Effect of Sericin Content on the Structural Characteristics and Properties of Electro-spun Regenerated Silk

Electro-spun silk web has attracted attention for biomedical applications because of its excellent bio-compatibility and facile fabrication method. Because biomedical applications require various performances of silk web, many studies have been conducted on the effect of the variables associated with their preparation on the structure and properties of silk web. In the present study, the effect of residual sericin content on the morphology, structural characteristics, and properties of electrospun regenerated silk web was examined. The regenerated silk without sericin (i.e., silk with 100 wt% fibroin) did not show good electro-spinnability. However, the electro-spinnability improved remarkably above a sericin content of 0.6 wt%. The crystallinity index of the electro-spun silk increased at 0.6 wt% sericin content and decreased above 8.2 wt% sericin. The mechanical properties of the electro-spun silk webs showed a similar trend as their crystallinity indices. The breaking strength and elongation improved significantly at 0.6 wt% sericin content and both parameters gradually decreased above this value. The thermal stability of the silk web decreased slightly upon increasing the sericin content.     

Key Characteristics of a Novel Silk Yarn from Fresh Cocoons

We studied the key characteristics of a novel silk yarn reeled from fresh cocoons. Compared with traditional silk yarn, this novel silk yarn displayed better mechanical properties, especially in terms of a higher breaking stress and toughness, and exhibited a different surface morphology. A cross-sectional observation and the sericin content results illustrated that different sericin coatings on the silk yarn reeled from fresh cocoons surface did not improve the mechanical properties. The degumming and tensile testing analysis indicated that degummed silk fibroin of novel silk yarn is able to resist deformation and fracture better than silk fibroin of traditional silk yarn. The FTIR results revealed that the selected techniques is an important contributor to the silk fibroin mechanical properties, because novel technique brought higher percentage beta-sheet structures in novel silk yarn fibroin than traditional silk yarn. The new technique that using novel silk yarn has improved its mechanical properties and it is expected that the silk yarn with superior mechanical properties could be used in fabrics transistors, electrodes and reinforced biomaterials.     

Metal ion adsorbability of electrospun wool keratose/silk fibroin blend nanofiber mats

In this study, electrospun wool keratose (WK)/silk fibroin (SF) blend nanofiber was prepared and evaluated as a heavy metal ion adsorbent which can be used in water purification field. The WK, which was a soluble fraction of oxidized wool keratin fiber, was blended with SF in formic acid. The electrospinnability was greatly improved with an increase of SF content. The structure and properties of WK/SF blend nanofibers were investigated by SEM, FTIR, DMTA and tensile test. Among various WK/SF blend ratios, 50/50 blend nanofiber showed an excellent mechanical property. It might be due to some physical interaction between SF and WK molecules although FTIR result did not show any evidence of molecular miscibility. As a result of metal ion adsorption test, WK/SF blend nanofiber mats exhibited high Cu²⁺ adsorption capacity compared with ordinary wool sliver at pH 8.5. It might be due to large specific surface area of nanofiber mat as well as numerous functional groups of WK. Consequently, the WK/SF blend nanofiber mats can be a promising candidate as metal ion adsorption filter.     

Effect of molecular weight and concentration on crystallinity and post drawing of wet spun silk fibroin fiber

Wet spun silk fibroin (SF) filaments have attracted considerable attention because of their potential in biotechnological applications including surgical sutures, tissue engineering and wound dressing. Although the molecular weight (MW) of polymers is one of key factors affecting the wet spinnability of dope along with the structural characteristics and properties of wet spun filament, no related study has been conducted. In this study, regenerated SFs with different MWs and concentrations were prepared by wet spinning. The effects of the SF concentration and MW on 1) wet spinnability and rheology of silk dope solution and 2) crystallinity index and post drawing performance of wet spun silk filament were examined. Their relationships were also investigated. The rheological measurements showed that an 80 mPa·s viscosity is needed to obtain a continuous wet spun SF filament. As the MW of SF increased, the peak position of the maximum draw ratio shifted to a lower SF concentration with a concomitant increase in the maximum draw ratio value at the peak. Interestingly, the crystallinity index obtained from Fourier transform infrared spectroscopy (FTIR) revealed a similar trend to the maximum draw ratio suggesting that the post drawing ability is strongly affected by the quantity of short-ordered crystalline regions in wet spun SF filaments. On the other hand, X-ray diffraction did not detect any crystallinity change in the SF filament produced from the formic acid solvent system. It was concluded that MW strongly affected the dope solution viscosity and the crystallinity index from FTIR and these determined the fiber formation of dope and post drawing performance of fiber.     

