Crystallization properties and thermal stability of polypropylene composites filled with wollastonite

The influence of wollastonite (CaSiO₃) content on the crystallization properties and thermal stability of polypropylene (PP) composites was investigated. The results showed that the crystallization temperature, crystallization end temperature and crystallization temperature interval, as well as the degree of crystallinity of the composites, were higher than those of the unfilled PP resin, while the crystallization onset temperature was little changed from that of the unfilled PP resin. The increase of degree of crystallinity for the composites could be attributed to the heterogeneous nucleation of the CaSiO₃ in the PP matrix. The thermal stability increased with increasing filler weight fraction (ϕ_f); the thermal decomposition rate decreased nonlinearly with increasingϕ_f. Finally, the dispersion of the filler particles in the matrix was observed, and the mechanisms of thermal stability and crystallizing behavior were discussed.     

Isothermal crystallization kinetics of polypropylene/POSS composites

Polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (POSS) composites were prepared by two different processing methods: reactive blending and physical blending, and the crystallization behavior of PP and PP/POSS composites was studied by means of differential scanning calorimetry and polarized optical microscope. The results showed that the crystallization of PP in PP/POSS composites was strongly influenced by the different processing methods. POSS particles can act as effective nucleating agent, accelerating the crystallization of PP. The crystallization rate increased more dramatically for the reactive blending composite due to the stronger nucleating effect of PP grafted POSS. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1762–1772, 2008     

Metal functionalized POSS as fire retardants in polypropylene

This paper deals with the study of the combustion properties of dimeric and oligomeric Al-and Zn-isobutyl silsesquioxane (POSS)/polypropylene (PP) composites, in comparison with neat PP and PP/octaisobutyl POSS.The presence of Al-POSS leads to a decrease in combustion rate with respect to PP, resulting in a decrease of Heat Release Rate (−43% at 10 wt% POSS loading) as well as reduction in CO and CO₂ production rates, whereas a negative effect on the above parameters is obtained with octaisobutyl POSS. Zn-POSS does not significantly affect the PP combustion behaviour.The effect of Al-POSS is most likely related to its chemical activity, which favours the formation of a moderate amount of char residue, by catalysing secondary reactions in the polymer during combustion.     

Comparison of the effect of mica and talc and chemical coupling on the rheology,morphology, and mechanical properties of polypropylene composites

The effect of filler types of mica and talc on the oscillatory shear rheological properties, mechanical performance, and morphology of the chemically coupled polypropylene composites is studied in this work. The Maleic Anhydride grafted Polypropylene (MAPP) was used as an adhesion promoter for coupling mineral particles with the polypropylene matrix. The samples were prepared by a co‐rotating, L/D = 40, 25 mm twin screw extruder. The tensile tests carried out on the injection molded samples showed a reinforcing effect of talc up to 20 wt% on the Polypropylene (PP). The tensile strength of PP‐mica composites showed a slight decrease at all percentages of mica. The effect of chemical coupling by using MAPP on the tensile strength was more pronounced in increasing the tensile strength for PP‐mica than PP‐talc composites. The complex viscosity curve of pure PP and the composites, showed a Newtonian plateau (η₀) up to 30 wt% at low frequency terminal zone. By increasing the filler content to 40 and 50 wt%, the complex viscosity at very low shear rates sharply increased and showed yield behavior that can be due to the formation of filler particles networks in the melt. At the optimum amount of coupling agent, a minimum in cross over frequency curve against MAPP content is observed. The optimum amount of coupling agent for PP‐talc composites is about 1.5%, and about 3% for PP‐mica formulations. The analysis of viscosity behavior at power‐law high region, revealed the more shear thinning effect of mica than talc on the PP matrix resin. Copyright © 2009 John Wiley & Sons, Ltd.     

