Blends of poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB) plasticized with a lactic acid oligomer (OLA) added at three different concentrations (15, 20 and 30 wt% by weight), were prepared by an optimized extrusion process to improve the processability and mechanical properties of these biopolymers for flexible film manufacturing. Morphological, chemical, thermal, mechanical, barrier and migration properties were investigated and formulations with desired performance in eco-friendly films were selected. The efficiency of OLA as plasticizer for PLA_PHB blends was demonstrated by the significant decrease of their glass transition temperatures and a considerable improvement of their ductile properties. The measured improvements in the barrier properties are related to the higher crystallinity of the plasticized PLA_PHB blends, while the overall migration test underlined that all the proposed formulations maintained migration levels below admitted levels. The PLA_PHB blend with 30 wt% OLA was selected as the optimum formulation for food packaging, since it offered the best compromise between ductility and oxygen and water vapor barrier properties with practically no migration.
Natural rubber containing graphene and carbon nanotubes (CNTs) composites were prepared by ultrasonicallyassisted latex mixing. Natural rubber filled by both graphene and CNTs show significant enhanced tensile strength, while graphene exhibits a better reinforcing effect than CNTs. Strain-induced crystallization in natural rubber composites during stretching was determined by synchrotron wide-angle X-ray diffraction. With the addition of CNTs or graphene, the crystallization for natural rubber occurs at a lower strain compared to unfilled natural rubber, and the strain amplification effects were observed. The incorporation of graphene results in a faster strain-induced crystallization rate and a higher crystallinity compared to CNTs. The entanglement-bound rubber tube model was used to analyze the chain network structure and determine the network parameters of composites. The results show that the addition of graphene or CNTs has an influence on the molecular network structure and improves the contribution of entanglement to the conformational constraint, while graphene has a more marked effect than CNTs.
Targeted kinetic strategy for improving the thermal conductivity of epoxy composite containing percolating multi-layer graphene oxide chains
T. Zhou, H. Koga, M. Nogi, T. Sugahara, S. Nagao, T. T. Nge, K. Suganuma, H-W. Cui, F. Liu, Y. Nishina
Vol. 9., No.7., Pages 608-623, 2015
Vol. 9., No.7., Pages 608-623, 2015
By adding 2 wt% multi-layer graphene oxide (MGO) to an epoxy resin, the thermal conductivity of the composite reached a maximum, 2.03 times that of the epoxy. The presence of 2 wt%MGO percolating chains leads to an unprecedentedly sharp rise in energy barrier at final curing stage, but an increased epoxy curing degree (αIR) is observed; however, this αIR difference nearly disappears after aging or thermal annealing. These results suggest that the steep concentration gradient of –OH, originated from the 2 wt%MGO percolating chains, exerts the vital driving force on the residual isolated/trapped epoxy to conquer barrier for epoxy-MGO reaction. A modified Shrinking Core Model customized for the special layered-structure of MGO sheet was proposed to understand the resistance variation during the intercalative epoxy-MGO reaction. It shows that the promoted intercalative crosslinking is highly desirable for further improving the thermal conductivity of the composite, but it meets with increased resistance. Guided by the kinetic studies, targeted optimization on the cure processing strategy was accordingly proposed to promote the intercalative crosslinking, a thermal conductivity, 2.96 times that of the epoxy, was got with only a small amount (30°C) increase of the post-heating temperature.
A multiblock copolymer termed as PCL-PIBMD, consisting of crystallizable poly(ε-caprolactone) (PCL) segments and crystallizable poly(3S-isobutyl-morpholine-2,5-dione) (PIBMD) segments, has been reported as a material showing a thermally-induced shape-memory effect. While PIBMD crystalline domains act as netpoints to determine the permanent shape, both PCL crystalline domains and PIBMD amorphous domains, which have similar transition temperatures (Ttrans) can act as switching domains. In this work, the influence of the deformation temperature (Tdeform = 50 or 20°C), which was above or below Ttrans, on the structural changes of PCL-PIBMD during uniaxial deformation and the shapememory properties were investigated. Furthermore, the relative contribution of crystalline PCL and PIBMD amorphous phases to the fixation of the temporary shape were distinguished by a toluene vapor treatment approach. The results indicated that at 50°C, both PCL and PIBMD amorphous phases can be orientated during deformation, resulting in thermallyinduced crystals of PCL domains and joint contribution to the switching domains. In contrast at 20°C, the temporary shape was mainly fixed by PCL crystals generated via strain-induced crystallization.
Side chain discotic polysiloxane with 2,3,6,7-tetrakis(hexyloxy)-10-methoxytriphenylene-11-undecanoate moieties is synthesized by hydrosilylation reaction. The phase behavior and thermooptical properties of the polysiloxane and the side chain precursor 2,3,6,7-tetrakis(hexyloxy)-10-methoxytriphenylene-11-undecanoate are examined by polarizing optical microscopy, thermooptical analysis, differential scanning calorimetry and wide angle X-ray scattering studies. A columnar planar alignment of LC in the layers has been determined. The pronounced alignment makes this polymer a promising material for application in optoelectronic devices. The differences in phase transitions and morphology between the triphenylene precursor and the discotic polysiloxane are discussed.
The curing of bisphenol A-aniline based benzoxazine was studied applying different accelerators (4,4'-thiodiphenol, o-dianisidine, 2-mercaptobenzimidazole and 4-mercaptophenol) to initiate the catalytic ring-opening of benzoxazine. Possible pathways of benzoxazine ring-opening, polymerization and cross-linking without and with the addition of different accelerators are presented. The curing kinetics was investigated by model-free kinetic analysis of experimental data obtained by differential scanning calorimetry (DSC). The addition of different accelerators significantly reduced the onset temperature of curing in dynamic experiments. The effects of accelerators on the results of isothermal conversion prediction were studied and discussed in detail. Among the used accelerators, thiodiphenol showed the best accelerating efficiency and was consequently used in further studies, where its amount was varied. By low heating rate DSC analysis the catalytic ring-opening, thermally accelerated ring-opening and the diffusion-controlled steps were identified. The amount of added accelerator affected particularly the ring-opening and diffusion-controlled steps.
Polypropylene (PP) composites are used in a wide range of structural applications. Except for fiber reinforced PP, most PP particle composites are commonly considered to be isotropic or at least quasi-isotropic. In this paper, however, the anisotropy of several PP composites containing soft (rubber) and hard (talc) particles and glass fibers is characterized in detail in terms of the material microstructure as well as the resulting mechanical properties in monotonic tensile and compressive experiments. The microstructural investigations showed that all composites displayed a certain surface-core layer structure of distinctly different orientation patterns and with a higher degree of orientation in the surface layer. Also in mechanical testing an anisotropic behavior was observed with the degree of anisotropy being more pronounced in tension than compression. Moreover, the compression/tension asymmetry also strongly depends on filler type and orientation.