A new consolidation system for aged silk fabrics: Interaction between ethylene glycol diglycidyl ether,silk Fibroin and Artificial Aged Silk Fabrics

Consolidation of fragile historic silks is of great importance for further displays and researches. An effective and convenient method to consolidate aged silk fabric has been proposed by using a silk fibroin (SF)/ethylene glycol diglycidyl ether (EGDE) consolidation system. Artificial aged silk fabrics treated with SF/EGDE show great improvement in mechanical properties. The chemical reaction between EGDE and silk fabrics has been proved in previous paper. And in this paper, mechanical test, field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrum (FTIR) test and amino acid analysis (AAA) were applied to illustrate the interactions between SF and silk fabric, EGDE and SF. Results show that SF takes part in the consolidation in the form of adhesions on the surface of silk fibers. The chemical reactions and film adhesion are both responsible for the improvements of mechanical properties in the consolidation.     

Preparation and characterization of silk sericin/glycerol/graphene oxide nanocomposite film

Sericin (SS) is a protein that is secreted by silkworms, but it is usually discarded during the degumming process. To obtain and make use of the sericin, we prepared sericin/glycerol/graphene oxide nanocomposite film. The inherent brittleness of pure sericin film was improved by the addition of glycerol (Glc) as a plasticizer. To compensate for the reduced stiffness, we added graphene oxide (GO) into the SS/Glc film. At concentrations of up to 0.8 wt% relative to SS, GO dispersed evenly in the SS matrix without any agglomeration. The maximum tensile strength (9.5±0.7 MPa) and Young’s modulus (414.4±23.2 MPa) were obtained when the GO content was 0.8 wt% relative to SS. The elongation of SS/Glc/GO nanocomposite film also increased by approximately 40 % compared to SS/Glc film. The strong interfacial interaction between the SS and the GO was responsible for the increased stiffness. The increased elongation was due to the reduced crystallinity of the sericin matrix in the presence of GO.     

Air-gap spinning of cellulose/ionic liquid solution and its characterization

In order to study the effects of the spinning conditions on the structure and the properties of the regenerated fiber, cellulose was dissolved in ionic liquid and then spun into fiber using an air-gap spinning process. The solution concentration, the take-up speed and the fixation of the fiber ends during coagulation improved the crystallinity and the tensile strength at the same time. The fiber surface became smooth by addition of DMF (dimethylformamide). However, it decreased the crystallinity and the tensile strength of the fibers. We revealed that the developed structure during coagulation determined the morphology and the properties of the fibers. The co-solvent resulted in smooth surface of the fiber and also changed the mechanical properties.     

Electrospinning of <Emphasis Type="Italic">Bombyx mori</Emphasis> silk fibroin nanofiber mats reinforced by cellulose nanowhiskers

Cellulose nanowhisker (CNW) reinforced electrospun Bombyx mori silk fibroin (SF) nanofibers were fabricated. The morphology, structure, and mechanical properties of nanofibers were investigated by FE-SEM, TEM, FTIR, and tensile testing. It was found that the nanofiber size decreased obviously from 250 nm in the unreinforced mat to 77–160 nm in the CNW reinforced mats depending on the CNW content due to the increased conductivity of spinning dope. In the reinforced mats, the CNWs were embedded in the SF matrix separated from each other, and aligned along the fiber axis. There was a positive correlation between the CNW content and the tensile strength and Young’s modulus of reinforced mats. However the strain at break dropped gradually with the increase of CNW. When the CNW content was 2 w/w%, the tensile strength and Young’s modulus of reinforced SF nanofiber mats were about 2 times higher than those of unreinforced mat.     

