A novel methodology for designing thermal processes in order to optimize stabilization of polyacrylonitrile (PAN) fibers

The aim of this work is to describe a novel methodology for optimizing the stabilization of polyacrylonitrile (PAN) fibers, through designing of proper thermal treatment. The methodology is based on a set of design rules and the procedure for implementing them, utilizing the time‐temperature‐transition (TTT) and the maximum permittable stress (max.stress) plots. The proposed approach is implemented in order to optimize the stabilization of commercial PAN fibers, resulting in a series of multistage thermal treatments. The changes of both physical and chemical structures of PAN during the progress of the multistage treatments were investigated and showed that the fibers were progressively converted into completely stabilized material; this gradual transformation permitted improvement of fiber annealing and minimized the effect of the decomposition reactions. The proposed methodology can be universally applied for achieving the global optimum of the stabilization process for any PAN precursor.     

Electrokinetic and permeation characterization of hydrolyzed polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane

PAN membrane and hydrolyzed PAN membranes with the same pore size were used to investigate the relationship between the electrokinetic property and permeation performance by streaming potential measurement and ion exchange technology. SEM and FT-IR/ATR spectra were employed to analyze the reaction and the presence of the amide groups. The thickness of the polyacrylic acid (PAA) layer on the membrane surface measured by ion-exchange titration technology increased with the reaction time, and that on membrane hydrolyzed for 50 min could reach 10.8 nm. Streaming potential measurement was used to study the influence of the carboxylic and nitrile group on the membrane surface on their separation property. Zeta potential measured in pure water had close relationship with the permeation property. This measurement also proved that there was a maximum zeta potential between zero and the concentration tested. For the ionization or dissociation of the carboxylic group on the membrane surface, treated membranes had a more flexible zeta potential range than that of the untreated membrane in the pH range of 3–9. They were all negative in pure water and 1 g·L⁻¹ KCl solution, while the membranes hydrolyzed for 30 min and 50min had IEPs at pH 5.5 and 6.1 in 1 g·L⁻¹ MgCl₂ solution. Special inflection points of all the membranes were observed in AlCl₃ solution for the positive colloid structure of Al(OH)₃.     

Properties of partially hydrolyzed PAN fibers

The properties of base PAN (polyacrylonitrile) fibers and their partially hydrolyzed PAN-COOH fibers were characterized by means of a Fourier transform infrared spectrophotometer, elemental analyzer, specific surface area analyzer etc. The main factors that can affect the strength of the base PAN fibers and how the hydrolysis reaction happens in alkaline conditions are discussed. Acidic hydrolyzed PAN-COOH fibers, having a strength of 9.6 cN/dtex, capacity of 0.26 mmol/g, BET area of 0.58 m²/g (calculated on dry basis) were prepared. The conversion rate from -CN to -COOH, the ways that groups of -COOH array on the surface of the fibers and the possible maximum amounts of -COOH are discussed in detail. __________ Translated from Transactions of Beijing Institute of Technology, 2008, 28(2) (in Chinese)     

超临界CO2方法制备的聚丙烯腈的表面特性

根据Washburn浸渍理论(Penetration theory)和van Oss-Good-Chaudhury的组合理论及应用柱状灯芯技术(Column wicking technique)，测试了用超临界CO2方法制备的不同分子量聚丙烯腈(PAN)的表面特性。结果显示，PAN的分子量影响其表面性能。与一般聚合物的表面能随分子量增大而增大的规律不同，超临界方法制备的聚丙烯腈(PAN)的表面能随着分子量的增大而降低，但其Lifshitz-van der Waals力却随分子量的增大而增大。与常规方法生产的PAN的表面性能比较，超临界方法可能使PAN的极性减少。     

Preparation of porous ultrafine polyacrylonitrile (PAN) fibers by electrospinning

A facile method for the preparation of porous ultrafine nanofibers was demonstrated. The PAN/NaHCO₃ composite nanofibers were electrospun, and then NaHCO₃ was removed by a selective dissolution and reaction with the solution of hydrochloric acid (10 wt%). The obtained PAN fibers showed highly porous surfaces after the extraction of NaHCO₃. The structure and properties of ultrafine PAN nanofibers were characterized by Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), and thermogravimetry (TG). The results indicated that NaHCO₃ could be introduced into the PAN solution and successfully electrospun. CO₂ is released and pores are formed on the fibers. The morphology image of the fibers was detected by scanning electron microscope (SEM) and showed that many pores aligned the nanofibers. Copyright © 2008 John Wiley & Sons, Ltd.     

