Stress relaxation and inverse stress relaxation in silk fibers

Stress‐relaxation experiments on four varieties of Indian silk fiber show that stress relaxation is significantly greater in non‐Mulberry silks than in the Mulberry silk and that the differences among non‐Mulberry silk fibers are relatively small. All the fibers studied also exhibit inverse stress relaxation. It has been shown that the Maxwell–Wiechert model, with two Maxwell elements in parallel, can be used to analyze and explain both the stress‐relaxation and inverse stress‐relaxation behaviors. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1147–1154, 2001     

A study of one‐bath alkali–amine hydrolysis and silk‐fibroin finishing of polyester microfiber crepe fabric

In this study, the synergistic aminolysis (sodium hydroxide and ethylene diamine in one bath) mechanism of polyethylene terephthalate (PET) microfiber crepe fabric was preliminarily investigated. The results showed that not only active groups (i.e., ? NHR, ? COOH, and ? OH) but also considerable cracks and craters were introduced onto PET fibers, which provided locations for a subsequent crosslinking reaction and mechanical attachment and so facilitated the silk‐fibroin finishing. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1467–1473, 2001     

Physical properties of silk fibers grafted with vinyltrimethoxysilane

Silk fibers from Bombyx mori silkworms were grafted using a novel grafting monomer, vinyltrimethoxysilane (VTMSi), with various grafting initiators. The effects of these grafting initiators were evaluated. It was possible to successfully copolymerize VTMSi within the silk fiber matrix without disturbing the fine structure of the fiber matrix, which was shown by FTIR analysis and refractive index measurements. The physical properties of VTMSi grafted silk were analyzed and compared to fibers grafted with conventional monomers such as methyl methacrylate, methacrylamide, and 2‐hydroxyethyl methacrylate. No trend in the tensile strength and elongation at break was observed when grafting silk fibers with VTMSi. Crease recovery in the wet state improved significantly, suggesting that this new grafting technique is important for the production of washable silk fabrics. The thermal stability of VTMSi grafted silk fibers was improved as shown by the shift of the endothermic peak for the thermal decomposition toward higher temperatures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1764–1770, 2001     

Preparation of metal‐containing protein fibers and their antimicrobial properties

Bombyx mori silk, Antheraea pernyi silk, and wool fibers were chemically modified by treatment with tannic acid (TA) or by acylation with ethylenediaminetetraacetic (EDTA) dianhydride. Kinetics of TA loading or acylation with EDTA‐dianhydride varied from fiber to fiber. B. mori silk and wool displayed the highest weight gains with TA and EDTA‐dianhydride, respectively. The uptake of different metal ions (Ag⁺, Cu²⁺, Co²⁺) by protein fibers, either untreated or chemically modified, was studied as a function of weight gain and pH of the aqueous metal solution. Below pH 7, absorption of metal ions by untreated and TA‐treated fibers was negligible. Acylation with EDTA‐dianhydride enabled protein fibers to absorb and bind significant amounts of metal ions in the acidic and neutral pH range. The levels of metal desorption at acidic pH depended on the fiber‐metal combination. Untreated protein fibers usually displayed the lowest stability of the metal complex. Metal complexes with protein fibers exhibited prominent antimicrobial activity against the plant pathogen Cornebacterium. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 638–644, 2003     

Effect of the chain‐transfer‐agent content on the emulsion polymerization process and adhesive properties of poly(n‐butyl acrylate‐co‐acrylic acid) latexes

The effect of water on regenerated silkworm silk fibers has been studied and compared with that of water on natural silkworm silk fibers. Regenerated fibers are spun from an N‐methylmorpholine‐N‐oxide (NMMO) fibroin solution through a wet‐spinning process, leading to fibers with two distinct tensile behaviors, labeled as brittle and ductile, respectively. Regenerated fibers show a significant contraction when immersed in water. Contraction increases further after drying. In contrast, natural silkworm silk fibers show a negligible contraction when submerged in water. Regenerated fibers tested in water are considerably more compliant than samples tested in air, though their stiffness and tensile strength are significantly reduced. It has been shown that the tensile properties of brittle regenerated fibers can be modified by a wet‐stretching process, which consists of deforming the fiber while immersed in water. Regenerated wet‐stretched fibers always show a ductile behavior independent from their initial tensile behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Grafting vinyl monomers onto silk (Bombyx mori) using different initiators: Properties of grafted silk

