Mechanism of Electrospinning for Poly(amic acid)/Polyacrylonitrile Fiber Fabrication

A poly(amic acid) (PAA) solution in xylene was prepared for electrospinning in order to fabricate fibers. However, jet breaking occurred at the point of the occurrence of whipping instability, resulting in forming micro-particles. This was an exceptional jet behavior compared with the general electro-spraying process that occurs directly from the surface of the polymer droplet. It is important to understand the mechanism of electrospinning and the instability of PAA in order to form fibers for mat deposition. Thus, the behavior of the jet breaking was clearly observed by a high-speed camera and the dynamic behavior of the jet was explored by an image analysis technique. Furthermore, polyacrylonitrile (PAN) was added to the PAA/xylene solution with various concentrations to change the elongation viscosity. Uniform diameter fibers were obtained by increasing the content of PAN to the level that the drag force between the polymer chains increased enough to overcome the drawing force. As a result the optimum content ratio of the PAA/PAN mixed solution to obtain the desired fiber spinning and deposition was determined as being 5:5.     

YBCO/聚丙烯腈杂化膜及其超导性研究

报告了一种简单制备不依赖于基底结构的柔性YBCO/聚丙烯腈（PAN）厚膜的新方法.研究结果发现,PAN含量从0增加到10wt%的过程中,全部YBCO/PAN样品的超导临界温度T_c在900—920 K区间,表现出较好的超导电性.而且当PAN含量为10wt%时,YBCO/PAN杂化膜即具有一定柔性,膜厚约35 μm,临界电流密度Jc=29×10⁴Acm^-2(1 T, 10 K)和J< 关键词： 超导电性 YBCO 聚丙烯腈（PAN） 杂化膜     

Solution blends of polyacrylonitrile with segmented polyurethanes: Effect of soft segments

Solution blends of a modified polyacrylonitrile (PAN) with polyurethane (PU) obtained from 4, 4′-diphenylmethane diisocyanate (MDI) and two different types of polyols– i.e., ether-linked polytetramethylene ether glycol (PTEG) and ester-linked polytetramethylene adipate glycol (PTAG) – were prepared in N, N-dimethylformamide (DMF). The domains in the PTAG-PU blends were much finer than those in the PTEG-PU blends. Shift of the soft segment transition temperatures (T _gs) of PU toward lower temperature with increasing PAN was more significant for PTAG-PU blends. Miscibility was also examined through Fourier transform infrared spectra. These showed clear carbonyl peak shifts due to the different types of hydrogen bonding. The PTAG-PU/PAN (30/70) blend had the maximum draw ratio at failure, measured in 100°C water; it was over 2.5 times that of pure PAN.     

Damping,Thermal, and Mechanical Properties of Polycaprolactone-Based PU/EP Graft IPNs: Effects of Composition and Isocyanate Index

A series of polycaprolactone (PCL)-based polyurethane (PU)/epoxy resin (EP) graft interpenetrating polymer networks (IPNs) were prepared and their damping propertiesand thermal stability, as well as mechanical properties, were systematically studied in terms of composition and the values of the PU isocyanate index (R). The morphologies of the PU/EP IPNs were observed by scanning electron microscope (SEM) and atomic force microscope (AFM) characterization and the relationship between the morphologies and the properties is also discussed. The damping properties and thermal stability measurements revealed that the formation of PU/EP IPNs could significantly improve not only the damping properties but also the thermal stability. Meanwhile, the mechanical tests showed that the tensile strengths of the IPNs decreased, while their impact strengths increased with increasing PU content. The value of the PU isocyanate index also had significant impacts on the properties of the IPNs when the PU to EP ratio was fixed, which could be an effective means for manipulating the fabrication of PU/EP IPNs. From the results obtained, the PCL-based PU/EP IPNs hold promise for use in structural damping materials.     

Chemorheological studies on a thermoset PU/clay nanocomposite system

Chemorheology of neat polyurethane (PU) system, composed of a diisocyanate and a polyol, and a PU/clay nanocomposite system with an organoclay 5 phr was investigated. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were used to study the polymerization behavior of both systems. The PU/clay nanocomposite system showed a faster polymerization rate than neat PU system. The rheological property change during isothermal and dynamic polymerization of both systems was measured using a rheometer to analyze chemorheology of them. A viscosity function that can describe viscosity change of a thermoset resin system during polymerization was adopted to analyze the viscosity data obtained from the rheometer. The PU/clay nanocomposite system had shorter gelation time than neat PU system. Structural analyses of the PU/clay nanocomposite were performed by X-ray diffractometer (XRD) and transmission electronic microscope (TEM).     