Fibrillar structure development of polyacrylonitrile fibers treated by ultrasonic etching in oxidative stabilization

Polyacrylonitrile fibers were oxidatively stabilized through 10 gradient‐elevated temperature zones in sequence. The ultrasonic etching method was used for fibril separation of fibers heated at different temperatures, and the fibrillar structure development was studied by scanning electron microscopy. The voids among fibrils are the weak combination points. Under ultrasonic etching, the voids are enlarged. Subsequently, the solvent enters and spreads among fibrils, which results in the separation of fibrils. Separated fibrils with diameters of 100–400 nm appear in fibers heated at less than 235°C. Fibrils in fibers heated from 195°C to 235°C tend to adhere to each other, and the observed macrofibrils are composed of several to dozens of fibrils. For fibers heated from 195°C to 245°C, only a few fibril bundles emerge on the skin near the fiber end, and the fibrils manifest themselves as numerous protuberances on the cross section. In the ranges of 255–275°C, fibrils compactly combine with each other, which suggests insolubility and infusibility, and no separated fibrils appear. The fibrils arrange in a systematic way along the fiber axis and grooves parallel to the fiber axis on the fibers' surface. These grooves are the macro behavior of fibrils arranging on the fiber surface. Copyright © 2017 John Wiley & Sons, Ltd.     

Effects of microstructure, crosslinking density, temperature and exterior load on dynamic pH-response of hydrolyzed polyacrylonitrile-blend-gelatin hydrogel fibers

The preparation of a smart hydrogel fiber based on hydrolyzed polyacrylonitrile-blend-gelatin is presented. The kinetics of the hydrogel fibers in response to pH change was reported. The effects of a number of factors were systematically studied, including the fiber diameter, concentration of crosslinker, environmental temperature and exterior load. The micro-morphology was also observed by SEM to verify the theoretical analysis. The experimental results revealed good consistence with Tanaka-Fillmore theory and Flory-Huggins theory, and it was found that the hydrogel fibers with high content of gelatin showed excellent and stable pH-response ability. Studies of dynamic elongation and contraction behaviors assist understanding and controlling of the pH-response of hydrogel fibers.     

Detection of anti-tetanus toxoid antibody on modified polyacrylonitrile fibers

Accurate determination of concentration of immunoglobulin (IgG) to tetanus toxoid is important in order to evaluate the immunogenicity of tetanus toxoid vaccines, immune competence in individual patients and to measure the prevalence of immunity in populations. Surface modified polyacrylonitrile (PAN) fibers were evaluated as a matrix to develop highly sensitive method for the detection of anti-tetanus antibody in a sandwich ELISA format. In the proposed method tetanus toxoid immobilized on modified PAN fibers was used to detect anti-tetanus antibody (raised in horse hence represented as horse anti-tetanus toxoid or HAT-Ab) with horse raddish peroxidase enzyme conjugated with Rabbit anti-Horse IgG (RAH-HRP) as the label within 2.5 h. A sigmoidal pattern for the detection of different concentration of antibody ranging from 1.0 to 0.0001 IU mL⁻¹ was validated. The immunoassay recorded a very high sensitivity as concentration as low as 0.0005 IU mL⁻¹ of HAT-Ab was detected. The intra- and inter-assay precision for 3 parallel measurements of 0.01 and for 0.001 IU mL⁻¹ of antibody varied from 5.4% to 11% and 5.7% to 20% respectively. PAN fibers were also used to qualitatively access the presence of different level of anti-tetanus antibody spiked in human blood. Seroepidemiological studies to measure the immunity against tetanus were conducted with twenty-five human beings belonging to various age groups using modified PAN-ELISA. The sensitivity, specificity and the reproducibility of the developed immunoassay indicate the potential application of modified PAN fibers in the field of immunodiagnostics.     

