Kinetics of water sorption in flax and PET fibers

Composite materials are usually reinforced by synthetic fibers as carbon, glass etc…. Because of their good mechanical properties and low density, natural fibers are being considered more preferentially as reinforcement. The application of natural fibers as reinforcements in composite materials requires a strong adhesion between the fiber and the matrix. The poor resistance towards water absorption is one of the drawbacks of natural fibers which makes it more important to understand the dynamic properties of penetration of water molecules through these heterogeneous materials. Water vapour sorption kinetics in natural flax fibers have been performed at 25 °C by using an electronic microbalance (IGA, Hiden). By using the Fickian model for a complete cylinder water diffusion coefficients have been determined and calculated at short times (first half-sorption) and long times (second half-sorption) of kinetic curve and for different water activities. The values obtained for D₁ and D₂ are rather similar on the all range of water activity. Generally, water diffusivity increases and then decreases with water activity. The increase of diffusivity at low water activities may be explained on the basis of the dual mode sorption (Langmuir and Henry sorption’s combination) whereas the decrease for the higher activities can be attributed to the immobilization of sorbed water molecules due to the water clustering.     

Biocomposites based on Alfa fibers and starch‐based biopolymer

Biocomposite materials based on Alfa cellulose fibers (esparto grass plant) as reinforcing element and starch‐based biopolymer matrix were prepared and characterized in terms of mechanical performance, thermal properties, and water absorbance behavior. The fibers and the matrix were first mixed in the melted state under mechanical shearing using a plastograph and the obtained composites were molded by injection process. The tensile mechanical analysis showed a linear increase of the composite flexural and tensile modulus upon increasing the fiber content, together with a sharp decrease of the elongation at break. The fibers′ incorporation into the biopolymer matrix brings about an enhancement in the mechanical strength and the impact strength of the composite. Dynamic mechanical thermal analysis (DMTA) investigation showed two relaxations occurring at about ?30 and 35°C. The addition of Alfa fibers enhanced the storage modulus E′ before and after T_α, which is consistent with the reinforcing effect of Alfa cellulose fibers. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and photocatalytic activity of B,Ce Co-doped TiO2 hollow fibers photocatalyst

A series of B, Ce co-doped TiO₂ (B, Ce-TiO₂) photocatalytic materials with a hollow fiber structure were successfully prepared by template method using boric acid, ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500°C in an N₂ atmosphere for 2 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, and UV-visible spectroscopy (UV-Vis) were employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photocatalytic performance of the samples was studied by photodegradation phenol in water under UV light irradiation. The results showed that the TiO₂ fiber materials have hollow structures, and the fiber structure materials showed better photocatalytic properties for the degradation of phenol than pure TiO₂ under UV light. In the experiment condition, the photocatalytic activity of B, Ce co-doped TiO₂ fibers was optimal of all the prepared samples. In addition, the possibility of cyclic usage of B, Ce co-doped TiO₂ fiber photocatalyst was also confirmed, the photocatalytic activity of TiO₂ fibers remained above 90% of that of the fresh sample after being used four times. The material was easily removed by centrifugal separation from the medium. It can therefore be potentially applied for the treatment of water contaminated by organic pollutants.     

Estimation of electrokinetic and hydrodynamic global properties of relevant amyloid‐beta peptides through the modeling of their effective electrophoretic mobilities and analysis of their propensities to aggregation

