PHB/PBS and PHBV/PBS blends are prepared via in situ compatibilization using DCP as a free‐radical grafting initiator. A considerable reduction in PBS particle size and a significant increase in the interfacial adhesion between the PHB(V) and PBS phases are observed after the compatibilization. The elongation at break of the PHBV/PBS blends was considerably increased. The local deformation mechanism indicates that matrix yielding together with dilatation, deformation, and fibrillation of the PBS particles are responsible for the improved tensile toughness of the compatibilized PHBV/PBS blends. The tensile strength, impact toughness, and elongation at break of injection‐molded PHB(homopolymer)/PBS blends are also increased after in situ compatibilization.
Physical patterns were created on hydrated PSS/PDADMAC multilayers without using external force. A typical process was to put a PDMS stamp onto the wet and swollen multilayers, which were then put into an oven and maintained for a period of time to micromold the multilayers. The influence of molding temperature and time, multilayer thickness, solvent quality, and multilayer compositions on pattern formation were elucidated. Evolution of the patterns from double lines, double strips, and meniscus‐shaped ridges to high ridges was observed under all conditions, revealing that this is a universal principle for this process. Finally, patterns on PAA/PAH and PSS/PAH multilayers were also prepared at the optimal conditions, highlighting its wide generality on the multilayer patterning.
A novel CMRF is synthesized from modified silicone oil, containing composite polyurethane microsphere additives, and surface‐coated iron particles. The CMRF is designed to act as a liquid spring with controllable damping properties in a damper system. The fluid compressibility is characterized by force/displacement measurements. The addition of composite polyurethane‐microspheres increases the strength and compressibility of the fluid. It also decreases the concentration of iron particles needed in order to achieve the same yield stress as commercially available MRF. Surface coating surface of the iron particles with poly(2,3,4,5,6‐pentafluorostyrene) via RAFT provides dispersion stability.
To improve the physical properties of poly(trimethylene terephthalate) (PTT), a series of nanocomposites based on PTT and exfoliated graphite (EG) are prepared via melt compounding and their structures, thermal stabilities, mechanical, and electrical properties are studied. XRD and SEM show that graphene nanosheets are well dispersed in the PTT matrix without forming crystalline aggregates even at high EG content. Thermal stability and dynamic mechanical moduli of the nanocomposites are substantially improved by EG addition, and a pronounced increase in electrical volume resistivity from an insulator to almost a semiconductor is observed with increasing EG content. The electrical percolation threshold of the nanocomposites is found to be formed at the EG concentration between 3.0 and 5.0 wt.‐%.
The acetylation of cellulose in ionic liquids (ILs) and the subsequent dry/wet spinning of these processing solutions were investigated. The homogeneous acetylation in ILs was carried out using different molar ratios of acetic anhydride to the anhydroglucose unit (AGU). The obtained solutions of cellulose acetates were characterised analytically by means of rheological methods. DS and of the prepared cellulose acetates were determined. Furthermore the processing solutions of the acetylation were shaped by means of a dry/wet spinning process to fibres with varied properties. The resulting fibre properties were discussed in consideration of the DS and in comparison with unsubstituted cellulose fibres.
The fractional crystallization kinetics and phase behavior of PEO with different molecular weights (MWs) in its miscible crystalline/crystalline blends with PBS are studied. Both fractional crystallization kinetics and phase segregation of PEO in PBS/PEO blends are dramatically influenced by its MW. PEO with a medium MW (20 kDa) shows a significant fractional crystallization in the blends with PBS crystallized at a high TIC,PBS, which, however, is dramatically depressed in the blends with a very low or high MW of PEO. This indicates that the PEO component with a medium MW is more ready to segregate into the interlamellar region of PBS crystals than those with a very low or high MW. The MW‐dependent fractional crystallization kinetics and phase segregation of PEO component in the PBS/PEO blends are discussed.
The fabrication of tissue engineering scaffolds based on the polymerization of crosslinked polylactide using leaching and batch foaming to generate well‐controlled and interconnected biodegradable polymer scaffolds is reported. The scaffold fabrication parameters are studied in relation to the interpore connectivity, pore morphology, and structural stability of the crosslinked PLA scaffold. In vitro cell culture and in vitro degradation are used to analyze the biocompatibility and biodegradability of the scaffolds. The new crosslinked PLA thermoset scaffolds are highly suitable for bone tissue engineering applications due to their complex internal architecture, thermal stability, and biocompatibility.
In this study, the effects of processing parameters on the mechanical properties of injection molded thermoplastic polyolefin (TPO) foams are investigated. Closed cell TPO foams were prepared by injection molding process. The microstructure of these foamed samples was controlled by carefully altering the processing parameters on the injection molding machine. The foam morphologies were characterized in terms of skin thickness, surface roughness, and relative foam density. Tensile properties and impact resistance of various injection molded TPO samples were correlated with various foam morphologies. The findings show that the mechanical properties are significantly affected by foam morphologies. The experimental results obtained from this study can be used to predict the microstructure and mechanical properties of cellular injection molded TPO foams prepared with different processing parameters.
Surface modification of sulfur by vacuum plasma polymerization with acetylene was applied in order to modify its surface properties without losing reactivity for vulcanization. A nm‐thin layer of crosslinked polyacetylene was deposited on the surface of the sulfur powder. Its surface energy was decreased as monitored by wetting in liquids of various polarities. A delay in the onset of weight loss by sublimation in thermal gravimetric analysis was shown by the plasma‐modified sulfur. Scanning electron microscopy showed a core/shell structure of the coated sulfur. In 50:50 blends of styrene‐butadiene rubber and ethylene‐propylene‐diene rubber, the encapsulated sulfur samples resulted in pronounced improvements in the mechanical properties relative to the use of unmodified sulfur.