High water content silk protein-based hydrogels with tunable elasticity fabricated via a Ru(II) mediated photochemical cross-linking method

Silk is very promising in the field of biomaterials as a natural biomacromolecule. Silk protein can be made into various forms of materials, including hydrogels. However, silk protein-based hydrogels have not attracted much attention due to its weak mechanical properties. Here, we report high water content silk protein-based hydrogels with tunable elasticity which were fabricated through Ru(II) mediated photochemically cross-linking tyrosine residues in regenerated silk protein. The regenerated silk protein was characterized by Fourier transform infrared spectroscopy (FTIR). The gelation kinetics of the silk protein was studied by rheology measurements. The compressive mechanical properties of the silk protein-based hydrogels was investigated using compressive tests and dynamic mechanical analysis (DMA). Compressive modulus of the hydrogels reached 349±64 MPa at 15 % strain. The fabricated silk protein-based hydrogels were also characterized by Scanning electron microscopy (SEM), revealing an interconnected porous network structure, typical of hydrogels, with an average pore size of approximately 130 μm. Finally, biocompatibility of the silk protein-based hydrogels was demonstrated through cell culture studies using a human fibroblast cell line, HFL1. The reported silk protein-based hydrogels represent a promising candidate for biomaterial applications.     

Effect of degree of polymerization on the mechanical properties of regenerated cellulose fibers using synthesized 1-allyl-3-methylimidazolium chloride

1-Ally-3-methylimidazolium chloride ([AMIM]Cl) was successfully synthesized and was used as a green spinning solvent for cellulose. The celluloses of various degrees of polymerization (DP) were dissolved in the [AMIM]Cl to obtain 5 % (w/w) cellulose solutions, which were regenerated to cellulose fibers through wet spinning process. Of three different regenerated cellulose fibers with different DPs, a DP of 2,730 was gave the strongest regenerated fiber without drawing having a tensile strength of 177 MPa and an elongation at break of 9.6 % respectively, indicating that celluloses of higher molecular weight can be entangled and oriented more easily. Also maximum draw ratio of the as-spun fibers increased from 1.2 to 1.7 with increasing degree of polymerization leading to a tensile strength and modulus of 207 MPa and 48 GPa, respectively. Particularly the tensile modulus was substantially higher than those of lyocell and high performance viscose fibers of 20 GPa or less. The higher DP of pristine cellulose was critical in increasing the mechanical properties such as tensile strength and elongation at break of the as-spun fibers coupled with higher tensile modulus after drawing.     

An effective and simple process for obtaining high strength silkworm (Bombyx mori) silk fiber

This article describes a new process for strengthening natural silk fibers. This process is simple yet effective for mass production of high strength silk fibers, enabled by drawing at a lower temperature and immediately heat setting at a higher temperature. The processing conditions were investigated and optimized to improve the strength. Silk fibers drawn to the maximum ratio at room temperature and then heat set at 200 °C show best tensile properties. Some salient features of the resulting fibers are tensile strength at break reaching 533±10.2 MPa and Young’s modulus attaining 12.9±0.57 GPa. These values are significantly higher than those of natural silk fibers (tensile strength increased by 44 % and Young’s modulus by 135 %). Wide-angle X-ray diffraction and FTIR confirm the transformation of silk I to silk II crystalline structure for the fiber obtained from this process. DSC and TGA data also provide support for the structural change of the silk fiber.     

Mechanical and thermal degradation behavior of sisal fiber (SF) reinforced recycled polypropylene (RPP) composites

The present investigation focuses on the effect of fiber surface treatment on the mechanical, thermal and morphological properties of sisal fiber (SF) reinforced recycled polypropylene (RPP) composites. The surface of sisal fiber was modified using different chemicals such as silane, glycidyl methacrylate (GMA) and O-hydroxybenzene diazonium chloride (OBDC) to improve the compatibility between fiber surface and polymer matrix. The experimental results revealed an improvement in the tensile strength to 11 %, 20 % and 31.36 % and impact strength to 78.72 %, 77 % and 81 % for silane, GMA and OBDC treated sisal fiber reinforced recycled polypropylene (RPP/SF) composites respectively as compared to RPP. The thermo gravimetric analysis (TGA), Differential scanning calorimeter (DSC) and heat deflection temperature (HDT) results revealed improved thermal stability as compared with RPP. The morphological analysis through scanning electron micrograph (SEM) supports improves surface interaction between fiber surface and polymer matrix.     

Investigation on mechanical behaviour of twisted natural fiber hybrid composite fabricated by vacuum assisted compression molding technique

Nowadays, automotive, packaging and sport equipment industries are using natural fibre based composite materials as they are cheap, abundantly available and having a lot of ecological advantages. The main objective of this paper is to introduce a new concept of fibre twisting and to investigate the effect of twisting and the fibre orientation on the mechanical properties of bio degradable green composites. Here, the composites are fabricated by vacuum assisted compression molding technique in which the problems of hand lay process are eliminated. Here, two fibers namely twisted neem and twisted kenaf are sandwiched between layers of glass fibres to enhance the stiffness and strength of the laminates. Initially, the fibers are alkalized to increase the mechanical properties. The result shows that there is a significant improvement in mechanical properties of composites due to the presence of twisted fibers. It also shows the influence of fiber orientation on mechanical properties.     