Neuronal activity loss may be due to toxicity caused by amyloid‐beta peptides forming soluble oligomers. Here amyloid‐beta peptides (1–42, 1–40, 1–39, 1–38, and 1–37) are characterized through the modeling of their experimental effective electrophoretic mobilities determined by a capillary zone electrophoresis method as reported in the literature. The resulting electrokinetic and hydrodynamic global properties are used to evaluate amyloid‐beta peptide propensities to aggregation through pair particles interaction potentials and Brownian aggregation kinetic theories. Two background electrolytes are considered at 25°C, one for pH 9 and ionic strength I = 40 mM (aggregation is inhibited through NH₄OH) the other for pH 10 and I = 100 mM (without NH₄OH). Physical explanations of peptide oligomerization mechanisms are provided. The effect of hydration, electrostatic, and dispersion forces in the amyloidogenic process of amyloid‐beta peptides (1–40 and 1–42) are quantitatively presented. The interplay among effective charge number, hydration, and conformation of chains is described. It is shown that amyloid‐beta peptides (1–40 and 1–42) at pH 10, I = 100 mM and 25°C, may form soluble oligomers, mainly of order 2 and 4, after an incubation of 48 h, which at higher times evolve and end up in complex structures (protofibrils and fibrils) found in plaques associated with Alzheimer's disease.     

Effect of montmorillonite content and the type of its modifier on the thermal properties and flammability of polyimideamide nanocomposite fibers

The effects of montmorillonite (MMT) content (1, 3, 5%) and the type of its modifiers on the thermal properties and flammability of PIA nanocomposite fibers have been assessed. Sodium montmorrilonite was modified with aminododecane acid and octadecylamine. Samples of PIA nanocomposite containing commercial MMT: Nanomer PGW from Nanocor were also included in the comparative analysis. It has been found that the glass transition temperature (T _g) of the fibers under investigation depends on the type of MMT’s modifier. On the other hand this parameter does not affect the thermal stability of fibers defined with T ₅ and T ₅₀ indicators since the thermal decomposition of modifiers takes place at lower temperatures.     

ELECTRICAL CONDUCTIVITY OF IODINE DOPED POLY(PHTHALOCYANINATOSILOXANE)/PPTA BLEND FIBERS

Poly(phthalocyaninatosiloxane), [Si(Pc)O]n, with the number average degree of polymerization of about 130 was prepared by heating its monomer Si(Pc) (OH)_2, in solid state at 420℃for 42 hrs at 10~(-3) torr dynamic vacuum. The [Si(Pc)O]n powder was iodine doped with I_2-bensene solution for 48 hrs. Pure iodine doped poly(phthalocyaninatosiloxune), {[Si(Pc)O]I_y}n, fibers and {[Si(Pc)O]I_y}n/poly(p-pbenylene terephthalamide) blend fibers were wet-spun with dry nltrogen-sealed Teflon lined device. D.C. electrical conductivity of the fibers was measured by the four-probe method with an automated charge transport measurement system from 80K to room temperature. It was found that the dependence of conductivity, σ, on temperature, T, could fit a group of thermal fluctuation-induced tunnelling (TFIT) equations, and that the dependence of conductivity on volume fraction, φ, of the iodine doped {[Si(Pc)O]I_y}n could fit a group of modified percolation equations. A thrce-dimensioual composite plot of σ-1 / T-φshows that these two groups of equations match each other quite well. It has been pointed out that for the blend fibers their composition is the most important factor for both mechanical and electrical properties.     

新型SiBNC陶瓷先驱体——聚硼硅氮烷的合成与表征

以甲基氢二氯硅烷、三氯化硼、六甲基二硅氮烷为起始原料, 采用共缩合的方法合成了一种新型的可溶可熔的SiBNC陶瓷先驱体--聚硼硅氮烷(PBSZ). 该法合成工艺简单, 且合成收率约为91% (w%). 采用元素分析、傅立叶红外光谱、核磁共振波谱、X射线光电子能谱、动态热机械分析、热重分析等对PBSZ的组成、结构和性能进行了表征. 结果表明, 先驱体的主要骨架为-Si-N-B-, 其中, B, N以硼氮六环形式存在, 而C则以Si-CH₃形式存在. 该先驱体熔点为69 ℃, 数均分子量为10802, 分子量分散系数为1.50. 此外, 所合成的先驱体具有优良的成型性, 在80 ℃的N₂气氛中可纺丝得到15～20 μm的有机纤维, 1000 ℃时相应陶瓷产率约为63% (w%).     

