Two propylene copolymers with similar comonomer content and molecular weight were electrospun from solution. The 1‐octene and 1‐decene copolymers yielded ribbon‐like fibers. Isotactic poly(propylene) prepared by both heterogeneous and homogeneous catalyst systems could not be electrospun from the same solvent system used for the copolymers. The presence of the higher 1‐alkene comonomers in small amounts (about 1 mol‐%) not only affects the crystallinity of the polymer compared to the homopolymer, but appears to influence the solubility as well. The combined effect of lowering crystallinity and increasing solubility indicates that the use of higher 1‐alkene comonomers in low amounts could be a route to prepare poly(propylene) based electrospun fibers.
The traditional PA 6.6 production route, i.e. solution melt polymerization followed by extrusion, is applied to the in situ intercalation of PA 6.6/clay nanocomposites. Organoclays of different types are tested and the derived nanocomposites are thoroughly characterized in terms of molecular weight, thermal properties and morphology. Reaction acceleration is found in the presence of fully exchanged organoclays, which is attributed to a chain extension mechanism based on clay SiOH groups. Analysis of the nanocomposites' nanostructure indicates that the applied solution melt polymerization process results in some flocculation of the tested organoclays, which is improved in some cases after extrusion and leads to partially exfoliated nanocomposites.
In this work, polyacrylonitrile (PAN) and carbon nanofibers with controllable nanoporous structures were successfully prepared via electrospinning technique. For the preparation of porous PAN nanofibers, two kinds of polymers of PAN and polyvinylpyrrolidone (PVP) were used as electrospun precursor materials, and then the bicomponent nanofibers of PAN and PVP were extracted with water to remove the PVP in the composite polymer nanofibers. By altering the ratio of PAN/PVP in the precursor, the pore size and pore distribution of porous PAN nanofibers could be easily controlled. By using the porous PAN nanofibers as structures directing template and through heat treatment, carbon nanofibers with nanoporous structures were obtained. The porous nanofibers were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT‐IR), differential thermal analyses (DTA), Brunauer–Emmett–Teller (BET) nitrogen adsorption, X‐ray diffraction (XRD), and Raman spectra.
Novel materials were prepared from dual photo and thermal polymerization of hybrid thiol‐ene/cationic systems. In the first stage, the thiol‐ene system proceeded to high conversions, while the cationic photopolymerization was inhibited. The formation of sulfides during this stage was the main factor for the inhibition of the cationic photopolymerization of the epoxy monomers. Once those sulfides were formed, they reacted with the oxonium‐terminated growing polyether chains to form trialkylsulfonium salts. These salts promoted the thermal polymerization of the epoxy monomers in the second stage. The viscoelastic properties of the resulting polymers were measured by DMA.
Copolymers of 3,4‐ethylenedioxythiophene and 3‐methylthiophene have been prepared by recurrent potential pulses using monomer mixtures with various concentration ratios, their properties being compared with those of the corresponding homopolymers. In addition, different technological applications have been tested for the generated copolymers. Results indicate that the properties of the copolymers are closer to those of poly(3,4‐ethylenedioxythiophene) than to those poly(3‐methylthiophene). Furthermore, the ability of the copolymers to store charge and to interact with plasmid DNA suggest that they are very promising materials.
A straightforward method, which is termed novel handspinning, is reported for producing uniaxially aligned sPP nanofibers. As demonstrated by SEM analysis, the morphologies of handspun sPP nanofibers are strongly dependent upon the processing conditions such as spinning method and solvent system. Compared to the normal electrospun sPP nanofibers, the handspun sPP nanofibers show smoother morphologies. FT‐IR analysis demonstrates a significant difference in polymer chain conformation between the handspun and electrospun sPP nanofibers. Moreover, interestingly, the handspun sPP single nanofibers show higher Young's modulus and tensile strength than electrospun sPP single nanofibers.
In the present work, the functionalisation of oxidised SWCNTs and MWCNTs is studied. The functionalised fillers are characterised by Raman spectroscopy and TGA. The functionalised fillers are dispersed in a PBT‐PTMO thermoplastic elastomer matrix via in situ polymerisation. The functionalisation causes a fine filler dispersion right at beginning of nanocomposite manufacturing. The fillers act as nucleating agents for crystallisation and evidences for a grafting from PBT at the surface of the functionalised nanotubes are found. An outstanding reinforcement effect by the functionalised CNTs is confirmed by tensile tests.
A bilayer‐structured PEI/CNF composite fabricated by a facile solution casting method is described, showing dramatically improved static dissipation properties at a rather low loading level. Compared to the conventional monolayer nanocomposite with high static dissipation rate, the bilayer‐structured composite exhibited a 91.4 wt.‐% reduction in CNF loading, while it is volumetric and surface static dissipation rates were ca. 1 000 and 20 times higher, respectively. The interface region in the bilayer structure accounts for such a remarkable improvement. It is believed that this design could significantly benefit the applications requiring high antistatic capability of polymeric materials.
A new completely biodegradable shape‐memory elastomer consisting of PLLCA reinforced by in situ PGA fibrillation is described. The manufacturing processes and shape‐memory effects of the composites are discussed. DMA results reveal a strong interface interaction between in situ PGA fibrillation and PLLCA. Compared with the SMP‐based composites that are commonly used, the shape‐memory test shows that in situ PGA fibrillation can improve the recovery properties of PLLCA; in fact, the shape‐recovery rate increases from 80.5 to 93.2%.