Behaviors and mechanisms of copper adsorption on hydrolyzed polyacrylonitrile fibers

Polyacrylonitrile fiber (PANF) was hydrolyzed in a solution of sodium hydroxide and the hydrolyzed polyacrylonitrile fiber (HPANF) was used as an adsorbent to remove copper ions from aqueous solution. Scanning electron microscopy (SEM) showed that the hydrolysis process made the surface of HPANF rougher than that of PANF. Fourier transform infrared (FTIR) spectroscopy revealed that the HPANF contained conjugated imine (-Cz=Nz-) sequences. Batch adsorption results indicated that the HPANF was very effective in adsorbing copper, and the adsorption equilibrium could be reached within 10-20 min. Atomic force microscopy (AFM) showed that some aggregates formed on the surface of the HPANF after copper ion adsorption and the average surface roughness (R(a)) value of the HPANF changed from 0.363 to 3.763 nm due to copper adsorption. FTIR analysis indicated that copper adsorption caused a decrease of the light adsorption intensity of the imine (-Cz=Nz-) groups at 1573 and 1406 cm(-1) wavenumbers, and X-ray photoelectron spectroscopy (XPS) showed that the binding energy (BE) of some of the nitrogen atoms in the HPANF increased to a greater value due to copper adsorption. The FTIR and XPS results suggest that the adsorption of copper ions to the HPANF is attributed to the imine groups on the surface of the HPANF.     

Thermal behavior of drawn acrylic fibers

The effect of stretching on the thermal behavior of acrylic fibers was investigated with differential scanning calorimetry (DSC), thermogravimetric analysis, and Fourier transform infrared spectroscopy (FTIR). In air atmosphere, the peak temperature of the dynamic DSC thermogram was significantly lowered from 289 to 273 °C when the gel fibers (undrawn) were drawn to a draw ratio of 11.2. However, the initiation temperature was unchanged at 202 °C. The shoulder in the region of 310–380 °C was gradually converted to a sharp peak during the drawing process. However, the dynamic DSC in nitrogen atmosphere did not change in all cases. In air atmosphere the total heat liberated, ΔH, for gel fiber was 851 J g^?1. However, upon drawing to 11.2, ΔH increased to 1580 J g^?1 showing an increase in the total chemical changes. An intimate relationship of chemical changes during the heating process was observed with FTIR of heated samples at various temperatures. The initiation of a DSC exotherm in air begins with nitrile cyclization, and subsequently dehydrogenation was initiated between 220 and 260 °C. An increase in the X‐ray orientation factor and sonic modulus gave a correlation between the stretching draw ratio and crystalline/overall molecular orientation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2949–2958, 2003     

Studies on phase separation and coarsening in blends of poly(vinylidene-fluoride) and poly(ethyl-acrylate)

The phase diagram of blends of poly(vinylidene fluoride) and poly (ethyl acrylate) was established by X-ray scattering, optical microscopy and calorimetric techniques. Structure formation, involving phase separation and coarsening was analyzed as a function of temperature variations and annealing times. The variations consisted of increasing or decreasing the temperature stepwise, starting either in the one-phase or in the two-phase state of the melt.Dedicated to Prof. R. Bonart (Univ. Regensburg) on the occasion of his 60^th birthday     

预氧化过程中张力对聚丙烯腈预氧化纤维微缺陷结构的影响

本文报道用同步辐射二维小角X射线散射(2D\|SAXS)研究预氧化过程中张力对PAN纤维缺陷的影响.     

