The effect of casting solvent on the structural characteristics and miscibility of regenerated silk fibroin/Poly(vinyl alcohol) blends

Regenerated silk fibroin(SF)/Poly(vinyl alcohol)[PVA] blend films were prepared using different casting solvents, water and formic acid, to elucidate the effect of casting solvent on the structure and miscibility of SF/PVA blends. FTIR and XRD measurement suggested thatβ-sheet conformation of SF was not changed by addition of PVA in case of formic acid casting and the casting solvent determined the crystallized component of SF/PVA, leading to a different trend in the overall crystallinity between the two blends. The casting solvent had a dominant role in deciding phase behavior and molecular miscibility of blend films. SEM observation and DMTA measurement elucidated that water solvent produced phase-separated blend films while formic acid yielded one phase blend films with partial miscibility in molecular level indicating that the miscibility of SF blend can be improved by choosing a proper co-solvent.     

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.     

Blend films based on silk fibroin/hyaluronic acid

Protein and polysaccharide was the most important extracellular matrix in dermal tissue. In this study, Silk fibroin (SF) / hyaluronic acid (HA) blend films mimicking the dermal tissue components were prepared and investigated. The results indicated that HA and SF has a good miscibility, HA interfered with SF to form crystal structure. By using EDC as cross-linker, effective cross-linking function on SF and HA macromolecules was reacted, the water solubility of the blend films decreased obviously after being cross-linked by EDC. The existence of EDC could promote SF to form Silk I structure. L929 cells were seeded on these blend films and showed normal attachment morphology. Cell-matrix interactions established by newly formed extracellular matrix were observed after 5 days in culture. The MTT assay showed that cell proliferation on the SF/HA blend films were enhanced significantly compared with that on the SF and HA films. These new 2D SF/HA blend films provided a favorable microenvironment for the proliferation of L929 cells and hold a potential for dermal tissue regeneration.     

The effect of the processing factors on the physical properties of high shrinkable nylon composite yarns

This paper is aiming to develop high shrinkable differential shrinkage and mixed fibre nylon composite yarns by applying the high shrinkable polyester manufacturing technology. The wet and dry thermal shrinkages and mechanical properties of developed nylon composite yarns are measured and discussed with processing factors in the spinning and texturing processes. And the effects of the processing factors on the physical properties of high shrinkable nylon composite yarns are investigated. For this purpose, twenty seven nylon 30d/12f SDY were prepared with variation of spinning temperature, 2nd godet roller temperature and draw ratio on the spinning machine. The optimum spinning condition which showed maximum wet thermal shrinkage and stress was determined and high shrinkable nylon 30d/12f SDY spun under this optimum condition used as a core and three kinds of regular nylon filaments used as sheath were processed on the texturing machine with variation of 1st and 2nd heater temperatures. The optimum texturing process condition was decided through analysis of dry thermal shrinkage of these core and sheath nylon filaments. Finally, high shrinkable differential shrinkage and mixed fibre nylon composite yarns were made under the optimum texturing condition on the texturing machine, its wet thermal shrinkage was 13.8 %, which was much more higher than that of regular nylon composite yarns. The differential shrinkage effect of the developed nylon composite yarns was found in the yarn surface and cross section profiles by microscope and SEM.     

Characterization of PET/PP blend fiber and it’s application to wig

As PET (Polyester) fiber has better heat resistance than PVC fiber or modacryl fiber, it has been used as wig fiber for human hair alternatives. However, PET is heavier and has higher specific gravity than human hair, and therefore the authors attempted to make lighter wig fiber by blending PP (polypropylene) into PET by mixing the PET/PP blend with a compatibilizer, a ethylene-acrylic ester-GMA(EAG) component grafted material, to overcome poor compatibilities of PET and PP. The thermal properties of the PET/PP blend mixed with EAG were measured using DSC, and the results showed that EAG affected melting point and crystallization temperature of the blend polymer. As blend ratio of PP increased, specific gravity of blend fiber reduced and thermal shrinkage rate increased. Blend ratio of PP was greater for shorter lengths of initial curl, although curl loosening increased as time elapsed.     

