Fibrils separated from polyacrylonitrile fiber by ultrasonic etching in dimethylsulphoxide solution

A novel method for the separation of polyacrylonitrile (PAN) fibrils from fibers by ultrasonic etching in a 90 wt % aqueous dimethylsulphoxide (DMSO) solution at 75 °C ± 2 °C for 6 h with a frequency of 40 kHz is demonstrated. These fibrils with a diameter of about 450 nm were systematically investigated by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), and wide‐angle X‐ray diffraction (WAXD). It was found that the fibrils consisted of microfibrils with about 200 nm diameter, including periodic lamellae with thickness of 30–45 nm perpendicular to the fiber axis. The PAN fiber crystallinity and crystal size slightly decreased under the ultrasonic etching. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 617–619, 2010     

Highly charged nanocrystalline cellulose and dicarboxylated cellulose from periodate and chlorite oxidized cellulose fibers

Softwood cellulose pulp was oxidized by a two-step oxidation process with sodium periodate followed by sodium chlorite at pH 5.0. The oxidized product was first separated into two fractions by centrifugation, and the supernatant was further separated in two fractions by addition of ethanol and centrifugation. Different levels of oxidation were performed on cellulose, and the mass ratio and carboxyl content of each fraction were determined. The first precipitate, which amount decreases with increasing oxidation level, consists of short fiber fragments (microfibrils) with length of 0.6–1.8 μm and width around 120 nm, which for sufficiently high oxidation levels, could readily be made into cellulose nanofibrils by stirring. The second precipitate (after alcohol addition) has a very high crystalline index of 91 % and contains rod-like particles with length of 120–200 nm and diameter around 13 nm, reminiscent of nanocrystalline cellulose. The supernatant contains water-soluble dicarboxylated cellulose, as proven by liquid C-13 NMR.     

Comparative physical and chemical analyses of cotton fibers from two near isogenic upland lines differing in fiber wall thickness

The thickness of cotton fiber cell walls is an important property that partially determines the economic value of cotton. To better understand the physical and chemical manifestations of the genetic variations that regulate the degree of fiber wall thickness, we used a comprehensive set of methods to compare fiber properties of the immature fiber (im) mutant, called immature because it produces thin-walled fibers, and its isogenic wild type Texas Marker-1 (TM-1) that is a standard upland cotton variety producing normal fibers with thick walls. Comprehensive structural analyses showed that im and TM-1 fibers shared a common developmental process of cell wall thickening, contrary to the previous report that the phase in the im fiber development might be retarded. No significant differences were found in cellulose content, crystallinity index, crystal size, matrix polymer composition, or in ribbon width between the isogenic fibers. In contrast, significant differences were detected in their linear density, cross-section micrographs of fibers from opened bolls, and in the lateral order between their cellulose microfibrils (CMFs). The cellulose mass in a given fiber length was lower and the CMFs were less organized in the im fibers compared with the TM-1 fibers. The presented results imply that the disruption of CMF organization or assembly in the cell walls may be associated with the immature phenotype of the im fibers.     

Using collagen fiber as a template to synthesize hierarchical mesoporous alumina fiber

Hierarchical mesoporous alumina fiber was synthesized by using collagen fiber as the template, and characterized by means of scanning electron microscopy, transmission electron microscopy, N2 adsorption techniques, X-ray photoelectron spectroscopy, and X-ray diffraction. The alumina fiber obtained is approximately 1-4 microm in outer diameter and 0.5-1 mm in length. The pore size distribution of the alumina fiber is narrow (2-20 nm), and its pore size is controllable by varying preparation methods. This study indicates that collagen fiber, which has hierarchical supermolecular structure, could be used as an ideal template to prepare well-defined porous metal oxide fibers.     

