Preparation and characterization of bacterial cellulose/hydroxypropyl chitosan blend as-spun fibers

In the work, N-methylmorpholine-N-oxide monohydrate (NMMO·H₂O) was used as a solvent to solve bacterial cellulose (BC) and hydroxypropyl chitosan (HPCS) together, and regenerated bacterial cellulose (RBC)/HPCS blend as-spun fibers were prepared by blending BC with HPCS via wet-spinning in the Lyocell process. Structure and properties of the blend as-spun fibers were characterized by different techniques, together with the antibacterial activity of the blend as-spun fibers against Staphylococcus aureus. Results revealed that HPCS was mixed with BC very well. The blend as-spun fibers showed a rough and folded surface morphology and an interior pore structure on the cross-section. Compared with pure RBC as-spun fibers, the blend as-spun fibers had lower degree of crystallinity and thermal stability. Although extension at break of the blend as-spun fibers was lower than the pure RBC as-spun fibers, their tensile strength and modulus had been enhanced obviously. The blend as-spun fibers were also found to exhibit excellent antibacterial activities against S. aureus.     

Manufacture and performance of O-carboxymethyl chitosan sodium salt/cellulose fibers in N-methylmorpholine-N-oxide system

A series of O-carboxymethyl chitosan sodium salt (NaCMCh) with different degree of substitution (DS) of -CH₂COONa agent were successfully prepared by altering the reaction temperature and time. Both fourier transform infrared spectroscopy (FTIR) and ¹³C-Nuclear Magnetic Resonance (¹³C-NMR) were used to study the structure of NaCMCh. And the impact of DS on the antibacterial activity of NaCMCh was investigated. Then, the NaCMCh with optimal antibacterial activity was selected to prepare NaCMCh/cellulose fibers in N-methylmorpholine-N-oxide (NMMO) system. The structure, crystallization behavior, thermal property and morphology of obtained fibers were carefully studied with FTIR, Wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermal gravimetric (TG) and scanning electron microscope (SEM), respectively. Meanwhile, the antibacterial activity as well as mechanical properties of resultant fibers was also investigated. The results demonstrated that the fibers had strong antibacterial activity against Escherichia coli (E. coli), acceptable mechanical properties and good water retention.     

Novel fibers prepared from cellulose in NaOH/thiourea/urea aqueous solution

The regenerated cellulose fibers were prepared by wet-spinning from NaOH/thiourea/urea aqueous solvent system for the first time. The effects of coagulation and stretch conditions on the structure, morphology, and mechanical properties of the prepared fibers were investigated by wide-angle X-ray diffraction (WAXD), scanning electron microscope (SEM), and tensile tester, respectively. When the cellulose spinning dope was coagulated in 10% H₂SO₄/12.5% Na₂SO₄ aqueous solution at 15 °C, the prepared fibers had a typical crystalline structure of cellulose II and circular cross-sectional shapes with smooth surface and slightly high tensile properties to viscose fibers.     

Preparation and radiopaque properties of chitosan/BaSO4 composite fibers

Chitin and chitosan have been extensively investigated as a matrix of organic/inorganic composite. Barium, one of the radiopaque inorganic materials, can provide chitosan with radiopaque property by blending of chitosan and BaSO₄. The filtered and deaerated chitosan/BaCl₂ solutions were extruded into NaOH and Na₂SO₄ coagulation bath through a nozzle by gear pump. BaSO₄ was synthesized by the reaction between BaCl₂ and Na₂SO₄ in the coagulation bath, in which acidic chitosan solution was also solidified at the same time. In XRD, the introduction of BaSO₄ into chitosan fibers reduced the inherent peak of chitosan fibers. In angiographic observation, chitosan/BaSO₄ hybrid fibers exhibited the clear contrast images which become clear with an increase in BaSO₄ content.     

