纳米CaCO3/EPO/PP复合材料性能与结构的研究

研究了纳米CaCO3／EPO／PP复合材料的力学性能、熔体流变性能及纳米CaCO3粒子在PP基体中的分散状况。结果表明：弹性体EPO对PP有很好的增韧效果，当EPO用量为4份时，PP从脆性断裂转变成韧性断裂；当EPO用量为10份时，PP复合材料的室温和低温缺口冲击强度均有大幅度的提高。在EPO／PP复合材料中加入纳米CaCO3不仅可以显著提高复合材料的室温和低温缺口冲击强度，而且可显著提高复合材料的弯曲弹性模量和MFR，改善复合材料的加工流动性能；纳米CaCO3粒子在PP中达到了纳米级分散。     

Preparation and characterization of injection‐homo‐polypropylene filled with nano‐CaCO3

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     

Crystallization and impact energy of polypropylene/CaCO3 nanocomposites with nonionic modifier

Isotactic polypropylene (PP) and calcium carbonate (CaCO₃) nanocomposites were prepared by melt extrusion in a twin screw extruder. The commercial CaCO₃ nanoparticles had a poor dispersion in PP matrix. The addition of a small amount of a nonionic modifier during melt extrusion greatly improved the dispersion of CaCO₃ nanoparticles. The influence of CaCO₃ nanoparticles on the crystallization of PP was studied by wide angle X-ray diffraction and polarized optical microscopy. The introduction of CaCO₃ particles resulted in small and imperfect PP spherulites, decreased spherulite growth rate and induced formation of β-form PP. The yield strength of PP decreased gradually while its Young's modulus increased slightly with increasing CaCO₃ loading. By adding 1.5 wt% of nonionic modifier to PP/CaCO₃ (85/15) nanocomposite these tensile properties were not changed much but the notched Izod impact energy of the composites was significantly increased.     

Investigation on β‐polypropylene/PP‐g‐MAH/ surface‐treated calcium carbonate composites

β‐Polypropylene composites containing calcium carbonate treated by titanate coupling agent (T‐CaCO₃) and maleic anhydride grafted PP (PP‐g‐MAH) were prepared by melt compounding. The crystallization, morphology and mechanical properties of the composites were investigated by means of differential scanning calorimetry, wide‐angle X‐ray diffraction, polarized light microscopy, scanning electron microscopy and mechanical tests. It is found that both T‐CaCO₃ and NT‐C are able to induce the formation of β‐phase, and NT‐C greatly increases the β content and decreases the spherulitic size of PP. PP‐g‐MAH facilitates the formation of β‐form PP and improves the compatibility between T‐CaCO₃ and PP. Izod notched impact strength of β‐PP/T‐CaCO₃ composite is higher than that of PP/T‐CaCO₃ composite, indicating the synergistic toughening effect of T‐CaCO₃ and β‐PP. Incorporation of PP‐g‐MAH into β‐PP/T‐CaCO₃ composite further increases the content of β‐crystal PP and improves the impact strength and tensile strength when T‐CaCO₃ concentration is below 5 wt%. The nonisothermal crystallization kinetics of β‐PP composites is well described by Jeziorny's and Mo's methods. It is found that NT‐C and T‐CaCO₃ accelerate the crystallization rate of PP but the influence of PP‐g‐MAH on crystallization rate of β‐PP composite is marginal. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Mechanical properties and morphologies of PP/mPE/filler composites

Because of the poor impact behavior of polypropylene (PP) at low temperatures, the blending of PP with metallocene‐polymerized polyethylene (mPE) elastomers was investigated in this study. However, a reduced modulus of the overall blend was inevitable because of the addition to elastomers. To obtain a balance of the properties, we introduced rigid inorganic fillers to PP/mPE blends. The performance of the composites was characterized with tensile and Charpy notched impact tests, and the fracture morphology was examined with scanning electron microscopy. The results showed that the effects of fillers in a brittle matrix and in a ductile matrix were quantitatively different. For PP/mPE/filler ternary composites, the dependence of Young's modulus and yield strength on CaCO₃ content was not significant compared with that of PP/filler binary composites, whereas the elongation at break and tensile toughness at room temperature for PP/mPE/filler systems were more improved. The impact strength of the PP/mPE blends filled with untreated glass beads and CaCO₃ at a low temperature was lowered because of the weak interfacial bond. However, the values of the impact strength of the PP/mPE/filler composites at a low temperature remained at a high level compared with that of pure PP. In particular, a PP/mPE blend filled with surface‐treated kaolin had a higher low‐temperature impact toughness than the unfilled blend. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3029–3035, 2002; DOI 10.1002/app.2333     