Thermomechanical and crystallization behavior of polylactide-based flax fiber biocomposites

In this work, the rheological, thermal and mechanical properties of melt-compounded flax fiber-reinforced polylactide composites were investigated. The effect of compounding on fiber length and diameter, and the relationship between fiber content and the crystallization behavior of the biocomposites, at various temperatures, were also examined. After melt-compounding, fiber bundles initially present were, to a large extent, broken into individual fibers and the fiber length was decreased by 75 %, while the aspect ratio was decreased by nearly 50 %. The crystallization half-time was found to decrease with increasing flax fiber content, and showed a minimum value at 105 °C for all systems. The elastic modulus was increased by 50 % in the presence of 20 wt% flax fibers. The addition of maleic anhydride-grafted polylactide had a positive effect on the mechanical properties of the biocomposite. This system is particularly interesting in the context of sustainable development as it is entirely based on renewable resources and biodegradable.     

Controlled and scalable torsional actuation of twisted nylon 6 fiber

Large‐scale torsional actuation occurs in twisted fibers and yarns as a result of volume change induced electrochemically, thermally, photonically, and other means. A quantitative relationship between torsional actuation (stroke and torque) and volume change is here introduced. The analysis is based on experimental investigation of the effects of fiber diameter and inserted twist on the torsional stroke and torque measured when heating and cooling nylon 6 fibers over the temperature range of 26–62 °C. The results show that the torsional stroke depends only on the amount of twist inserted into the fiber and is independent of fiber diameter. The torque generated is larger in fibers with more inserted twist and with larger diameters. These results are successfully modeled using a single‐helix approximation of the twisted fiber structure. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1278–1286     

The nanostructure of kraft pulp 1: evaluation of various mild drying methods using field emission scanning electron microscopy

Wood pulp fiber consists of carbohydrate fibrils containing crystalline cellulose microfibrils of a few nanometer width. The structure of the fibril in water is currently unclear due to the difficulty of imaging pulp fiber in water at nanometer resolution. An alternative method is to observe the sample dried with a mild drying method to preserve the structure of the wet sample. In this study, we studied softwood kraft pulp fibers which were dried with various mild drying methods and then imaged by field emission scanning electron microscopy at nanometer resolution. Both mild dried samples, as well as air dried samples, showed 10–20 nm wide fibrils, the width of which corresponded to a crystalline cellulose microfibril or bundles of them. The mild dried sample, which was critical point dried with liquid CO₂ (CPD), mainly showed 20–40 nm thick fibrils, in addition to the 10–20 nm fibrils. The existence of the thick fibril implies that the fibril itself has a swelling nature in water, although the possibility that the thick fibril was an artifact of the CPD process could not be excluded. Further investigation as to the extent that the thick fibrils found in the CPD samples reflect the nanostructure of pulp fiber in water is warranted.     

Nanofibrillation of dried pulp in NaOH solutions using bead milling

The drying process in typical pulp production generates strong hydrogen bonding between cellulose microfibrils in refined cell walls and increases the difficulty in obtaining uniform cellulose nanofibers. To investigate the efficacy of alkaline treatment for cellulose nanofibrillation, this study applied a bead-milling method in NaOH solutions for the nanofibrillation of dried pulps. NaOH treatments loosened the hydrogen bonding between cellulose microfibrils in dried pulps and allowed preparation of cellulose nanofibers in 8 % NaOH with a width of approximately 12–20 nm and a cellulose I crystal form. Both the nanofiber suspensions prepared in 8 and 16 % (w/w) NaOH were formed into hydrogels by neutralization because of surface entanglement and/or interdigitation between the nanofibers. When the dried pulp was fibrillated in 16 % (w/w) NaOH, the sample after neutralization had a uniquely integrated continuous network. These results can be applied to the preparation of high-strength films and fibers with cellulose I crystal forms without prior dissolution of pulps.     