Isothermal crystallization kinetics of PP in PP/Mg(OH)2 composites

The crystallization and melting behavior of PP/Mg(OH)₂ composites was investigated, and the crystallization kinetic parameters and thermal characteristics were investigated according to the Avrami method. Optical polarizing microscope (POM) analysis suggested that the presence of Mg(OH)₂ particles gave rise to an increase in the number of nuclei and a decrease in PP spherulitic size. The Avrami exponent n of the PP and composites increased with increasing crystallization temperature, and markedly deceased with the addition of low Mg(OH)₂ content. A significant increase in crystallization kinetic constant, and a decrease in crystallization half time of PP were observed in the presence of Mg(OH)₂ particles, indicating a heterogeneous nucleating effect of Mg(OH)₂ upon crystallization of PP. The melting temperature and equilibrium melting temperature of PP in the composites decreased with increasing the Mg(OH)₂ content, which is directly related to the size of the PP crystals. The difference of PP melting enthalpies in the PP and composites demonstrated that the presence of Mg(OH)₂ can effectively enhance the crystalline of PP. The crystallization thermodynamics of PP and composites were studied according to the Hoffman theory. Surface free energy of PP chain folding for crystallization of PP/Mg(OH)₂ composites was lower than that of PP, confirming the heterogeneous nucleation effect of Mg(OH)₂. However, the evaluation of the nucleation activation energy of PP suggested the presence of a large amount of Mg(OH)₂ particles in the PP matrix reduced the mobility of PP segments and restricted the development of PP nucleation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1914–1923, 2005     

Preparation and properties of polycarbonate/polyhedral oligomeric silsesquioxanes (POSS) hybrid composites

Octaphenylsilsesquioxane (PH‐POSS) and octa(γ‐methacryloxypropyl)silsesquioxane (MA‐POSS) were successfully synthesized by hydrolytic condensation of phenyltrichlorosilane and γ‐methacryloxypropyltrimethoxysilane, and characterized by Fourier transform infrared (FT‐IR), ¹H and ²⁹Si nuclear magnetic resonance (NMR), and matrix‐assisted laser desorption/ionization‐time of flight (MALDI‐TOF) mass spectrum. Morphology, degradation behavior, thermal, and mechanical properties of hybrid composites were studied by transmission electron microscopy (TEM), polarized optical microscopy (POM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), surface contact angle (SCA), tensile, and impact testing. Domains of PH‐POSS and MA‐POSS dispersed in the matrix with a wide size distribution in a range of 0.1–0.5 µm, while PH‐POSS exhibited a preferential dispersion. Because of the possible homopolymerization of MA‐POSS during the melt blending, the glass transition temperature of polycarbonate (PC)/MA‐POSS composites remained nearly unchanged with respect to PC/PH‐POSS composites that showed a depression of T_g due to the plasticization effect. It is interesting to note that the incorporation of POSS retarded the degradation rates of PC composites and thus significantly improved the thermal stabilities. Si? O fractions left during POSS degradations were a key factor governing the formation of a gel network layer on the exterior surface. This layer possessed more compact structures, higher thermal stabilities, and some thermal insulation. In addition, percentage residues at 700°C (C₇₀₀) significantly increased from 10.8% to 15.8–22.1% in air. Fracture stress of two composites showed a slight improvement, and the impact strength of them decreased monotonically with the increase of POSS loading. Copyright © 2011 John Wiley & Sons, Ltd.     

The influence of wood flour and compatibilizer (<Emphasis Type="Italic">m</Emphasis>-TMI-<Emphasis Type="Italic">g</Emphasis>-PP) on crystallization and melting behavior of polypropylene

Wood flour/polypropylene composites (WPC) were prepared by melt extruding with different wood flour (WF) loadings. The non-isothermal crystallization and melting was studied with different WF loadings, for W40P60 and W40P60M6, the melting was investigated after non-isothermal and isothermal crystalline. Comparing with neat polypropylene, the melting behavior of the composites, both non-isothermally and isothermally, was investigated by differential scanning calorimetry (DSC). The results showed that WF was an effective heterogeneous nucleating agent, as evidenced by an increase in the crystallization temperature and the crystallinity for melt crystallization of PP with increasing WF content. For the non-isothermal samples, the origins of the double melting behaviors were discussed, based on the DSC results of PP. The XRD measurements confirmed that no crystalline transition existed during the non-isothermal crystallization process. With m-TMI-g-PP adding, due to compatibilization phenomenon were probably responsible for decreasing T _m, X _c. In the DSC scan after isothermal crystallization process, the single melting behaviors were found and each melting endotherm had a different origin.     

接枝改性POSS对PLLA结晶行为的影响*

以二氯甲烷为溶剂,利用溶液共混法将三种聚笼形多面体倍半硅氧烷(POSS)分别与聚左旋乳酸(PLLA)进行共混,制备了不同POSS含量的单氨基POSS(POSS-NH₂)/PLLA、POSS接枝聚乙二醇(POSS-PEG)/PLLA和POSS接枝聚乳酸(POSS-g-PLLA)/PLLA复合材料。利用差示扫描量热仪(DSC)、热重分析仪(TGA)、偏光显微镜(POM) 分别对复合材料的本体结晶行为、热稳定性及结晶形貌和生长速率进行了观察。结果表明当加入不同质量分数(1 wt%, 5 wt%, 10 wt%)的POSS-PEG时,PLLA的结晶能力均得到改善,而POSS-NH2和POSS-g-PLLA仅在质量分数较低(1wt%)时对PLLA起成核剂的作用,具有较高质量分数时会阻碍PLLA分子链段的运动,从而限制其结晶。三种复合材料中仅POSS-PEG在一定程度上提高了PLLA的热稳定性,利用POM观察球晶生长过程发现POSS-PEG的加入提高了PLLA的球晶生长速率。     