Melt spinning of syndiotactic 1, 2-polybutadiene for preparation of carbon fibers

The thermal crosslinking and loss of vinyl unsaturation of syndiotactic 1, 2-polybutadiene(_s-PB) at 180–230°C were prevented by stabilizers with 3, 5-di-t-butyl-4-hydroxybenzyloxy group. The _s-PB samples (mp 140–198°C and MW 20,000–70,000) that contained the stabilizers could be melt-spun at a temperature below 220°C into 1-denier fibers to be used for the preparation of carbon fibers. The _s-PB fibers with higher mp and/or higher MW could be obtained by the addition of a high boiling solvent such as tetralin. The relationship between the molecular structures of _s-PB and the properties of resulting _s-PB fibers, including the degree of molecular orientation measured by birefringence and x-ray diffraction, is presented. Spun fibers showed small swellings here and there along the fiber axis, which would have resulted from the inhomogeneity of the melt of _s-PB spun at a temperature slightly above the melting point. The gelation was unlikely to occur.     

Modification of natural fibers from Thespesia lampas plant by in situ generation of silver nanoparticles in single-step hydrothermal method

Ligno-cellulosic fibers have a great market and propose higher value addition and options to develop various products but they do not have inherent antimicrobial properties. In this study, a simple hydrothermal method was applied to build up antimicrobial properties to natural fibers by in situ-generating silver nanoparticles (AgNPs) in them. Herein, the ligno-cellulosic Thespesia lampas natural fibers were selected to develop antimicrobial activity using silver nitrate (AgNO₃) solution by hydrothermal method. The modified fibers were characterized by SEM, FTIR, XRD, TGA, and antibacterial activity tests. The modified fibers had spherical AgNPs with an average size of 95?nm. The thermal stability of the modified fibers was higher than that of the unmodified fibers. The modified fibers exhibited good antibacterial activity against both the Gram negative and Gram positive bacteria. These modified fibers can be considered as fillers in polymer matrices to make antibacterial composites.     

1:1 alternating copolymer of acrylonitrile and vinyl acetate

Copolymerization of the acrylonitrile-zinc chloride complex with excess vinyl acetate has been investigated. Alternating 1:1 copolymers of acrylonitrile and vinyl acetate of high molecular weights have been successfully prepared. The alternating structure has been ascertained by means of high-resolution nuclear magnetic resonance spectroscopy. The copolymer is amorphous (T_g = 85°C) and has shown thermal and oxidative stability better than those of polyacrylonitrile. The copolymer is soluble in acetone as well as in more powerful solvents such as dimethylformamide, dimethyl sulfoxide, nitromethane, and N-methylpyrrolidone. The copolymer has been processed into films and fibers from its acetone solutions. Films show tensile properties similar to those of cellulose acetate under ambient conditions; they suffer drastic loss in tensile properties at above 50°C and retain their good tensile properties at subzero temperatures (determined as low as ?40°C). Fibers show tensile properties comparable to those of modacrylic fibers under ambient conditions but suffer marked loss in stiffness at 40°C in water and 60°C in air. The fibers also retain their good properties at subzero temperatures (measured down to ?60°C).     

Water Accessibilities of Man-made Cellulosic Fibers – Effects of Fiber Characteristics

The dynamic vapor water sorption and desorption experiments were performed on cellulosic fibers with different characteristics. The hysteresis between moisture sorption and desorption cycle at 10% relative humidity (RH) was independent on the total moisture regain and approximately 45% for all materials except for viscose fibers. Brunauer–Emmett–Teller surface volume (V_m) for moisture sorption and retention capacity of liquid water (WRV) were also measured. The V_m and WRV increase in proportion to the total amount of moisture sorption (M_inf(total)) in all specimen except in poplar fiber. The coefficients of parallel exponential kinetics (PEK) were estimated by the curve-fitting of experimental data of the moisture regain, and the influences of the fiber characteristics on the PEK coefficients, the moisture regain, the hysteresis, V_m and WRV are discussed. The total equilibrium moisture content in the viscose fibers was higher but the moisture uptake and release rate was slower than the lyocell and poplar fibers. The cationization and the modification of shape of cross section accelerated the total equilibrium moisture content in the viscose fiber. A drying process at low temperature enhanced both the equilibrium moisture content and the moisture uptake and release rate in lyocell fibers while a spin finish retarded them. The total equilibrium moisture content was heightened by the crosslinking of the fiber, however, no obvious effect of the crosslinking on the moisture uptake and release rate was found. Effects of the type of the specimen and linear density on the moisture accessibilities are also discussed.     