Low Temperature Preparation of Titania Coated PAN Fiber and Its Photocatalytical Property

Titania thin film was deposited successfully on polyacrylonitrile (PAN) fiber by the sol‐gel process with the assistance of tetraethyl silicate (TEOS) at low temperature. It was found that the densification and crystallization of the film was a result of the post‐treatment in boiling water because of the hydrolysis of the Si‐O‐Ti bonds and dissolution of the silica component formed in the film. XRD patterns revealed the existence of anatase phase in the continuous titania layer. The product, titania coated polyacrylonitrile fiber (TiO₂/PAN), showed a high photocatalytic property and good repetition on the photodegradation of methylene blue (MB). The proposed method is expected to be used for the preparation of novel photo‐catalysts based on thermally sensitive substrates.     

Fabrication of carbon fibers with nanoporous morphologies from electrospun polyacrylonitrile/poly(L‐lactide) blends

Porous carbon nanofibers were prepared through electrospinning a blend solution of polyacrylonitrile and poly(L ‐lactide), followed by carbonization at different temperatures and in different atmospheres. Structural features of these porous carbon nanofibers were characterized using scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, X‐ray powder diffraction, and Raman spectroscopy. Surface area and pore structure were evaluated using the nitrogen adsorption technique. It was found that carbon fibers prepared by this scalable and relatively economical method exhibited a porous surface morphology with high specific surface area and large pore volume. The fiber diameter, surface area, pore volume, bulky crystalline structure, and surface crystalline structure of these carbon nanofibers showed a strong dependence on the polymer precursor composition and carbonization condition. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 493–503, 2009     

Morphology of solidified polysulfone structures obtained by wet phase separation

Evidence is presented that all three theoretically predicted modes of phase separation take place in the ternary system polysulfone(PSf)/N,N-dimethyl acetamide(DMA)/water during the process of wet phase separation (WPS). The elementary process of solidification is reconsidered with regard to the (non-) equilibrium phase separation. Cast solutions with more than 15 wt% of PSf undergo nucleation and growth of the polymer lean phase with formation of separation membranes characterised by a cellular structure. When cast solutions with about 5-7 wt% of PSf undergo WPS, somewhere inside the ternary system conditions are established so that alongside other solidified PSf structures the bicontinuous spinodal structures superimposed by bead-like structures are also formed. Variety of lacy PSf structures with less/more polymer beads is the manifestation of the primary phase separation by the spinodal mode superimposed by the secondary phase separation taking place by heterogeneous nucleation and growth of the polymer rich phase mode. Latex formation during the WPS will also be explained. Skin formation on the cast solution - coagulation bath interface by direct accumulation of polymer is established regardless of the PSf content in the cast solution.     

Viscoelastic properties of polyacrylonitrile terpolymers during thermo‐oxidative stabilization (cyclization)

A study on the thermo‐oxidative stabilization (cyclization) of polyacrylonitrile (PAN) terpolymers using dynamic mechanical thermal analysis (DMTA) is reported in this article. When the changes in viscoelastic properties were monitored in a rectangular tension mode, besides the tan δ peak characteristic of the glass transition observed below 200°C, the copolymer and the terpolymer displayed a second peak above 200°C due to the cyclization leading to the formation of ladder structures. The initiation temperature of the cyclization process as well as the peak temperature is found to depend on the acid value and the composition of the precursor polymer. The results presented show that monitoring the changes in viscoelastic properties during cyclization provides insight into the material properties as a result of the chemical changes that are taking place. These observations were confirmed by structural characterization using IR spectroscopy, and the observed chemical changes agree with the literature studies, as due to the thermal cyclization process. Copyright © 2008 John Wiley & Sons, Ltd.     

Process optimization and empirical modeling for electrospun polyacrylonitrile (PAN) nanofiber precursor of carbon nanofibers

Ultrafine fibers were spun from polyacrylonitrile (PAN)/N,N-dimethyl formamide (DMF) solution as a precursor of carbon nanofibers using a homemade electrospinning set-up. Fibers with diameter ranging from 200 nm to 1200 nm were obtained. Morphology of fibers and distribution of fiber diameter were investigated varying concentration and applied voltage by scanning electric microscopy (SEM). Average fiber diameter and distribution were determined from 100 measurements of the random fibers with an image analyzer (SemAfore 5.0, JEOL). A more systematic understanding of process parameters was obtained and a quantitative relationship between electrospinning parameters and average fiber diameter was established by response surface methodology (RSM). It was concluded that concentration of solution played an important role to the diameter of fibers and standard deviation of fiber diameter. Applied voltage had no significant impact on fiber diameter and standard deviation of fiber diameter.     

