PVA is reinforced with SWCNTs using green tea extract as a dispersant to achieve good dispersion of the SWCNTs in an organic solvent and finally high‐performance composite fibers. A combination of green tea extract/DMSO/SWCNT/PVA is found to disperse larger aggregates of SWCNTs to individual or thin bundles of a few nanotubes. Incorporation of 0.5 wt% SWCNTs into PVA fibers yields a tensile strength of 2.42 GPa, a Young's modulus of 46 GPa, toughness of 105 J · g?1 at a failure strain of 11%, and a loop strength of 245 MPa, much higher than the values of commercial PVA fibers. The incorporation of highly dispersed SWCNTs suppresses the fibrillation tendency of the PVA fibers. The applied load is effectively transferred from the matrix to the SWCNTs.
The cobalt‐mediated radical polymerization of acrylonitrile in DMSO using cobalt (II) acetylacetonate [Co(acac)2] as mediator is studied. Both the evolution of molecular weight and conversion over time under various conditions are monitored. Molecular weights increase sharply at the beginning of the reaction and subsequently grow linearly with conversion. No branching of the polymer is observed by 13C NMR. By a careful design of the reaction parameters, number‐average molecular weights >1.2 · 105 g · mol?1 with a PDI around 2.4 together with conversions of up to 90% within 24 h are achieved. The copolymerization parameters of acrylonitrile with methyl methacrylate in DMSO at 30 °C are determined using the Kelen‐Tüdõs approach giving rAN = 0.33, rMMA = 0.71.
Coaxial electrospinning using surfactants as sheath fluid for preparing high‐quality polymer nanofibers is studied. PAN nanofibers are fabricated using this process with Triton X‐100 solutions in DMF. FESEM demonstrates that the Triton X‐100 solution has a significant influence on the quality of the nanofibers. The nanofiber diameters can be controlled by adjusting the concentration of Triton X‐100 in the sheath fluids with a scaling law D = 640 C?0.32. The mechanism of the influence of Triton X‐100 solutions on the formation of PAN fibers is discussed and it is demonstrated that coaxial electrospinning with surfactant solution is a facile method for achieving high‐quality polymer nanofibers.
The electrospinning method was used to fabricate nanostructures of Nafion‐poly(vinyl alcohol) (PVA) and Nafion‐poly(ethylene oxide) (PEO). Depending on the ratio between the two polymers, nanospheres and/or nanofibers could be obtained in a reproducible manner. The Nafion‐PVA mats were found to be more conductive than the Nafion‐PEO ones, possibly because of their better mechanical properties when swollen by water. The fiber morphology was always found to be more conductive than the sphere morphology. However, all electrospun mats presented ionic conductivities slightly lower than extruded Nafion 115 or Nafion‐PVA cast films.
Elastomeric EPDM fibers with diameters of 200–400 nm are prepared by coaxial electrospinning of PVP/EPDM fibers, subsequent vulcanization of the polymers and finally removal of the outer PVP layer using ethanol. The initially applied PVP layer restricts the elastic recovery of the EPDM fibers. The crosslinking density of the EPDM fibers reaches 8.44 × 10?5 mol · cm?3. The original morphology of EPDM is preserved after removing the PVP layer. The ultrafine EPDM fibers are expected to be useful in many fields, such as brittle plastics toughening, as well as applications in extremely high or low temperatures.
Novel foam composites comprising functionalized graphene (f‐G) and polyvinylidene fluoride (PVDF) were prepared and electrical conductivity and electromagnetic interference (EMI) shielding efficiency of the composites with different mass fractions of f‐G have been investigated. The electrical conductivity increases with the increase in concentration of f‐G in insulating PVDF matrix. A dramatic change in the conductivity is observed from 10?16 S · m?1 for insulating PVDF to 10?4 S · m?1 for 0.5 wt.% f‐G reinforced PVDF composite, which can be attributed to high‐aspect‐ratio and highly conducting nature of f‐G nanofiller, which forms a conductive network in the polymer. An EMI shielding effectiveness of ≈20 dB is obtained in X‐band (8–12 GHz) region and 18 dB in broadband (1–8 GHz) region for 5 wt.% of f‐G in foam composite. The application of conductive graphene foam composites as lightweight EMI shielding materials for X‐band and broadband shielding has been demonstrated and the mechanism of EMI shielding in f‐G/PVDF foam composites has been discussed.