Mesoporous structures in never-dried softwood cellulose fibers investigated by nitrogen adsorption

Nitrogen adsorption was used to characterize mesoporous structures in never-dried softwood cellulose fibers. Distinct inflections in desorption isotherms were observed over the relative vapor pressure (P/P₀) range of 0.5–0.42 for never-dried cellulose fibers and partially delignified softwood powders. The reduction in N₂ adsorption volume was attributed to cavitation of condensed N₂ present in mesopores formed via lignin removal from wood cell walls during delignification. The specific surface areas of significantly delignified softwood powders were ~150 m² g^?1, indicating that in wood cell walls 16 individual cellulose microfibrils, each 3–4 nm in width, form one cellulose fibril bundle surrounded with a thin layer of lignin and hemicelluloses. Analysis of N₂ adsorption isotherms indicates that mesopores in the softwood cellulose fibers and partially delignified softwood powders had peaks ranging from 4 to 20 nm in diameter.     

Anionic surfactant sensor based on a hetero-core structured optical fiber

A simple method of fiber optic spectrophotometric measurement for anionic surfactant is described. The probe was fabricated from hetero-core structured fiber optic that consisted of multi mode fibers and a short length of single mode fiber which was inserted in the multi mode fibers. The sensor surface was treated with octyltrimethoxysilane to adsorb the surfactant-methylene blue complex via hydrophobic interaction between the octyl group on the fiber surface and the hydrophobic group of the surfactant. Methylene blue—anionic surfactant complex adsorbed on the sensor surface caused propagating light loss because of evanescent wave interaction that was generated at the cladding. The propagating loss spectrum of the fiber showed a peak at around 610 nm. Absorbance increases with the concentration of the surfactant to reach an upper level at a concentration of 30?μm. The response time is within 30 min.     

Formation of ZnO within flexible polymer fibers

In the process of fiber production from Zinc acetate and Polyvinylpyrrolidone using the electrospinning method, ZnO forms at temperature as low as 120 °C. The fibers were characterized using scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and ultraviolet–visible (UV–Vis) spectroscopy. Upon heating at 120 °C for 12 h some fibers shrink in diameter down to about 100 nm while others remain in the 400–900 nm range. Within the hybrid fibers, ZnO crystallizes in the wurtzite structure with a bang gap of 3.3 eV. The hybrid fibers exhibit the flexibility of polymer component and optical properties of ZnO phase, and promise to be very useful in various applications.     

Synthesis and characterization of sol–gel derived ZrV2O7 fibers with negative thermal expansion property

Novel ZrV₂O₇ fibers with negative thermal expansion were prepared via combination of sol–gel process and thermal decomposition. The as-prepared fibers were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy and Raman spectroscopy. The results showed that the synthetic pH value had little influence on the crystal structure of products while showed significant effect on morphology. The fibers obtained at pH = 9 exhibited cylindrical morphology and its mean diameter was about 1 μm. The thermal expansion property of the as-prepared fibers was investigated by in situ XRD and thermal mechanical analyzer. All of the as-prepared fibers showed positive thermal expansion first and then negative thermal expansion, resulting from a phase transition from 3 × 3 × 3 superstructure to 1 × 1 × 1 cubic structure. The macro thermal expansion coefficients of ZrV₂O₇ ceramic rods increased with decreasing of fiber diameter. The mechanism of the phase transition was also discussed.     

Structural coarsening of aspen wood by hydrothermal pretreatment monitored by small- and wide-angle scattering of X-rays and neutrons on oriented specimens

Structural changes across multiple length scales associated with hydrothermal pretreatments of biomass were investigated by using small- and wide-angle X-ray and neutron scattering on oriented specimens. Isotropic and anisotropic scattering components were numerically separated and then interpreted as contributions from matrix and cellulose components, respectively. Equatorial diffraction peaks present in the isotropic component became sharper after hydrothermal treatments or ammonia treatment. Before pretreatment the wet cell wall was found to be homogeneous in the 10–100 nm range and scattering below Q = 0.5 (nm^?1) was dominated by surface scattering from the lumen. After pretreatment with acid or steam at 160 or 180 °C, density fluctuation developed in the cell wall at length scales above 10 nm, most likely due to lateral coalescence of microfibrils that partially co-crystallize to give larger apparent crystal sizes. A density fluctuation up to about 100 nm appeared in the isotropic component after acid and steam pretreatments due to morphological changes in the hemicellulose and lignin matrix.     