The effects of blend composition and blending time on the ester interchange reaction and tensile properties of PLA/LPCL/HPCL blends

PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly(ε-caprolactone) (LPCL), and high molecular weight poly(ε-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable filament sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by¹H-NMR, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreased by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at 220 °C for 30–60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three polymers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.     

Effect of acrylonitrile content on the glass transition temperature and melt index of PVC/SAN blends

PVC and SAN are often mixed to compensate for the disadvantages of each polymer. Miscibility and thermal stability of PVC/SAN blend were investigated in this study by blending SAN polymer having 20, 24, 28, 32 % of acrylonitrile contents. Two polymers were mixed using a melt blending method with a single screw extruder. DSC them ogram was used to evaluate miscibility of the two polymers. SAN having 24 % of acrylonitrile showed the best miscibility with PVC. In order to evaluate degradation behavior, blended polymer was heat treated in DSC furnace and glass transition temperature was measured consecutively. Glass transition temperature increased continuously with annealing time due to degradation and cross-linking of polymer chains. Melt index of blended polymer was always higher than that of PVC.     

Improved thermal bonding behaviour of polypropylene non-wovens by blending different molecular weights of PP

Polypropylene filaments were spun from a mixture of PP chips of two different Melt Flow Index (MFI) (3 MFI and 35 MFI). A significant difference was observed in the melting characteristics of the resultant filaments from either of the individual components as observed from the DSC. The main difference being in the degree of melting achieved at any temperature in the initial stages of the melting range, which was found to be higher in case of the filaments spun from the blend. These filaments were then thermally bonded using silicon oil bath and heated roller method. Subsequently the bond strength of the filaments was measured on the Instron Tensile Tester using the loop technique. The values of the bond strengths obtained from the blend were compared with those made from the individual component. It was found that the bond strength of the bonds obtained from the blended filament at a given temperature was higher than that of the bonds made from the filaments of either of the individual components, which is also suggested by the DSC curves. The difference in the bond strength was found to be as high as 25% in case of the blend with 60:40 composition ratios of the 3 MFI and 35 MFI components respectively.     

Miscibility and performance evaluation of natural-flour-filled PP/PBS and PP/PLA bio-composites

This research evaluates the miscibility and performance of polypropylene (PP)/polybutylene succinate (PBS) and PP/polylactic acid (PLA) blend and natural-flour-filled, PP/PLA and PP/PBS blend bio-composites. The melting temperature (T _m ) and glass transition temperature (T _g ) of pure PP, PBS and PLA showed a single peak but differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) presented two peaks for the T _m and T _g of the PP/PBS and PP/PLA blends. These results indicated that the PP/PBS and PP/PLA blend systems existed as immiscible blends. These results were also confirmed by the scanning electron microscopy (SEM) micrographs of the tensile fracture surface of the PP/PBS and PP/ PLA blends. At a PP/PBS and PP/PLA blend ratio of 70/30, the tensile and flexural strengths of bamboo flour (BF)- and wood flour (WF)-filled, PP/PBS and PP/PLA blend bio-composites were similar to those of BF- and WF-filled, PP and PBS bio-composites. In addition, these strengths of maleic anhydride-grafted PP (MAPP)- and acrylic acid-grafted PP (AAPP)-treated, BF- and WF-filled, PP/PBS and PP/PLA blend bio-composites were higher than those of non-treated bio-composites.     