The graft–copolymerization of silk with methacrylamide (MAA), 2‐hydroxyethyl methacrylate (HEMA), and methyl methacrylate (MMA) was studied using three different free‐radical initiators: an inorganic peroxide [ammonium persulfate (APS)] and two azo compounds [2,2′‐azobisisobutyronitrile (AIBN) and 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (ADC)]. The rate and yield of grafting followed the order: APS > AIBN > ADC. The performance of AIBN was close to that of APS in terms of weight gain attained. The degree of yellowing of grafted silk varied as a function of the initiator–monomer system used. APS induced the highest degree of yellowing, regardless of which monomer was used, whereas silk grafted with the MAA/AIBN system displayed the lowest level of yellowing. Moisture regain of grafted silk changed as a function of the hydrophilic/hydrophobic character of the grafted polymer, regardless of the kind of initiator used. Accordingly, tensile properties showed a tendency to decrease with increasing weight gain of grafted silk, the extent of which was independent of the kind of monomer and initiator used. The different initiators did not induce any appreciable change in the fine structure of silk, as demonstrated by optical measurements. Uneven surface deposition of homopolymer was detected to variable extent with MMA and HEMA grafting, whereas the surface of MAA‐grafted silk was completely free of any foreign deposit, independently of the initiator used. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1401–1409, 2001     

Preparation and characterization of poly[(butylene succinate)‐co‐(butylene adipate)]/carbon nanotube‐coated silk fiber composites

Biodegradable composites consisting of aliphatic polyesters (poly[(butylenes succinate)‐co‐(butylenes adipate)] (PBSA)) and Bombyx mori silk fibers coated with carbon nanotubes (CNTs) were prepared by melt compression molding. The mechanical properties of PBSA were enhanced by the incorporation of a small amount (3 wt%) of CNT‐coated silk fibers, while allowing its potential biodegradability to be retained, which could make these composites good candidates for commodity materials such as general‐purpose plastics. This improvement is attributed to the interactions between PBSA and CNT‐coated silk fibers in the composites. The average interfacial shear strength of the composites consisting of CNT‐coated silk fibers and PBSA matrix was 1.7 MPa, as measured by the microbond droplet test, while that of composites consisting of pure silk fibers and PBSA was only 1.1 MPa. The morphology of the CNT‐coated silk fiber‐reinforced composites was observed using scanning electron microscopy. Copyright © 2007 Society of Chemical Industry     

The Development of Fibers That Mimic the Core–Sheath and Spindle‐Knot Morphology of Artificial Silk Using Microfluidic Devices

Spider and silkworm produce diverse silk fibers from spinning dopes through smart spinnerets. Spider's capture silk is composed of core thread and periodic spindle‐knots, while silkworm silk consists of fibroin core and sericin outer layer. To mimic the morphologies of natural heterostructured silks, artificial fibers are dry‐spun using a multichannel microfluidic chip, served with a highly viscous core solution of regenerated silk fibroin and low viscosity sheath solution of sericin. Silk fibers with core–sheath, groove, and spindle‐knot structures are obtained by controlling the flow rates and viscosities of the two microfluids depending on the laminar flow, Kelvin–Helmholtz instability, or Plateau–Rayleigh instability.     

Tensile stress–strain and recovery behavior of Indian silk fibers and their structural dependence

The tensile stress–strain and recovery behavior of all the four commercial varieties of Indian silk fibers, namely Mulberry, Tasar, Eri, and Muga, have been studied along with their structures. Compared to the non‐Mulberry silk fibers, Mulberry silk fiber is much finer and has crystallites of smaller size, higher molecular orientation, and a more compact overall packing of molecules. These structural differences have been shown to result in (1) the presence of a distinct yield and a yield plateau in non‐Mulberry silk and their absence in Mulberry silk, and (2) relatively higher initial modulus and tenacity along with lower elongation‐to‐break and toughness and superior elstic recovery behavior of mulberry silk compared to non‐Mulberry silk. It is also observed that fine silk fibers have a relatively more ordered and compact structure with higher orientation compared to their coarse counterparts, and this gives rise to higher initial modulus and higher strength in the finer fibers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2418–2429, 2000     