Properties and performance of polypyrrole (PPy)-coated silk fibers

Different silk substrates in form of spun silk tops, nonwoven web, yarn, and fabric were coated with electrically conducting doped polypyrrole (PPy) by in situ oxidative polymerization from an aqueous solution of pyrrole (Py) at room temperature using FeCl₃ as catalyst. PPy-coated silk materials were characterized by optical (OM) and scanning electron (SEM) microscopy, FT-IR spectroscopy, and thermal analysis (DSC, TG). OM and SEM showed that PPy completely coated the surface of individual silk fibers and that the polymerization process occurred only at the fiber surface and not in the bulk. Dendrite-like aggregates of PPy adhered to the fiber surface, with the exception of the sample first polymerized in the form of tops and then spun into yarn using conventional industrial machines. FT-IR (ATR mode) showed a mixed spectral pattern with bands typical of silk and PPy overlapping over the entire wavenumbers range. DSC and TG showed that PPy-coated silk fibers attained a significantly higher thermal stability owing to the protective effect of the PPy layer against thermal degradation. The mechanical properties of silk fibers remained unchanged upon polymerization of Py. The different PPy-coated silk materials displayed excellent electrical properties. After exposition to atmospheric oxygen for two years a residual conductivity of 10–20 % was recorded. The conductivity decreased sharply under the conditions of domestic washing with water, while it remained essentially unchanged upon dry cleaning. Abrasion tests caused a limited increase of resistance. PPy-coated silk tops were successfully spun into yarn either pure or in blend with untreated silk fibers. The resulting yarns maintained good electrical properties.     

Effects of drawing speed and water on microstructure and mechanical properties of artificially spun spider dragline silk

The effects of drawing speed and water on the microstructures and mechanical properties of Araneus Ventricosus spider dragline silk were investigated with polarized Raman spectroscopy and mechanical property tester. The major ampullate silk (MAS), spider dragline silk was made by drawing from major ampullate glands of Araneus Ventricosus spider at the rates of 1, 10, 20, 40, and 110 mm/s, respectively. It was found that MAS silk drawn at 20 mm/s contained the most of β-sheet polypeptides with the high orientation and the least of α-helix. The results also revealed that dragline silk spun at aqueous condition (WDS) had lower content and orientation of β-sheets than those at ambient condition (DDS); the existence of water led to smaller tensile strength at break and initial modulus, but larger tensile strain at break of dragline silk.     

Enhanced mechanical properties of silk fibroin-based composite plates for fractured bone healing

We successfully fabricated bacterial cellulose/silk fibroin (BC/SF) composite plates having similar strength to that of human cortical bone (12.8–17.7 GPa). The mechanical properties of the BC/SF composite plates were investigated at various BC nanofiber contents. The BC nanofibers acted as good reinforcements for the stress transfer produced by the interactions between the BC nanofibers and the SF matrix, as confirmed by the molecular deformation of the BC nanofibers. The BC/SF composite plates have a promising potential as a replacement material for existing metal bone plate.     

Characterization of plant and animal based natural fibers reinforced polypropylene composites and their comparative study

Natural fibers are largely divided into two categories depending on their origin: plant based and animal based. Plant based natural jute fiber reinforced polypropylene (PP) matrix composites (20 wt% fiber) were fabricated by compression molding. Bending strength (BS), bending modulus (BM), tensile strength (TS), Young’s modulus (YM), and impact strength (IS) of the composites were found 44.2 MPa, 2200 MPa, 41.3 MPa, 750 MPa and 12 kJ/m², respectively. Animal based natural B. mori silk fiber reinforced polypropylene (PP) matrix composites (20 wt% fiber) were fabricated in the same way and the mechanical properties were compared over the silk based composites. TS, YM, BS, BM, IS of silk fiber reinforced polypropylene composites were found 55.6 MPa, 760 MPa, 57.1 MPa, 3320 MPa and 17 kJ/m² respectively. Degradation of composites in soil was measured upto twelve weeks. It was found that plant based jute fiber/PP composite losses its strength more than animal based silk fiber/PP composite for the same period of time. The comparative study makes it clear that mechanical properties of silk/PP composites are greater than those values of jute/PP composites. But jute/PP composites are more degradable than silk/PP composites i.e., silk/PP composites retain their strength for a longer period than jute/PP composites.     