The Relationship between Microstructure and Properties in PP/Rubber Powder/nano‐CaCO3 Ternary Blends

Summary: A new kind of rubber powder with “salami” structure (RPS) was prepared by spray drying the mixture of styrene‐butadiene rubber latex and nano‐CaCO₃ slurry. It was found that RPS is an effective toughener with synergistic toughening effect on poly(propylene) (PP). The Izod impact strength of PP/RPS blend is not only higher than that of PP/rubber powder or PP/nano‐CaCO₃ blends, but also higher than that of a PP/rubber powder/CaCO₃ blend. TEM images show that the microstructure of the PP/RPS blend is an “island‐sea” structure with “salami” structure in RPS, in which nano‐CaCO₃ particles are embedded in styrene‐butadiene rubber particles. The relationship between properties and microstructure has been studied by using TEM, SEM, DSC, etc.

     

Influence of the incorporation of fine calcium carbonate particles on the impact strength of polypropylene/polystyrene‐block‐poly(ethylene butene)‐block‐polystyrene blends

The Izod impact strength of two kinds of ternary composites was investigated. One consisted of polypropylene (PP), the triblock copolymer polystyrene‐block‐poly(ethylene butene)‐block‐polystyrene (SEBS), and calcium carbonate (CaCO₃) particles, and the other consisted of PP, carboxylated SEBS (C‐SEBS), and CaCO₃ particles. The mean size of the CaCO₃ particles was about 160 nm. According to scanning electron microscopy observations, the composite with SEBS showed a morphology in which SEBS domains and CaCO₃ particles were independently dispersed in the PP matrix. On the other hand, the composite with C‐SEBS showed a morphology in which CaCO₃ particles were encapsulated by C‐SEBS; that is, a core–shell structure was formed. The Izod impact strength of the composite with SEBS was higher than that of the composite with C‐SEBS and the PP/SEBS and PP/C‐SEBS binary blends. According to observations of the fractured surface, the stress‐whitened area was larger in the composite with SEBS than in the composite with C‐SEBS and the PP/SEBS and PP/C‐SEBS binary blends. The toughening mechanism of the composite, using nanometer‐sized CaCO₃ particles in combination with SEBS, was examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of interfacial interaction on the crystallization and mechanical properties of PP/nano‐CaCO3 composites modified by compatibilizers

To investigate the effect of interfacial interaction on the crystallization and mechanical properties of polypropylene (PP)/nano‐CaCO₃ composites, three kinds of compatibilizers [PP grafted with maleic anhydride (PP‐g‐MA), ethylene–octene copolymer grafted with MA (POE‐g‐MA), and ethylene–vinyl acetate copolymer grafted with MA (EVA‐g‐MA)] with the same polar groups (MA) but different backbones were used as compatibilizers to obtain various interfacial interactions among nano‐CaCO₃, compatibilizer, and PP. The results indicated that compatibilizers encapsulated nano‐CaCO₃ particles, forming a core–shell structure, and two interfaces were obtained in the compatibilized composites: interface between PP and compatibilizer and interface between compatibilizer and nano‐CaCO₃ particles. The crystallization and mechanical properties of PP/nano‐CaCO₃ composites were dependent on the interfacial interactions of these two interfaces, especially the interfacial interaction between PP and compatibilizer. The good compatibility between PP chain in PP‐g‐MA and PP matrix improved the dispersion of nano‐CaCO₃ particles, favored the nucleation effect of nano‐CaCO₃, increased the tensile strength and modulus, but reduced the ductility and impact strength of composites. The partial compatibility between POE in POE‐g‐MA and PP matrix had little effect on crystallization and mechanical properties of PP/nano‐CaCO₃ composites. The poor compatibility between EVA in EVA‐g‐MA and PP matrix retarded the nucleation effect of nano‐CaCO₃, and reduced the tensile strength, modulus, and impact strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Impact‐toughening mechanisms of calcium carbonate‐reinforced polypropylene nanocomposite

The impact fracture mechanisms of polypropylene (PP), containing 9.2 vol % of calcium carbonate (CaCO₃) nanoparticles, were investigated using optical microscopy and transmission electron microscopy. The incorporation of CaCO₃ nanoparticles reduces the size of spherulites and induces the formation of β‐phase crystallites, which leads to a more ductile PP matrix. Double‐notch four‐point bending (DN‐4PB) Charpy impact specimens and notched Izod impact specimens were utilized to study the fracture mechanism(s) responsible for the observed toughening effect. A detailed investigation reveals that the CaCO₃ nanoparticles act as stress concentrators to initiate massive crazes, followed by shear banding in PP matrix. These toughening mechanisms are responsible for the observed, improved impact strength. A comparison of the fracture mechanisms observed between DN‐4PB Charpy and Izod impact tests is also made to show the effectiveness of DN‐4PB for investigation of impact fracture mechanisms of polymeric systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3070–3076, 2006     