Macromorphology of polypropylene homopolymer tacticity mixtures

The macromorphology of isotactic/atactic (iPP/aPP) and isotactic/syndiotactic (iPP/sPP) polypropylene mixtures is examined by optical microscopy. The spherulitic macrostructure of equimolecular weight [weight‐average molecular weight (M_w) = 200k] iPP/aPP blends is volume‐filling to very high aPP concentrations when the crystallization temperature is 130 °C. Similar spherulitic macrostructures (spherulite size and volume‐filling nature) are observed for iPP homopolymer and a 50/50 iPP/aPP blend at low crystallization temperatures (115–135 °C). At higher crystallization temperatures (140–145 °C), a equimolecular weight (M_w = 200k) 50/50 iPP/aPP blend exhibits nodular texture that blurs the spherulitic boundaries. Double temperature jump experiments show that the nodular texture is due to melt phase separation that develops prior to crystallization. The upper critical solution temperature (UCST) of a 50/50 iPP/aPP blend (M_w = 200k) lies below 155 °C, and the blend is miscible at conventional melt processing temperatures. The UCST behavior is controlled by the blend molecular weight and aPP microstructure. aPP microstructures containing increased isospecific sequencing (although still noncrystalline) exhibit a reduced tendency for phase separation in 50/50 mixtures (M_w = 200k) and the absence of nodular texture at low undercoolings (140–145 °C). Equimolecular weight (M_w = 200k) 50/50 iPP/sPP mixtures exhibit phase‐separated texture at all crystallization temperatures. The size scale of the phase‐separated texture decreases with decreasing crystallization temperature because of a competition between crystallization and phase separation from a melt initially well mixed from the initial solution blending process. Extended melt annealing experiments show that the 50/50 iPP/sPP mixture (M_w = 200k) is immiscible in the melt at conventional melt processing temperatures. The iPP/sPP pair shows a much stronger tendency for phase separation than the iPP/aPP polymer pair. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1947–1964, 2000     

Isothermal crystallization behavior of exfoliated‐PP/IMMT nanocomposites via in situ polymerization

Highly exfoliated isotactic‐polypropylene/alkyl‐imidazolium modified montmorillonite (PP/IMMT) nanocomposites have been prepared via in situ intercalative polymerization. TEM and XRD results indicated that the obtained composites were highly exfoliated PP/IMMT nanocomposites and the average thickness of IMMT in PP matrix was less than 10 nm, and the distance between adjacent IMMT particles was in the range of 20–200 nm. The isothermal crystallization kinetics of highly exfoliated PP/IMMT nanocomposites were investigated by using differential scanning calorimeter(DSC) and polarized optical microscope (POM). The crystallization half‐time t_1/2, crystallization peak time t_max, and the Avrami crystallization rate constant K_n showed that the nanosilicate layers accelerate the overall crystallization rate greatly due to the nucleation effect, and the crystallization rate was increased with the increase in MMT content. Meanwhile, the crystallinity of PP in nanocomposites decreased with the increase in clay content which indicated the PP chains were confined by the nanosilicate layers during the crystallization process. Although the well‐dispersed silicate layers did not have much influence on spherulites growth rate, the nucleation rate and the nuclei density increased significantly. Accordingly, the spherulite size decreased with the increase in MMT content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2215–2225, 2009     

A novel polypropylene composite filled by kaolin particles with β-nucleation

Kaolin-filled polypropylene (PP) composites generally form α-crystal due to the effect of kaolin with α-nucleation. The transition from α- to β-nucleation of kaolin has been investigated, and a novel kaolin with β-nucleation (β-kaolin) and kaolin-filled PP composites with high β-crystal content were prepared first. The DSC and WAXD results indicated that the β-kaolin exhibits stronger β-nucleating ability than CaPA as β-nucleating agent for PP crystallization. It is found that the β-crystal content has been influenced little by filler contents in β-kaolin-filled PP composites. Mechanical properties and spherulitic morphology of filled PP composites was characterized. The synergistic effect of filler and β-crystal significantly improved impact strength of kaolin-filled PP composites.