Thermal,swelling and stability kinetics of chitosan based semi-interpenetrating network hydrogels

The present study is focused on studying the swelling kinetics, thermal and aqueous stabilities, and determination of various forms of water in the chitosan (CS) and polyacrylonitrile (PAN) blend and semi-interpenetrating polymer network (sIPN). CS/PAN blend hydrogel films were prepared by solution casting technique. The blend film with optimum swelling properties was selected for the synthesis of sIPN. CS in the blend was crosslinked with the vapors of Glutaraldehyde (GTA) to prepare sIPN. The fabricated CS/PAN blend and sIPN hydrogels films were characterized with Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA) and field emission scanning electron microscope (FESEM). The kinetics of swelling, bound and unbound waters and aqueous stability were determined experimentally. FESEM showed good miscibility between CS and PAN, FTIR showed no chemical interaction between CS and PAN; however, it did show a doublet for the sIPN, TGA showed improved thermal stability and swelling kinetic followed second order kinetics. The degree of swelling of the sIPN hydrogels samples at room temperature varied from ~2200 % (with a fair degree of stability (~30 %)) to ~1000 % (with high degree of aqueous stability (43 %)) with increase in the crosslinking time. The calculated unbound water (W_UB) max., for the blend was 52.3 % whereas for the bound (W_B) the max., was 41.9 %. However, for sIPN hydrogel films, the W_UB water decreased (max. 21.0 %) where as the W_B increased (max. 52.0 %). The decrease in W_UB and increase in the W_B is attributed to the formation of a compact structure and increase in the contact area between the water and polymers in sIPN hydrogels due to the induction of new water contacting point in these hydrogel films, respectively.     

Silk fibroin/hyaluronic acid porous scaffold for dermal wound healing

The use of silk protein as a biomaterial has been studied for decades. In this study, silk fibroin (SF)/hyaluronic acid (HA) blend scaffolds were prepared by freeze-drying technique. The structure and properties of the blend scaffolds were examined and analyzed. The results demonstrated that the secondary structures of the SF/HA scaffolds were mainly amorphous and β-sheet structures. The pore radius and porosity of the scaffolds decreased with a decrease in the freezing temperature decrease and an increase in the HA ratio. The pore radius and porosity were regulated from 32.22 μm to 290.76 μm and from 74.1 % to 91.15 %, respectively. In vitro, the SF/HA scaffolds could support the fibroblast cell adhesion and proliferation and showed good cytocompatibility. In vivo, the SF/HA scaffolds were implanted into the dorsum of Sprague Dawley rats to evaluate their bioactivity for dermal tissue reconstruction. The vascular-like structures appeared more rapidly in SF/HA scaffolds than that in the PVA group, and a new dermal layer was formed, as determined by histological analysis. The SF/HA porous scaffolds have promise as a dermal substitute.     

Miscibility and crystallization behaviors of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends of various compositions were prepared by the solution-blending and melt-blending methods. The changes in miscibility and crystallization behaviors of the blends upon thermal treatment above the melting temperature of the blends at 280°C were investigated by using DSC, DMA,¹H NMR, and SAXS analyses. Without any thermal treatment, the blend systems were not miscible, and the thermal transitions, such as glass transition, cold crystallization, and crystal melting of the individual components were observed in the DSC and DMA analyses. With thermal treatment, though, they became miscible as the thermal transitions of each component disappeared and single glass transition peaks were observed in the thermal analysis. The chain randomness determined using¹H NMR spectroscopy revealed that thermal treatment at 280°C for more than 30 min brought about transesterification reactions between the PTT and PEN segments resulting in an increase in their miscibility. These results were confirmed by the small angle X-ray analysis conducted to determine the long period (L), the thickness of the crystalline lamella stack (l _c ), and the thickness of the amorphous region (l _a ). After short thermal treatment, the melt-blended sample followed the values for the individual components. However, with extended thermal treatment, the blend became homogeneous, possessing different crystalline morphologies which resulted in different values ofL, l _c , andl _a .     

