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1.
In order to increase the isotactic content of β‐nucleated polypropylene (β‐iPP) and decrease the cost of its production, the investigation and development of novel highly efficient β‐nucleators are important issues. Nano‐CaCO3 was used as a support to prepare a supported β‐nucleator, nano‐CaCO3‐supported calcium pimelate. Fourier transform infrared spectral analysis shows that an in situ chemical reaction takes place between nano‐CaCO3 and pimelic acid. Differential scanning calorimetry results indicate that the crystallization and melting temperatures of β‐phase in supported β‐nucleator‐nucleated iPP are higher than those of calcium pimelate‐nucleated iPP. The β‐nucleating ability of the supported β‐nucleator is little influenced by the cooling rate and crystallization temperature over a wide range. The decreased content of pimelic acid in the supported β‐nucleator slightly decreases the crystallization temperature of iPP but it has no influence on the content of β‐phase in nucleated iPP. A novel supported β‐nucleator has been successfully synthesized via pimelic acid supported on the surface of CaCO3. The crystallization temperature of iPP and melting temperature of β‐phase in iPP nucleated using the supported β‐nucleator are higher than those of iPP nucleated using calcium pimelate. The concept of a supported nucleator will provide a new way to increase the efficiency of polymer additives and to decrease the amounts of them that need to be used by using nanoparticles as supports. Copyright © 2010 Society of Chemical Industry  相似文献   

2.
Poly(L ‐lactide) (PLLA) was prepared via melt blending and nucleated using three layered metal phosphonates, i.e. zinc phenylphosphonate (PPZn), calcium phenylphosphonate (PPCa) and barium phenylphosphonate (PPBa). The morphology, crystallization and enzymatic hydrolysis of PLLA nucleated using PPZn, PPCa and PPBa were investigated. The results of both wide‐angle X‐ray diffraction and transmission electron microscopy observations show that the layers of PPZn, PPCa or PPBa are barely exfoliated or intercalated by PLLA chains in the melt‐blending process. PPZn, PPCa and PPBa serve as effective nucleating agents, accelerating both non‐isothermal and isothermal crystallization and enzymatic hydrolysis of PLLA. An interesting aspect is that the nucleating ability of PLLA incorporating PPZn, PPCa and PPBa decreases in the order PPZn > PPCa > PPBa, whereas the enzymatic hydrolysis of PLLA incorporating PPZn, PPCa and PPBa decreases in the reverse order, which is due to the different dispersion and interfacial interactions of PPZn, PPCa and PPBa throughout the PLLA matrix. Copyright © 2010 Society of Chemical Industry  相似文献   

3.
The isothermal crystallization and subsequent melting behavior of poly(trimethylene terephthalate) (PTT) composites filled with nano‐CaCO3 were investigated at designated temperatures with differential scanning calorimetry. The Avrami equation was used to fit the isothermal crystallization. The Avrami exponents were determined to be 2–3 for the neat PTT and PTT/CaCO3 composites. The particles of nano‐CaCO3, acting as nucleating agents in the composites, accelerated the crystallization rate, with the half‐time of crystallization decreasing or the growth rate constant (involving both nucleation and growth rate parameters) increasing. The crystallization activation energy calculated from the Arrhenius formula was reduced as the nano‐CaCO3 content increased from 0 to 2%, and this suggested that nano‐CaCO3 made the molecular chains of PTT easier to crystallize during the isothermal crystallization process. Subsequent melting scans of the isothermally crystallized composites exhibited triple or double melting endotherms: the greater the content was of nano‐CaCO3, the lower the temperature was of the melting peak. The degree of crystallization deduced from the melt enthalpy of composites with the proper concentration of nano‐CaCO3 was higher than that of pure PTT, but it was lower when the nano‐CaCO3 concentration was more than 2%. The transmission electron microscopy pictures suggested that the dispersion state of nano‐CaCO3 particles in the polymer matrix was even when its concentration was no more than 2%, whereas some agglomeration occurred when its concentration was 4%. Polarized microscopy pictures showed that much smaller or less perfect crystals formed in the composites because of the interaction between the molecular chains and nano‐CaCO3 particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

