Quantification of degradation and surface morphology of NB7 silk fibers irradiated by 8 MeV electron beam using XRD and SEM techniques

NB7 silk fiber (Bombyx mori) was irradiated with the maximum dose range of 100 kGy using 8 MeV electron beam at room temperature. Irradiation effect in these fibers is quantified in terms of the changes in microstructural parameters employing X-ray diffraction line profile analysis technique. For this purpose we have used three asymmetric distribution functions for column lengths in a crystal. The decreasing trend of crystallite size values (〈N〉 as well as D _s ) and crystallinity with increasing dosage of radiation clearly indicates the degradation of fiber. Of the several factors responsible for such a behavior, we presume that the chain scission of polymer network is a significant one over others and it is well pronounced here, leading to low molecular weight of the samples. This degradation is attributed to many changes in tensile properties of the polymer. Comparison of SEM photographs also confirms the X-ray results.     

The role of thermal stabilization on the structure and mechanical properties of polyacrylonitrile precursor fibers

The thermal stabilization stage of polyacrylonitrile (PAN) fibers is characterized by a steady and continuous reduction in fiber diameter and linear density values together with color changes from reddish brown to shiny black with increasing stabilization time. Thermally stabilized PAN fibers acquire infusible and nonburning characteristics prior to the carbonization stage. Structural characterization of thermally stabilized polyacrylonitrile fibers was carried out using an indepth analysis of equatorial X-ray diffraction traces. Curve fitting of X-ray diffraction traces provided accurate peak parameters which were subsequently used for the evaluation of apparent crystallinity, apparent crystallite size and X-ray stabilization index. The results showed the loss of crystallinity due to the amorphization processes together with a steady and continuous decrease in lateral crystallite size with increasing stabilization time. With the progress of thermal stabilization, a new amorphous phase with a crosslinked and aromatized structure is formed which is expected to withstand high carbonization temperatures. Mechanical properties of the thermally stabilized PAN precursor fibers were found to be adversely affected with the progress of stabilization time. Due to the influence of thermal degradation mechanisms heavily involving chain scission along the fiber axis direction, tensile strength and tensile modulus values were found to decrease by significant proportions with the prolonged stabilization times.     

An in depth study of crystallinity, crystallite size and orientation measurements of a selection of poly(ethylene terephthalate)fibers

A selection of commercially available poly(ethylene terephthalate) fibers with different degrees of molecular alignment and crystallinity have been investigated utilizing a wide range of techniques including optical microscopy, infrared spectroscopy together with thermal and wide-angle X-ray diffraction techniques. Annealing experiments showed increased molecular alignment and crystallinity as shown by the increased values of birefringence and melting enthalpies. Crystallinity values determined from thermal analysis, density, unpolarized infrared spectroscopy and X-ray diffraction are compared and discussed in terms of the inherent capabilities and limitations of each measurement technique. The birefringence and refractive index values obtained from optical microscopy are found to decrease with increasing wavelength of light used in the experiments. The wide-angle X-ray diffraction analysis shows that the samples with relatively low orientation possess oriented non-crystalline array of chains whereas those with high molecular orientation possess well defined and oriented crystalline array of chains along the fiber axis direction. X-ray analysis showed increasing crystallite size trend with increasing molecular orientation. SEM images showed micro-cracks on low oriented fiber surfaces becoming smooth on highly oriented fiber surfaces. Excellent bending characteristics were observed with knotted fibers implying relatively easy fabric formation.     

X-ray diffraction studies of poly(aryl ether ether ketone) fibers with different degrees of crystallinity and orientation

A selection of commercially available poly(ethylene terephthalate) fibers with different degrees of molecular alignment and crystallinity have been investigated utilizing a wide range of techniques including optical microscopy, infrared spectroscopy together with thermal and wide-angle X-ray diffraction techniques. Annealing experiments showed increased molecular alignment and crystallinity as shown by the increased values of birefringence and melting enthalpies. Crystallinity values determined from thermal analysis, density, unpolarized infrared spectroscopy and X-ray diffraction are compared and discussed in terms of the inherent capabilities and limitations of each measurement technique. The birefringence and refractive index values obtained from optical microscopy are found to decrease with increasing wavelength of light used in the experiments. The wide-angle X-ray diffraction analysis shows that the samples with relatively low orientation possess oriented non-crystalline array of chains whereas those with high molecular orientation possess well defined and oriented crystalline array of chains along the fiber axis direction. X-ray analysis showed increasing crystallite size trend with increasing molecular orientation. SEM images showed micro-cracks on low oriented fiber surfaces becoming smooth on highly oriented fiber surfaces. Excellent bending characteristics were observed with knotted fibers implying relatively easy fabric formation.     

