Poultry feather fiber is transformed into biothermoplastics using a twin screw extruder, and the plasticizing effect of four different plasticizers on the material properties is investigated. Conformational changes, viscoelastic behavior, thermal degradation, and phase transitions are assessed by means of FTIR spectroscopy, DMA, TGA, and DSC, respectively. The mechanical properties of the plasticized resins are assessed by tensile measurements, while optical transmittance is recorded using UV‐Vis spectrophotometry. The water uptake behavior of the fiber keratin and plasticized resins is also investigated.
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.
Poly(propylene)‐clay nanocomposites and poly(propylene) containing conventional inorganic fillers such as calcium carbonate (CaCO3) and glass fiber were used in a comparative study focusing on dimensional stability, structure, mechanical and thermal properties. Micro‐ and nanocomposites were prepared by melt blending in a twin‐screw extruder. The relative influence of each filler was observed from dimensional stability measurements and structural analysis by WAXD, TEM, and thermal and mechanical properties. At equal filler loadings, PP/clay nanocomposites exhibit an improvement in dimensional stability and were the only composites capable of reduced shrinkage in both in‐flow and cross‐flow directions. The flexural modulus of PP increased nearly 20% by compounding with 4% organoclay, as compared to a similar performance obtained by compounding with 10 wt.‐% of CaCO3 or approximately 6 wt.‐% of glass fiber. The HDT and thermal stability of PP were enhanced by using nanoclay as filler.
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.
1, 2, 3, 5, and 7.5 wt% MWCNTs are incorporated into PS in a twin‐screw extruder at varying speeds, throughputs and extruder barrel temperatures. Increased SME at enhanced processing speeds seems to have the single largest effect in enhancing dispersion. A relative evaluation of PS/MWCNT interactions indicate an interfacial layer growth of 24% for 2 wt% MWCNT at 1100 rpm compared to 18% growth at 500 rpm. Raman analysis does not show an MWCNT peak shift but a constant increase in FWHM is observed irrespective of the MWCNT content. A significant enhancement of thermal stability occurs up to 2 wt% MWCNT loading while 1–2 wt% shows the rheological threshold. The volume resistivity decreases dramatically in a 2 wt% sample processed at 1100 rpm compared to those processed at 500 rpm.
The crystallization behavior of poly(L ‐lactide) (PLLA) was investigated in the presence of benzenetricarboxylamide (BTA) derivatives as crystal nucleators. BTA‐cyclohexyl (BTA‐cHe) was the most effective nucleating agent, but induced a complete loss of transparency of the processed material. On the other hand, BTA‐n‐hexyl (BTA‐nHe) enhanced crystallization with little increase in haze. PLLA containing BTA‐cHe enhanced PLLA crystallization in α‐form crystal whereas BTA‐nHe enhanced α′‐form (incomplete α‐form) with forming smaller spherulites. TEM revealed BTA‐nHe had completely dissolved in the PLLA matrix in melt and recrystallized during the thermal annealing process. It was also found that the size of the recrystallized BTA‐nHe was in the nanometer range to effectively nucleate the PLLA crystals.
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%.
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.
The solid and thermally instable azoinitiators V‐65 and VR‐110 were embedded within a polymer particle by using the miniemulsion process and afterwards quickly decomposed by thermal treatment below the glass temperature of the polymer. The resulting nitrogen gas overpressure inside the particles leads to a disruption of the polymer particle and a possible sudden release of encapsulated substances. It is shown, by electron microscopic measurements, that the number of burst particles correlates with the applied temperatures as well as the heating time. The surface deformation could be verified by scanning electron microscope analyses.
Acrylate‐based nanocomposite coatings prepared from uniformly sized, nanoscaled inorganic, i.e., BaSO4‐ and CaF2‐ as well as organometallic, i.e., Al‐maleate‐derived nanoparticles were prepared applying photochemical curing. Excellent mechanical and thermal stability as well as high optical transparency was achieved as compared to standard SiO2‐based coatings. The performance of CaF2‐based nanocomposites could be further enhanced by addition of nanocorundum. A comprehensive data set on surface and Martens hardness, the penetration depths, glass transition temperatures, and UV–Vis transparency of the final coatings is presented.