     

Properties of in-situ filled polyethylene

Polyethylene-filler composites (kaolin, BaSO₄, and TiO₂) have been prepared by in-situ polymerization using a metallocene catalyst and by extrusion mixing in the melt. TiO₂ influences the polymerization process. In-situ polymerization was found to be advantageous with respect to encapsulation, dispersion of the filler particles leading to improved mechanical properties, except for TiO₂ containing composites. No significant influence on crystallization was observed.     

RHEOLOGICAL BEHAVIOR OF KAOLIN TOUGHENED POLYPROPYLENE COMPOSITES

The relation between the rheological behavior and various interfacial properties ofKaolin rigid particle toughened polypropylene (PP / Kaolin) composites were studied bymeans of parallel-plate rheometer, melt flow rate apparatus, scanning electron microscopy(SEM) and other testing methods. The results show that addition of interfacial modffier toPP/Kaolin composites is advantageous to homogeneous dispersion of filler in PP matrix,formation of flexible interlayer between Kaolin particles and PP matrix and Amprovementof the melt processibility of the composites.     

ELECTRICAL RESISTIVITY, CRYSTALLIZATION AND MECHENICAL PROPERTIES OF POLYPROPYLENE/MULTI-WALLED CARBON NANOTUBE/CALCIUM CARBONATE COMPOSITES PREPARED BY MELT MIXING

 Polypropylene (PP)/multi-walled carbon nanotube (MWCNT)/calcium carbonate (CaCO₃) composites are prepared by melt mixing using two types of CaCO₃ of different sizes. The electrical resistivities of the composites with the two types of CaCO₃ are all lower than those of the corresponding PP/MWCNT composites at various MWCNT loadings (1 wt%-5 wt%). The morphology of the composites is investigated by field emission scanning electron microscopy (FESEM). The crystallization behavior of PP in the composites is characterized by differential scanning calorimetry (DSC). The storage modulus, as measured by dynamic mechanical analysis (DMA), increases significantly by the presence of CaCO₃.     

聚丙烯/凹凸棒土纳米复合材料结晶形态和形貌研究

采用熔融共混的方法 ,制备聚丙烯 凹凸棒土纳米复合材料 .通过X射线衍射 (XRD)分析凹凸棒土在聚丙烯复合材料中晶面间距的变化以及对聚丙烯晶型的影响 ,结果表明凹凸棒土在复合材料中晶面间距没有变化 ;聚丙烯晶型没有发生变化但晶粒尺寸增加了 .用示差扫描量热法 (DSC)分析聚丙烯复合材料的结晶度的变化 ,发现凹凸棒土的加入使复合材料的结晶温度提高 ,结晶速率增大 ,结晶度增加 .用偏光显微镜(POM)观察凹凸棒土对聚丙烯球晶的影响 ,结果表明凹凸棒土的加入起到了成核剂的作用 ,使得聚丙烯球晶尺寸减小 ,当凹凸棒土的加入量到 10 %左右时 ,观察不到完整的球晶 .利用扫描电子显微镜 (SEM)和原子力显微镜 (AFM)观察凹凸棒土在聚丙烯中的分散 ,发现凹凸棒土在聚丙烯基体中分散比较均匀 ,但呈无序分布 .     

Microstructure evolution of isotactic polypropylene during annealing: Effect of poly(ethylene oxide)

The microstructure evolution of isotactic polypropylene(iPP) during annealing is reported.A few amount of poly(ethylene oxide)(PEO) which exhibits much lower melt temperature compared with /PP was introduced into /PP in this work.The crystalline structure of /PP was detected using differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD),and the relaxation of /PP was characterized using dynamic mechanical analysis(DMA).The variation of PEO morphology was investigated by scanning electron microscopy(SEM).The results show that the crystallization, including the primary crystallization and second crystallization during annealing,as well as the relaxation of /PP matrix is promoted with the presence of PEO.     

Non-isothermal crystallization kinetics of UHMWPE composites filled by oligomer-modified CaCO3

The processability of ultrahigh molecular weight polyethylene (UHMWPE) improved by oligomer-modified calcium carbonate (CaCO₃) was observed in our previous work. In order to understand the effect of oligomer-modified CaCO₃ on the crystallization of UHMWPE, the non-isothermal crystallization behavior and crystallization kinetics of UHMWPE composites filled by oligomer-modified CaCO₃ was studied by differential scanning calorimetry in this work. Jeziorny and Mo methods were used to describe the non-isothermal crystallization kinetics of UHMWPE composites. The effect of modified filler content and cooling rate on the crystallization temperature and crystallization rate was discussed. The heterogeneous nucleation of modified CaCO₃ slightly increases the crystallization temperature of UHMWPE. The crystallization enthalpy of UHMWPE composites is significantly higher than that of UHMWPE. The crystallization rate of UHMWPE composites depends on the filler contents and cooling rate.