Structural factors and physical properties of needle-punched nonwovens based on Co-PET/PA bicomponent fibers via alkali treatment

Needle-punched nonwovens are widely used in industrial fields. However, they are limited to some applications such as high-efficiency filters, high-performance synthetic leathers, and high-absorption wipes because of their low surface area and large pore size. In this study, needle-punched nonwovens composed of Copolyethylene terephthalate (Co-PET)/Polyamide (PA) sea-island bicomponent fibers were treated in NaOH solution with various conditions for preparing nonwovens composed of ultra-fine fibers. The effect of NaOH concentration and treatment temperature on the structural factors and physical properties of nonwovens was investigated. The morphological structures of Co-PET and PA components were analyzed by scanning electron microscope. After alkali treatment, fiber diameter was significantly reduced from 23.65 to 3.95 μm, specific surface area of nonwovens increased more than five times, calculated and experimental mean pore diameter decreased by 83.6 % and 20.8 %, respectively. By increasing NaOH concentration and treatment temperature, pore diameter was reduced, thereby decreasing the air permeability of nonwovens. Meanwhile, tensile strength increased and tearing strength decreased as NaOH concentration and treatment temperature were increased in both machine and cross direction, respectively. The treatment temperature of alkali treatment was significantly influenced by the physical properties of nonwovens.     

Extraction of cellulose nanowhiskers from natural fibers and agricultural byproducts

In this work the feasibility of extracting cellulose from cotton, sisal and flax fibers, corn stover and rice husk by means of usual chemical procedures such as acid hydrolysis, chlorination, alkaline extraction, and bleaching was analyzed. Cellulose nanowhiskers from these sources, and from commercial cellulose, were produced by the acid hydrolysis of the obtained celluloses. The final products were characterized by means of Thermogravimetric Analysis (TGA), Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), Scanning Electronic Microscopy (SEM) and Atomic Force Microscopy (AFM). The chemical procedure used to obtain cellulose nanowhiskers was effective in all cases but differences on the thermal stability, chemical composition, crystallinity and morphology were found due to the dissimilar nature of the different sources. Thus, this work demonstrates that the morphology and physical properties of cellulose nanowhiskers synthesized by the same conditions are strongly dependent on their source.     

Preparation and characterization of aminobenzyl cellulose by two step synthesis from native cellulose

Synthesis and structural characterizations of nitro- and aminobenzyl cellulose were carried out. Cellulose derivatives were synthesized by etherification. Nitrobenzylation produced 80 % yield by treating a mixture of microcrystalline cellulose, 4-dimethyl aminopyridine, and 4-nitrobenzyl chloride at 80 °C for 10 h. Nitrobenzyl cellulose was then reduced to aminobenzyl cellulose with 93 % yield using indium metal in ethanol and saturated aqueous ammonium chloride. In addition to their structural characterizations by FT-IR and ¹³C CP/MAS NMR, TGA will also be described. These reactions serve as models for future cotton fiber finishing technology with applications in flame resistance.     

Evaluation of procedures to quantify solvent retention in electrospun fibers and facilitate solvent removal

Electrospun fiber scaffolds crafted from polyesters are studied extensively for potential tissue engineering applications. For translation of electrospun fibers into the clinic, the FDA requires analysis and quantification of any organic solvent that may be retained in the fibers since many organic solvents can negatively affect cells and tissues. If a significant amount of solvent is retained, then developing procedures for efficient solvent removal may enhance the clinical potential of these materials. In this study we use fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and nuclear magnetic resonance spectroscopy (NMR) to analyze solvent retention. A correlative analysis shows that both FTIR and TGA accurately predicted retention of two different solvents (HFP and chloroform) in our electrospun PLLA scaffolds, thus validating these procedures. We also assess the efficacy of various fiber treatment methods to facilitate organic solvent removal and conclude that submersion in 70 % ethanol and heat treatment at 100 °C were the most efficient methods of removing solvent from electrospun PLLA fibers.     