Surface modifications of natural Kanchipuram silk (pattu) fibers using glow discharge air Plasma

Experimental investigations have been carried out to modify the surface properties of natural Kanchipuram silk (pattu) fibers using a low temperature DC glow discharge air Plasma. Silk is an externally spun fibrous protein secretion formed into fibers. Plasma treatment is an eco-friendly, dry, and clean process over wet chemical method and does not suffer from any environmental and health concerns. Experiments have been performed considering three parameters such as discharge current, treatment time, and working pressure. The structural, thermal, morphological, optical, and mechanical studies of raw and plasma treated silk fibers have been obtained out using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), thermo gravimetric analyzer (TGA), scanning electron microscope (SEM) with energy dispersive spectroscopy (EDS), diffuse absorbance spectroscopy, and tensile test. A comparative study has been done for the untreated and different treated fibers. Various characterization analyses reveal that surface roughness of the plasma treated silk fiber is increased and also crystallite size of treated samples is enhanced, plasma treated silk fibers maintain the whiteness effect and it is observed that UV transmittance region (A & B) is more for the treated fiber which signifies enhanced UV protection.     

Mechanical properties of flax-g-poly(methyl acrylate) reinforced phenolic composites

In order to develop composites with better mechanical properties and environmental performance, it becomes necessary to increase the hydrophobicity of the natural fibers and to improve the interface between matrix and natural fibers. Graft copolymerization of natural fibers is one of the best methods to attain these improvements. Only few workers have reported the use of graft copolymers as reinforcing material in the preparation of composites. So in the present paper, we report the preparation of graft copolymers of flax fibers with methyl acrylate (MA) using Fenton’s reagent (FAS-H₂O₂) as redox system. Synthesized flax-g-poly(MA) was characterized with FTIR, TGA/DTA, scanning electron microscopy (SEM), and X-ray diffraction (XRD) techniques. Composites were prepared using flax-g-poly(MA) as a reinforcement and phenolformaldehyde (PF) as the binding material. Mechanical properties of phenol-formaldehyde composites were compared and it has been found that composites reinforced with flax-g-poly(MA) showed improvement in mechanical properties. Composites reinforced with flax-g-poly(MA) showed better tensile strength (235 N) and compressive strength (814 N) in comparison to composites reinforced with original flax fiber which showed lesser tensile strength (162 N) and compressive strength (372 N). Composites reinforced with flax-g-poly(MA) shows the improved MOR, MOE, and SP.     

Stress-strain curves and corresponding structural parameters in mulberry and non-mulberry silk fibers

Mulberry fiber (Bivoltine) and non-mulberry fiber (Tassar) were subjected to stress-strain studies and the corresponding samples were examined using wide angle X-ray scattering studies. Here we have two different characteristic stress-strain curves and this has been correlated with changes in crystallite shape ellipsoids in all the fibers. Exclusive crystal structure studies of Tassar fibers show interesting feature of transformation from antiparallel chains to parallel chains.     

Structural and physical properties ofAntheraea pernyi silk fibroin fiber treated with I2-KI aqueous solution

Silk fibroin (SF) fiber from theAntheraea pernyi silkworm was treated with a 1.23 N iodine-potassium iodide (I₂-KI) aqueous solution, and the structure and physical properties were investigated to clarify the effects of the iodine treatment. The noticeably high weight gain value of SF fiber, about 25 wt% was attributed to the absorption of polyiodide ions in the form of I₃ ^? and I₅ ^?. Fourier transform infrared spectroscopy and X-ray diffraction measurements suggested that polyiodide ions mainly entered the amorphous region. In addition, a new sharp reflection on the meridional direction, corresponding to a period of 7.0 Å, was observed and indicated the possibility of the formation of mesophase structure ofβ-conformation chains. Dynamic viscoelastic measurements showed that the damping tanδ peak at 270°C gradually shifted to lower temperature in the iodinated SF fibers, suggesting an enhancement of the molecular motion of the fibroin chains induced by the presence of polyiodide ions. With heating above 254 °C, the iodine component introduced intermolecular cross-linking of SF, and the melt flow of the sample was inhibited. The thermal decomposition stability of fibroin molecules was greatly enhanced by iodine treatment.     