Chemical modification of Bombyx mori silk with calcium‐salt treatment and subsequent glycerin triglycidyl ether crosslinking

In this article, we propose a new modification method for obtaining porous silk fibers with excellent wet elastic resilience and flexibility. Bombyx mori silks were modified by calcium‐salt treatment and subsequent epoxy crosslinking with glycerin triglycidyl ether. The effects of temperature, time, and catalyst (sodium carbonate) on the crosslinking reaction of the silk fibers were investigated, and the best conditions of reaction were determined as a temperature of 120°C, a crosslinking agent concentration of 7%, and immersion for 1 h with 2% Na₂CO₃ solution before the crosslinking reaction. The change in the structure and the physical properties of the silk fibers after calcium‐salt treatment and epoxy crosslinking was studied. Separating behavior of the microfibers occurred on the surface of the silk fiber after calcium‐salt treatment, and a porous structure formed in the interior of the silk. This porous structure of the silk was enlarged by subsequent epoxy crosslinking, and accordingly, the moisture conduction of the silk fibers improved remarkably. The breaking strength, breaking elongation, and wet elastic resilience of the silk fibers increased evidently after modification, and the modified silks exhibited a better flexibility. The conformation of silk fibroin fibers changed from β sheet to random coil after calcium‐salt treatment, whereas the β‐sheet content in the silk fibers increased after subsequent epoxy crosslinking. The significant reductions in the crystallinity and crystalline sizes in the silk fibers after the crosslinking reaction indicated that the crosslinking reaction occurred within the crystalline region because the calcium‐salt treatment increased the reaction accessibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Analysis of the structural characteristics of nanoscale silk particles

Nanoscale silk particles were prepared from silk fibers by a special pretreatment with the aid of specially designed machinery and techniques. Scanning electron micrographs showed that the particle sizes of the silk powders produced from silk fibers around 9–11 μm in diameter decreased from a microscale to a nanoscale after three stages of pulverization, and this was further confirmed with a laser particle size analyzer. Fourier transmission infrared analysis showed that there were no substantial changes in the chemical structure of the silk after the pulverization processes. The silk powders after the second and third pulverizations slightly differed from that of the silk fiber and the particles after the first pulverization with a greater amount of the primary aliphatic amines. Also, there were secondary amides present in the silk fiber and the powders after the first and second pulverizations but absent in the powders after the third pulverization. Moreover, the silk powders after the third pulverization had a greater number of C(CH₃)₃ groups than the silk fibers and the powders after the first and second pulverizations. X‐ray diffraction analysis showed that the crystallinity of the silk powders decreased when the particle sizes decreased, particularly to nanoscales. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 268–274, 2006     

Performance of flame retardancy silk modified with water‐soluble vinyl phosphoamide

In this article, a water‐soluble flame retardant monomer dimethyl(methacryloyloxyethyl)phosphoramidate (DMMEPN) was synthesized and applied onto silk fabric via graft copolymerization technique initiated with potassium persulfate (KPS). The results of attenuated total reflection infrared spectroscopy (ATR), scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS) indicated that DMMEPN was successfully grafted onto silk fiber surface. X‐ray diffraction (XRD) patterns showed that grafting process didn't change the crystalline structure of silk fibers and the reaction mainly occurred at the amorphous region of silk fibers. DMMEPN grafted silk fabric exhibited self‐extinguish property when ignited with a candle like fire with LOI of 32.38% and could pass vertical flammability test with char length of 42 mm. Thermal gravimetric analysis showed that grafted silk fibers had different thermal decomposition mode with control silk fibers and tended to produce more char after combustion. This article also investigated the physical properties like whiteness index, hygroscopicity, and tensile strength of grafted silk fabrics. The results showed that physical properties had some loss but had no negative effect on final uses. Laundering durability test demonstrated treated silk fabrics still showed flame retardancy after enduring 30 hand wash cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical and thermal properties of waste silk fiber‐reinforced poly(butylene succinate) biocomposites