Influence of the viscosity and the substrate on the surface hydrophobicity of polyurethane coatings

Tailor-made polyurethane (PU) dispersions were synthesized as coatings for paperboard for dry food packaging. For this purpose a low moisture-vapor transmission rate and a high surface hydrophobicity are desirable characteristics, which are both met by PU. However, it was found that the surface hydrophobicity of water-borne PU dispersions depends strongly on the viscosity of the dispersion. This dependency was studied by static contact angle measurements (SCA) as well as a novel technique using digital pulsed-force mode atomic force microscopy (DPFM-AFM). Comparison of the results validated that DPFM-AFM is a valuable tool to characterize the surface hydrophilicity. Both techniques confirmed that the surface hydrophobicity varies with the viscosity and that an optimum viscosity for the PU coating with a maximum surface hydrophobicity can consequently be determined. It was found that both lower as well as higher viscosities led to a less hydrophobic surface.     

Interfacial reaction of silver ultra-thin film deposited on interpenetrating polymer network substrate by liquor-phase reduction

The interfacial reaction, metal transformations, and nonmetal bond types of silver ultra-thin film deposited on polyurethane (PU) based interpenetrating polymer networks (IPN) substrate by the liquor-phase reduction at room temperatures were studied by atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). The IPN substrate was prepared by dip-pulling precursors onto a silicon wafer or a glass plate, followed by solidification at room temperature. The interpenetrate structures of IPN with two crosslinked networks restricted the aggregation of silver during the reduction and deposition. The devised -OH terminal group in PU simplified the determination of reactive site in IPN and reinforced the adhesion between IPN and silver through interfacial reaction. The XPS results, which matched well with the ATR-FTIR results, verified the chemical reactive site of PU in IPN with silver in the oxide state.     

Effect of melt viscosity and surface tension of polymers on the percolation threshold of conductive-particle-filled polymeric composites

The electrical conductivities of carbon-black-filled low-density polyethylene (LDPE), poly(methyl methacrylate) (PMMA), and poly(vinyl chloride)-vinyl acetate (PVC/ VAc) copolymer were measured as functions of carbon content and melt viscosity of the matrix at the temperatures at which the composites were prepared. Sharp breaks in the relationship between the carbon filler content and the conductivity of composites were observed in all specimens at some content of the carbon filler. The conductivity jumps as much as 10 orders of magnitude at the break point. This phenomenon has been known as the “percolation threshold”. The critical carbon content corresponding to the break point     

Fabrication and Characterization of Acid Dyeable Polyacrylonitrile Blend Fiber

Poly(N,N‐dialkylaminoethylacrylate) (PDA), which contains a basic group, was prepared as a material to blend with poly(acrylonitrile) (PAN). Using the wet spinning method, an acid dyeable PAN/PDA blend fiber was fabricated. It was found that the dye up‐take of the blend fiber is increased remarkably, reaching up to 93%. Based on IR, x‐ray diffraction, DSC characterization, and mechanical measurements, it was shown that the crystallinity and glass transition temperature (Tg) are changed for the blend fiber, that it has acceptable mechanical properties and can be spun.     

Mechanical,Thermal, and Rheological Properties of EPDM-graft-methyl Methacrylate and Styrene (EPDM-g-MS)/Methyl Methacrylate-Styrene Copolymer (MS Resin) Blends

