Mechanical property optimization of wet-spun lignin/polyacrylonitrile carbon fiber precursor by response surface methodology

Lignin, nature’s abundant polymer with a remarkably high carbon content, is an ideal bio-renewable precursor for carbon fiber production. However, the poor mechanical property of lignin-derived fibers has hindered their industrial application as carbon fiber precursor. In this work, process engineering through the application of computational modeling was performed to optimize wet-spinning conditions for the production of lignin precursor fibers with enhanced mechanical properties. Continuous lignin-derived precursor fibers with the maximum possible lignin content were successfully produced in a blend with polyacrylonitrile, as a wet-spinning process facilitator. Response surface methodology was employed to systematically investigate the simultaneous influence of material and process variables on mechanical properties of the precursor fibers. This allowed generating a mathematical model that best predicted the tensile strength of the precursor fibers as a function of the processing variables. The optimal wet-spinning conditions were obtained by maximizing the tensile strength within the domain of the developed mathematical model.     

Spinnability in pre-gelled gel spinning of polyacrylonitrile precursor fibers

The spinnability in pre-gelled gel spinning of polyacrylonitrile (PAN) precursor fibers was investigated. The spinning solutions were aged at 25 °C for different times prior to fiber spinning. The pre-gelled spinning solution aged for 2.5 h was much more strain hardening than the ungelled one, which can increase the spinnability of the solution. The maximum take-up velocity of the first winding roller V _1m, which reflects the spinnability of the spinning solutions, was found to be largest when the aging time was 1.5 h. The spinnability increased with the increase of the air gap length and the lengthdiameter ratio L/D of the spinnerette. Once the L/D increased beyond 15, the spinnability hardly changed. The fibers spun from the spinning solution aged for 1.5 h had the best mechanical properties and favorable structure, showing that good spinnability favors the performance increase of resultant PAN precursor fibers.     

Grafting of casein onto polyacrylonitrile fiber for surface modification

Polyacrylonitrile (PAN) fiber was grafted with casein after alkaline hydrolysis and chlorination reactions of the original fiber. The structures and morphologies of the casein grafted fiber were characterized by Fourier transform infrared spectroscopy (FTIR), X-Ray diffraction (XRD), and scanning electron microscope (SEM). Moisture absorption, specific electric resistance, water retention value, and mechanical properties were also investigated. The results showed that casein was grafted onto the surface of the PAN fiber and the grafted PAN fiber presented better hygroscopicity compared with the untreated fiber. With proper tensile strength, the modified fiber could still meet the requirement for wearing. A mechanism was proposed to explain the deposit of casein on the synthetic acrylic fiber.     

Depositon of ZnO on polyacrylonitrile fiber by thermal solvent coating

In this study, the surface functionalization of polyacrylonitrile (PAN) fibers was achieved by depositing ZnO nanoparticles using thermal solvent coating. surface morphology, crystalline structure, surface chemistry, thermal stability and washing stability of the ZnO coated PAN fibers were investigated by scanning electron microscope (SEM), X-ray diffractometer (XRD), Fourier transform Infra red spectroscopy (FT-IR), Thermo-gravimetric analyses (TGA) and washing stability test, respectively. In addition, the weight changes after coating and washing were studied at different coating and washing conditions. The SEM images revealed that the ZnO was well coated on the surface of the PAN fibers and the coating was obviously affected by the experimental temperature. The FT-IR spectra indicated the chemical features of the deposited ZnO nanostructures. The XRD patterns showed that there was a typical crystalline structure of ZnO nanogains formed on the PAN fibers after coating. The TGA results revealed that the thermal stability of the PAN fibers was improved by the ZnO coating. The experimental results of washing stability revealed the effect of temperature on the washing stability. Weight measurements indicated that the amount of ZnO deposited on PAN fibers increased with the increasing of coating temperature from 60 to 70 °C. Weight measurements also revealed that the weight of the ZnO coating on fibers decreased with the increase in washing temperature and washing time.     

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.     

Study of hydrogen peroxide,potato enzymes and blackspot

The rate of oxidation of tyrosine, p-cresol and catechol by potato enzyme diminished as H₂O₂ concentration increased. By contrast, the rate of oxidation of chlorogenic acid in the presence of H₂O₂ increased. Bovine catalase destroyed H₂O₂ and thus effectively prevented either H₂O₂-induced inhibition or acceleration of oxidation of the four substrates by potato enzyme. Horseradish peroxidase in the presence of H₂O₂ did not oxidize either monophenol, but oxidized both polyphenols. Possible association of H₂O₂, peroxidase and catalase with blackspot susceptibility is discussed.     