PHBV is produced by bacteria as intracellular carbon storage. It is advantageous concerning biocompatibility and biodegradability, but its low crystallization rate hinders the melt‐processing of fibers. This problem can be overcome by combining PHBV with PLA in a core/sheath configuration and introducing a new spin pack concept. The resulting PHBV/PLA bicomponent fibers show an ultimate tensile stress of up to 0.34 GPa and an E‐modulus of up to 7.1 GPa. XRD reveals that PLA alone is responsible for tensile strength. In vitro biocompatibility studies with human fibroblasts reveal good cytocompatibility, making these fibers promising candidates for medical therapeutic approaches.
A range of bio‐based rubbery thermosets have been synthesized by the cationic copolymerization of conjugated soybean oil, styrene, and 1,5‐hexadiene or isoprene as flexible crosslinkers. The thermal, and mechanical properties, as well as the wear behavior, of these new bio‐rubbers are reported. The amount of styrene and the type of diene incorporated have the greatest influence on the properties of the final materials. The largest variations are found in glass transition temperature, storage modulus, tan δ values, crosslink density, and abrasive wear depth, while thermal degradation and extraction analyses showed minimal variations with changes in composition.
Blends of isotactic poly(propylene) and low‐density polyethylene with different composition ratios were prepared through direct melt compounding on a twin‐screw extruder. The specimens with various geometric configurations were injection‐molded using a gas counterpressure process, using blends to which 0.5 wt.‐% of a blowing agent was added. The influence of blend composition and specimen geometry on the structure and morphology of the samples was investigated by SEM and WAXS. The thermal behavior of the blends was analyzed by DSC. It was found that the morphology of each region depended on the composition ratio and specimen geometry.
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.
This study concerns with the investigation of the effect of irradiation conditions on grafting of styrene into FEP films by the pre‐irradiation method. EPR spectroscopy was used to characterize the base polymer material regarding the trapped radical species and their concentration. Radiation‐induced changes in the chemical structure were studied by IR spectroscopy. Tensile strength and elongation at break as well as yield of grafting were found to be strongly influenced by irradiation temperature. Main‐chain scissions were identified to be the reason for the deterioration of the mechanical properties after radiation treatment at temperatures below glass transition temperature.
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.
A 3D spongy collagen cryogel was prepared using DAS as the cross‐linker. FTIR and CD studies demonstrate that crosslinking is achieved through the reaction of the DAS aldehyde groups with the free amino groups in collagen without affecting the triple helix of collagen. SEM demonstrates that the cryogel has a heteroporous structure with interconnecting pores. DSC measurements reveal that the cryogels have improved thermal stability in comparison with pure collagen. Moreover, the ESR shows that the water uptake of the cryogel decreases with DAS content. Evaporation tests indicate that the cryogel can hold moisture for a long time. Since both collagen and DAS are nontoxic and the resultant cryogel is blood‐compatible, the cryogel is expected to be useful, e.g., as wound dressing.
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.
Polyurethanes with narrow‐disperse (ND) and polydisperse (PD) hard segment (HS) distributions were prepared in a two‐step process. First, a poly(propylene oxide) end‐capped with MDI (4,4′methylenebis(phenyl isocyanate) was synthesized. To this prepolymer either a diamine–diamide was added to form ND HSs or a mixture of a diamine–diamide and additional MDI to form PD HSs in the copolymers. The polyurethanes displayed a ribbon‐like crystalline morphology, and it was found that the copolymers with ND HSs were more crystalline, had a higher modulus, a less temperature‐dependant modulus, and a higher melting temperature than their PD counterparts. Overall, the polyurethanes with the narrow‐dispersed HSs displayed superior properties.
Curaua fibers were treated with ionized air to improve the fiber/phenolic matrix adhesion. The treatment with ionized air did not change the thermal stability of the fibers. The impact strength increased with increase in the fiber treatment time. SEM micrographs of the fibers showed that the ionized air treatment led to separation of the fiber bundles. Treatment for 12 h also caused a partial degradation of the fibers, which prompted the matrix to transfer the load to a poorer reinforcing agent during impact, thereby decreasing the impact strength of the related composite. The composites reinforced with fibers treated with ionized air absorbed less water than those reinforced with untreated fibers.