Highly fluorescent cotton fiber based on luminescent carbon nanoparticles via a two-step hydrothermal synthesis method

A kind of highly fluorescent cotton fibers, in which the luminescent carbon nanoparticles (CNPs) are generated in the lumen and the mesopores directly, have been prepared by the method of hydrothermal synthesis in situ using citric acid and urea as raw materials, and hexadecyl trimethyl ammonium bromide and tributyl phosphate as active agents. The CNPs/cotton fibers were characterized by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS), respectively. The optical properties are investigated by fluorescence spectrofluorometry and PR-305 long afterglow phosphors tester. The results showed that the CNPs were self-assembled successfully in the lumen as well as in the mesopores of cotton fibers. The CNPs/cotton fibers could emit bright and colorful photoluminescence under excitation lights of different wavelengths. The afterglow decay process could be divided into fast decay and slow decay stages and the emission of CNPs/cotton fiber had two peaks at 450 nm and 570 nm respectively when the wavelength of excitation changed from 310 nm to 500 nm. The preparation of highly fluorescent cotton fibers by self-assembly method has great significance to the functionalization of cotton fibers.     

Morphological study on poly-p-phenylenebenzobisoxazole (PBO) fiber

Morphological survey on new PBO fiber (Zylon®) was conducted by X-ray and transmission electron microscopic studies. Crystal size, orientation of the crystal, fibrils, microvoids, and fine structure were discussed. It was found that the molecule in the fiber showed high orientation (more than 0.99 in Hermann's orientation function for heat-treated fiber) and relatively small crystal sizes in the longitudinal (160 Å) and the transverse (110 Å) directions. Crystal modulus estimated by extrapolation to perfect orientation on the plot of the fiber modulus as a function of fiber orientation (Northolt's method) shows discrepancy from the crystal modulus directly obtained by X-ray scattering. This discrepancy means that the Northolt's model is insufficient to describe the Young's modulus of PBO fiber. Microvoids elongated to the fiber direction were examined by small-angle X-ray scattering and transmission electron microscopic methods. The diameter of the microvoids was 20 Å to 30 Å and the fiber had a very thin microvoids-free layer (0.2 μm). Preferential orientation of the a-axis of crystal in the fiber was also confirmed. Summarizing these results, a structure model of the PBO fiber was proposed. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 39–48, 1998     

Initial stage of fiber structure development in the continuous drawing of poly(ethylene terephthalate)

The initial stage of fiber structure development in the continuous neck‐drawing of amorphous poly(ethylene terephthalate) fibers was analyzed by in situ wide‐angle X‐ray diffraction, small‐angle X‐ray scattering, and fiber temperature measurements. The time error of the measurements (<600 μs) was obtained by synchrotron X‐ray source and laser irradiation heating. A highly ordered fibrillar‐shaped two‐dimensional (smectic‐like) structure was found to be formed less than 1 ms after necking. By analyzing its (001′) and (002′) diffractions, the length of the structure 60–70 nm were obtained. A three‐dimensionally ordered triclinic crystal began to form with the vanishing of the structure around 1 ms after necking. The amount and size of the crystal were almost saturated within several milliseconds of necking, during which time a mainly exothermic heat of crystallization was also observed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2126–2142, 2008     

Mechanical property evaluation of glass–jute fiber reinforced polymer composites

The natural fibers such as jute, coir, hemp, sisal etc. are randomly used as reinforcements for composite materials because of its various advantages such as low cost, low densities, low energy consumption over conventional fibers. In addition, they are renewable as well as biodegradable, and indeed wide varieties of fibers are locally available. In this study, glass–jute fiber reinforced polymer composite is fabricated, and the mechanical properties such as tensile, flexural and impact behavior are investigated. The materials selected for the studies were jute fiber and glass fiber as the reinforcement and epoxy resin as the matrix. The hand lay‐out technique was used to fabricate these composites. Fractured surface were comprehensively examined in scanning electron microscope (SEM) to determine the microscopic fracture mode. A numerical procedure based on the finite element method was then applied to evaluate the overall behavior of this composite using the experimentally applied load. Results showed that by incorporating the optimum amount of jute fibers, the overall strength of glass fiber reinforced composite can be increased and cost saving of more than 30% can be achieved. It can thus be inferred that jute fiber can be a very potential candidate in making of composites, especially for partial replacement of high‐cost glass fibers for low load bearing applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and characterization of cellulose nanofibers from partly mercerized cotton by mixed acid hydrolysis