     

Study of the morphology and properties of melt-mixed polycarbonate-POSS nanocomposites

In this work, the morphology and thermo-mechanical behaviour of nanocomposites formed by a polycarbonate (PC) matrix and polyhedral oligomeric silsesquioxane with phenethyl substituents (Ph-POSS) have been studied. The Ph-POSS nanocages were added to the PC by direct melt blending at loadings between 0% and 15 wt%. Good dispersion was achieved up to 5 wt% of nanofiller. At higher loadings micron-sized aggregates were observed in the nanocomposites by scanning and transmission electron microscopy. Increasing of Ph-POSS content lead to phase separation, agglomeration and low values on the final properties. The DSC and DMA analyses showed that increasing the amount of nanocages caused a continuous decrease on the composite’s T_g. Although little increments on the polycarbonate decomposition temperature were found, the presence of Ph-POSS did not improve significantly the thermal stability. Under nitrogen atmosphere the degradation mechanism of PC was not affected by the POSS. The residual weights obtained under oxygen atmosphere were in agreement with the theoretical weights of the Ph-POSS added. With respect to the nanocomposites mechanical properties the most remarkable trend was an improvement on the composite’s yield stress having the maximum at 5 wt% of nanofiller. Higher amounts of Ph-POSS lead to a decrease on the yield stress, finding even lower values than the one corresponding to the neat matrix. This behaviour has been attributed to the presence of large POSS agglomerates with low adhesion to the polymer matrix. A continuous decrease on the strain at break was also observed, reflecting the brittle character of the formed composites.     

Thermal and microstructural characterization of compatibilized polystyrene/natural fillers composites

Composites of polystyrene (PS) with cellulose microfibres and oat particles, obtained by melt mixing, were examined. The compatibilization of the composites was carried out by addition of maleic anhydride-functionalized copolymers (SEBS-g-MA, PS-co-MA) and poly(ethylene glycol) to improve the fibre–matrix interfacial interactions. The plain components and their composites were characterised by FT-IR, DSC, TGA, SEM microscopy and mechanical tests. The properties of the various systems were analysed as a function of both fibre and compatibilizer amount. The compatibilized PS composites showed enhanced fibre dispersion and interfacial adhesion as a consequence of chemical interactions between the anhydride groups on the polymer chains and the hydroxyl groups on the fibres, as demonstrated by FT-IR spectroscopy. DSC analysis pointed out a neat increase of T _g of composites on addition of SEBS-g-MA, as compared to PS-co-MA. The thermal stability of composites was also influenced by the type and amount of fibres, as well as by the structure and concentration of compatibilizer. The effect of the reactive copolymers on the composites properties was accounted for on the basis of the polymer–polymer miscibility and chemical interactions at the matrix/filler interface.     

Preparation and enhanced properties of poly(propylene)/ silica‐grafted‐hyperbranched polyester nanocomposites

A series of poly(propylene) silica‐grafted‐hyperbranched polyester nanocomposites by grafting the modified hyperbranched polyester (Boltorn? H20), possessing theoretically 50% end carboxylic groups and 50% end hydroxyl groups, which endcapped with octadecyl isocyanate (C19), onto the surface of SiO₂ particles (30 nm) through 3‐glycidoxy‐propyltrimethoxysilane (GPTS) was prepared. The effect of silica‐grafted‐modified Boltorn? H20 on the mechanical properties of polypropylene (PP) was investigated by tensile and impact tests. The morphological structure of impact fracture surface and thermal behavior of the composites were determined by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. The melt viscosity of composites was investigated by melt flow index (MFI). The obtained results showed that: (1) the modified Boltorn? H20 was successfully grafted onto the SiO₂ surface confirmed by FT‐IR and X‐ray photoelectron spectroscopy (XPS) analysis; (2) the incorporation of silica‐grafted‐modified Boltorn? H20 (3–5 wt% SiO₂) greatly enhanced the notched impact strength as well the tensile strength of the composites; (3) the incorporation of silica‐grafted‐modified Boltorn? H20 had no influence on the melting temperature and crystallinity of PP phase; (4) the MFI of PP composites increased when the silica‐grafted‐modified Boltorn? H20 particles were added compared with PP/SiO₂ or PP/SiO₂‐GPTS composites. Copyright © 2004 John Wiley & Sons, Ltd.