Investigation of the effect of cupric chloride on thermal stabilization of polyamide 6 as carbon fiber precursor

An investigation on the role of cupric (Cu²⁺) ion incorporation during the thermal stabilization of polyamide 6 fibers was carried out using a combination of differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and X-ray diffraction (XRD) measurements. Cupric chloride pretreated and thermally stabilized polyamide 6 (PA6) fibers was characterized by a reduction in fiber diameter and linear density values together with color changes from light brown to black with increasing stabilization time. PA6 fibers were properly stabilized after 8 h of stabilization time prior to carbonization. The results obtained from DSC and TGA measurements indicated that there was an improvement in the thermal stability when cupric (Cu²⁺) ions were incorporated into the polymer structure. TGA thermograms showed the relative improvement in thermal stability as indicated by increasing char yield with progressing time. Char yield reached a maximum value of 33.6 % at 1000 °C for the cupric chloride pretreated PA6 fibers stabilized for 12 h at 180 °C. Experimental results obtained from DSC and X-ray diffraction methods suggested the loss of crystallinity as a result of perturbation of hydrogen bonds with progressing time. The formation of cupric ion-amide coordination bonds improved the thermal stabilization by encouraging the development of ladder-like structures. The investigation resulted in a new method of evaluation of X-ray stabilization index specifically intended for the thermally stabilized PA6 fiber.     

A study on structural characterization of thermal stabilization stage of polyacrylonitrile fibers prior to carbonization

Structural transformations taking place during the thermal stabilization of polyacrylonitrile (PAN) fiber used for the production of carbon fiber were characterized using a combination of polarized infrared spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and density measurements. Direct relationship between the increasing oxygen content and the density values was confirmed with increasing stabilization time. Linear density values were found to be directly influenced by the stabilization time. Thermal stability of stabilized precursor fibers was evaluated in terms of weight loss and residual weight fraction. The results showed that a residual weight fraction of 65 % at 1000 °C can be obtained but longer stabilization time resulted in a loss of residual weight fraction due to excessive thermal degradation. SEM was used for the observation of surface morphological features of stabilized precursor fibers. Polarized infrared spectroscopy showed the loss of molecular orientation of methylene (CH₂), nitrile (Ct=N), and carbonyl (C=O) groups in direct response to the effects of cyclization, dehydrogenation, and amorphization (i.e. decrystallization) processes taking place during the stabilization stage.     

Surface Treated Jute Fiber Induced Foam Microstructure Development in Poly(lactic acid)/Jute Fiber Biocomposites and their Biodegradation Behavior

Poly(lactic acid) (PLA)/jute fiber biocomposites with: i) untreated jute fiber, ii) NaOH treated jute fiber, and iii) (NaOH+silane) treated jute fibers were prepared by melt extrusion process. Microcellular foaming of the injection molded samples was carried out by using single stage batch process. The effects of jute fiber content as well as that of matrix-fiber phase adhesion, in composites with surface treated jute fibers, on the foam microstructure were studied. Further, water absorption, thickness swelling, and biodegradation behavior of the foamed biocomposites were studied and correlated with their foam microstructures. It was observed that on increasing jute fiber content in PLA/JFU biocomposites, cell density increased from 6.5×10⁷ to 8.1×10⁷, while the cell size and expansion ratio decreased from 40 to 23 μm and 2.41 to 1.45, respectively. Again, on increasing the extent of the jute fiber surface treatment in the biocomposites, cell size and expansion ratio increased from 40 to 78 μm and 2.41 to 2.80 respectively. This study also revealed that the rate of biodegradation accelerated with increase in the jute fiber content in the biocomposites while the same retarded with increase in the extent of jute fiber surface treatment.     

Surface modification of polyester fibers by thermal reduction with silver carbamate complexes

In this study, the surface of polyester fiber was modified by means of thermal treatment with a silver carbamate complex. We used scanning electron microscopy (SEM), an X-ray diffraction technique (XRD), and X-ray photoelectron spectroscopy (XPS) to allow a detailed characterization of the silver-coated polyethylene terephthalate (PET) fibers. The results revealed remarkable changes in the surface morphology and microstructure of the silver film after thermal reduction. On SEM, the silver nanoparticles (AgNPs) were seen to be uniformly and densely deposited on the fiber surface. The XRD pattern of the silver-coated fiber indicated that the film has a crystalline structure. A continuous layer of AgNPs, between 30 and 100 nm in size, was assembled on the PET fibers. The PET/Ag composite was found to impart high conductivity to the fibers, with an electrical resistivity as low as 0.12 kΩ·cm.     