Preparation,structure and properties of boron modified high-ortho phenolic fibers

Boron modified high-ortho phenolic fibers (o-BPFs) were prepared by melt-spinning from boron modified highortho phenolic resins (o-BPRs) with the weight-average molecular weight of 4973 g/mol, followed by being cured in a solution of formaldehyde and hydrochloric, and then heat-treated under high temperature. Gel permeation chromatography (GPC) and nuclear magnetic resonance spectroscopy (NMR) were used to measure the average molecular weight and ortho/para (o/p) ratio of o-BPRs. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were used to characterize the chemical and morphological structures of o-BPRs and o-BPFs. Thermogravimetric analysis (TGA) was employed to examine the thermal stability properties of different resins and fibers and the tensile strength of fibers was measured by a tensile tester. It was found that under proper curing and heat-treatment conditions, the tensile strength of o-BPFs reached 213.6 MPa and the char yield in N₂ atmosphere at 800 °C attained 75.4 %. Compared with phenolic fibers (PFs), the decomposition temperatures at 5 % weight loss of o-BPFs in N₂ and air atmospheres were increased by 156.8 °C and 219.0 °C, respectively.     

Preparation and properties of 2-(2-aminoethoxy) ethyl chitosan/cellulose fiber using N-methylmorpholine-N-oxide process

N-methylmorpholine-N-oxide (NMMO) is used widely in the manufacturing of man-made cellulose fibers and functional lyocell fibers due to its environment-friendly advantage. Although chitosan is known as a natural antibacterial polymer it has poor solubility in neutral to basic medium and the antibacterial activity is shown only in acidic medium. Chitosan’s poor solubility in NMMO is the disadvantage for the production of antibacterial lyocell fibers. This paper investigates a more “NMMO soluble” derivative of chitosan, 2-(2-aminoethoxy) ethyl chitosan (AECS). AECS has greatly improved solubility in NMMO hydrate, and stronger antibacterial activity than chitosan. AECS was introduced to modify the lyocell fiber spun in a co-solution of cellulose and AECS in NMMO hydrate. The physical properties and antibacterial activity of the fibers were examined and the results indicated that the modified lyocell fiber, containing more than 2 wt% of AECS, exhibits good antibacterial activity against E. coli and slightly decreased tensile strength compared with unmodified fibers.     

Preparation and characterization of modified collagen/PAN blending fibers

Graft modification of collagen with acrylonitrile in concentrated aqueous solution of sodium thiocyanate (NaSCN) is developed in this paper. This modification can largely change it’s solubility in water and can be applied in fiber production. Grafting modified collagen is characterized by infrared spectrum and wide angle X-ray diffraction. Wet spinning of PAN fibers containing several content of modified collagen is performed. The tests about these fibers show that breaking strength and sonic orientation decrease as the amount of collagen is raised. The addition of collagen can largely improve the moisture regain of PAN fiber. Micro-appearance of fibers observed under scanning electron microscope (SEM) presents circular cross section and longitudinal grooves on surface, the depth of grooves increases with the increasing draw ratio.     

Preparation and antibacterial properties of nanocomposite fibers made of polyamide 6 and silver-doped hydroxyapatite

Nanocomposite fibers of polyamide 6 (PA6) and hydroxyapatite (HA) were prepared and doped with silver to investigate antibacterial activities due to good potential for textile modification. Nano-sized HA could be synthesized using agarose and ethanol as thickener and washing medium, respectively. The PA6/HA nanocomposite fibers could be doped with silver by dipping the fibers having HA in aqueous AgNO₃ solution containing 300 ppm of Ag ion for 1 min utilizing HA as a carrier to load silver through ion-exchange mechanism. It was found that silver was successfully doped to PA6/HA nanocomposite fibers from the EDS spectra. The nanocomposite fibers containing 3.3 wt% of HA after silver doping demonstrated such excellent antibacterial activities against K. pneumonia and E. coli that they are expected to serve as functional antibacterial materials in various application fields.     

Preparation and characterization of carboxymethyl cellulose nonwovens by a wet-laid process

In this study, micro-porous carboxymethyl cellulose (CMC) nonwovens were prepared by carboxymethylation of cellulose nonwovens produced by a wet-laid process and their properties were investigated for potential applications as adhesion prevention barriers. After carboxymethylation, the thickness and mean pore size of the cellulose nonwovens were increased, whereas their pore size distribution became narrower. Tensile strength of cellulose nonwovens was proportional to basis weight, and dramatically increased after carboxymethylation. CMC nonwovens immediately absorbed a phosphate buffered saline solution and showed swollen phase within 1 min. It was found that the thickness and pore size distribution of CMC nonwovens could be easily controlled by the wet-laid process. It is expected that the CMC nonwovens can be used as adhesion prevention barriers.     