4.
Nano‐calcium carbonate (nano‐CaCO3) was used in this article to fill acrylonitrile–butadiene–styrene (ABS)/poly(methyl methacrylate) (PMMA), which is often used in rapid heat cycle molding process (RHCM). To achieve better adhesion between nano‐CaCO3 and ABS/PMMA, nano‐CaCO3 particles were modified by using titanate coupling agent, aluminum–titanium compound coupling agent, and stearic acid. Dry and solution methods were both utilized in the surface modification process. ABS/PMMA/nano‐CaCO3 composites were prepared in a corotating twin screw extruder. Influence of surface modifiers and surface modification methods on mechanical and flow properties of composites was analyzed. The results showed that collaborative use of aluminum–titanium compound coupling agent and stearic acid for nano‐CaCO3 surface modification is optimal in ABS/PMMA/nano‐CaCO3 composites. Coupling agent can increase the melt flow index (MFI) and tensile yield strength of ABS/PMMA/nano‐CaCO3 composites. The Izod impact strength of composites increases with the addition of titanate coupling agent up to 1 wt %, thereafter the Izod impact strength shows a decrease. The interfacial adhesion between nano‐CaCO3 and ABS/PMMA is stronger by using solution method. But the dispersion uniformity of nano‐CaCO3 modified by solution method is worse. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

5.
Nanosized calcium carbonate (nano‐CaCO3)‐filled poly‐L ‐lactide (PLLA) biocomposites were compounded by using a twin‐screw extruder. The melt flow behavior of the composites, including their entry pressure drop, melt shear flow curves, and melt shear viscosity were measured through a capillary rheometer operated at a temperature range of 170–200°C and shear rates of 50–103 s?1. The entry pressure drop showed a nonlinear increase with increasing shear stress and reached a minimum for the filler weight fraction of 2% owing to the “bearing effect” of the nanometer particles in the polymer matrix melt. The melt shear flow roughly followed the power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Hence, adding a small amount of nano‐CaCO3 into the PLLA could improve the melt flow behavior of the composite. POLYM. ENG. SCI., 52:1839–1844, 2012. © 2012 Society of Plastics Engineers  相似文献   

6.
Hongwei He  Kaixi Li 《Polymer Composites》2012,33(10):1755-1758
Four different types of composites were prepared based on unmodified and modified epoxy matrices: (A) unmodified epoxy/carbon fiber composites, (B) modified epoxy/carbon fiber composites by silane coupling agent/nano‐CaCO3 master batch, (C) modified epoxy/carbon fiber composites by nano‐CaCO3 particles directly, and (D) modified epoxy/carbon fiber composites by nano‐CaCO3 particles and silane coupling agent together. The interlaminar shear strength (ILSS) of the carbon fiber‐reinforced composites was investigated. The results show that the silane coupling agent/nano‐CaCO3 master batch can increase the ILSS to the highest degree. Nevertheless, Sample D, i.e., modified by nano‐CaCO3 particles and silane coupling agent together, even presents a decrease of the ILSS. The integration effect of silane coupling agent/nano‐CaCO3 master batch was concluded. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers  相似文献   

7.
T ernary composite of nano‐CaCO3/ethylene‐propylene‐diene terpolymer (EPDM)/polypropylene (PP) with high content of nano‐CaCO3 was prepared by two step compounding route, in which EPDM and nano‐CaCO3 were mixed first, and then melt compounding with PP matrix. The influence of mixing time during the second compounding on distribution of nano‐CaCO3 particles and the impact strength of the ternary composite have been investigated. It was found that the Izod impact strength of composite decreased with increasing mixing time. The observation of transmission electron microscopy obviously showed that nano‐CaCO3 particles transported from EPDM to PP matrix firstly and then from PP to the vicinity of EPDM dispersed phase with the increase of mixing time. This phenomenon can be well explained by the minimization of the dissipative energy and the Young's equation. The scanning electron microscope images show that lots of nano fibrils exist at the interface between nano‐CaCO3 agglomerates and matrix, which can dissipate lots of energy. The toughening mechanism has been interpreted in terms of three‐stage‐mechanism: stress concentration, void and shear band formation, and induced shear yielding. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

8.
The crystallization behavior of polypropylene (PP) copolymer obtained by in situ reactor copolymerization with or without a nucleating agent and/or nano‐CaCO3 particles was investigated both by thermal analysis and by polarized light microscopy. The Avrami model is successfully used to describe the crystallization kinetics of the studied copolymer. The results of the investigation show that a dramatic decrease of the half‐time of crystallization t1/2, as well as a significant increase of the overall crystallization rate, are observed in the presence of the nucleating agent. These effects are further promoted in the presence of the nano‐CaCO3 particles. The incorporation of the nucleating agent and nano‐CaCO3 particles into PP copolymer remarkably improved the mechanical properties and heat distortion temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 431–438, 2004  相似文献   

