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.
Natural rubber (NR) composites containing graphene (GE) are prepared by ultrasound‐assisted latex mixing and in situ reduction. The fatigue crack propagation of the composite is examined. It is observed that GE has an opposite effect on crack growth resistance of NR, i.e., at lower fatigue strains, the inclusion of GE accelerates the crack growth, whereas at higher strains, the crack growth is retarded. It is suggested that the reason for this behavior is a competition between strain‐induced crystallization and cavitation at crack tip. Through microfocus hard‐X‐ray diffraction beamline with high spatial resolution, fatigue crack resistance is correlated to strain‐induced crystallization and new insights into the mechanism of fatigue crack growth are obtained.
The effects of nucleobases, especially uracil, on the nonisothermal and isothermal crystallization, melting behavior, spherulite morphology, and crystalline structure of bio‐based and biodegradable PLLA are studied. The melt‐ and cold‐crystallization rates of PLLA increase with increasing uracil loading. The melting behavior of nonisothermally melt‐ and cold‐crystallized PLLAs depends on the uracil content. The isothermal crystallization kinetics is analyzed based on an Avrami model. The incorporation of uracil changes the t1/2/Tc profile of PLLA due to the more distinct heterogeneous nucleation effects at small supercooling. The crystalline structure of PLLA is not affected by uracil presence. The nucleation density increases and the spherulite size decreases by uracil incorporation.
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.
A set of amorphous poly[ethylene‐co‐(1,4‐cyclohexanedimethylene terephthalate)] (PECT) copolymers containing 25 and 30% of 1,4‐cyclohexane dimethylene (CHDM) units and small amounts of branching agent pentaerythritol (PER) is investigated. The level of long chain branching was estimated by analyzing the positive deviation from law. Branching also produced melt elasticity enhancement which is desirable for certain processing methods. Capillary extrusion experiments at 180 °C generated flow‐induced crystallization in PECT containing 25% of CHDM. Crystallization increased with the amount of PER added, which was explained by the favorable effect of branching to increase elongational rate at the entrance of the capillary. Linear and branched PECTs containing 30% of CHDM did not crystallize.
The effect of CO2‐induced crystallization on the mechanical properties, in particular the yield and the ultimate stresses, of polyolefins is studied. PP and SEBS copolymer blends are used as examples and foamed after sorption of CO2 at temperatures below Tm. CO2 sorption thickens the crystalline lamellae and consequently increases Tm from 160 to 178 °C for both pure PP and PP/SEBS blend systems. Foams with an average cell size smaller than 250 nm retain the ultimate stress at the level of the polymer before foaming, even without the effect of CO2‐induced crystallization. Including CO2‐induced crystallization, the yield and the ultimate stresses of the foam can be improved by 30 and 50% over solid PP and by 22 and 40%, for solid PP/SEBS blends, respectively.
The effects of incorporated nano/micro‐diamond (NMD) on the physical properties, crystallization, thermal/hydrolytic degradation of poly(L ‐lactic acid) (PLLA) were investigated for a wide NMD concentration range of 0–10 wt.‐%. Incorporated NMD increased the tensile modulus and strength of PLLA films but decreased the elongation at break of PLLA films. Incorporated NMD accelerated the crystallization of PLLA during heating and cooling and increased the absolute crystallization enthalpy of PLLA films (except for an NMD concentration of 10 wt.‐% during cooling) but did not alter the crystallization mechanism. Incorporated NMD increased and decreased the thermal stability of PLLA films for NMD concentrations of 1–5 and 10 wt.‐%, respectively, and increased the hydrolytic degradation resistance of PLLA films.
Native and nucleated PHB has been melt‐spun and the properties of the resulting fibers have been investigated. Biocompatible nucleating agents such as HAP and THY were compared to BN as a reference material. DSC was used to investigate the non‐isothermal crystallization kinetics as a function of processing temperature and cooling rate. It was found that particularly the choice of process temperature can ensure sufficient primary crystallization of native PHB: heating not higher than 10–15 K above the melting temperature induced a favorable crystallization behavior of native PHB. Thus, melt spinning at low process temperatures without additives was demonstrated to be the key to the formation of well‐defined hollow PHB fibers.
