Crystallization Behavior Of Nanocomposites Research Articles

Effect of Surface Properties of Nanoparticles on the Crystallization Behavior of Polypropylene/Polypropylene‐g‐Silica Nanocomposites

AbstractIn order to investigate the effect of surface properties of nanoparticles (NPs) on the crystallization behavior of nanocomposite, three kinds of silica (SiO2) NPs are dispersed in isotactic polypropylene (iPP) matrix by solution blending method. Specifically, the poor compatibility between inorganic bare SiO2 NPs and organic PP matrix triggers the formation of aggregates and induces the fractionated crystallization with two crystallization peaks at higher particle loading (Φ), i.e., main crystallization peak (MCP) and low temperature crystallization peak (LCP, always located at 124.0 °C). Once short PP chains (0.9 × 104 g mol−1) are grafted onto the surface of SiO2 NPs, the nanocomposites with all Φ only exhibit a single MCP which is attributed to the strong interfacial interaction. With the increase of grafting chain length (9 × 104 g mol−1), the more stretched conformation of grafting chains can provide numerous heterogeneous nucleation sites and significantly accelerate the crystallization rate of PP chains near the surface of SiO2 NPs, which lead to the formation of an extra high temperature crystallization peak (HCP, almost kept constant at 133.0 °C). The occurrence of various crystallization peaks implies that the surface properties of nanoparticles play a vital role in the nucleation ability of nanoparticles.

The influence of grafting on flow-induced crystallization and rheological properties of poly(ε-caprolactone)/cellulose nanocrystal nanocomposites

The influence of poly(ε-caprolactone) (PCL) grafts on the rheology and crystallization behavior of nanocomposites based on PCL and cellulose nanocrystals (CNC) both under quiescent and shear conditions is investigated. Under quiescent conditions, the grafted nanocrystals have high nucleation efficiencies. Under the influence of shear, the non-grafted nanocrystals were, however, more efficient in orienting the polymer chains and accelerating the flow-induced crystallization. The addition of large amounts of grafted material decreases the viscosity of the composites and thereby also the efficiency of shear-induced orientation.

Crystallization Behavior of Nanocomposites Synthesized from the Poly (L-lactide)-poly (Propylene Glycol) and Organoclay

This study explored the thermal behavior of PLLA–PPG nanocomposite with added organoclay. The modified clay was evenly dispersed into the matrix of LPG1000 to synthesize the nanoscale polymer. Thermogravimetric analysis and differential scanning calorimetry were used to measure the thermal properties of the PLLA–PPG copolymers. Wide-angle X-ray diffraction was used to identify the crystal structure of PLLA–PPG copolymer. The crystal growth of PLLA–PPG copolymer with various proportions of added clay was observed by using polarized optical microscopy and transmission electron microscopy. The results show that adding clay could enhance the thermal stability of LPG1000 and significantly change its crystal property.

Nonisothermal crystallization and morphology of poly(butylene succinate)/layered double hydroxide nanocomposites

Biodegradable poly(butylene succinate) (PBS) and layered double hydroxide (LDH) nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy (TEM), which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.

Production and characterization of UHMWPE/fumed silica nanocomposites

AbstractUltrahigh‐molecular‐weight polyethylene (UHMWPE)/fumed silica nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler‐Natta catalytic system. Nanocomposites with different nanoparticle weight fractions were produced in order to investigate the effect of fumed silica on thermal and mechanical properties of UHMWPE/fumed silica nanocomposites. The viscosity average molecular weight (M) of all samples including pure UHMWPE as the reference sample and nanocomposites were measured. Scanning electron microscope (SEM) images showed the homogenous dispersion of nanoparticles throughout the UHMWPE matrix while no nanoparticle cluster has been formed. Crystallization behavior of nanocomposites was investigated by differential scanning calorimetry (DSC), which showed a slight increase in melting temperature by enhancing the nanoparticle concentration while no significant change was observed in the crystallization temperature as the fumed silica concentration enhanced. The improvement in all thermal stability parameters was recorded by thermogravimetric analysis (TGA). Besides, via tensile testing, it was confirmed that addition of nanoparticles caused considerable improvement in such mechanical properties as Young's modulus, yield stress, and tensile strength of samples while the elongation at break declined by addition of more nanoparticles. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers

Functionalization of Multiwalled Carbon Nanotubes by Poly (Ethlylene Glycol) and Non-Isothermal Crystallization Kinetic Study