Extraction of natural cellulosic fibers from cornhusk and its physico-chemical properties

A natural long staple ligno-cellulosic fibers have been extracted from the cornhusks using an alkali treatment. Physico-chemical properties such as chemical composition, length, fineness, crystallinity, surface properties, etc. measured by standard methods are reported in this paper. The physico-chemical and morphological properties of the extracted cornhusk fibers are discussed in detail and compared with other cellulosic like cotton and ligno-cellulosic fibers such as jute. Scanning electron microscopy was used to study the morphological and cross-sectional view and energy dispersive X-ray and FTIR were used for the identification and quantification of elements, groups present in the cornhusk and other cellulosic and lignocellulosic fibers. In addition, fibers are characterized by thermo-gravimetric analysis. Results showed that morphological and physico-chemical behavior is more or less similar to other multicellular ligno-cellulosic fibers like jute.     

Eco-dyeing and antimicrobial properties of chlorophyllin copper complex extracted from Sasa veitchii

Cotton fabrics were dyed with the natural chlorophyll derivates (chlorophyllin, Chlin) after treatment with and without chitosan. The water-soluble Chlin extracted from Sasa veitchii based on Japanese bamboo leaves were investigated in order to improve the textile coloration and antimicrobial activity. The antimicrobial activity of the dyed fabrics that had been pretreated with chitosan as a biomordant over a concentration range of 0∼0.7 % was tested against two common gram pathogens: Staphylococcus aureus and Klebsiella pneumoniae. The color depth as measured by the K/S value, the color difference and the colorfastness to washing and light were also evaluated. The fabrics treated with chitosan resulted in an increase in dye uptake in all cases compared with the corresponding untreated fabrics, and did not affect fastness of washing and light. The cotton fabrics dyed with mordant and CuSO₄ extracts appeared to have over 99.9 % of antimicrobial activity, while MeOH extracts showed 71.8 %.     

Preparation and characterization of polysulfone membrane incorporating cellulose nanocrystals extracted from corn husks

Cellulose nanocrystals (CNCs) extracted from corn husks were used as additive to modify the hydrophilicity and anti-fouling properties of polysulfone (PSf) membrane. The PSf/CNCs blend membranes were prepared via an immersion phase inversion method. The influence of CNCs content on the morphology, structure, and performances of PSf membrane were carefully investigated by SEM, TG, DTG, DSC, break strength, elongation-at-break, Young modulus, contact angle and filtration experiment. The results showed that the isolated CNCs from corn husks were a promising additive for modifying the properties of PSf membrane. CNCs can improve mechanical property, thermal stability, hydrophilicity and anti-fouling performance of the pure PSf membrane. The PSf/CNCs blend membrane reached optimal properties at 2 wt% CNCs content, which was 2.76 and 1.57 times in pure water flux and FRR values respectively as compared to pure PSf membrane. Meanwhile, PSf-2 also can maintain a relatively high BSA rejection.     

Synthesis and properties of Nylon 4/5 copolymers for hydrophilic fibers

Nylon 4, which can be synthesized by anionic ring-opening polymerization, has good mechanical properties and a very high affinity for water owing to its high polarity. On the other hand, despite its high melting temperature, the polymer has not been commercialized because of its low thermal stability. In this study, copolymerization of 2-pyrrolidone (C4) with 2-piperidone (C5) was performed to reduce the melting temperature of Nylon 4 homopolymer. The copolymerization reaction was controlled by changing the comonomer content, catalyst content, temperature, initiator content, and reaction time. The Nylon copolymers were characterized by ¹H-nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The hydrophilic properties of Nylon 4 and its copolymers were evaluated by surface free energy analysis and moisture regain measurement. The intrinsic viscosity and polymerization yield of Nylon 4 increased with increasing catalyst concentration until 5 mole% and decreased with further increases in catalyst loading. The proton NMR spectrum revealed the composition of the Nylon 4/5 copolymer to be 62.5 % C4 moiety at a 5:5 comonomer feed ratio. The melting temperature of the Nylon 4/5 copolymers decreased considerably according to the composition. The moisture regain of the Nylon 4/5 copolymer was higher than 6.4 % even at 77.3 % C4 in composition.     

