This paper demonstrates how the electric‐field‐assisted thermal annealing of octadecylamine‐functionalized SWNT/PMMA films induces an increase in the composite transversal conductivity of several orders of magnitude and a decrease in the lateral conductivity. This difference has been rationalized in terms of the nanotube alignment into the polymer matrix along the electric field direction. This result provides an initial understanding of how electric fields can be used to control the bulk physical properties of such nanocomposites.
The effects of the CTA concentration on polymerization kinetics, polymer microstructure, particle morphology, and adhesive performance of waterborne hybrid PSAs prepared by simultaneous free‐radical and addition miniemulsion polymerizations are studied. The development of the microstructure is shown to differ from waterborne acrylic PSAs obtained by free‐radical polymerization because of the contribution of the addition reaction, which in turn causes marked differences in the adhesive performance of the final films. A computer simulation is developed to obtain detailed information about the microstructure of PU/acrylic hybrids and to correlate the microstructure with the final adhesive properties.
Surface properties of epoxy coatings are modified by PDMS additives in cationic UV curing of a cycloaliphatic epoxy resin. The cured films show a very high hydrophobicity that does not depend on PDMS concentration, indicating that a threshold is reached even at 0.3 wt% additive. A slight increase of the water contact angle as a function of PDMS molecular weight is observed. The additive selectively modified the air‐side of the film, while the glass‐side retains the surface properties of the pure resin. This segregation phenomenon permits to obtain highly hydrophobic films with still good adhesion properties on polar substrates, which is an important advantage over common surface‐modified resins.
Soy protein concentrate (SPC) is modified by blending with gelling agents such as agar, Agargel, and Phytagel and the properties of the blended films are characterized. Gelling agent addition significantly improves the mechanical properties, thermal stability, and moisture resistance. SPC blended with 30% PG show over 180% increase in the tensile stress and Young's modulus and the moisture regain decreases from 17.9 to 13.9%. The glass transition temperature of the SPC films increases from 132 to 148 °C after blending with Agargel and Phytagel. IPN‐like structure formation after adding gelling agents is responsible for the improvements. The results also suggest that the gelling agent chemistry determines the amount of gelling agent required to form IPN‐like structures.
A new technique for design and preparation of self‐reinforced starch films is introduced. The films were based on a high‐amylose corn starch that was chemically modified in different ways. Hydroxypropylation was used to decrease gelatinization temperature and improve processability. The reinforcing component consisted of cross‐linked starch granules, where the crosslinking increased granule thermal stability and moisture resistance. Distribution of the cross‐linked starch was imaged by CLSM, and the matrix/particle interface was studied by SEM. Modulus and tensile properties of the starch film were increased by about 30 and 20%, respectively, after addition of rigid cross‐linked starch particles. A perfect interface between matrix and reinforce agent was obtained.
The existence of lignin in lignocellulosic fibers increases the loss in breaking tenacity and elongation of fibers when they are exposed to heat and light. Delignification by sulfonation helps to remove some of the lignin from the fibers without affecting the breaking tenacity. The delignified fibers have higher resistance to heat and light exposure compared to the raw fibers. The effect of lignin on the heat and light resistance of kenaf and cornhusk fibers with three different lignin contents was studied in comparison to cotton at various periods of heat and light exposure. The changes in the breaking tenacity, breaking elongation and yellowness of the samples were studied.
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.
This paper describes a novel process that is stretching‐controlled thermal micromolding, to fabricate bionic superhydrophobic polyethylene films. Low‐density polyethylene was thermally pressed in a vacuum oven onto PDMS stamps replicated from lotus leaves. After being cooled and peeled off from the stamps, the polyethylene films with superhydrophobic surface were created, exhibiting a water contact angle of 154.1 ± 3.5° and a rolling angle of ≈7°. SEM imaging showed that the superhydrophobic surface had micro‐papillas much higher than those on the lotus leaf, demonstrating the papillas had been stretched longer from the holes on the stamp during the separating process. This study shows that micromolding is a promising technique for large scale production of superhydrophobic films, even if the holes on the mold are not deep enough.
Toughness enhancement of S‐(S/B)‐S triblock copolymers via a molecular‐weight‐controlled pathway is demonstrated. The post‐yield crack toughness behavior of the triblock copolymers uniquely reveal a brittle‐to‐semiductile‐to‐ductile transition with increasing while keeping the basic molecular architecture fixed. TEM and SAXS investigations indicated three distinct morphologies as a function of χeffN as a consequence of the increase in : (i) a homogeneous structure without phase‐separation, (ii) a weakly segregated structure, and (iii) a lamellar structure. The increase in crack toughness is also reaffirmed from kinetic and strain field analysis studies concerning dynamics of crack growth in block copolymers with high PS content.
A series of hydrogels based on poly(ethylenglycol) methyl ether methacrylate (PEGMEMA) is synthesized using macromonomers of three different molecular weights, in combination with varied degrees of chemical crosslinking. The effects of PEGMEMA, initiator, and crosslinker concentrations on gel yield and swelling properties are studied. In addition, the chemical structure of the gels is characterized by FTIR and solid‐state NMR spectra. The swelling and rheological behaviors of hydrogels as well as protein partitioning into the gels are discussed in terms of the network mesh size. Low protein sorption and bacteria deposition tendencies indicate that PEGMEMA‐based hydrogels could be highly beneficial for uses as fouling‐resistant materials, for instance, as protective coatings for desalination membranes.