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 facile technique is presented to prepare discrete µm‐sized spherulitic particles of BAPC in thin polymer films. Unlike in bulk precipitation or spray crystallization, the present technique offers a method to prepare three‐dimensional semicrystalline particles of narrow particle size distribution that can be readily isolated and collected from the glass substrate as discrete particles. We report the effects of polymer molecular weight, polymer type, and the precursor polymer film thickness on the formation of spherulitic particles and their morphologies. The three‐dimensional spherulitic particles prepared in this study have large specific surface areas, higher crystallinity and melting temperature than the bulk precipitated and crystallized polycarbonate particles.
As‐received poly(ethylene terephthalate) (asr‐PET) may be reorganized by precipitation from trifluoroacetic acid upon gradual addition to a large excess of rapidly stirred acetone (p‐PET). Unlike asr‐PET, p‐PET repeatedly crystallizes rapidly from the melt, and can be used in small quantities (a few %) as an effective self‐nucleating agent to control and improve the bulk semi‐crystalline morphology and properties of asr‐PET. Nuc‐PET film has significantly increased hardness and Young's modulus and is much less permeable to CO2, while its un‐drawn fibers exhibit higher tenacities and moduli. Because nuc‐PET contains no incompatible additives, it may be readily recycled.
An experimental correlation between the non‐linear behaviour of commercial polyethylene melts in LAOS flow, and the pressure fluctuations associated with melt flow instabilities developed in capillary rheometry are presented. Polyethylene melts with enhanced non‐linear behaviour under LAOS conditions present larger pressure fluctuations during capillary extrusion, and consequently, larger surface distortions on the extrudate. The combination of both methods can be a tool to predict the development of melt flow instabilities in the extrusion process of polyethylene melts, and can elucidate their correlation with material structural properties ( , MWD and topology).
Near‐monodisperse, size‐controllable, poly(methyl methacrylate)‐pigment nanoparticle composites were produced using electrohydrodynamic atomization (EHDA). The geometric mean diameters of the composite particles were in the 0.91 to 1.90 µm‐diameter range with geometric standard deviations of approximately 1.05 to 1.12. Increasing the polymer volume fraction and liquid flow‐rate resulted in an increase in the diameter of the composite particles, which agreed well with droplet scaling relations for EHDA. The results here demonstrate that EHDA can be used for polymer‐nanoparticle‐composite production and as an alternative to conventional inkjet printing.
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.
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 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.
Nanoparticles based on Al(III) and Zr(IV) melamine phosphate and sulfate, respectively, are prepared. Cone calorimeter measurements reveal that compared to an unfilled polyacrylate matrix the polyacrylate‐based nanocomposites containing the novel nanoparticles display significantly improved flame‐retardant properties as evidenced by the corresponding values for the peak heat release rate, the time‐to‐ignition, the values for the peak rate of heat release, the total heat evolved, the time to the CO peak and the CO yield. Concomitantly, the mechanical properties of the acrylate‐based composite coatings, i.e., the Martens and surface hardness, can also be significantly improved.
Epoxy/BaTiO3 hybrid materials are prepared as good candidates for organic capacitors. The hybrid system is cured by using camphorquinone and a iodonium salt through a free‐radical promoted cationic polymerization using a long‐wavelength tungsten halogen lamp. The cured films are fully characterized. Morphological characterization shows a well‐dispersed inorganic phase within the organic matrix. Electrical characterization demonstrates a linear increase of the dielectric constant with increasing filler content, while low dielectric loss values are obtained.
New talc/PBAT hybrid materials were prepared through reactive extrusion. First, PBAT was free‐radically grafted with MA to improve the interfacial adhesion between PBAT and talc. Then, the resulting MA‐g‐PBAT was reactively melt‐blended with talc through esterification reactions of MA moieties with the silanol functions from talc. Sn(Oct)2 and DMAP were used as catalysts. Interestingly, the tensile properties for these compatibilized composites were improved due to a better interfacial adhesion between both partners. XPS showed the formation of covalent ester bonds between the silanol functions from talc particles, and the MA moieties grafted onto the polyester backbones.