Rheological behavior and spinnability of ethylamine hydroxyethyl chitosan/cellulose co-solution in N-methylmorpholine-N-oxide system

In this work, the novel chitosan derivative ethylamine hydroxyethyl chitosan (EHC) was synthesized and blended with cellulose in an aqueous N-methylmorpholine-N-oxide (NMMO) solution in order to fabricate antibacterial chitosan/cellulose fiber. The rheological behaviors of the obtained co-solution in both steady and dynamic states were carefully investigated to determine the spinnability of the co-solution. In steady state, the addition of EHC was found to preserve the power-law flow characteristics of cellulose in the aqueous NMMO solution, while broadening the first Newtonian fluid-flow area. Under dynamic conditions, both Han-plot and viscoelastic analyses indicated the homogeneity of the co-solution. EHC/cellulose antibacterial fibers were successfully spun via the lyocell process using aqueous NMMO as the solvent, confirming the excellent spinnability of the EHC/cellulose co-solution. Scanning electron microscopy was used to observe the morphology of the obtained EHC/cellulose fibers; they were also investigated for antibacterial activity. The obtained EHC/cellulose fiber exhibited good spinning consistency and strong antibacterial activity against Escherichia coli, demonstrating potential applications for the material in antibacterial textiles.     

Surface modification of cellulose fibers by layer-by-layer self-assembly of lignosulfonates and TiO2 nanoparticles: Effect on photocatalytic abilities and paper properties

Depositing of TiO₂ nanoparticles on cellulose fiber surface has potential technological applications in the field of photocatalysis. With this motivation, multilayers composed of lignosulfonates (LS) and TiO₂ nanoparticles were constructed on cellulose fiber surface via layer-by-layer (LBL) self-assembly technique. X-ray photoelectron spectroscopy (XPS), zeta potential measurement and atomic force microscopy (AFM) were used to characterize the LS/TiO₂ multilayers on cellulose fiber surface. Moreover, the photocatalytic activities of modified cellulose fibers (decomposition of methyl orange and antibacterial test) were investigated. The decomposition efficiency of methyl orange for a (LS/TiO₂)₅ multilayer modified cellulose fibers was 74.7 % under 5 h UV irradiation. Photocatalytic decomposition efficiency of methyl orange by LS/TiO₂ multilayer modified cellulose fibers under the same UV irradiation time increased linearly with the number of bilayers. Antibacterial tests results revealed that the cellulose fibers modified with LS/TiO₂ multilayers exhibited excellent antibacterial activity against E.coil. The degree of E.coil growth inhibition for a (LS/TiO₂)₅ multilayer modified cellulose fiber reached as high as 93 %. In addition, the effect of LS/TiO₂ multilayers on properties of handsheets made from modified cellulose fibers was also considered. The air permeability of the handsheet prepared from fibers modified with TiO₂/LS multilayers had 6.1–24.3 % higher compared with that of handsheet prepared from original fibers. The wetting properties measurement results demonstrated that the water contact angle of handsheet oscillated with the increasing number of layers depended on building block which was in the outermost layer.     

Acetylation of wheat straw hemicelluloses in N,N-dimethylacetamide/LiCl solvent system

Hemicellulose acetates were prepared under homogeneous reaction conditions in the system N,N-dimethylacetamide/lithium chloride by reacting the native hemicelluloses with acetic anhydride in the presence of 4-dimethylaminopyridine within 72 h at 60–85°C. The products obtained were characterised by means of Fourier transform infrared chromatography, gel permeation chromatography, and thermal analysis. The degree of substitution of acetylated hemicelluloses ranged between 0.74 and 1.49 as a function of experimental conditions. Under an optimum reaction condition (85°C, 60 h), over 80% hydroxyl groups in native hemicelluloses were acetylated. The molecular weight measurements showed that a significant degradation and hydrolysis of the products appeared at only a prolonging period of 72 h. It was found that the thermal stability of the products increased by esterification.