Cellulose nanofibers with a diameter of 70 nm and lengths of approximately 400 nm were fabricated from partly mercerized cotton fibers by acid hydrolysis. Morphological evolution of the hydrolyzed cotton fibers was investigated by powder X-ray diffraction, Fourier transform infrared analysis and field emission scanning electron microscopy. The XRD results show that the cellulose I was partially transformed into cellulose II by treatment with 15 % NaOH at 150° for 3 h. The crystallinity of this partially mercerized sample was lower than the samples that were converted completely to cellulose II by higher concentrations of NaOH. The intensities of all of the diffraction peaks were noticeably increased with increased hydrolysis time. Fourier transform infrared results revealed that the chemical composition of the remaining nanofibers of cellulose I and II had no observable change after acidic hydrolysis, and there was no difference between the hydrolysis rates for cellulose I or II. The formation of cellulose nanofibers involves three stages: net-like microfibril formation, then short microfibrils and finally nanofibers.     

Fabrication of nanofibers with uniform morphology by self-assembly of designed peptides

Fabrication of controlled peptide nanofibers with homogeneous morphology has been demonstrated. Amphiphilic beta-sheet peptides were designed as sequences of Pro-Lys-X(1)-Lys-X(2)-X(2)-Glu-X(1)-Glu-Pro. X(1) and X(2) were hydrophobic residues selected from Phe, Ile, Val, or Tyr. The peptide FI (X(1)=Phe; X(2)=Ile) self-assemble into straight fibers with 80-120 nm widths and clear edges, as examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The fiber formation is performed in a hierarchical manner: beta-sheet peptides form a protofibril, the protofibrils assemble side-by-side to form a ribbon, and the ribbons then coil in a left-handed fashion to make up a straight fiber. These type of fibers are formed from peptides possessing hydrophobic aromatic Phe residue(s). Furthermore, a peptide with Ala residues at both N and C termini does not form fibers (100 nm scale) with clear edges; this causes random aggregation of small pieces of fibers instead. Thus, the combination of unique amphiphilic sequences and terminal Pro residues determine the fiber morphology.     

Short cellulose nanofibrils as reinforcement in polyvinyl alcohol fiber

Short cellulose nanofibrils (SCNF) were investigated as reinforcement for polyvinyl alcohol (PVA) fibers. SCNF were mechanically isolated from hard wood pulp after enzymatic pretreatment. Various levels of SCNF were added to an aqueous PVA solution, which was gel-spun into continuous fibers. The molecular orientation of PVA was affected by a combination of wet drawing during gel spinning and post-hot-drawing at a high temperature after drying. A maximum total draw ratio of 27 was achieved with various SCNF contents investigated. The PVA crystal orientation increased when small amounts of SCNF were added, but decreased again as the SCNF content was increased above about 2 or 3 %, likely due to SCNF percolation resulting in network formation that inhibited alignment. SCNF fillers were effective in improving PVA fiber tensile properties (i.e., ultimate strength and elastic modulus). For example, the ultimate strength and modulus of PVA/SCNF composite fiber with a SCNF weight ratio of 6 were nearly 60 and 220 % higher than that of neat PVA. Shifts in the Raman peak at ~1,095 cm^?1, which were associated with the C–O–C glycosidic bond of SCNF, indicated good stress-transfer between the SCNF and the PVA matrix due to strong interfacial hydrogen bonding. Cryogenic fractured scanning electron microscopy images of filled and unfilled PVA fibers showed uniform SCNF dispersion.