EPDM-graft-methyl methacrylate and styrene (EPDM-g-MS) were synthesized by solution graft copolymerization of methyl methacrylate (MMA) and styrene (St) onto ethylene-propylene-diene terpolymer (EPDM). EPDM-g-MS/MS resin blends (MES) tht were prepared by melt blending EPDM-g-MS and methyl methacrylate-styrene copolymer (MS resin). The mechanical properties, compatibility, thermal stabilities and rheological properties of MES were studied by the pendulum impact tester and the tension tester, differential scanning calorimetric (DSC), thermogravimetry analysis (TGA), and the capillary rheometry, respectively. The results showed that EPDM-g-MS had an excellent toughening effect on MS resin; the notched Izod impact strength of MES reached 20.7 kJ/m² when EPDM content in MES was 25 wt%, about 14 times that of MS resin. EPDM-g-MS and MS resin were partially compatible, and the compatibility increased with an increasing MMA/St ratio of EPDM-g-MS. MES had excellent heat-resistance, which increased as the EPDM content in MES and MMA/St ratio of EPDM-g-MS rose. MES melt flow confirmed pseudoplastic flow characteristics. The apparent viscosity (η _a ) of MES decreased with an increasing shearing rate (γ) and temperature, but increased with an increasing EPDM content in MES and MMA/St ratio of EPDM-g-MS. The flow activation energy of MES was lower than that of MS resin.     

Damping,thermal, and mechanical properties of polyurethane based on poly(tetramethylene glycol)/epoxy interpenetrating polymer networks: effects of composition and isocyanate index

A series of polyurethane (PU) samples based on poly(tetramethylene glycol)/epoxy resin (EP) graft interpenetrating polymer networks (IPNs) were prepared and their damping, thermal, and mechanical properties were systematically studied in terms of composition and the value of the PU isocyanate index (R). The damping properties and thermal stability measurements revealed that the formation of PU/EP IPN could improve not only the damping capacity but also the thermal stability. Meanwhile, mechanical tests showed that the tensile strengths of the IPNs decreased while their impact strengths increased with increasing PU content. The value of R also had significant impacts on the properties of the IPNs when the PU and EP ratio was fixed, which could be an effective means for manipulating the fabrication of PU/EP IPNs. The morphologies of the PU/EP IPNs were observed by SEM and AFM characterization and the relationship between the morphologies and properties is discussed. With the results in hand, the PU/EP IPNs hold promise for use in structural damping materials.     

Lube oil chemistry influences on autoignition as measured in an ignition quality tester

Derived Cetane Numbers (DCNs) of engine lubricating oil/multicomponent 95 Research Octane Number (RON) gasoline surrogate mixtures were measured in an Ignition Quality Tester (IQT). Measurements separately assess the effects of calcium- and magnesium-based detergent additive fraction, oil viscosity, oil degradation, and base oil classification on mixture ignition propensity at conditions with relevance to low speed pre-ignition (LSPI) in gasoline engines. Testing of 0–25% (by mass) oil blended into a six-component surrogate mixture representing an unleaded “average” European gasoline blend is used to determine sensitivity of DCN responses to variations in the properties. With one exception, mixture DCNs were found to increase with lubricating oil content. Despite variation in calcium and magnesium concentrations, DCN responses for all oil blends indicate no statistically significant effect of either calcium or magnesium. Similarly, neither aging of nor peroxide addition to the oil yields significant DCN changes compared to untreated oils. However, a distinct response is found for variations in the base lubricant chemical structural properties. At 25% oil blending with gasoline surrogate, the measured DCNs (RONs) of different group base oils range from 19.6 (95.7) to 42.1 (46.2). The DCN increases with increasing base oil API Group Number (I through IV); however, mixture DCN was found to decrease for a 25% blend of Group V-B with the gasoline surrogate. Using quantitative ¹H NMR, the Group Number trend is interpreted to be a consequence of linear vs. branched character of the paraffinic base oil composition. Taken together, the present results indicate that at ASTM D6890 DCN test conditions, there is no significant ignition effect attributable to reasonable variations in the lubricant's calcium or magnesium content, viscosity, or degree of degradation. Instead, the isomeric character of the paraffinic base oil appears to be most significant in controlling lubricant autoignition properties relative to those of gasolines.     

Aminated polyacrylonitrile blends with cellulose acetate

Polyacrylonitriles (PANs) were synthesized and aminated with ethylene diamine (2DA), hexamethylene diamine (6DA), and dodecane diamine (12DA), followed by blending with cellulose acetate (CA). Effects of amination and chain length of diamine on the miscibility of the aminated PAN with CA were studied. Scanning electron microscopy (SEM) micrographs of cryogenically fractured surfaces of the blends showed coarse elliptical dispersions of CA in PAN. The dispersed CA domains decreased in size with an increase in aminated PAN content. The dispersed domain size further decreased with increasing chain length of diamine. and eventually the morphology became almost homogeneous with 12DA-modified PAN blends. With increasing chain length of the diamines, the dynamic loss peak temperature of PAN in blends showed a movement toward that of CA. Fourier transform infrared (FTIR) measurements showed that the specific interaction between the aminated PAN and cellulose acetate is the hydrogen bonding between aprotic hydrogen in aminated PAN and the ester carbonyl of CA, the interactions being increased with increasing chain length of diamine.     