A new target collector was designed for taking up aligned nanofibers by electrospinning. The collector consists of a rotor around which several fins were attached for winding electrospun filaments continuously in large amounts. The alignment of the nanofibers wound on the collector was affected by the electrospinning conditions, such as the needle‐to‐collector distance and the applied voltage, but not by the rotation speed of the collector. At a voltage of 0.5 kV · cm?1, about 60% of the fibers were found to be aligned within an angle of ± 5° relative to the rotational direction of the collector. The fiber alignment was improved to 90% by drawing the fiber bundle 2–3 times at 110 °C. The drawing was also effective for crystal orientation of the fibers as revealed by WAXD. The drawn fibers show improved mechanical properties.
Summary: Pyrolytic carbon black (CBp) has been prepared by rubber crumb pyrolysis under nitrogen flow at 700 °C. The CBp obtained by this process had an average surface area of 81 m2 · g?1 and was obtained in 43% yield over the starting rubber crumb. Although the CBp surface area can be increased up to 109 m2 · g?1 by washing away the Zn‐ and Si‐based ashes with HF treatment, the CBp was tested in a standard NR/SBR‐based formulation without any purification and ash extraction. CBp was tested at increasing loading levels as partial or full replacement of a standard N339 furnace carbon black. CBp depresses the physical properties of the rubber compound in a way which is directly proportional to the amount added. The reason of this result and the limited reinforcing effect is discussed in terms of low surface area and low structure in comparison to N339 carbon black as well as in terms of low surface activity, the interference of the ashes and the poor dispersion. Ideas of further development works are outlined.
Summary: The effect of silica and its surface treatment on the mechanical properties of composites was studied as part of the evaluation of cyanate ester matrices as potential electronic encapsulants. Three filler surface treatments were used, as a qualitative interfacial adhesion scale, in an attempt to gauge the magnitude of interfacial adhesion between untreated filler and the cyanate ester matrix. There was strong interfacial adhesion between matrix and untreated filler. The level of silica content most affected composite modulus and fracture toughness. Filler surface treatment most affected composite strength and fracture toughness/energy. Composite fracture was found to occur via crack pinning and/or crack blunting depending on the strength of adhesion. The composites evaluated were found to possess suitable mechanical properties for potential use as electronic encapsulants.
Long‐aliphatic‐segment polyamides were prepared based on hexamethylenediamine and α,ω‐(CH2)x biosynthetic diacids (x = 10, 11, 12). The pertinent monomers (salts) were isolated as solids, thoroughly characterized for the first time, and then submitted to an anhydrous melt prepolymerization technique. The obtained prepolymers exhibited in the range of 5 100–11 800 g · mol?1, and the molecular weight was further increased by up to 55% through solid‐state finishing. The suggested overall polyamidation cycle was conducted at short melt‐reaction times, so as to avoid any thermal degradation, and was proved efficient, indicating similar reactants polymerizability independently of the methylene content.
Summary: Using sulfonium groups to create a novel fiber material, methionine‐containing hybrid fibers were prepared from S‐methylated poly(L ‐methionine) and poly(L ‐lysine, L ‐methionine) solutions with gellan solution by polyion complex (PIC) formation via self‐assembly at the aqueous interface. The breaking strain of the PIC fibers were increased by incorporation of methionine residues into the poly(L ‐lysine). These findings may provide a new approach for preparing a wool‐like fiber in aqueous media using the synthetic water‐soluble methionine‐containing poly(amino acid)s.
SEM image of Met‐containing PIC fiber: (a) poly[Met19Met(SMe)81]‐gellan fiber (magnification, ×500). 相似文献
Low‐MW urethanes were investigated to control domain formation as well as inhibiting cleavage reactions during vapor phase polymerization of PEDOT. A diurethanediol (DUDO) was identified as a highly efficient mediator for the process, resulting in PEDOT films exceeding conductivities of 1 000 S · cm?1. All the urethanes investigated had the desired inhibiting effect on the polymerization, but all apart from DUDO also introduced unwanted domain formation on the micrometer scale. The addition of PEG generally improved conductivity by suppressing the domain formation and, with an optimized combination of DUDO and PEG, conductivities over 1 200 S · cm?1 were achieved.
Summary: A novel hyperbranched poly(β‐ketoester) was synthesized from 2‐(acetoacetoxy)ethyl acrylate by the Michael addition in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as catalyst. 1H NMR integration experiments revealed that the degree of branching in the poly(β‐ketoester) was remarkably high at a level of 82.9%. The number‐average molecular weight of the polymer was between 2 100 and 12 000 and increased with reaction temperature and conversion.