9.
Acrylonitrile‐butadiene‐styrene (ABS)/poly(methyl meth‐acrylate) (PMMA)/nano‐calcium carbonate (nano‐CaCO3) composites were prepared in a corotating twin screw extruder. Four kinds of nano‐CaCO3 particles with different diameters and surface treatment were used in this study. The properties of the composites were analyzed by tensile tests, Izod impact tests, melt flow index (MFI) tests, and field emission scanning electron microscopy (FESEM). This article is focused on the effect of nano‐CaCO3 particles' size and surface treatment on various properties of ABS/PMMA/nano‐CaCO3 composites. The results show that the MFI of all the composites reaches a maximum value when the content of nano‐CaCO3 is 4 wt%. In comparison with untreated nano‐CaCO3 composites, the MFI of stearic acid treated nano‐CaCO3 composites is higher and more sensitive to temperature. The tensile yield strength decreases slightly with the increase of nano‐CaCO3 content. However, the size and surface treatment of nano‐CaCO3 particles have little influence on the tensile yield strength of composites. In contrast, all of nano‐CaCO3 particles decrease Izod impact strength significantly. Stearic acid treated nano‐CaCO3 composites have superior Izod impact strength to untreated nano‐CaCO3 composites with the same nano‐CaCO3 content. Furthermore, the Izod impact strength of 100 nm nano‐CaCO3 composites is higher than that of 25 nm nano‐CaCO3 composites. POLYM. COMPOS., 31:1593–1602, 2010. © 2009 Society of Plastics Engineers  相似文献   

10.
Nonisothermal crystallization behavior and crystal morphology of poly(trimethylene terephthalate) (PTT) composites filled with modified nano‐calcium carbonate (CaCO3) had been investigated by using differential scanning calorimetry and polarized optical microscopy. The modified Avrami equation and Ozawa theory were used to investigate the nonisothermal crystallization, respectively. The particles of nano‐CaCO3, acting as a nucleation agent in composites, accelerated the crystallization rate by decreasing the half‐time of crystallization or increasing the parameters of Zc and K(T). Moreover, the nano‐composite with 2 wt% nano‐CaCO3 exhibited the highest crystallization rate. The Avrami and the Ozawa exponents, n and m of the nano‐composites, were higher than those of neat PTT, suggesting more complicated interaction between molecular chains and the nanoparticles that cause the changes of the nucleation mode and the crystal growth dimension. The effective activation energy calculated from the Friedman formula was reduced as nano‐CaCO3 content increased, suggesting that the nano‐CaCO3 made the molecular chains of PTT easier to crystallize during the nonisothermal crystallization process. The optical micrographs showed that much smaller or less perfect crystals were formed in composites because of the presence of the nano‐CaCO3 particles. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers  相似文献   

11.
In this study, microcellular foaming of low‐density polyethylene (LDPE) using nano‐calcium carbonate (nano‐CaCO3) were carried out. Nanocomposite samples were prepared in different content in range of 0.5–7 phr nano‐CaCO3 using a twin screw extruder. X‐ray diffraction and scanning electron microscopy (SEM) were used to characterize of LDPE/nano‐CaCO3 nanocomposites. The foaming was carried out by a batch process in compression molding with azodicarbonamide (ADCA) as a chemical blowing agent. The cell structure of the foams was examined with SEM, density and gel content of different samples were measured to compare difference between nanocomposite microcellular foam and microcellular foam without nanomaterials. The results showed that the samples containing 5 phr nano‐CaCO3 showed microcellular foam with the lowest mean cell diameter 27 μm and largest cell density 8 × 108 cells/cm3 in compared other samples. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

12.
Nano‐CaCO3/homo‐PP composites were prepared by melt‐blending using twin‐screw extruder. The results show that not only the impact property but also the bending modulus of the system have been evidently increased by adding nano‐CaCO3. The nano‐CaCO3 particles have been dispersed in the matrix in the nanometer scale which was investigated by means of transmission electron microscopy (TEM). The toughening mechanism of nano‐CaCO3, investigated by means of dynamical mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM), lies on that the nano‐CaCO3 particles take an action of initiating and terminating crazing (silver streak), which can absorb more impact energy than the neat PP. At the same time, the nano‐CaCO3 particles, as the nuclear, decrease the crystal size of PP, the results of which were investigated by means of polarized optical microscope (POM). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