Mechanical Properties of Organic-Inorganic Hybrid Materials Determined by Indentation Techniques

Summary. The mechanical properties of hybrid materials consisting of polystyrene (PS), which was cross-linked with different proportions of the multifunctional cluster Zr₆O₄(OH)₄(methacrylate)₁₂ (Zr6) were investigated. With the help of (micro)indentation and scratch testing, the influence of the Zr6 clusters on mechanical properties, such as hardness, stiffness, creep, craze initiation, and scratch resistance was shown. There was only a slight increase in hardness and in indentation modulus with higher cluster loadings. While this observation was in agreement with the compression behaviour of the materials, the tensile properties showed a much stronger dependence on the Zr6 content. With increasing cluster loading, an increase of craze initiation stress, as determined by ball indentation experiments, was found. Performing scratch testing with constant load, a reduction of pile-up and a stronger recovery were observed for the hybrid materials compared to the neat PS. Scratch tests with a constant increase of load showed an increase of the critical load for crack opening during scratching.     

Mechanical Properties of Organic-Inorganic Hybrid Materials Determined by Indentation Techniques

The mechanical properties of hybrid materials consisting of polystyrene (PS), which was cross-linked with different proportions of the multifunctional cluster Zr₆O₄(OH)₄(methacrylate)₁₂ (Zr6) were investigated. With the help of (micro)indentation and scratch testing, the influence of the Zr6 clusters on mechanical properties, such as hardness, stiffness, creep, craze initiation, and scratch resistance was shown. There was only a slight increase in hardness and in indentation modulus with higher cluster loadings. While this observation was in agreement with the compression behaviour of the materials, the tensile properties showed a much stronger dependence on the Zr6 content. With increasing cluster loading, an increase of craze initiation stress, as determined by ball indentation experiments, was found. Performing scratch testing with constant load, a reduction of pile-up and a stronger recovery were observed for the hybrid materials compared to the neat PS. Scratch tests with a constant increase of load showed an increase of the critical load for crack opening during scratching.     

Correlation between Performances of Hollow Fibers and Flat Membranes for Gas Separation

This work presents an attempt at correlating the available permeability/selectivity literature data for hollow fibers and flat membranes. Therefore, this paper gathers the information pertaining to membrane materials for which membrane properties of flat membranes and hollow fibers have both been reported. An overview of the relations between selectivity and permeance of hollow fiber membranes for various gas pairs (O₂/N₂, CO₂/CH₄, CO₂/N₂, H₂/N₂, H₂/CO₂, H₂/CH₄ and He/N₂) is presented first. The upper bound lines are the ones proposed by Robeson, which were calculated by assuming a one-micron-thick skin layer as proposed by Robeson in 2008. From the results obtained, a relation between the selectivity ratio in both kinds of membranes (α_H/α_f) and skin layer thickness (l) calculated from flat membranes and hollow fibers gas permeation data for these pairs of gases is also presented. The skin layer thicknesses measured using seven different experimental techniques for six commercial membranes are compared. The influences of spinning parameters on the morphology and performance of hollow fiber membrane gas separation are discussed. Finally, an analysis is made of the reasons why the dense skin layer thicknesses of a hollow fiber calculated using permeance and permeability data vary for different gases and also differ from direct experimental measurements.     