Preparation and characterization of a novel antibacterial fiber modified by quaternary phosphonium salt on the surface of polyacrylonitrile fiber

A novel antibacterial fiber named MTPB-PANF was synthesized by chemical modification of polyacrylonitrile fiber (PANF). The PANF was firstly reacted with alkali solution to get Na-PANF with -COONa functional groups. Na-PANF was then reacted with different concentration of methyltriphenyl phosphonium bromide (MTPB) into flasks, and the whole system was immersed into a to and fro vibrator. During the synthesis process, this paper investigated on the initial concentration of MTPB, the contact time, the reaction temperature and the pH of the solution that may have effect on the properties of the final fiber. The properties of MTPB-PANF were discussed by fourier transform infrared spectroscopy (FTIR), thermo gravimetric analyzer (TGA), scanning electron microscope (SEM) and the stability of organophosphorus groups on MTPB-PANF examined by inductively coupled plasma atomic emission spectrometry (ICP-AES). The antibacterial activity of MTPB-PANF was examined against pathogenic Escherichia coli and Staphylococci aureus by improved shake flask method in sterile saline and was evaluated by the viable cell counting method. The obtained results showed an excellent antibacterial activity of MTPB-PANF. And the antibacterial mechanism was discussed by the concentration of K⁺ released from cells after bacterial testing.     

Studies on a novel polyacrylonitrile copolymer/cellulose acetate blending water absorbency fiber

Polyacrylonitrile copolymer (CPAN) was obtained by water-deposit polymerization, using acrylonitrile (AN), vinyl acetate (VAc), potential crosslinking moiety (hydropropyl acrylate, HQ) as monomer, NaClO₃ as initiator. CPAN was blended with cellulose acetate (CA) to prepare CPAN/CA blending fiber via wet spinning. The fiber was post-crosslinked and hydrolyzed to get water absorbency fiber. The structures and properties of the fibers were studied and the results showed that potential crosslinking moiety was necessary in making CPAN/CA blending water absorbency fiber. The saponification reaction was accelerated after blended with CA and the interfacial microvoids enhanced the water absorbency ability.     

Effect of peroxide and softness modification on properties of ramie fiber

Ramie fiber is one of the natural cellulose fibers that have undergone rapid development due to its good performance. This study confirmed that hydrogen peroxide and isopropyl alcohol can be used as very efficient agents for simultaneous removal of non-cellulosic substances and improvement of ramie fiber properties. The factors influencing the properties of modified fiber with combined chemicals were investigated. Optimum treatment conditions were achieved at 85 °C, 60 min, pH 11.0, hydrogen peroxide concentration 7 %, and isopropyl alcohol concentration 4 %. SEM, XRD, and FT-IR were used to elucidate the effects of preparation and modification. Results showed that fiber preparation and chemical modification process in the same bath solution could successfully remove most of the gummy materials. The treated fibers demonstrated improved softness, elongation, and fineness properties as compared to the alkali or peroxide method.     

Processing and characterization of polyacrylonitrile/soy protein isolate/polyurethane wet-spinning solution and fiber

Using dimethyl sulfoxide (DMSO) as a solvent, the polyacrylonitrile/soy protein isolate/polyurethane (PAN/SPI/PU) blend solutions and wet-spun fibers were prepared. The rheological properties of the PAN/SPI/PU solution were investigated. Investigations of the structure and properties of the PAN/SPI/PU fibers involved Fourier transform infrared, enzymatic hydrolysis, scanning electron microscopy, mechanical properties, dye adsorption, contact angle, and moisture regain measurements. The results showed that all PAN/SPI/PU solutions possess pseudoplastic properties, and there are opposite effects of SPI and PU in the PAN/DMSO solution. The apparent viscosity, the amount of non-Newtonian fluid and the extent of structuralization of the PAN/DMSO solution increase with the addition of SPI, whereas these features all decrease with the addition of PU. The biodegrability, the absorption of acidic dye and the moisture regain increase with the proportional increase in weight of SPI in the fiber blend.     

Dyeing behavior of polyacrylonitrile nanofibers: Physicochemical parameters of dyeing with basic dye in comparison with regular polyacrylonitrile fibers

Polyacrylonitrile nanofibers were produced using the electrospinning method and dyed with a basic dye alongside regular polyacrylonitrile fibers. In order to investigate the effect of high surface area to volume ratio of nanofibers on their adsorption behavior in comparison with regular fibers, the dyeing conditions for both types of fibers were kept just the same. Physiochemical parameters of dyeing such as adsorption isotherm, standard affinity, enthalpy change, rate of dyeing constant, diffusion coefficient, and activation energy of diffusion were investigated for both types of fibers. The results showed that the adsorption process can be well described with the Langmuir adsorption isotherm for both types of fibers whereas the standard affinity of dye to nanofibers was higher than regular fibers and the higher negative values of enthalpy changes were obtained for regular fibers. The nanofibers rate of dyeing was faster than regular fibers with higher amounts of diffusion coefficients and lower amounts of activation energy of diffusion. This study also revealed that in spite of the approximately same amount of dye exhaustion for both types of fibers, the color strength of regular fibers was noticeably higher than nanofibers.     