13.
Nano‐CaCO3 was used as nano‐scale filler and poly(1,2‐propylene glycol adipate) (PPA) was used as polymeric plasticizer in flexible poly(vinyl chloride) (PVC) sheets for the partial replacement of di(2‐ethyl hexyl) phthalate (DOP) in this paper. The effect of PPA and nano‐CaCO3 on restraining DOP migration was evaluated via extraction tests. The results showed that the introduction of nano‐CaCO3 can decrease the extraction rate of DOP in the PVC matrix. The tensile strength and elongation at break of CaCO3‐1/PPA‐20/DOP‐30/PVC were similar to those of DOP‐50/PVC, and CaCO3‐1/PPA‐20/DOP‐30/PVC exhibited the superior suppression of DOP migration compared with DOP‐50/PVC. Thermogravimetry analysis (TGA) indicated that the addition of nano‐CaCO3 effectively improved the thermal stability of the nanocomposites. Therefore, the combination of PPA and nano‐CaCO3 is an effective approach to suppress the migration of DOP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

14.
In this study, various polypropylene (PP) nanocomposites were prepared by melt blending method. The effects of different spherical nanofillers, such as 50 nm CaCO3 and 20 nm SiO2, on the linear viscoelastic property, crystallization behavior, morphology and mechanical property of the resulting PP nanocomposites were examined. Rheological study indicated that coincorporation of nano‐SiO2 and nano‐CaCO3 favored the uniform dispersion of nanoparticles in the PP matrix. Differential scanning calorimeter (DSC) and polarizing optical microscopy (POM) studies revealed that the coincorporation of SiO2 and CaCO3 nanoparticles could effectively improve PP crystallizability, which gave rise to a lower supercooling temperature (ΔT), a shorter crystallization half‐life (t1/2) and a smaller spherulite size in comparison with those nanocomposites incorporating only one type of CaCO3 or SiO2 nanoparticles. The mechanical analysis results also showed that addition of two types of nanoparticles into PP matrix gave rise to enhanced performance than the nanocomposites containing CaCO3 or SiO2 individually. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

15.
Poly(para‐dioxanone) (PPDO)‐based composites have been prepared by blending PPDO with three different types of CaCO3 particles, CC1 (nano‐CaCO3), CC2 (CaCO3 whisker), and CC3 (silane‐coated CaCO3 whisker). The effects of particles size, interface adhesion, and crystallinity of composites on mechanical properties were discovered through analysis of the morphology of fracture surfaces, thermal characteristics, and crystalline structure. DSC revealed that the CaCO3 particles acted as a nucleating agent and promoted crystallinity of PPDO. The effect of CaCO3 particles on crystallization of PPDO was clearly revealed by using the nucleating efficiency. Smaller size particles exhibit greater nucleating efficiency. Adhesion between PPDO and the CaCO3 particles plays major roles on the mechanical properties of composites. The tensile strength of PPDO was improved over 54%. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers  相似文献   

16.
To improve the mechanical properties and structure of poly(vinyl chloride) (PVC)/nano‐CaCO3 nano composite, a core (nano‐CaCO3)/shell (SR) structured filler (40–60 nm) was successfully prepared by refluxing methyl vinyl silicone rubber (SR) and nano‐CaCO3 particles (coupling agent KH550, KH560, or NDZ‐101 as interfacial modifier) in toluene with vigorous stirring, according to an encapsulation model. It is effective in rigid PVC composite's toughness and reinforcement. The interfacial modifier's structure and interaction of nanocomposites of PVC/SR/nano‐CaCO3 were studied. The results indicate that KH560 has the optimal interfacial modificatory effect. The environmental scanning electron microscope (ESEM) study testified that PVC/SR/nano‐CaCO3 nanocomposites had a typical rubber–plastics‐toughening mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2560–2567, 2006  相似文献   