Molecular weight distribution and mechanical behavior of PBI fibers

Two different polybenzimidazole (PBI) samples have been investigated in order to correlate the differences in molecular weight distribution (MWD) with changes in the elastic modulus and strength of undrawn and drawn fibers. It has been found that within the weight-average molecular weight range (7,000 ≤ M_w ≤ 13,000) there was no obvious correlation with M_w and M_n. However, one sample had a narrow unimodal molecular weight distribution and the other a wide bimodal molecular weight distribution. The small percentage of high molecular weight present in the latter sample gave its fibers better mechanical properties. X-ray diffraction studies showed that the orientation in both drawn fiber samples was equal. This isolated the effects of the molecular weight distribution on mechanical properties.     

Synthesis and magnetic properties of nanocomposite Ni1?xCoxFe2O4–BaTiO3 fibers by organic gel-thermal decomposition process

Nanocomposites of ferrite and ferroelectric phases are attractive functional ceramic materials. In this work, the nanocomposite Ni_1−x Co _x Fe₂O₄–BaTiO₃(x = 0.2, 0.3, 0.4, 0.5) fibers with fine diameters of 3 ~ 7 μm and high aspect ratios were synthesized by the organic gel-thermal decomposition process from the raw materials of citric acid and metal salts. The structure, thermal decomposition process and morphologies of the gel precursors and the resultant fibers derived from thermal decomposition of the gel precursors were characterized by Fourier transform infrared spectroscopy, thermogravimetric differential thermal analysis, X-ray diffraction and scanning electron microscopy. The magnetic properties of the nanocomposite fibers were measured by vibrating sample magnetometer. The nanocomposite fibers of ferrite Ni_1−x Co _x Fe₂O₄ and perovskite BaTiO₃ are formed at the calcination temperature of 900 °C for 2 h. The average grain sizes of Ni_1−x Co _x Fe₂O₄ and BaTiO₃ in the nanocomposite fibers increase from about 15 nm to approximately 67 nm with the increasing calcination temperatures from 900 to 1,180 °C. The saturation magnetization of the nanocomposite Ni_1−x Co _x Fe₂O₄–BaTiO₃(x = 0.2, 0.3, 0.4, 0.5) fibers increases with the increase of grain sizes of Ni_1−x Co _x Fe₂O₄ and Co content, while the coercivity reaches a maximum value at the single-domain size of about 65 nm of Ni_0.5Co_0.5Fe₂O₄ obtained at the calcination temperature of 1,100 °C.     

Preparation of cellulose nanofibers and their improvement on ultradrawing properties of ultrahigh molecular weight polyethylene nanocomposite fibers

Novel ultrahigh molecular weight polyethylene (UHMWPE)/cellulose nanofiber (CNF) (F₁₀₀CNF_y) and UHMWPE/modified cellulose nanofiber (MCNF^x) (F₁₀₀MCNF^x_y) as‐prepared nanocomposite fibers were successfully prepared by gel‐spinning F₁₀₀CNF_y and F₁₀₀MCNF^x_y gel solutions, respectively. CNF nanofillers with a specific surface area at 120 m²/g and a nanofiber diameter of 20 nm were successfully prepared by proper acid hydrolysis of cotton fibers using sulfuric acid solution. MCNF^x nanofillers were prepared by grafting various contents of maleic anhydride grafted polyethylene (PE_g‐MAH) onto CNF nanofillers. The ultimate σ_f value of the best‐prepared F₁₀₀MCNF^x_y drawn fiber reached 4.5 GPa, which is about 67% higher than that of the UHMWPE drawn fiber prepared without the addition of any nanofiller. To understand the interesting ultradrawing, orientation, and tensile properties of F₁₀₀CNF_y and F₁₀₀MCNF^x_y fibers, Fourier transform infrared, transmission electron microscopic analyses of the CNF and MCNF^x nanofillers, and scanning electron microscopic analyses of profile surfaces of the etched drawn fibers were performed. This is the first work in this area of research wherein very small amounts of MCNF^x nanofillers prepared from cotton fibers were efficiently used as nucleating agents to enhance the ultradrawing and ultimate tensile properties of F₁₀₀MCNF^x_y fibers. Copyright © 2016 John Wiley & Sons, Ltd.     