This article reports the mechanical and thermal properties of poly(butylene succinate) (PBS) biocomposites reinforced with industrially available waste silk fibers, fabricated with varying fiber contents and lengths. The result indicates that use of waste silk fibers may be a potential as reinforcement for effectively improving the static and dynamic mechanical properties of a biodegradable polymer matrix resin, depending on the waste silk fiber content and length in the present biocomposite system. The “as‐separated” waste silk/PBS biocomposites showed the maximum tensile and flexural properties at a fiber loading of 40 wt %, and the “chopped” waste silk/PBS biocomposites showed the optimal strength and modulus with waste silk fibers of 12.7 mm length. The chopped waste silk fibers play a more contributing role in improving the mechanical properties of waste silk/PBS biocomposites than the as‐separated waste silk fibers at a fixed fiber loading. Above the glass transition temperature, the storage modulus of waste silk/PBS biocomposites was significantly greater than that of PBS resin, especially in the higher temperature region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4972–4980, 2006     

Structure for electro‐spun silk fibroin nanofibers

Electro‐spinning was made using silk fibroin and it was found that silk fibroin nanofibers of partially oriented amorphous structure are producible using HFIP(1,1,1,3,3,3 hexafluoro‐2‐propanol) as a solvent for fibroin via the electro‐spinning setup equipped with parallel electrodes as a collector. Transformation from amorphous to silk I of a highly contracted beta‐turn form or amorphous to silk II of a regular array of antiparallel beta‐sheets occurred preferentially via the treatment with water vapor or ethanol, respectively. In addition the c‐axis of crystallites was oriented parallel to the fiber axis. When the electro‐spinning was made using a dish‐type collector filled with ethanol, a peculiar web texture was obtained. Such a web texture seems to be brought about by the shrinkage of fiber due to the crystallization of fibroin and/or surface tension of ethanol droplets formed between the fibers. In this spinning setup, the c‐axis of crystallites was also oriented parallel to the fiber axis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Softness evaluation of keratin fibers based on single‐fiber bending test

The evaluation of single‐fiber softness by bending is an ingenious and vital approach for the basic investigation of both the fiber bending properties and the textile softness. The bending behavior and bending modulus of wool, alpaca and silk fibers have been measured by an axial‐buckling method developed by the authors, which uses the fiber compression bending analyzer (FICBA). The bending properties of single fibers were quantified by calculating the equivalent bending modulus and the flexural rigidity by measuring the protruding length and diameter of fiber needles and the critical force, P_cr, obtained from the peak point of the force‐displacement curve. The measured data showed that the equivalent bending modulus of the alpaca fiber is higher than that of wool fiber, and even the rigidity is 10 times as high as wool, but its friction coefficient is lower than that of wool, which means that the soft handle of alpaca fabrics is mainly due to the smooth surface and low friction coefficient of alpaca fibers in contrast to that of wool fiber. For the silk fiber, despite high equivalent bending modulus, the smoother handle of silk should be mainly due to the thin fiber diameter in contrast to that of keratin fibers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 701–707, 2006     

Grafting of methyl methacrylate (MMA) onto Antheraea assama silk fiber

Graft copolymerization of methyl methacrylate (MMA) onto nonmulberry silk fiber Antheraea assama was investigated in aqueous medium using the KMnO₄–oxalic acid redox system. Grafting (%) was determined as a function of the reaction time, temperature, and monomer and initiator concentrations. The rate of grafting increased progressively with increase of the reaction time up to 4 h and then decreased. The extent of grafting was maximum at 55°C. The extent was also dependent upon monomer and initiator concentrations up to 75.5 × 10^?2 and 6 × 10^?3 M, respectively. The grafted products were evaluated by infrared spectroscopy and their thermal decompositions were studied by TG and DTG techniques in static air at 20°C min^?1 and 30°C min^?1 in the range 30–800°C. The kinetic parameters for ungrafted and grafted fibers were evaluated using the Coats and Redfern method. The grafted products were found to be thermally more stable than were those of the ungrafted fibers. The surface characteristics of the ungrafted and grafted fibers were evaluated by scanning electron microscopy. The water‐retention values (WRVs) of the grafted fibers were in decreasing order with increase in the grafting (%). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2633–2641, 2001     