Fabrication and surface modification of melt-electrospun poly(D,L-lactic-co-glycolic acid) microfibers

In this study, biodegradable poly(D,L-lactic-co-glycolic acid) (PLGA) fibers were prepared by a melt-electrospinning and treated with plasma in the presence of either oxygen or ammonia gas to modify the surface of the fibers. The effects of processing parameters on the melt-electrospinning of PLGA were examined in terms of fiber morphology and diameter. Among the processing parameters, the spinning temperature and mass flow rate had a significant effect on the average fiber diameter and its distribution. The water contact angle of melt-electrospun PLGA fibers decreased significantly from 123 ° to 55 ° (oxygen plasma treatment) or to 0 ° (ammonia plasma treatment) by plasma treatment for 180 sec, while their water content increased significantly from 2.4 % to 123 % (oxygen plasma treatment) or to 189 % (ammonia plasma treatment). Ammonia gas-plasma enhanced the surface hydrophilicity of PLGA fibers more effectively compared to oxygen gas-plasma. X-ray photoelectron spectroscopy analysis supported that the number of polar groups, such as hydroxyl and amino groups, on the surface of PLGA fibers increased after plasma treatment. Overall, the microfibrous PLGA scaffolds with appropriate surface hydrophilicity and fiber diameter could be fabricated by melt electrospinning and subsequent plasma treatment, without a significant deterioration of fiber structure and dimensional stability. This approach of controlling the surface properties and structures of fibers could be useful in the design and tailoring of novel scaffolds for tissue engineering.     

Modeling and differential evolution optimization of PAN carbon fiber production process

In this research, results of an experimental and artificial neural network fuzzy interface system (ANFIS) modeling of operating parameters on tensile strength of the carbon fibers are investigated. To do these experiments, the commercial polyacrylonitrile (PAN) fiber of Polyacryl Iran Corporation (PIC) was used as the precursors. The results show that increasing all of parameters improves tensile strength performance. ANFIS was applied to predict tensile strength of carbon fibers as a function of stabilization temperature at first stage (STFIS), stabilization temperature at second stage (STSS), stabilization temperature at third stage (STTS), stabilization temperature at fourth stage (STFOS), and carbonization temperature (CT). The optimum levels of influential factors, determined for tensile strength are STFIS 200 °C, STSS 225 °C, STTS 240 °C, STFOS 260 °C, CT, and 1400 °C. The modeling results showed that there is an excellent agreement between the experimental data and the predicted values. Furthermore, the fiber process is optimized applying differential evolution (DE) algorithm as an effective and robust optimization method.     

Organic Wastes for Improving Soil Physical Properties and Enhancing Plant Growth in Container Substrates

Summary

Increasing rates (5, 10, 25 and 40% v/v) of 6 sources of organic wastes were substituted for peat to assess changes in the physical properties of peat-perlite substrates and investigate the relationship between plant response and these properties. Wastes were either fresh or composted bio-filter sludge (FBF and CBF), sewage sludge (FSS and CSS), and de-inked paper sludge (FDP and CDP). Geranium plants (Pelagornium× hortorum ‘Orbit Hot Pink’) were grown in the substrates. Growing substrates' saturated hydraulic conductivity (K_s), air-filled porosity (f _a), pore tortuosity (t), and relative gas diffusivity (D_s/D_o) all increased linearly (p = 0.0001) as the rate of organic wastes increased. Geranium plant height (PHT), shoot dry mass (SDM) and root dry mass (RDM) were either linearly or quadratically decreased (p = 0.0001) as the amount of waste increased in the substrates. During both growing seasons, Geranium SDM and RDM were either linearly or quadratically correlated with D_s/D_o and t. Organic waste types and their rate of application strongly affected the aeration status of the substrates. D_s/D_o and t better expressed the relationship between plant growth and the physical conditions of the root zone.     

Multifunctional modification of wool fabric using graphene/TiO<Subscript>2</Subscript> nanocomposite

In this study, a new finishing technique is introduced through treatment of wool fabric with graphene/TiO₂ nanocomposite. Graphene oxide/titanium dioxide nanocomposite first applied on the wool fabric by hydrolysis of titanium isopropoxide in graphene oxide suspension and then this coating chemically converted by sodium hydrosulfite to graphene/TiO₂ nanocomposite. The homogenous distribution of the graphene/TiO₂ nanocomposite on the fiber surface was confirmed by field emission scanning electron microscopy (FE-SEM), Energy-dispersive X-ray spectroscopy (EDS) and X-ray mapping. X-ray diffraction patterns proved the presence of titanium dioxide nanoparticles with a crystal size of 127 Å on the treated wool fabric. Also, the defect analysis based on X-ray photoelectron spectroscopy (XPS) established the composition of the nanocomposite. Other characteristics of treated fabrics such as antibacterial activity, photo-catalytic self-cleaning, electrical resistivity, ultraviolet (UV) blocking activity and cytotoxicity were also assessed. The treated wool fabrics possess significant antibacterial activity and photo-catalytic self-cleaning property by degradation of methylene blue under sunlight irradiation. Moreover, this process has no negative effect on cytotoxicity of the treated fabric even reduces electrical resistivity and improves UV blocking activity.     