17.
The shear rheological properties of polystyrene (PS)/nano‐CaCO3 composites were studied to determine the plasticization of nano‐CaCO3 to PS. The composites were prepared by melt extrusion. A poly(styrene–butadiene–styrene) triblock copolymer (SBS), a poly(styrene–isoprene–styrene) triblock copolymer (SIS), SBS‐grafted maleic anhydride (SBS–MAH), and SIS‐grafted maleic anhydride were used as modifiers or compatibilizers. Because of the weak interaction between CaCO3 and the PS matrix, the composites with 1 and 3 phr CaCO3 loadings exhibited apparently higher melt shear rates under the same shear stress with respect to the matrix polymer. The storage moduli for the composites increased with low CaCO3 concentrations. The results showed that CaCO3 had some effects on the compatibility of PS/SBS (or SBS–MAH)/CaCO3 composites, in which SBS could effectively retard the movement of PS chain segments. The improvement of compatibility, due to the chemical interaction between CaCO3 and the grafted maleic anhydride, had obvious effects on the rheological behavior of the composites, the melt shear rate of the composites decreased greatly, and the results showed that nano‐CaCO3 could plasticize the PS matrix to some extent. Rheological methods provided an indirect but useful characterization of the composite structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006  相似文献   

18.
In this article, the morphology, crystallization, and rheological behaviors of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) binary blend and PP/EPDM/calcium carbonate nanoparticles (nano‐CaCO3) ternary blend were investigated. Two processing methods, i.e., direct extrusion and two‐step extrusion, were employed to prepare the PP/EPDM/CaCO3 blend. The influence of EPDM and nano‐CaCO3 respectively on phase morphology and properties of PP/EPDM blend and PP/EPDM/CaCO3 blend were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and dynamic rheometer. The crystallinity and crystallization temperature of PP/EPDM blend were improved in comparison to pure PP due to addition of EPDM, but kept invariable with the increased EPDM loading. As the EPDM content was increased, the mobility of PP molecular chains was weakened. Compared with direct extruded blend, less and finer nano‐CaCO3 was dispersed in matrix of two‐step extruded blend. Accordingly, the increased nano‐CaCO3 in matrix gave rise to a weaker increment in crystallinity and crystallization temperature of two‐step extruded blend, and a later platform of tanδ curve. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

19.
To obtain isotactic polypropylene (iPP) nanocomposites with high β‐crystal content, TMB5, calcium pimelate and calcium pimelate supported on the surface of nano‐CaCO3 were used as β‐nucleating agent and MWCNT filled β‐nucleated iPP nanocomposites were prepared. The effect of different β‐nucleating agent and MWCNT on the crystallization behavior and morphology, melting characteristic and β‐crystal content of β‐nucleated iPP nanocomposites were investigated by DSC, XRD and POM. The results indicated that addition of MWCNT increased the crystallization temperature of iPP and MWCNT filled iPP nanocomposites mainly formed α‐crystal. The β‐nucleating agent can induce the formation of β‐crystal in MWCNT filled iPP nanocomposites. The β‐nucleating ability and β‐crystal content in MWCNT filled β‐nucleated iPP nanocomposites decreased with increasing MWCNT content and increased with increasing β‐nucleating agent content due to the nucleation competition between MWCNT and β‐nucleating agents. It is found that the calcium pimelate supported on the surface of inorganic particles as β‐nucleating agent has stronger heterogeneous β‐nucleation than calcium pimelate and TMB5. The MWCNT filled iPP nanocomposites with high β‐crystal content can be obtained by supported β‐nucleating agent. POLYM. COMPOS., 36:635–643, 2015. © 2014 Society of Plastics Engineers  相似文献   

20.
CaCO3/acrylonitrile‐butadiene‐styrene (ABS) and CaCO3/ethylene‐vinyl acetate copolymer (EVA)/ABS nanocomposites were prepared by melting‐blend with a single‐screw extruder. Mechanical properties of the nanocomposites and the dispersion state of CaCO3 particles in ABS matrix were investigated. The results showed that in CaCO3/EVA/ABS nanocomposites, CaCO3 nanoparticles could increase flexural modulus of the composites and maintain or increase their impact strength for a certain nano‐CaCO3 loading range. The tensile strength of the nanocomposites, however, was appreciably decreased by adding CaCO3 nanoparticles. The microstructure of neat ABS, CaCO3/ABS nanocomposites, and CaCO3/EVA/ABS nanocomposites was observed by scanning electron microscopy. It can be found that CaCO3 nanoparticles were well‐dispersed in ABS matrix at nanoscale. The morphology of the fracture surfaces of the nanocomposites revealed that when CaCO3/EVA/ABS nanocomposites were exposed to external force, nano‐CaCO3 particles initiated and terminated crazing (silver streak), which can absorb more impact energy than neat ABS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

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