Conducting electrospun fiber mats based on PLA and PAni blends were obtained with average diameter values between 87 and 1 006 nm with PAni quantities from 0 to 5.6 wt.‐%. Structural characteristics of fiber mats were compared to cast films with the same amount of PAni and studied by SEM, SAXS, and AFM. Thermal properties of fiber mats and cast films were compared by DSC analyses. Mechanical properties of fiber mats were also evaluated. It was found that electrospinning process governs the crystal structure of the fibers and strongly affects fiber properties. New properties of PLA/PAni blends are reported due to the size fiber reduction.
1,3,5‐Benzenetrisamide‐based supramolecular nucleating agents for poly(butylene terephthalate) (PBT) are reported. 1,3,5‐Benzenetrisamides combine excellent thermal stability with chemical resistance, basic requirements for the use in high‐melting thermoplastics. To establish structure–property relationships, the central core and peripheral substituents are varied systematically. Dissolution and crystallization behavior of the additives in the PBT melt and the crystallization temperature of PBT are investigated as a function of the additive concentration. Efficient nucleating agents can increase the crystallization temperature of PBT by 10.6 °C to 199.1 °C. A visualization of supramolecular nano‐objects formed in the polymer melt is provided.
An effective approach is presented for designing and tailoring diffusion‐controlled systems for targeted release rate profiles. The diffusion‐controlled system consists of PBA networks with precisely controlled crosslink densities via RAFT copolymerization of BA with ethylene glycol dimethacrylate, which gives a desired diffusivity. One‐dimensional releases in the crosslinked PBA matrix (CPM) slabs are evaluated with a hydrophobic dye. Fick's second law is used to model the transient mass transfers in the CPMs with a mixed Newton‐Tikhonov regularization method for determination of their diffusion coefficients. A two‐layer CPM (CPM‐2) with controlled crosslink densities is constructed. The dye release results from the CPM‐2 agreed well with theoretical predictions.
A process we term “natural fiber welding” is demonstrated by which loose fibers are transformed to create a congealed network using an IL solvent. Several examples are discussed that include cellulosic and protein‐based materials. SEM shows the fusion of fibers upon treatment. XRD and FT‐IR spectroscopy of cellulosic materials show that significant amounts of the native polymer structure are retained after the process is completed. Data suggest that material at the fiber exterior is preferentially transformed while material in the fiber core is left in the native state. Data also demonstrate that the amount of material modified can be tailored by control of variables such as the IL solvent concentration, the process temperature, and the processing time.
Unmodified (LDH) and modified (mLDH) layered double hydroxides have been added to gum and ZnO‐cured carboxylated nitrile rubber (XNBR). It was observed that both LDH and mLDH inhibit the formation of ionic cross‐links between XNBR and ZnO quite significantly, as is evident from DMA and FT‐IR studies. The suppression of ionic cross‐links formation was also reflected in the mechanical properties of the resulting composites. A tentative sketch has also been suggested for the possible mechanism involved in the inhibition of ionic cross‐links by LDHs. X‐ray diffraction and STEM studies were performed to see the dispersion of LDH's in the elastomer matrix.
Additive processing technologies are rapidly growing in all fields of application. A large number of scientific publications were investigated in order to provide a comprehensive overview of rapid prototyping methods for polymers and their applications, of currently available materials and research concerning additive processes. The current problems of additive processes are described, together with their potential solutions. Furthermore, this article delivers an insight into possible future trends of additive technologies.
Polyurethanes based on vegetable oil were synthesized with castor oil and toluene diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate, using dibutyltin dilaurate as a catalyst. The effects of the nature of the diisocyanate on the evolution of the kinetics, as well as the physical and mechanical properties and the thermal stability, of the different synthesized polyurethanes were investigated, and these complement data from the literature on equivalent systems. The polymerization kinetics, degree of swelling and mechanical properties were greatly affected by the diisocyanate nature, whereas the rheological properties and thermal stability were found to be similar for all polyurethanes.
Novel fluoroalkyl end‐capped oligomer/hydroxyapatite nanocomposites have been easily prepared by the reaction of disodium hydrogenphosphate and calcium chloride in the presence of self‐assembled molecular aggregates formed by fluoroalkyl end‐capped oligomers in aqueous media. The fluorinated hydroxyapatite nanocomposites thus obtained were found to exhibit a good dispersibility in a variety of media, and were applied to the surface modification of glass.
Well‐defined correlations exist between the maxima in mechanical loss factor and the local maxima in temperature‐ or loading‐speed‐dependent fracture toughness. The non‐linear viscoelastic fracture processes and small‐strain deformations are characterised by the same Arrhenius‐type activation enthalpies. The local increase in toughness is linearly correlated with the relaxation strength of molecular relaxation processes. Stable crack propagation can be understood as a three‐phase process resulting in steady‐state stable crack growth. The normalised steady‐state crack‐tip‐opening displacement is independent of matrix material, temperature and loading speed.
The filler networking process promoted by multiwalled CNTs is studied in neat and CB‐filled poly(1,4‐cis‐isoprene) matrices. TEM analysis, tensile, dynamic‐mechanical, and electrical measurements reveal that the CNTs form a filler network at low concentration in neat PI and a continuous hybrid filler network at a lower CNT concentration in the presence of CB, with a remarkable increase of the nonlinear dynamic‐mechanical behavior of the nanocomposites at low deformation. A synergistic effect between CB and CNTs is demonstrated. The addition of CNTs to the CB‐filled PI matrix leads to initial modulus values much larger than those calculated by simple addition of the two initial moduli of the composites containing only CB and only CNTs, respectively.