Synthesis of hyperbranched polymer by Michael addition of AAEA. 相似文献
Summary: Halogen‐free, flame retardant low density polyethylene (LDPE) composites, using magnesium hydroxide sulfate hydrate (MHSH) whiskers as a flame retardant, combined with microencapsulated red phosphorous (MRP) as a synergist, have been prepared using a two‐roll mill. Their fire properties were determined by using the limiting oxygen index (LOI), the UL‐94 test and cone calorimetry. The results showed that MRP was a good synergist in improving the flame retardance of the LDPE/MHSH whisker system. Poly[ethylene‐co‐(vinyl acetate)] (EVA), used as a compatibilizer, increased the fire performance of LDPE/MHSH whisker composites.
Intrinsically conducting polymer fibers are prepared from P3HT by melt spinning. High crystallinity is achieved by drawing the fibers after the spinning process, applying a draw ratio of 1:2. DSC and XRD measurements confirm the continuous increase of crystalline phases with drawing. For comparison, poly(ethylene terephthalate) fibers are coated with P3HT and drawn as well. Again, the drawing of the coated fiber results in a significant increase in crystallinity of the P3HT coating. The high amount of crystalline phases is associated with a dramatic increase in conductivity (350 S · cm?1) after doping with FeCl3 in nitromethane.
When it comes to the design of extrusion line components such as single‐screw extruders or extrusion dies, no one has yet succeeded in developing a well‐functioning concept for wall‐slipping materials. This article examines the fundamental influences of the wall slippage effect on flow behavior in the extrusion die and plastification unit. New and extended methods of calculation for describing this flow phenomenon are presented for both these extrusion line components, and the general possibilities for linking the two approaches are discussed.
Diagram of the flow curve (τ = shear stress, = shear rate) of wall‐slipping plastics for constant pressure. 相似文献
Summary: This paper reports the phase behavior of photochemically crosslinked poly(butyl acrylate) networks in nematic liquid crystal (LC) solvents. The swelling properties are studied as a function of temperature for two low molecular weight nematic LCs, 4‐cyano‐4′‐pentylbiphenyl (5CB) and the eutectic mixture of cyanoparaphenylenes (E7). Chemically crosslinked polymer networks were formed by the UV radiation of initial solutions of the reactive monomer, butyl acrylate, a crosslinker (hexanediol diacrylate), and a photoinitiator. To obtain different network densities, the ratio of butyl acrylate to hexanediol diacrylate was varied prior to polymerization/crosslinking reactions. Immersion in an excess of the LC solvent allowed for the measurement of size increase by polarized optical microscopy in terms of temperature. Length, width, and diagonal ratios were calculated considering swollen to dry network states of the samples. In general, swelling leads to an increase in the network size by increasing the temperature with a significant dependence on the degree of crosslinking. A large shift in the swelling ratio was found in the vicinity of the nematic to isotropic transition temperatures of the LCs.
Summary: Polycarbonate (PC)/polyethylene (PE) blend was injection molded at different molding temperatures. The morphological observation by scanning electronic microscope (SEM) indicated that the sample molded at 190 °C contained only uniformly dispersed spherical PC particles. The samples molded at 230 and 275 °C had a typical skin‐core structure, and there were many injection‐induced PC fibers in the subskin. While the sample molded at 190 °C had the usual stress‐strain behavior, the samples obtained at 230 and 275 °C showed apparently double yielding behavior. It was suggested that the double yielding points were morphology‐dependent. The first one was the result of the yielding of PE at low strain, and the second one was caused by the yielding of the PC fibers. Moreover, it is the frictional force in the interfaces between PC and PE that transferred the stress to the PC fibers, hence giving rise to the reinforcement of PE by PC.
Stress‐strain curves of PC/PE blends injection molded at various temperatures showing first (I) and second (II) yielding points. 相似文献
Synthesis, structure, and properties of rigid‐rod polymers with special emphasis on poly(p‐phenylene benzobisoxazole) (PBO) and poly(p‐phenylene benzobisthiazole) (PBZT) have been reviewed. Recent studies on chemical modifications and molecular simulations have also been given. After nearly 20 years of research and development, PBO fiber was commercialized in the late 1990s. However, due to processing difficulties, the concept of the so called molecular composites has not been successful. Development of the high compressive strength M5 and dihydroxy‐PBI fibers clearly suggest that there is potential for further developing properties of this class of materials. Opto‐electronic properties have also been reviewed.