Modelling net photosynthetic rate of field-grown cocksfoot leaves under different nitrogen, water and temperature regimes

A simple multiplicative model using temperature, foliage nitrogen (N) concentration and water status was developed to predict the maximum photosynthetic rate (Pmax) of field‐grown cocksfoot (Dactylis glomerata L.) leaves when none, one, two or all the factors were limiting. The highest Pmax was 27·4 μmol CO₂ m^–2 s^?1 in non‐limited conditions, which was defined as the standardized Pmax value dimensionless (Pmax_s=1). Pmax_s increased 0·058 units per °C from 10°C to the optimum range (19–23°C) (Pmax_s=1) and then declined 0·077 units of Pmax_s per °C from 23 to 31°C. Pmax_s=1 was also measured from 59 to 52 g N kg^?1 dry matter (DM) foliage N. Pmax_s then decreased at the rate of 0·115 units per 10 g N kg^?1 DM from 52 to 26 g N kg^?1 DM, and 0·409 units of Pmax_s per 10 g N kg^?1 DM from 26 to 15 g N kg^?1 DM. For predawn leaf water potential (ψ_lp), Pmax_s=1 was measured from ?0·1 to ?1·2 bar but declined linearly at a rate of 0·078 units per bar of ψ_lp from ?1·2 to ?14·0 bar because of a linear decrease in stomatal conductance. An interaction between low N content (≤20 g N kg^?1 DM) and high temperature (>23°C) was also detected. Together, this multiplicative model accounted for 0·82 of the variation in Pmax_s.     

Modification of polyacrylonitrile precursor fiber with hydrogen peroxide

Polyacrylonitrile (PAN) precursor fibers were modified for different periods of time using hydrogen peroxide aqueous solution. A variety of tests were employed to characterize the fibers. The modification could induce cyclization and oxidation in the precursor fibers, as reflected by the changes in length and diameter of the fibers, and the results of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Compared with the unmodified fiber, the modified fibers released less heat during a heating process similar to stabilization of PAN precursor fiber. Also, the modified fibers showed lower characteristic temperatures on differential scanning calorimetry (DSC) thermograms, and lower onset temperature of weight loss on thermal gravimetry (TG) curves. The modified fibers had more surface defects and hence exhibited lower tenacity and tensile modulus. Compared with the unmodified fibers, however, the modified fibers had smoother surface and fewer defects after stabilization. The strain decreased with increasing temperature under a constant tension for all the fibers. At the temperatures above 200 °C, the shrinkage of the fibers decreased with the increase of modification time, because a certain degree of cyclization and oxidation occurred in modified fibers, making them shrink less in the temperature range equivalent to stabilization.     

The effects of UV irradiation exposure on the structure and properties of polypropylene/ZnO nanocamposite fibers

Unfilled polypropylene and polyropylene/ZnO nanocomposite fibers were produced using a melt spinning apparatus; then the fibers were exposed to UV irradiation. The structure and properties of the fibers were examined using scanning electron microscopy, tensile measurements, wide angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy, birefringence measurements and differential scanning calorimetry (DSC). Following 150 hours of exposure to UV irradiation, some transverse cracks on the surface of unfilled polypropylene fibers were observed. It was observed that both carbonyl and hydroperoxide indexes, which are the criteria for the detection of UV degradation of the fibers, were increased due to the increase in the UV irradiation exposure time and the increase in these indexes was smaller for nanocomposite fibers than those of unfilled Polypropylene fibers. It was also observed that crystallinity, crystallite size and total molecular orientation of UV irradiated nanocomposite fibers were increased in comparison with non-irradiated nanocomposite fibers. It was also found that the extent of increase in molecular orientation of the fibers was higher comparing to that for the nanocomposite fibers due to the UV irradiation exposure for the unfilled polypropylene fibers. Tensile properties of both unfilled and nanocomposite fibers were decreased after UV irradiation; this reduction correlated with the extent of the increase in molecular degradation of the fibers, as determined by measuring carbonyl and hydroperoxide indexes.     

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.