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.
MMA‐EHA copolymers with different compositions and with a low amount of AA were synthesized and used as impact modifier for epoxy networks. The effect of the copolymers on the tensile and dynamic mechanical properties as well as impact resistance of the epoxy network was evaluated. The addition of 10 phr of low‐molar‐mass MMA‐EHA copolymer with defined composition resulted in a significant increase in impact resistance without any significant changes in the tensile strength, modulus, and glass transition temperature. The morphology of the modified epoxy network depends upon the copolymer composition.
Reconstituted collagen gels are widely used as scaffolds even though their low strength and poor elasticity limit their applications in VTE. Here, two approaches are adopted to modify their mechanical behavior: in the first, gels prepared under physiologic conditions are remodeled by cell‐mediated contraction; in the second, gels prepared in non‐physiologic conditions are chemically crosslinked. Samples are tested under cyclic loading and their viscoelastic behavior is assessed. The results show that both approaches result in lattices with adequate strength, and crosslinking significantly reduces hysteresis and permanent deformation. SEM shows that SMCs are capable of contracting and remodeling all the lattices, confirming that these are suitable supports for tissue regeneration.
Microcellular biodegradable polymer foam with an open porous structure was prepared from amorphous poly‐L,D ‐lactic acid (PL ,D LA) blended with polystyrene (PS), or polymethyl methacrylate (PMMA). The blends were prepared by polymerizing either styrene or methyl methacrylate (MMA) in a PL ,D LA matrix. The styrene and MMA monomers are good cell‐opening agents and constituents for an IPN. Pressure‐quench batch foaming was conducted using carbon dioxide as a foaming agent at 80 °C under 10 MPa. The effects of monomers and a cross‐linking agent on the foamability and OCC were investigated. Manipulation of the monomer and the cross‐linking agent concentrations was able to change the viscoelasticity and partial miscibility of the blend and control the cell size at the micron scale as well as open pore content in the range of 20–90%.
A recently developed electrohydrodynamic printing method is described that can be used to create ordered structures and complex patterns using coarse processing needles and two polymeric materials. The results highlight the method's potential for direct 3D writing of biomedical polymers and composites for a variety of biomedical applications.
10‐Ethyl‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide ( 1 ) can be nitrated using acetic anhydride and fuming nitric acid. The nitro group is reduced using palladium on charcoal and hydrogen. These reaction conditions are used for the synthesis of an analogous DOPO‐based diaminic hardener ( 7 ). An evaluation of the curing behavior, mechanical properties and flammability of a neat resin made of DGEBA and 7 (DGEBA + 7 ) and of a carbon fiber‐reinforced resin made of DGEBA, 4,4′‐diaminodiphenylsulfon (DDS) and 7 (DGEBA + DDS + 7 ) shows the potential of this hardener to lead to flame‐retardant systems while keeping relevant properties on a high level; especially when compared to a similar system (DGEBA + DDS + 1 ).
The scientific and industrial history of polyurethane wire enamels during the previous six decades is reviewed. Their main use is as coatings for wires in miniature electrical devices and in electronics, where fast solderability at low temperatures is crucial. Market trends for polyurethane enamels are discussed, and an outlook is provided as to how future developments might influence the industrial use of polyurethane wire enamels.
The properties of MIPs synthesized by minisuspension polymerization are studied. The template is cyclododecyl 2,4‐dihydroxybenzoate ( 1 ), which behaves as good mimic of the estrogenic mycotoxin zearalenone. 2‐DAEM and EGDMA are used as functional and crosslinker monomers, respectively. The synthesized particles are characterized by optical and electronic microscopy, N2 sorption measurements, and FT‐IR spectroscopy. The molecular recognition capability of MIPs is evaluated by comparing the adsorption Freundlich isotherms of MIPs to those of the corresponding non‐imprinted polymers. It is concluded that MSP is an attractive alternative for molecular imprinting because it is easy to apply and produces high yield of spherical particles of “tunable” size with acceptable molecular recognition capabilities.
Cyano‐OPV moieties were covalently incorporated into a PETG backbone to create ductile amorphous polymers which change their PL and absorption color as a function of deformation. The cyano‐OPV concentration was systematically varied, and the composition was related to the material's optical response. This approach afforded PETG/dye copolymers which upon annealing display characteristics of aggregated dye molecules. The materials exhibit a significant color change upon compression, consistent with disassembly of the dye aggregates. This mechanochromic response is irreversible and can be detected by the unassisted eye.
Hybrid polymeric inlays, patterned by nanoimprint lithography, are used to rapidly mass replicate pillar‐like nanostructures by injection moulding. This is difficult to achieve with traditional nickel inlays due to the rapid heat transfer of the metal, which results in premature cooling of the molten polymer and improper filling of nanoscale features. Using hybrid inlays, nanopillars can reliably be stretched by up to 40% of their designed height by adjusting moulding parameters. Hybrid inlays display longevity of more than 2000 cycles and can rapidly be fabricated to firmly establish injection moulding as an exceptionally useful tool for the high volume prototyping and production of nanopatterned polymeric devices.