H2O2浸种对晚直播油菜生长及产量的影响

H2O2浸种能够促进低温胁迫下油菜种子的物质代谢,为适应直播油菜不同播期生产需求,研究H2O2浸种对不同播期油菜生长发育的影响,提高晚直播油菜产量。2017年以南农油4号为材料,设置播期(早播10月5日,晚播10月25日)和0.05%的H2O2浸种两个因素,采用露天盆栽试验观察油菜在越冬期的光合特性及全生育期生长发育动态。结果表明:(1)晚播使油菜苗期延长而蕾薹期缩短,初花前可利用积温从1349.5℃·d减少至1095.5℃·d,导致油菜营养生长期干物质积累减少,而生殖生长期活动积温升高,相比早播的1042.5℃·d升高为1119.5℃·d。由于晚播生育期缩短,活动积温减少,干物质积累降低,最终显著减产8.3%。(2) H2O2浸种处理对早播油菜萌发出苗及地上部生物量无显著影响,但显著抑制了地下部生物量及光合能力,降低了越冬期干物质积累,继而影响后期产量形成,最终造成油菜显著减产,降幅为10.9%。(3) H2O2浸种处理促进了晚播油菜萌发出苗,增大叶面积,促进了油菜干物质积累使产量显著升高,增幅为15.7%。因此在油菜晚直播条件下,可通过H2O2浸种处理以提高产量。     

Effect of hydrogen peroxide and ozone treatment on improving the malting quality

The effect of hydrogen peroxide (HP) and ozone (O₃) treatment during barley steeping on the quality of malt produced from two barley varieties (GrangeR and AC Metcalfe) by micro-malting was investigated. The two steeping oxidation treatments that was observed to promote barley acrospire growth. Ozone treatment improved the malt enzyme activity of endo-protease, α-amylase, free beta-amylase and total limit dextrinase to differing extents, with GrangeR improving to a greater degree. HP treatment contributed to the increase of α-amylase, β-glucanase and endo-protease. Surprisingly, HP or ozone oxidation during malting resulted in different and novel outcomes for total beta-amylase in GrangeR and AC Metcalfe. In GrangeR, total beta-amylase activity reduced with respect to the control in both treatments. In comparison with AC Metcalfe there was a substantial increase of 78% with HP and 90% O₃ in total beta-amylase activity. Malt quality including wort free amino nitrogen, β-glucan, turbidity and diastatic power was differentially increased by the oxidation induction treatment during steeping in malting. Gene expression analysis indicated that the effects of the steep oxidation treatments on enzyme and malt quality were putatively linked with the up-regulation of certain genes involved in GA synthesis (GA20ox1) and ABA catabolism (ABA8′OH). Barley grain germination assay results also showed that moderate HP induction could improve barley germination tolerance to the ABA effect. Malting including steep oxidation induction was shown to be beneficial to malt quality by improving the resultant wort quality and the efficiency of the beer brewing process. These observations point the way towards improving malt quality and the efficiency of the malting process.     

Preparation of aminated polyacrylonitrile porous fiber mat and its Application for Cr(VI) ion removal

Porous polyacrylonitrile (PAN) fiber mat was prepared by electrospinning PAN in N,N-dimethylformide solution with poly(methyl methacrylate) (PMMA) as pore-forming agent. Then, the porous PAN fiber mat was chemical modified by the tetraethylenepentamine to acquire aminated porous polyacrylonitrile (APPAN) fiber mat. Common aminated PAN fiber mat was also prepared for comparison. The surface morphologies of the APPAN and PAN fiber mat were characterized by scanning electron microscopy (SEM) and the corresponding specific surface areas were also measured. FT-IR/ATR spectra of the APPAN and PAN fiber mat were recorded for analysis of the surface chemical structures. The Cr(VI) absorption results demonstrated that the porous structure in the fiber could obviously increase the absorption capacity of the fiber mat.     

