Polymer Crystallization

Lignin is the second most abundant pollution-free biomass material. However, most of lignin is discarded as waste in river or burned as fuel, which results in serious environmental pollution problems and low utilization efficiency of lignin at present. Thus, high-value utilization of lignin has become a hot research field. Herein, nanolignin (nano-Lig) is prepared successfully by the self-assembly method, and then nano-Lig and isotactic polypropylene (iPP) are mixed to prepare a series of nano-Lig/iPP composites by the solution blending method. Nano-Lig not only enhance thermostability of iPP but also improve crystallization properties of iPP. When 1.0 wt% nano-Lig was added in iPP, the crystallinity of iPP increased by 6.39% compared to iPP. Nano-Lig can increase the crystallization rate of iPP through investigation of kinetics of nonisothermal crystallization, suggesting nano-Lig can be used as a nucleating agent for iPP.

Composites of polylactide containing graphite nanoplates as a filler in the concentration range 1–20 wt% were prepared in methylene chloride using the sonication technique. The thermal characteristics and phase transitions were studied by DSC and TGA methods. The temperatures and heats of glass transition, crystallization, and melting were determined, and the degree of crystallinity during primary and secondary heating was calculated. It is shown that the introduction of graphite nanoplates leads to an increase in the elastic modulus and a decrease in the breaking stress and elongation at break. These changes are especially pronounced at 20% GNP content in the composition, when the corresponding mechanical parameters are characteristics of brittle polymer systems. The study of the electrical properties of the composites showed that the percolation threshold in these materials is close to 7 wt%, which is significantly lower than in the case of spherical particles of comparable density. The SEM study of the filled composites showed a system of pores, which were apparently formed during the evaporation of solvent in the process of their preparation. Diverse structures of PLA/GNP composites films after hot pressure were established by the SEM method.

The β-nucleating agent (β-NA), zinc phthalate (ZnPht), was prepared from a mixture of zinc oxide (ZnO) and phthalic anhydride (Pht) during the extrusion of isotactic polypropylene (iPP). To establish the relationship between the crystalline characteristic of ZnO and the crystallization of iPP, single-crystalline ZnO (ZnO(S)) and polycrystalline ZnO (ZnO(P)) were selected and mixed with Pht, respectively, to in situ inducing the β-crystal form of iPP (β-iPP). Compared to ZnO(S)/Pht, ZnO(P)/Pht has the selectivity of β-crystal nucleation during the crystallization of iPP; indeed, the relative content of β-crystal () improved from 18.0% for ZnO(S)/Pht/iPP to 84.6% for ZnO(P)/Pht/iPP. Moreover, the impact strength of the ZnO(P)/Pht/iPP was nearly 2.0 times greater than pure iPP; for ZnO(S)/Pht/iPP, it was approximately 1.4 times greater than pure iPP. To explain these phenomena, we propose a mechanism that the content of ZnPht generated by ZnO(P)/Pht is more than that of ZnO(S)/Pht during its in situ reaction; evidence from Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and thermogravimetric infrared spectroscope analysis was consistent with this mechanism. This study may provide a new perspective to control the crystal type of polymorphic polymer by adjusting the crystalline characteristic of the nucleating agent.

The uniform bulk mesomorphic iPP is prepared by rapid compression, and its structural evolution under stretching at different temperatures is studied by combining wide-angle X-ray diffraction and small-angle X-ray scattering. Results show that stretching can induce mesophase to crystallize into α-phase or promote this phase transformation synergistically with temperature, which depends on the selection of stretching temperature. When the temperature is lower than the glass transition temperature of rigid amorphous fraction (RAF), stress could make RAF devitrify firstly and then induce meso-α phase transition during the strain-softening process. As the temperature increases, the high temperature could induce meso-α phase transition to occur before the strain softening, while stretching could promote this transition. When the temperature is higher than a critical value around 100°C, the mesophase can be transformed into α-phase completely during stretching. SAXS results show that all the transformed α-crystal exhibits nodular morphology, and they are ductile with greatly enhanced deformability. Based on the results, a reasonable mechanism of meso-α transformation in the stretching process is proposed, explaining the phase transition that goes through several different steps.

Many grades of homopolymer polypropylene (HPP) and impact copolymer PP (ICPP) with a wide range of mechanical properties have been developed for a variety of applications in different industrial sectors. Management of this wide range of materials is a challenge for material suppliers and manufacturers and product developers. This research was to provide insights for managing material supplies through formulating PP with specific mechanical properties using melt compounding of ICPP and HPP. ICPP and HPP were compounded with an internal mixer at different ratios and then the mixtures were injection molded into specimens for characterization. The mechanical behaviors, fracture surfaces, and thermal properties of the mixtures were then characterized. The fracture surface results indicated that the morphologies of the rubber particles in ICPP changed after compounding with HPP, leading to different mechanical and thermal behaviors of the mixtures. Notched and unnotched impact strengths increased linearly with increasing ICPP contents. The crystallization peak temperatures increased linearly with increasing ICPP contents while the degrees of crystallinity of the mixtures decreased linearly. The thermal compounding process and the original material properties mainly determine the final mixture behaviors, and the mixture properties can be predicted based on the weight ratios of the two components.

It is well known that the processing conditions in polymer processing have a high impact on the resulting material morphology and consequently the component’s mechanical behavior. However, especially for semicrystalline polymers, the tools available for predicting the final morphology of injection molding parts still have significant limitations. In order to investigate the potential of injection molding simulation for the prediction of the morphology, POM homopolymer specimens were injection molded. The crystallization kinetics data were measured, and simulations in 3D and 2.5D with and without crystallization analysis were conducted in Autodesk Moldflow. The simulations are found to be good accordance with the experiments. Predicted spherulite size and crystalline orientation factor reveal a good qualitative correlation with optical micrographs. Also, the evolution of these parameters along the flow path is plausible. The simulation is found to be a powerful tool for morphology prediction in polymeric parts. Its applicability, however, is still limited to 2.5D models in Autodesk Moldflow, which, of course, is insufficient for complex, thick-walled 3-dimensional parts.