The Prenucleation Equilibrium of the Parathyroid Hormone Determines the Critical Aggregation Concentration and Amyloid Fibril Nucleation

Nucleation and growth of amyloid fibrils were found to only occur in supersaturated solutions above a critical concentration (c_crit). The biophysical meaning of c_crit remained mostly obscure, since typical low values of c_crit in the sub-μM range hamper investigations of potential oligomeric states and their structure. Here, we investigate the parathyroid hormone PTH₈₄ as an example of a functional amyloid fibril forming peptide with a comparably high c_crit of 67±21 μM. We describe a complex concentration dependent prenucleation ensemble of oligomers of different sizes and secondary structure compositions and highlight the occurrence of a trimer and tetramer at c_crit as possible precursors for primary fibril nucleation. Furthermore, the soluble state found in equilibrium with fibrils adopts to the prenucleation state present at c_crit. Our study sheds light onto early events of amyloid formation directly related to the critical concentration and underlines oligomer formation as a key feature of fibril nucleation. Our results contribute to a deeper understanding of the determinants of supersaturated peptide solutions. In the current study we present a biophysical approach to investigate c_crit of amyloid fibril formation of PTH₈₄ in terms of secondary structure, cluster size and residue resolved intermolecular interactions during oligomer formation. Throughout the investigated range of concentrations (1 μM to 500 μM) we found different states of oligomerization with varying ability to contribute to primary fibril nucleation and with a concentration dependent equilibrium. In this context, we identified the previously described c_crit of PTH₈₄ to mark a minimum concentration for the formation of homo-trimers/tetramers. These investigations allowed us to characterize molecular interactions of various oligomeric states that are further converted into elongation competent fibril nuclei during the lag phase of a functional amyloid forming peptide.     

Cellulose fibers modified with silver nanoparticles

Cellulose fibers modified with silver nanoparticles were prepared using N-methylmorpholine-N-oxide as a direct solvent and analyzed in this study. Silver nanoparticles were generated as a product of AgNO₃ reduction by means of three methods under varying light conditions (daylight and darkroom). Influence of generating conditions on the size, the type and the number weighting of created nanoparticles was examined. Dynamic Light Scattering technique (DLS) was used for determination of those parameters. DLS analysis showed that the best method, i.e. the one that allowed the generation of the greatest number of silver nanoparticles with the smallest diameter and the smallest agglomerates, was incubation of cellulose pulp with AgNO₃ in a darkroom for 24 h. Mechanical and hydrophilic properties of all obtained fibers were also determined. Results showed that the method of silver nanoparticles generation did not influence significantly mechanical and hydrophilic properties of the modified fibers, because in all cases only small decreases of the studied parameters were observed.     

pH‐Controlled Formation of a Stable β‐Sheet and Amyloid‐like Fibers from an Amphiphilic Peptide: The Importance of a Tailor‐Made Binding Motif for Secondary Structure Formation

The new amphiphilic peptide 1 is composed of alternating cyclohexyl side chains and guanidiniocarbonyl pyrrole (GCP) groups. In contrast to analogue 2 , which contains lysine instead of the GCP groups and only exists as a random coil owing to charge repulsion, peptide 1 forms a stable β‐sheet at neutral pH in aqueous medium. The weakly basic GCP groups (pK_a≈7) are key for secondary structure formation as they stabilize the β‐sheet through mutual interactions (formation of a “GCP zipper”). The β‐sheets further aggregate into left‐handed helically twisted fibers. However, β‐sheet formation is completely reversible as a function of pH. At low pH (ca. 4), peptide 1 is unstructured (random coil) as all GCP units are protonated. Only round colloidal particles are observed. The amyloid nature of the fibers formed at neutral pH was confirmed by staining experiments with Congo Red and thioflavin T. Furthermore, at millimolar concentrations, peptide 1 forms a stable hydrogel.