Blend fibers of polyacrylonitrile and water‐soluble chitosan derivative prepared from sodium thiocyanate solution

A water‐soluble chitosan derivative of N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), synthesized by the reaction of chitosan and glycidyltrimethyl ammonium chloride, and polyacrylonitrile (PAN) were blended using 46% (w/w) NaSCN aqueous solution as a common solvent. The total polymer concentration of blend solution was fixed at 12% (w/w), and the relative composition of PAN/HTCC in the blend solution varied from 0/100 to 80/20 by weight. The PAN/HTCC blend fibers with the appropriate physical property were prepared by a wet spinning and drawing process. The effect of HTCC content on the structural change, miscibility, and ability to be dyed of the blend fibers was investigated. The optical and scanning electron microscopic observation gave no indication of phase separation up to 20% HTCC content. Differential scanning calorimetry and dynamic mechanical measurements of the blend fibers show single glass transition temperatures that increase with increasing blend ratio of HTCC. All the experimental results exhibit that the blends are miscible on the molecular scale. The blend fibers could be dyed with an acid dye. This enhanced ability of the blend fibers to be dyed with acid dyes could be useful for one‐step dyeing when mixed with other fibers, such as wool and nylon. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1620–1629, 2001     

Synthesis of antimicrobial silver nanoparticles on silk fibers via γ‐radiation

Antimicrobial silver nanoparticles (NPs) were successfully synthesized on the surface of silk fibers via γ‐ray irradiation. The products were characterized with scanning electron microscope (SEM), energy dispersion spectrum, and X‐ray diffraction. The results revealed that the silver particles with a diameter of less than 20 nm were immobilized and well dispersed on the surface of silk fibers. The antimicrobial capability against the gram positive bacterium Staphylococcus aureus and the washing stability of the silk fibers produced with different conditions were tested and found to be excellent. The silk fibers treated with 1 mM solution and 10 kGy γ‐radiation showed 96% antimicrobial activity and still kept above 85% antibacterial activity after 10 washing cycles. Moreover, a mechanism for the formation of silver NPs on silk fibers under γ‐radiation was generally discussed. The resulting silk fibers coated with silver NPs can be useful as functional fabrics in a range of applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Antibacterial properties of raw and degummed silk with nanosilver in various conditions

This article is concerned with the effects of nanosized silver colloids on the antibacterial properties of silk fibers against two kinds of bacteria: Staphylococcus aureus and Escherichia coli. Different concentrations of silver nanoparticles (Ag NPs; 10, 25, 50, and 100 ppm) were applied to silk fibers by an exhaust method. The effect of medium pH on the Ag NP uptake on the fibers was studied. Also, sodium carbonate and sodium chloride were added to the liquor as auxiliaries. Scanning electron microscopy was used to observe the morphology of the silk fibers. The antibacterial activity was examined by a bacterial counting method. Energy‐dispersive X‐ray spectroscopy was also used to show the elements on the surface of the silk fibers. We observed that the antibacterial activity increased with silver treatment. It also increased with decreasing pH, especially for the raw silk. The use of NaCl improved the uniformity of the Ag NPs on the fiber surface and increased the antibacterial activities. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Acylation of silk and wool with acid anhydrides and preparation of water-repellent fibers

Silk and wool fibers were acylated with two acid anhydrides, dodecenylsuccinic anhydride (DDSA) and octadecenylsuccinic anhydride (ODSA), at 75°C with N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO) as the solvent, the latter of which allowed higher weight gains to be reached. The weight gain and acyl content of wool was always higher than that of silk. Tensile properties of silk remained unchanged regardless of weight gain, whereas wool displayed a noticeably higher extensibility at high weight gain. Fine structural changes of acylated wool were detected by DSC analysis. Moisture regain and water retention of acylated silk and wool decreased significantly, whereas water repellency increased. SEM analysis showed the presence of foreign material firmly adherent to the surface of both silk and wool, whose amount increased with increasing weight gain. These deposits were attributed to the presence of the modifying agents at the fiber surface on the basis of the characteristic IR bands. The possible application of silk and wool fibers acylated with DDSA or ODSA for the preparation of water-repellent textile materials is discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2832–2841, 2001