New dibenzoylgermanium derivatives are synthesized starting from various dithioacetal protected benzaldehydes by a coupling reaction with different dialkyldichlorogermanes and subsequent oxidative cleavage of the protecting group. The synthesized germanium compounds show a significantly stronger blue light absorption than camphorquinone. During irradiation, the dibenzoylgermanium derivatives undergo photodecomposition under formation of radicals. Therefore, the different dibenzoylgermanium derivatives are used as amine‐free visible‐light photoinitiators for dental cements and composites. Composites based on the different dibenzoylgermanes are storage‐stable and show a significantly improved bleaching behavior over composites with CQ/amine photoinitiators.
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.
A method for determining the correlation between the mixing of two reactive polymers and the structural and mechanical properties of the formed hydrogels is presented. Rheological measurements show that insufficient mixing gives rise to soft and not fully crosslinked hydrogels while excessive mixing beyond gel point results in weaker hydrogels due to potential breakage of their 3D network. Furthermore, the hydrogels swell significantly more in cell culture medium than in phosphate‐buffered saline, attributed to interactions with additional molecules such as proteins. Thus, moderate mixing gives rise to the most homogenous and mechanically stable hydrogels and the choice of medium e.g., for release experiments, should be consistent in order to avoid unnecessary variations in the data caused by different swelling profiles.
The present works aims to develop multi‐materials such as steel/polymer/steel hybrid system for weight savings in automotive industries. This laminate must be compatible with processing on the industrial line (steel/polymer lamination under 200 °C) and the structure must be flow‐resistant during the paint process curing (200 °C for 30 min). Consequently, a yield stress polymer system based on compatibilized PA11/copolymer of ethylene and octene blends has been developed. The yield stress property (for T > 200 °C) depends on the phase concentration and compatibilization strategy. It is observed that an annealing process (heating treatment for 1 h at 200 °C), simulating the painting process, provides a strong benefit for the polymer/steel properties after aging under humidity conditions.
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.
Sunflower oil‐based HBTPU/Ag and LTPU/Ag nanocomposites have been prepared by in situ catalytic reduction of a silver salt. The virgin polymer and their nanocomposites are soluble in various polar organic solvents and amenable for both solution‐casting and hot pressing. XRD, TEM, and UV spectroscopic analyses ascertained well‐dispersed, narrow‐sized Ag nanoparticles. Tensile testing, dynamic mechanical, thermogravimetric, and DSC analyses showed desirable mechanical and thermal features with improvement upon incorporation of Ag nanoparticles and the presence of a hyperbranched component in the nanocomposites. RSM has been used to evaluate the catalytic efficacy of the nanocomposites.
Living radical polymerization (LRP) techniques and their ability to improve the morphology of crosslinked polymer networks by controlling polymer chain growth are reviewed. Recent successes in the creation of improved molecularly imprinted polymer networks are also discussed. LRP offers the ability to control molecular weight, polydispersity, and tacticity while reducing microgel formation in polymers created via free‐radical polymerization (FRP). The improved network architecture of polymers created via LRP has great potential, especially when considering imprinted networks which have traditionally been plagued by heterogeneity in network morphology and binding affinities. Using LRP can considerably improve template recognition and further delay template transport in imprinted polymers.
A series of various soybean oil/dicyclopentadiene (DCP) thermosetting copolymers with renewable carbon percentages of 53–86% have been prepared by cationic copolymerization of regular (SOY) or 100% conjugated soybean oils (C100SOY) with DCP initiated by NFO ethyl ester modified and SOY‐ and C100SOY‐diluted BF3 diethyl etherate. The effects of stoichiometry, the type of soybean oil, and the initiator on the mechanical and damping properties of the copolymers have been investigated. The materials exhibit compressive stress/strain behavior ranging from soft rubbers to tough and ductile plastics, and possess good damping properties. They represent promising new materials for efficient sound and vibration damping applications over a broad temperature and frequency range.
A simple route for preparing robust polymer nanotubes by SI‐ATRP within porous anodic aluminum oxide membranes and subsequent removal of the templates is presented. The nanotubes are composed of a crosslinked poly(styrene‐co‐divinylbenzene) shell and an inwardly grafted functional P4VP or PGMA brush‐like internal surface. The crosslinked skin endows the nanotubes with stability against organic solvents while the inwardly grafted polymer brushes supply the nanotubes with reactivity and functionalities. The inward PGMA hairs are post‐modified with sodium azides to introduce azido groups along tubular internal surfaces which are further reacted with propargyl alcohol. Structure and properties of the nanotubes are studied by SEM, TEM, LSCM, and FT‐IR spectroscopy.
Strong honeycomb like nanocomposite sponges were fabricated from starch and PVA by using repeated cycles of freezing and thawing and reinforcing with cellulose whiskers. Their structure and properties were investigated with WAXD, FT‐IR, SEM, DMTA, rheological measurements, and LSCM. The results revealed that the repeated freezing/thawing cycles induced a physically crosslinked chain packing between starch and PVA, as well as a phase separation caused by the crystalline ice and syneresis. Thus, larger pores and tougher walls emerged in the sponges, leading to a high swelling degree. The sponges reinforced with cellulose whiskers exhibited improved dimensional stability and enhanced strength. These nanocomposite sponges are promising for wound dressing and tissue engineering applications.