Antibacterial mechanism of polyacrylonitrile fiber with organophosphorus groups against <Emphasis Type="Italic">Escherichia coli</Emphasis>

A series of novel polyacrylonitrile fibers (PANF) with organophosphorus groups (OPh-PANF) showing unique antibacterial activities were synthesized in our previous studies. To understand the antibacterial mechanism of OPh-PANF, E. coli was selected as the model of Gram-negative bacteria and a list of biological experiments were conducted and analyzed in the current study. Results from scanning electron microscope (SEM), transmission electron microscope (TEM) and flow cytometry (FCM) analyses showed that the integrity of the cell membrane was severely damaged, causing a large number of intracellular potassium ions and macromolecular proteins leaking out of the cells. In addition, OPh-PANF can disrupt the intracellular enzyme systems by FCM analysis. Results from sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and mass spectrometry (MS) analyses showed that after exposure to OPh-PANF, specific protein bands disappeared or weakened, indicating that OPh-PANF mainly inhibited synthesis and expression of structural proteins (OmpA) and functional proteins (HtpG, AhpC, FNM, CAD). On the basis of the above results, an antibacterial mechanism was proposed for OPh-PANF against E. coli. When OPh-PANF was exposed to E. coli, the first step was to adsorb E. coli on its surface, then organophosphorus groups pre-grafted on the fibers began to execute the function of killing bacteria through three combined ways, i.e. destruction of cell membrane structure, disordering of enzyme system and inhibition of protein synthesis.     

Using HPP (hydrogen peroxide plus) to inhibit potato sprouting during storage

Potatoes (Solanum tuberosum L.) samples, cv. Desiree, were treated for sprout control and stored at 10 ± 1 C for 6 months. Those treated four times with HPP (hydrogen peroxide plus), applied with the “Tabor Atomizing System”, had a 0% rate of sprouting. Those treated with CIPC (chloro-isopropyl N-phenyl carbamate) also had no sprouting, while the nontreated control had 84%. A single treatment with HPP or CIPC resulted, after 6 months of storage at 10 ± 1, in sprouting rates of 61 and 58%, respectively, vs. 87% in the untreated control.     

Direct dye removal by using UV/hydrogen peroxide/multiwalled carbon nanotubes

In this study, decoloration of Direct Blue 71 (DB71) and Direct Red 23 (DR23) has been discussed by using Multiwalled Carbon Nanotubes (MWCNTs) and Hydrogen peroxide under UV radiation. The purpose of this study is removal of organic compounds by using carbon nanotubes that are effective adsorbents for different types of pollutants, due to their porous nature and large surface area. It also causes catalytic decomposition of hydrogen peroxide. Adsorption rate was investigated under various parameters (initial dye concentration, salt, temperature and pH). The main objective of this study is to appraise the synergic effect between H₂O₂ and MWCNTs under UV radiation. The dye adsorption results of spectrophotometer, showed that by decreasing the dye concentration from 0.2 g/l to 0.05 g/l with the optimal value of MWCNTs 0.2 g/l and hydrogen peroxide 2 g/l at pH=4 and 6 cm distance from the UV lamp, the dye removal increased.     

Study on polyacrylonitrile fibers modified by blending with polyethylene glycol

A series of water absorbent porous modified polyacrylonitrile (PAN) fibers were prepared using the blends of PAN and various molecular weight of polyethylene glycol (PEG) by wet-spinning process and water bath post-treatment. The chemical structure and morphologies of the modified PAN fibers were studied. The water transportation, water retention, moisture absorption and mechanical properties of the fibers were discussed. Results show that there is no residual PEG in modified PAN fibers after drawing process in hot water bath and post-treatment. With the increase in PEG molecular weight, the fiber surface grooves become deeper, the inner pore size increases, while the mechanical properties decrease. The water absorbing and transferring capabilities of the modified PAN fibers can be improved in varying degrees due to the different pore structures left by series molecular weight of PEG removing.     

Preparation of amidoxime-modified polyacrylonitrile nanofibers immobilized with laccase for dye degradation

A novel approach to preparing multifunctional composite nanofibrous membrane was developed. Polyacrylonitrile (PAN) nanofibrous membrane was fabricated by electrospinning and then the nitrile groups in PAN copolymer was chemically modified to obtain amidoxime modified PAN (AOPAN) nanofiber membrane which was further used as a functional support for laccase immobilization. During the process of reactive dye degradation catalyzed by the AOPAN nanofiber membrane immobilized with laccase, metal ion adsorption occurred at the same time. The chemical modification was confirmed by Fourier transform spectroscopy (FTIR). Scanning electron microscope (SEM) was employed to investigate the surface morphologies of the electrospun nanofibers before and after laccase immobilization. The effects of environmental factors on laccase activity were studied in detail. It was found that the optimum pH and temperature for the activity of immobilized laccase was 3.5 and 50 °C. The relative activity retention of the immobilized laccase decreased dramatically during the initial four repeated uses. After 20 days’ storage, the activity retention of immobilized laccase was still high above 60 %. It has also proved that laccase immobilized on AOPAN nanofiber membrane performed well in dye degradation and metal ion adsorption.     

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.