Toughened Poly(Trimethylene Terephthalate) by Blending with a Functionalized Metallocenic Poly(Ethylene-Octene) Copolymer

New toughened poly(trimethylene terephthalate) (PTT) materials were obtained by melt blending with maleic anhydride grafted poly(ethylene-octene) (POEg). Rheological properties, mechanical properties, and morphological characteristics of PTT/POEg blends at four different compositions—95/5, 90/10, 80/20, and 70/30—were studied. The melt viscosity of the blends shows a linear decrease on increasing the POEg content. The addition of rubbery POEg to the PTT matrix increases the impact strength, while tensile properties decrease. Scanning electron microscopy (SEM) displayed a very good dispersion of POEg particles in the PTT matrix. Differential scanning colorimetry (DSC) experiments showed that for all samples the melting point was almost constant and the crystallinity did not show obvious differences. SEM results showed shear yielding of the PTT matrix was the major toughening mechanism.     

Application of phototransferred thermoluminescence (PTTL) for dose re-assessment in routine dosimetry using MTS-N (LiF:Mg,Ti) thermoluminescent detectors

Erasure of the thermoluminescence (TL) signal on detector readout is considered to be a disadvantage of TL dosimetry, as post-readout dose reassessment is then impossible in principle. A method of dose reassessment based on phototransferred thermoluminescence (PTTL) has been developed at the Institute of Nuclear Physics, Polish Academy of Sciences (IFJ PAN) and applied to MTS-N (LiF:Mg,Ti) detectors. We demonstrate the possibility of applying PTTL for dose reassessment in MTS-N TL detectors routinely applied in the dosimetric service at IFJ PAN. Readings of TL detectors exposed to relatively high doses by the customers of our dosimetry service can now be reassessed using our automatic readers. A major obstacle in applying the PTTL method at lower exposures is the presence of residual dose accumulated in LiF:Mg,Ti detectors after many field exposure and readout cycles. Since most of the TL detectors in our service have been already used for a long time (e.g. for over 10 years in the case of some detector batches), we find that our PTTL method of dose reassessment is possible only in detectors which had received doses exceeding 5 mSv.     

PVP/HEC分子间缔合作用机理探讨

通过粘度、紫外光谱、红外光谱和DSC谱的测定 ,探讨了PVP/HEC分子间的缔合机理 .结果表明 ,PVP/HEC复合体系相对于单一体系产生了粘度的负协同效应 ,NaCl的加入使单一体系和复合体系的粘度均下降 ;在紫外可见吸收光谱中 ,PVP/HEC复合体系的最大吸收波长λmax相对于PVP、HEC各自的λmax都发生红移 ;PVP/HEC复合物的红外光谱在 2 370cm-1出现新的吸收峰 ;DSC谱中复合物的峰温高于简单混合物 ,而其焓变低于简单混合物 ,这一切均证明HEC与PVP之间未发生疏水缔合 ,而是HEC的羟基与PVP的羰基之间通过氢键缔合成复合物 ,复合物的分子链排列较为紧密 .     

Assessment of thermal and antimicrobial properties of PAN/Zn-Al layered double hydroxide nanocomposites

Polyacrylonitrile-based Zn–Al layered double hydroxide composites (PAN/LDH) have been synthesised with different LDH content by in situ polymerisation technique. The nanocomposites were systematically studied by Fourier transform infrared spectroscopy, X-ray diffraction (XRD), thermo gravimetric analysis (TGA), field emission scanning electron microscope (FE SEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectroscopy (EDS) and antibacterial activity measurement. The successful formation of exfoliated nanocomposite was inferred from the XRD patterns and HRTEM images. The thermal decomposition of PAN was enhanced upon nanocomposite (PAN/LDH) formation. The antimicrobial activity of PAN/LDH nanocomposites is evaluated for antibacterial activity against some clinically important bacterial pathogens and the bacterial growth is monitored at different percentage of LDH. The PAN/LDH composites displayed considerable antibacterial activity, on the contrary the virgin PAN did not possess any antibacterial activity. The likely electrostatic interaction among LDH layers with charged surface of bacterial cell is assumed to be responsible for antimicrobial activity. The prepared nanocomposite has appreciable thermal stability in combination with antibacterial activities by which the material is suitable for packaging and fabrication in textile application.     