Investigation of a-PVA/s-PVA hydrogels prepared by freezing-thawing method

The hydrogels of atactic poly (vinyl alcohol) (a-PVA) and syndiotactic poly (vinyl alcohol) (s-PVA) with different blend ratios were prepared by freezing-thawing processes. The effect of s-PVA on gelation behavior of the blend was investigated in terms of gelation temperature (T _gel) and hydrogel melting temperature (T _gm). And swelling behavior, crystallization, thermal properties, morphology of the blend hydrogels were also studied. With the increase of s-PVA, T _gel of the blend solution and T _gm of the blend hydrogels increase. Both crystallinity and crystallite dimensions based on the XRD profiles are nearly monotonically increasing functions of s-PVA content. FTIR results indicate the number of hydrogen bonds raises with s-PVA increasing. DSC results demonstrate s-PVA favors improvement of hydrogels thermal stability. According to SEM images of hydrogels, the increase of cross-linking caused by s-PVA in the blend hydrogels results in denser structure, which in turn leads to increased gel fraction (G) and Hardness. 50/50 (a-PVA/s-PVA) blend hydrogel has a denser structure with EWC of 73.6 %, hardness of 22.8 HA and T _m of 236.15 °C. The result indicates blending a-PVA and s-PVA is a useful method to form the hydrogel having good thermal stability and relative high degree of swelling.     

Properties of crosslinked waterborne polyurethane adhesives with modified melamine: Effect of curing time, temperature, and HMMM content

A series of crosslinked waterborne polyurethane (WBPU) adhesives were prepared by prepolymer synthesis. Modified melamine, hexamethoxymethyl melamine (HMMM) was used as the crosslinking agent. It was elucidated by FTIR and ¹H-NMR spectroscopy that the crosslinking reaction occurred between the polyurethane carboxyl acid salt groups and the HMMM methoxy groups. The hydrophobicity of the WBPU films increased after HMMM crosslinking. As the HMMM content was increased (increasing mole ratio of HMMM/dimethylol propionic acid (DMPA)), the water uptake (%) of the film decreased, and the water contact angle increased. The thermal stability, tensile strength, and initial modulus increased with increasing HMMM content up to an optimum value (mole ratio of HMMM/DMPA=0.5) at which point the maximum thermal stability, tensile strength, and initial modulus were recorded. The adhesive strength was found to be dependent on HMMM content, curing time, and temperature. The adhesive strength of crosslinked WBPU in the case of optimum HMMM content (8.46 wt%) was only slightly affected after immersing adhesive bonded nylon fabrics in water (for up to 2 days).     

Effects of low temperature plasma on wool and wool/nylon blend dyed fabrics

Knitted wool and wool/nylon blend dyed fabrics were treated with low temperature plasma (LTP) to achieve optimum shrink-resistance without impairing surface topography, colour or fastness to washing of the fabrics. As LTP tends to impair handle of the fabrics, both wool and wool/nylon blend fabrics were submitted to industrial softening and/or biopolymer treatments after LTP treatment, leading to hydrophilic wool and wool/nylon blend fabrics with improved shrink-resistance without any colour changes and good fastness to washing. The results obtained were compared with those obtained by an industrial shrink-resist treatment.     

Preparation of electrospun silk fibroin/Cellulose Acetate blend nanofibers and their applications to heavy metal ions adsorption

Silk fibroin (SF)/Cellulose Acetate (CA) blend nanofibrous membranes were prepared by electrospinning and their heavy metal absorbabilities were examined in an aqueous solution after ethanol treatment. The electrospun nanofibrous membranes were comprised of randomly oriented ultrafine fibers of 100–600 nm diameters. As a result of field emission electron microscope (FEEM), the anti-felting properties of the blend nanofibrous membranes were markedly improved after treatment with 100 % ethanol when SF was blended with CA. Metal ion adsorption test was performed with Cu²⁺ as a model heavy metal ion in a stock solution. The SF/CA blend nanofiber membranes showed higher affinity for Cu²⁺ in an aqueous solution than pure SF and pure CA nanofiber membranes. Especially, the blend nanofibrous membranes with 20 % content of CA had an exceptional performance for the adsorption of Cu²⁺, and the maximum milligrams per gram of Cu²⁺ adsorbed reached 22.8 mg/g. This indicated that SF and CA had synergetic effect. Furthermore, the parameters affecting the metal ions adsorption, such as running time and initial concentration of Cu²⁺, had been investigated. The results showed that the adsorption of the Cu²⁺ sharply increased during the first 60 min, the amount of metal ions adsorbed increased rapidly as the initial concentration increased and then slope of the increase decreased as the concentration further increased. This study provides the relatively comprehensive data for the SF/CA blend nanofibrous membranes application to the removal of heavy metal ion in wastewater.     