Multi-walled carbon nanotubes (MWNT) were successfully chemically modified (MWNT-COOH) and reacted with polyethylene glycol (PEG) to prepare nanocomposites. As- prepared kinds of functionalized MWNT (MWNT-g-PEG) were characterized with FTIR, TGA and TEM. Nonisothermal crystallization kinetics of MWNT-g-PEG composites was investigated by differential scanning calorimeter (DSC). The kinetics was analyzed using the Ozawa and Avrami equation modified by Jeziorny. The results showed that the Ozawa approach failed to describe the crystallization behavior of nanocomposites, whereas the modified Avrami analysis could explain the behavior of MWNT-g-PEG nanocomposite only. It is observed that the presence of MWNT hindered the mobility of PEG chains and decreased the overall crystallization rate. It was found that the crystallization behavior of MWNT-g-PEG nanocomposite was strongly affected by the incorporation of MWNT. The data for the nonisothermal crystallization could be analyzed properly by the Avrami equation modified by Jeziorny. The results showed that the presence of MWNT decreased the overall nonisothermal crystallization rate of the PEG chains which were grafted onto the MWNT due to MWNT might act as physical hindrances retarding the mobility of PEG chains and decreased the crystallinity.

Effect of functionalized SWCNTs on microstructure of PP‐g‐MA/OMMT/f‐SWCNTs nanocomposite

AbstractThe aim of this work was to study the effect of functionalized single‐walled carbon nanotubes (f‐SWCNTs) on the microstructure of PP‐g‐MA/organic modified montmorillonite (OMMT)/f‐SWCNTs ternary nanocomposite. Pristine SWCNTs were chemically modified by maleic anhydride to improve the interaction between PP‐g‐MA and nanotubes. The dispersion states of OMMT in the different nanocomposites were investigated by wide angle X‐ray diffraction. The morphologies of the nanocomposites were characterized by scanning electron microscopy. Crystallization behaviors of nanocomposites were studied through differential scanning calorimetry and polarizing optical microscopy. Different than the PP‐g‐MA/OMMT binary nanocomposite, in which the OMMT is mainly in an exfoliated state, the ternary PP‐g‐MA/OMMT/f‐SWCNTs nanocomposite exhibits mostly intercalated OMMT. Furthermore, in the ternary nanocomposite, the crystallization of polymer is mainly induced by f‐SWCNTs rather than by OMMT. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Synthesis and crystallization behavior of acetal copolymer/silica nanocomposite by in situ cationic ring‐opening copolymerization of trioxane and 1,3‐dioxolane

AbstractThe acetal copolymer/silica nanocomposite was prepared by in situ bulk cationic copolymerization of trioxane and 1,3‐dioxolane in the presence of nanosilica. The crystallization behavior of acetal copolymer/silica nanocomposite was studied by AFM, DSC, XRD, and CPOM, and the macromolecular structure of acetal copolymer/silica nanocomposite was characterized by FTIR and 1H‐NMR. The 1H‐NMR results showed that the macromolecular chain of acetal copolymer had more than two consecutive 1,3‐dioxolane units in an oxymethylene main chain, while that of acetal copolymer/silica nanocomposite had only one 1,3‐dioxolane unit in an oxymethylene main chain. There existed interaction between the macromolecular chains and nanoparticles (such as hydrogen bonds and coordination). On one hand, nanoparticles acted as nucleation center, which accelerated the crystallization rate but reduced the crystallinity. The spherulite sizes also decreased with addition of nanoparticles attributed to the nucleation effect. On the other hand, the presence of nanoparticles interrupted the spherical symmetry of the crystallite. In conclusion, the high surface energy and small scale of nanoparticles have a prominent impact on the polymerization mechanism and crystallization behavior of nanocomposite. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Micro- and nano-structure in polypropylene/clay nanocomposites

Polypropylene (PP)/clay nanocomposites prepared by melt blending using different clays and coupling agents based on maleic anhydride-grafted PP (MA-PP) were studied. Clay dispersion using field emission gun scanning electron microscope (FEG-SEM) and transmission electron microscopy (TEM), and PP matrix morphology were characterized. Clay dispersion was improved in the presence of MA-PP, as shown by the higher particles surface density (number of particles/mm 2) at all micro-, sub-micro- and nano-levels. The PP spherulite diameter was affected by both the presence of MA-PP and clay dispersion. Clay intercalation, characterized by both complementary X-ray diffraction (XRD) and TEM, was greatly influenced by the characteristics of MA-PP. The use of low molecular weight ( M w) MA-PP led to a good and uniform intercalation but with no further possibility to exfoliation. The use of higher M w MA-PP led to a heterogeneous intercalation with signs of exfoliation. The crystallization behavior of nanocomposites was studied by differential scanning calorimetry (DSC). When fine clay dispersion was achieved with MA-PP, clay-nucleating effect was limited and lower crystallization temperature and rates were observed. It was also shown by wide angle X-ray diffraction (WAXD) that clay induced some orientation of α-phase PP crystallites.