heavy component ranges from 48.5 to 200 kD for poly-MMA copolymerized by the KPS reaction system and from 336 to 816 kD for the poly-MMA copolymerized by the TBB reaction system. The light component has an average molecular weight lower than 1,000 D and its value is almost similar in all the samples examined. Scanning electron microscopy (SEM) analysis revealed the presence of MMA oligomers formed on the fiber surface during grafting. The molar ratio between poly-MMA chains and silk fibroin attains a constant value that seems to be specific for a certain reaction system. A linear correlation has been observed between the weight gain and the average molecular weight of the poly-MMA chains. These findings suggest the effect of grafting parameters on the molecular weight and molecular weight distribution of the grafted polymer, as well as its influence on the physical properties and textile performances of MMA-grafted silk fibers.