Molecular mechanism of gelation upon the addition of water to a solution of poly(acrylonitrile) in dimethylsulfoxide

The solidification of a solution of poly(acrylonitrile) (PAN) in dimethylsulfoxide (DMSO) upon introduction of water into the solution is studied by Raman spectroscopy. In the absence of water, DMSO molecules are found to produce dipole-dipole bonds with PAN molecules. Upon the introduction of water, DMSO molecules produce hydrogen bonds with it and bands at 1005 and 1015 cm⁻¹ appear in the Raman spectrum, which are assigned to the valence vibrations of S=O bonds involved in the hydrogen bonds. Simultaneously, water molecules produce hydrogen bonds with PAN molecules: R-C≡N...H-O-H...N≡C-R, where R is the carbon skeleton of a PAN molecule. Accordingly, a band at 2250 cm⁻¹ arises in the Raman spectrum, which is assigned to the valence vibrations of C≡N bonds producing hydrogen bonds with a water molecule. When the water content is low and the DMSO concentration is high, the length of the hydrogen bonds varies in wide limits and the band at 2250 cm⁻¹ is wide. As the water content rises, DMSO molecules come out of PAN, the variation of the hydrogen bond length in it decreases (the band at 2250 cm⁻¹ narrows), and a high-viscosity system (gel) arises that consists of PAN molecules bonded to water molecules via “equally strong” hydrogen bonds.     

Preparation and Characterization of Poly (Acrylonitrile-co-1-Acryloylpyrrolidine- 2-Carboxylic Acid) with High Molecular Weight

1-acryloylpyrrolidine-2-carboxylic acid (APCA) monomer was copolymerized with acrylonitrile (AN) by aqueous suspension polymerization. High molecular weight (HMW) copolymers of AN and APCA [poly(AN-co-APCA)] with different copolymer composition were successfully prepared by employing azobisisobutyronitrile (AIBN) as initiator and polyvinyl alcohol (PVA) as dispersant in a H₂O/N,N-dimethylformamide (DMF) mixture at 60°C. The PAN homopolymer and copolymers were characterized by elemental analysis (EA), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). The EA results indicated that the content of oxygen increased significantly in PAN copolymers with increasing APCA content. The APCA copolymer composition calculated from the EA was higher than that from ¹H NMR spectra. The FTIR spectra of PAN and poly(AN-co-APCA) with different monomer ratios confirmed that the contents of APCA units in the copolymer chains increased with increasing APCA content in the feed. The DSC exotherms revealed that copolymerization with APCA could slow the rate of the exothermic reactions during the heat-treatment processes. The XRD results indicated that the PAN homopolymer and copolymers poorly crystallized and the crystallinity decreased with increasing APCA contents.     

Thermal Properties of Fe-octacarboxyl Acid Phthalocyanine/Polyurethane Blends

The thermal stability of PU has been a critical factor to influence its applications as engineering materials. In this paper, the thermal properties of Fe-octacarboxyl acid phthalocyanine (Fe-OCAP)/polyurethane (PU) blends were investigated. The glass transition temperatures (T_g) of Fe-OCAP/PU blends were analyzed by differential scanning calorimetry (DSC). The results showed that with increasing Fe-OCAP content up to 10% T_g of the samples decreased. Thermal stability of the samples was studied by thermogravimetric analysis (TGA). The decrease of the degradation rate of the samples with increasing Fe-OCAP content indicated an improvement of thermal stability for the modified samples. The activation energy of thermal degradation was calculated by the Freeman and Carroll method. The results showed that the activation energy increased with increasing Fe-OCAP content, which also indicated the improved thermal stability obtained in the modified samples. The thermal properties of the samples were influenced by the incorporation of Fe-OCAP.