Influence of N-, P- and Si-based Flame Retardant Mixtures on Flammability,Thermal Behavior and Mechanical Properties of PA6 Composite Fibers

This research investigated the influence of two flame retardant (FR) mixtures consisting melamine cyanurate (MeCy) and aluminum diethylphosphinate (AlPi), and MeCy and sodium aluminosilicate (SASi) at different weight ratios, on the flammability, thermal behavior and mechanical properties of polyamide 6 (PA6) composite yarns produced by meltspinning. The morphological and chemical properties of PA6/FR filaments were investigated by scanning electron microscopy and Fourier-transform infrared spectroscopy, flame retardancy by vertical burning test UL-94, thermal behavior by thermogravimetric and differential scanning calorimetric analyses, and mechanical properties by tensile tests. The results indicate that within the UL 94 V2 rating, the composite yarns differed significantly from each other in their burning and dripping behavior. The incorporation of both mixtures, MeCy+AlPi and MeCy+SASi, into the PA6/FR yarns significantly decreased the afterflame time relative to pristine PA6, confirming a lower production of flammable volatiles. This phenomenon was attributed mainly to MeCy, which caused an immediate extinguishment of the flame after the withdrawal of the igniting flame. Compared to one component MeCy, the incorporation of the MeCy+SASi mixture enhanced the thermooxidative stability of the PA6/FR yarns because of their additive effect at higher concentrations. In contrast, an antagonistic effect was obtained for the MeCy+AlPi mixture, irrespective of the concentration. Since the incorporation of MeCy+SASi did not drastically reduce the tensile properties of filaments, this mixture enables the production of the PA6/MeCy+SASi composite yarns with the enhanced flame retardancy and thermo-oxidative stability.     

Spinodal phase separation and isothermal crystallization behavior in blends of VDF/TrFE(75/25) copolymer and poly(1,4-butylene adipate) (I)

Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(1,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼34 °C above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (180 °C) to a two-phase region (205∼215 °C). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.     

Characterization of pre-gelatinized maize starch-zein blend films produced at alkaline pH

Biodegradable materials are considered as alternative to synthetic materials to alleviate the environmental burdens caused by petroleum based synthetic materials. Biopolymer blends have been extensively researched to improve the material properties of biopolymer-based materials for potential replacement of non-biodegradable materials. Compatible blends of pre-gelatinized maize starch (uncomplexed or complexed with stearic acid) and commercial zein in 0.1 M NaOH were used to produce the films. The effect of the ratio of uncomplexed starch, zein and starch complexed with stearic acid on the tensile, water vapour and oxygen barrier and thermal properties of the composite films were investigated. Blending zein with starch increased the tensile strength and reduced the tensile strain compared to starch films. Addition of starch complexed with stearic acid to the blend further increased the tensile strength and decreased the elongation at break. Both blending zein with starch and addition of starch complexed with stearic acid to the blend decreased the water vapour permeability, however, the oxygen permeability was increased compared to starch films. The starch-zein blend films had an endothermic temperature and thermal transition in between the uncomplexed maize starch and zein films suggesting possible compatibility at molecular level. The microstructure of the blend films also showed good miscibility of pre-gelatinized starch and commercial zein. In conclusion alkaline solvent (0.1 M NaOH) could produce compatible starch-zein blends that can produce films with improved tensile strength and water vapour permeability compared to starch films.     

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.