Structure and properties of silk fibroin modified cotton

In this research, a novel cotton fiber with a silk fibroin (SF) coating was prepared by the oxidation of a cotton thread with sodium periodate and subsequent treatment in a solution of silk fibroin. The structures of both the oxidized cotton samples and the SF modified cotton samples were investigated by Fourier transform infrared (FT-IR) in combination with X-ray photoelectron spectroscopy (XPS) analysis. Other performances such as surface morphology and breaking strength were also studied. The results indicated that the weight of the oxidized cotton samples increased during SF treatment, while that of the un-oxidized cotton (pure cotton) samples reduced after SF treatment. Compared with the pure cotton samples, the oxidized cotton clearly showed a characteristic absorption band at 1730 cm⁻¹ due to the stretching vibration of the C=O double bond of the aldehyde group. After being treated with the SF solution, the oxidized cotton fiber showed a weakened characteristic absorption band at 1730 cm⁻¹ and a new absorption band at round 1540 cm⁻¹, suggesting the formation of C-N bond between aldehyde groups in the oxidized cotton and primary amines in the silk fibroin. The results were also confirmed by XPS analysis. Compared with the oxidized cotton samples, the SF treated cottons had relatively smooth surfaces, similar breaking strength, and the improved wrinkle recovery angles. The results in this research suggest that cotton based materials with protein coating can be achieved without using any other crosslinking agents by the method introduced.     

The effect of multi-walled carbon nanotubes on the molecular orientation of poly(vinyl alcohol) in drawn composite films

Poly(vinyl alcohol) (PVA)/multi-walled carbon nanotube (MWNT) composite films were prepared by casting a DMSO solution of PVA and MWNTs, whereby the MWNTs were dispersed by sonication. A significant improvement in the mechanical properties of the PVA drawn films was achieved by the addition of a small amount of MWNTs. The initial modulus and the tensile strength of the PVA drawn film increased by 30% and 45% respectively, with the addition of 1 wt% MWNTs, which are close to those calculated from the rule of mixtures, and were strongly dependent upon the orientation of the PVA matrix. The mechanical properties, however, were not improved with a further increase in the MWNT content. The orientation of MWNTs in the composite was not well developed compared to that of the PVA matrix. This result suggests that the improvement of the molecular orientation of the PVA matrix plays a major role in the increase of the mechanical properties of the drawn PVA/MWNT composite films.     

Preparation,mechanical properties and microstructure of polyoxymethylene fiber through melt spinning and hot drawing by using injection-molding grade resins

The polyoxymethylene (POM) fiber was melt spun by use of different commercial grades of POM resin, and the effect of post-drawing on mechanical properties and microstructures was investigated extensively. The fiber obtained from the POM resin with a higher melt flow index (MFI) exhibits a better hot-drawing capability and also achieves a greater ultimate draw ratio. The mechanical evaluation reveals that the tensile strength and elastic modulus of POM fiber are improved significantly after post-drawing compared to the as-spun fibers. Although the greater draw ratios result in higher mechanical strength and modulus for the POM fiber, the fiber obtained from the POM resin with an MFI of 13.0 g/10 min achieves the optimal mechanical performance at the ultimate draw ratio. The morphologic and structural developments of POM fiber were studied by scanning electronic microscopy and X-ray powder diffraction. The results indicate that the POM fiber spun by the resin with an MFI of 13.0 g/10 min has a smooth lateral surface and a compact cross section after post-drawing. The fiber samples spun by the POM resins with low MFIs show some hollow disfigurements as well as a rough surface at the ultimate draw ratio, whereas the fiber obtained from the resin with a high MFI of 27.0 g/10 min presents the ununiformity of diameter after post-drawing. The POM fibers achieve a crystalline orientation during the hot-drawing process, which results in a transformation from the spherulitic crystals to the lamellar structure in the drawing direction. The level of crystalline orientation can be improved with an increase of draw ratio and thus results in a high modulus and strength for the resulting POM fiber samples. In addition, the thermal analysis indicates that the crystallinity of the as-spun fibers can be enhanced by post-drawing due to the orientation-induced crystallization.