A novel multi‐compound electrospinning method is described, using high‐conductivity aqueous solutions for the inner fluid and low‐conductivity polymeric solutions for the outer fluids. The driving fluid among inner fluids at the equivalent conductivity is switched at a certain frequency. The switching of the Taylor cone results in the alternative embedding of inner components. Also, the number of inner capillaries is proportional to the encapsulation components. Therefore, our method might be useful to alternatively encapsulate a variety of water‐soluble materials in fibers.
Developing co‐continuity in a polymer blend determines a multiphase system with enhanced properties which originate from the synergism of its constituents. Filling a blend with nanoparticles is a promising route to guide its morphology and eventually affect the co‐continuity transition. We add different kinds of nanoparticles to an HDPE/PEO blend to study how they affect the morphology of the blend as function of their surface properties and form factor. We find that PEO drop size is drastically reduced by particles adsorbed at the HDPE/PEO interface. However, we show that a drastic shifting of the co‐continuity threshold may only be achieved when particles affect the rheology of the interface.
Silane coatings with different thicknesses were synthesized on CNFs for reinforcement of polyethylene composites. The thickness of the silane coating was adjusted by using a basic catalyst to increase the overall reactivity of the silane groups, resulting in a thick coating of ≈46 nm (ca. 90% increase in fiber diameter). DMA performed on the polyethylene composites showed a substantial increase in storage modulus from 1.68 to 2.34 GPa (40%) at low temperatures in the composite with the thick silane coating (≈46 nm) at a low loading of 0.4 wt.‐%. We believe that the silane‐treated nanofillers with thick coatings are very promising for high‐performance nanocomposites with non‐polar polymer matrices.
Poly(lactic acid) (PLA) toughening is often associated with significant modulus and/or strength losses making it unsuitable for many consumer and biomedical applications. The major objective of this research was to toughen PLA without significant loss in modulus and strength and to introduce reactive acid groups using reactive blending of PLA with a combination of polymers. PLA was reactive blended with poly(acrylic acid) (PAA) followed by physical blending with poly(ethylene glycol) (PEG) in solution. The modified PLA was extruded into films using a co‐rotating twin‐screw extruder and characterized using tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical analyses (DMA). This technology resulted in films with a ten‐fold increase in toughness compared to neat PLA with little or no decrease in strength and modulus.
Xylan sulfates have been prepared under homogeneous reaction conditions in DMF/LiCl applying SO3/pyridine and SO3/DMF. The degree of substitution (DSSulfate) of the products obtained was determined by elemental analysis. DSSulfate reached values of up to 1.90 applying a molar ratio of 3 mol sulfating agent per anhydroxylose unit. The structure of the xylans and of the xylan sulfates was studied in detail by one‐ and two‐dimensional NMR spectroscopy and MALDI‐TOF mass spectrometry.
Cytocompatible nanocomposite films are prepared by blending α‐chitin whiskers and cellulose solution in NaOH/urea. Structure and properties of the chitin/cellulose composite films are characterized by FT‐IR, XRD, 13C NMR, SEM, UV‐Vis, TGA, and tensile tests. The results reveal that the chitin whiskers are dispersed homogeneously, leading to good miscibility and properties of the chitin/cellulose composite films. By varying the chitin whisker content, the tensile strength and elastic modulus of the films can be controlled. HeLa and T293 cells are seeded onto the surfaces of the nanocomposite films, showing that the composite films were nontoxic to both cell types and that the addition of chitin whiskers promotes cell adhesion and proliferation.
The effect of different bicomponent electrospinning techniques i.e., off‐centered coaxial electrospinning and side‐by‐side electrospinning, on the formation of tight nanocoils (nanosprings) was studied. Since right balance between the longitudinal compressive forces arising from the shrinking thermoelastic components and the rigidity emerging from the stiff component and conductivity is required for nanospring formation, conductive solutions of flexible and rigid components were used for the electrospinning. Under optimum conditions, nanofiber mats with almost 100% nanospring morphology were generated using off‐centered and side‐by‐side electrospinning techniques. Mechanical properties of aligned nanomats with and without nanosprings, produced at different collecting speeds are provided.
Using a single layer of SU‐8 photoresist to fabricate optical waveguide cores and microfluidic channels on Pyrex glass is an ideal way to achieve photonic/microfluidic integration on a single chip. To address the problem of poor bonding, a thin nanoscale intermediate polymer layer was applied to reduce the stress generated from the material processing while maintaining strong adhesion between the patterning polymer layer and Pyrex. It was found that a 186–600 nm thick intermediate layer of a specialty epoxy photoresist effectively served the purpose without deteriorating the optical performance of the involved waveguides. Quality photonic/microfluidic integrated devices with satisfied optical performance were fabricated.
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.
An electrospinning method to obtain well‐aligned self‐assembled PVDF fibers in the form of yarn structures is presented. Post‐treatments such as stretching at 100 °C and annealing improve the tensile modulus and strength of the fibers by 17 and 41%, respectively. The results reveal that post‐treatment on fiber yarns induce crystallinity and β‐crystalline phase formation, which in turn impart a noticeable effect on the strength and stiffness of the fibers. An ≈10% improvement in the ferroelectric β‐crystalline phase fraction is estimated for the post‐treated yarns. Such yarn structures with improved strength and ferroelectric β‐phase content can be useful for nanoscale and microscale electronic devices.