Polyurethanes were prepared from poly(tetramethylene oxide) end‐capped with MDI and PBT extenders. The PBT extenders were random‐disperse in length and their length varied from three to seven repeating units. The structure of the polyurethanes was studied by FT‐IR and AFM, their thermal and thermomechanical responses were measured by DSC and DMTA, and their elastic behavior was assessed by compression set measurements. The MDI‐PBT‐MDI hard segments had a ribbon‐like crystalline morphology. Increasing the PBT length gave rise to an increase of the storage modulus at room temperature and the melting point. The storage modulus depended strongly on temperature.
Rheological behavior and spinnability of biodegradable materials based on SPI and PVA were studied for the production of electrospun fibers. pH level, processing temperature, and heating time were adjusted to investigate the effects of denaturing of soy protein on the rheology of SPI/PVA solutions. The results show that zero shear viscosity and degree of shear thinning of the SPI solution can be controlled by adjusting pH level and thermal treatment. The continuous production of uniform SPI/PVA fibers was achieved by electrospinning. The presence and amount of soy protein in the electrospun fibers was determined by EMPA and elemental analysis, confirming that the SPI was well incorporated into the PVA and remained in the electrospun fibers.
Thermoresponsive nanofibers by very fast grafting of N,N‐isopropylacrylamide (NIPAAm) from electrospun atom transfer radical polymerization (ATRP) macroinitiator are presented in this work. The heterogenous grafting of NIPAAm onto macroinitiator fibers could be done in few minutes, i.e., in less than 5 min. The procedure involved electrospinning of an ATRP macroinitiator and subsequent PNIPAAm grafting using “grafting from” technique. The ATRP Macroinitiator was based on a copolymer of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA). The growth of the PNIPAAm layer on electrospun fibers was followed by IR‐spectroscopy and SEM analysis. The temperature‐dependent‐phase transition was proven by contact angle measurements and could be shown on the same surface for many cycles.
A new melt‐processable PTFE material is presented and characterized that provides new and economical solutions in polymer technology while bridging the gap between perfluorinated PTFE and fluorothermoplastic materials such as perfluoroalkoxy resins. Thermal transitions, MW and MWD, and microstructures of the melt‐processable PTFE materials are investigated and compared to standard PTFE, modified PTFE, and PFA materials. The influence of the polymerization type used for the preparation of the melt‐processable PTFE (emulsion and suspension polymerization) on the MWD and the comonomer distribution are discussed.
Cellulose‐based fibers were prepared by electrospinning from cellulose dissolved in NaOH/urea in the presence of a small amount of polyol binders. The as‐spun products were examined with SEM. Pure cellulose solution did not produce fibrous materials, because it often formed spherical nanoparticles with diameters ranging from 100 to 300 nm. However, bicomponent fibrous materials were obtained successfully from mixtures of cellulose and HMPEG or PVA by electrospinning. The cellulose/HMPEG electrospun fibers had average diameters of 400 nm. The content of NaOH and urea as well as the stiffness of cellulose chains were found to have significant effect on the electrospinning process.
Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. 1H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct2) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.
Highly‐aligned luminescent electrospun nanofibers were successfully prepared from two binary blends of PFO/PMMA and PF+/PMMA. The PFO/PMMA aligned electrospun fibers showed a core/shell structure but the PF+/PMMA fibers exhibited periodic aggregate domains in the fibers. The aligned fibers had polarized steady‐state luminescence with a polarized ratio as high as 4, much higher than the non‐woven electrospun fibers or spin‐coated film. Besides, the PF+/PMMA aligned electrospun fibers showed an enhanced sensitivity to plasmid DNA. Such aligned electrospun fibers could have potential applications in optoelectronic or sensory devices.
Short electrospun fibers were obtained by using UV cutting method. Either polymers with double bonds with a photocross‐linker (CL) and photoinitiator (PI) or known photochemistry of coumarin ([2 + 2] cycloaddition reaction) without the addition of CL and PI is utilized for making short electrospun fibers. The electrospun fibers were irradiated by UV light in the presence of a mask with a defined width of slits. The uncovered parts of fibers were cross‐linked and therefore became insoluble. The non‐cross‐linked parts were removed by immersion of the fibers into an appropriate solvent. The length of obtained short fibers can be controlled by changing the width of the slits of the employed mask.
The first reported use of two‐dimensional mesh thermoplastic fibers in an epoxy matrix for mendable composites is presented, yielding 100% restoration of GIC, failure energy, and peak loads over repeated damage‐healing cycles. SEM imaging and EDS mapping showed different surface structures between CFRPp and CFRPf and confirmed strength recoveries were attained by delivery of EMAA to the fracture plane which enabled the fractured surfaces to rebind after heating to 150 °C for 30 min.
The influence of the flow history experienced during injection molding on the mechanical properties of amorphous polymers is investigated. It is demonstrated that flow‐induced molecular orientation only causes a small anisotropic effect on the yield stress, which can be regarded as insignificant with respect to its absolute value. Its influence on the post‐yield strain‐hardening response is also shown to be imperceptible, in contrast to a orientation which is applied during deformation below the glas transition.
Flocculation of the filler particles in isotactic poly(propylene)/carbon black (iPP/CB) composite melts provides a way to understand electrical and rheological percolation processes. The iPP/CB composites were prepared by mild compounding to ensure a good filler dispersion. Electrical and dynamic rheological characterizations are used to monitor the network formation process in the composite melts. It is found that rheological percolation is more difficult to achieve than the electrical percolation in iPP/CB composites. The discrepancy comes from the different mechanisms for electron transport and stress transfer through the filler network.