Morphology and crystallization behavior of poly(vinylidene fluoride)/poly(methyl methacrylate)/methyl salicylate,and benzophenone systems via thermally induced phase separation

Poly(vinylidene fluoride) (PVDF) blend microporous membranes were prepared by PVDF/poly(methyl methacrylate) blend (with mass ratio = 70/30) via thermally induced phase separation. Benzophenone (BP) and methyl salicylate (MS) were used as diluents. The phase diagram calculations were carried out in terms of a pseudobinary system, considering the PVDF blend to be one component. The crytallization behaviors of PVDF in the dilutions were detected by differential scanning calorimetry measurement. In these two systems, the melting and crystallization temperatures leveled off in the low polymer concentration (<40 wt %), but shifted to a higher temperature when the polymer concentration >40 wt %. The calculated crystallinity of PVDF for samples with low polymer concentrations was greater than those with high polymer concentrations, because of the limited mobility of polymer chains at a high polymer concentration. The membrane structure as determined by scanning electron microscopy depended on the phase separation mechanism. The quenched samples mainly illustrated the occurrence of crystallization on the same time scale as the liquid–liquid phase separated, resulting in the obvious spherulitic structure with small pores in the spherulites. As the polymer concentration increased, the size of the spherulites and pores within the spherulite was decreased. The evaluated porosity for BP diluted system was higher than that for MS diluted system, and decreased with the increased polymer concentration. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 248–260, 2009     

Determination of Peroxyacetylnitrate (PAN) in Unpolluted Areas

Abstract

PAN is not only important as toxic product of photochemical pollution but may also act as an important reservoir for nitrogen oxides outside polluted areas.

However, only very few measurements of PAN in unpolluted areas have been reported in the literature, mainly as a result of the lack of simple, reliable and sufficiently sensitive techniques for the measurements of PAN in background air.

In our paper we will describe a completely automatic gas chromatographic system. Without enrichment it allows the determination of PAN with a lower limit of detection of ≈ 10ppt. Combined with an adsorptive enrichment procedure at low temperature detection limits of less than 1 ppt are possible. At these low concentrations, a complete separation from possible interfering atmospheric constituents (e.g. halocarbons) is necessary. This is achieved by separation on a 1 m long glass column, i.d. 2 mm, packed with 5% PEG 400 on Chromosorb WHP 80/100 mesh at ambient temperature. For field measurements-especially for in situ measurements on board of airplanes-a special light weight gas chromatograph with a peltier cooled oven was developed.     

Critical parameters controlling the properties of monolithic poly(lactic acid) foams prepared by thermally induced phase separation

Monolithic poly(lactic acid) (PLA) foams were produced by thermally induced phase separation. PLA solutions with concentrations 8–22 wt % were prepared in tetrahydrofuran/methanol (THF/MeOH) solvent/nonsolvent mixtures at 55 °C. Homogenous solutions were quenched at ?20 °C to induce phase separation and gelation. Resulting gels were mechanically stabilized by solvent exchange. Subsequent supercritical CO₂ drying yielded monolithic PLA foams. Crystal structure and degree of crystallinity of the foams were obtained by x‐ray diffractometry and differential scanning calorimetry. Morphologies were determined by scanning electron microscopy. Tuning the PLA concentration and THF/MeOH ratio enabled preparation of monolithic PLA foams. Depending on the experimental conditions various morphologies, such as: interconnected networks, thin platelets, lamellar stacks, axialites, and spherulites were formed. Monoliths obtained were highly crystalline. By changing the PLA concentration monoliths with controlled average pore sizes (170–1440 nm) and porosities (80–90%) were produced. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 98–108