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The impact of pristine multiwalled carbon nanotubes (MWCNTs), an ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and the ionic liquid-modified MWCNTs (IL-MWCNTs) on the crystallization behavior of melt-crystallized poly(vinylidene fluoride) (PVDF) has been investigated. Pristine MWCNTs accelerate crystallization of PVDF as an efficient nucleation agent, while the formed crystals are mainly nonpolar α crystal form with few polar β crystals. Incorporation of only ionic liquid results in depression of the PVDF melt crystallization rate due to the miscibility of IL with PVDF but leads to a higher content of polar crystals (β and γ forms) than MWCNTs. The ionic liquid and MWCNTs show significant synergetic effects on both the nucleation and the formation of polar crystals for PVDF by melt crystallization. Addition of IL-MWCNTs not only improves the MWCNTs dispersion in PVDF matrix but also increases the overall crystallization rate of PVDF drastically. More important, the melt-crystallized PVDF nanocomposites with IL-MWCNTs show 100% polar polymorphs but no α crystal forms. To the best of our knowledge, this is the first report on the achievements of full polar crystal form in the melt-crystallized PVDF without mechanical deformation or electric field. The IL to MWCNTs ratio and the IL-MWCNTs loading content effects on the crystallization behavior of PVDF in the nanocomposites were also studied. It is considered that the specific interactions between >CF2 with the planar cationic imidazolium ring wrapped on the MWCNTs surface lead to the full zigzag conformations of PVDF; thus, nucleation in polar crystals (β and γ forms) lattice is achieved and full polar crystals are obtained by subsequent crystal growth from the nuclei.

Additive manufacturing (commonly known as 3D printing) is defined as a family of technologies that deposit and consolidate materials to create a 3D object as opposed to subtractive manufacturing methodologies. Fused deposition modeling (FDM), one of the most popular additive manufacturing techniques, has demonstrated extensive applications in various industries such as medical prosthetics, automotive, and aeronautics. As a thermal process, FDM may introduce internal voids and pores into the fabricated thermoplastics, giving rise to potential reduction on the mechanical properties. This paper aims to investigate the effects of the microscopic pores on the mechanical properties of material fabricated by the FDM process via experiments and micromechanical modeling. More specifically, the three-dimensional microscopic details of the internal pores, such as size, shape, density, and spatial location were quantitatively characterized by X-ray computed tomography (XCT) and, subsequently, experiments were conducted to characterize the mechanical properties of the material. Based on the microscopic details of the pores characterized by XCT, a micromechanical model was proposed to predict the mechanical properties of the material as a function of the porosity (ratio of total volume of the pores over total volume of the material). The prediction results of the mechanical properties were found to be in agreement with the experimental data as well as the existing works. The proposed micromechanical model allows the future designers to predict the elastic properties of the 3D printed material based on the porosity from XCT results. This provides a possibility of saving the experimental cost on destructive testing.

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The poly(L-lactic acid)/poly(oxymethylene) (PLLA/POM) blends have been prepared by simply melt blending. The phase diagram, miscibility, glass transition temperatures, and physical properties have been investigated systematically. The PLLA/POM blends exhibit typical lower critical solution temperature (LCST) behaviors. PLLA and POM are miscible in the melt state at low temperature and become phase-separated at elevated temperatures. It was found that the weak interactions between the carboxyl groups of PLLA and methylene groups of POM (weak C−H ... O hydrogen bonding) account for the miscibility of the two components. Although the PLLA/POM blends are homogeneous at the melt state in the miscible temperature region, two distinct glass transition temperatures are observed for the all blends when quenched from the homogeneous state. More surprisingly, both POM and PLLA exhibit the apparent glass transition temperature (T g ) depression in the blends, compared with T g s of the neat polymers. The behaviors are totally different from other reported miscible or partially miscible polymer blends, in which T g s shift to each other or merge into one glass transition temperature. The investigation indicates that the crystallization of POM in the blend induces the phase separation of PLLA/POM blends and forms novel morphologies with the interpenetrated (cocontinuous) PLLA and POM phases. The double glass transition temperature depression of both PLLA and POM in the blends originates from the mismatch thermal shrinkage during cooling down from the high temperature. Moreover, we observed the improved ductility of the PLLA/POM blends as compared with the neat PLLA and POM, which has been attributed to higher molecular mobility due to the glass transition temperature depression for both PLLA and POM in the blends.

Nanostructured polymer blends have attracted significant attention recently. In this paper, the poly(lactic acid) (PLLA)/ethylene-co-acrylic ester-co-glycidyl methacrylate (E-AE-GMA) rubber (80/20) nanoalloys and microalloys were fabricated by melt blending and the structure-property relationships of the prepared alloys were investigated. In the nanoalloys, the rubber domains are homogeneously dispersed in the PLLA matrix with the overall domain size of <100 nm. Such nanoalloys exhibit not only high transparency in the visible region, but also significantly improved ductility and impact strength, compared with neat PLLA. Moreover, the nanodomains in the PLLA matrix enhance the crystallization rate of PLLA drastically. The overall crystallization rate of the PLLA nanoalloy is even higher than that of the PLLA nucleated by talc. In contrast, the PLLA microalloy has a phase structure with the size of the rubber domains being in the micrometer to submicrometer scale. The microalloy is opaque and displays almost the same tensile strength and modulus as the nanoalloy, but much higher impact strength than the nanoalloy.