Preparation and properties of nano‐CaCO3/acrylonitrile‐butadiene‐styrene composites

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     

Investigation of the microstructures,properties, and toughening mechanism of polypropylene/calcium carbonate toughening masterbatch composites

The morphologies, crystallization and melting behaviors, and mechanical, thermal and processing properties of polypropylene (PP)/CaCO₃ toughening masterbatch (CTM) composites were investigated. The good dispersion of CaCO₃ particles via appropriate surface encapsulation in the composites is proven by density measurements and scanning electron microscopy images. The crystallinity and tensile strength of PP decrease with the addition of CTM. The flexural modulus and storage modulus (E′) at 23 °C increase with CTM content, implying improved stiffness. A sharp increase in the Izod notched impact strength can be observed for the composites, and the critical ligament thickness (τ_c) is calculated to be 1.31 and 2.46 μm for PP (S1003) and PP (001 G) composites, respectively. The morphologies of the impact‐fractured surfaces of the specimens were observed, and the shear deformation is enhanced by the addition of CTM. The presence of CTM also increases the melt flowability and decreases the shrinkage of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45515.     

Mechanical properties of styrene–butadiene–styrene block copolymer composites filled with calcium carbonate treated by liquid polybutadienes

The factors influencing the mechanical properties of styrene–butadiene–styrene block copolymer (SBS) composites filled with liquid polybutadiene (LB)‐surface‐treated calcium carbonate (CaCO₃) were investigated with respect to the molecular structure of the LB, the amount of the LB adsorbed on the CaCO₃ surface, the heat treatment conditions, and the surface treatment method. The mechanical properties, such as the modulus, tensile strength at break, tear strength, storage modulus, and tension set, of the SBS composites were improved remarkably through the filling of CaCO₃ surface‐treated with a carboxylated LB with a high content of 1,2‐double bonds. The heat treatment of LB–CaCO₃ in air was also effective in enhancing such properties. When SBS, CaCO₃, and LB were directly blended (with the integral blend method), secondary aggregation of CaCO₃ took place, and the mechanical properties of the composite were significantly lower. In the integral blend method, LB functioned as a plasticizer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of the compounding route on the properties of polypropylene/nano‐CaCO3/ethylene–propylene–diene terpolymer tercomponent composites

The influence of the compounding route of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM)/nano‐CaCO₃ composites on their properties, including their mechanical properties, the dispersion degree of nano‐CaCO₃, and the morphology of EPDM, was studied. The results showed that the toughness of the composites and the morphology of the EPDM particles were markedly influenced by the compounding route, whereas the dispersion degree of nano‐CaCO₃ in the matrix was little influenced by the compounding route. The impact strength of composites prepared by one route was about 60 kJ/m² with 20 wt % nano‐CaCO₃. The results indicated that a sandbag of nano‐CaCO₃ embedded in EPDM could effectively improve the toughness of the composites. A sandbag composed of EPDM and nano‐CaCO₃ eliminated the deterioration effect of the nano‐CaCO₃ agglomerate on the toughness of the composites, whereas the nano‐CaCO₃ agglomerate separately dispersed in PP decreased the toughness of the tercomponent composite © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Toughening of polypropylene with calcium carbonate particles

Polypropylene-CaCO₃ composites were prepared on a twin screw extruder with a particle content of 0-32 vol%. The influence of particle size (0.07-1.9 μm) and surface treatment of the particles (with and without stearic acid) on the toughening properties were studied. The matrix molecular weight of the polypropylene was also varied (MFI 0.3-24 dg/min). The experiments included tensile tests, notched Izod impact tests, differential scanning calorimetry (DSC), scanning electron microscopy and rheology experiments. The modulus of the composites increased, while the yield stress was lowered with filler content. This lowering of yield stress was connected to the debonding of the particles from the polypropylene matrix. From DSC experiments it was shown that the particle content had no influence on the melting temperature or crystallinity of the PP phase, also particle size showed no effect on the thermal properties. The impact resistance showed large improvement with particle content. The brittle-to-ductile transition was lowered from 90 to 40 °C with the addition of CaCO₃ particles. Notched Izod fracture energy was increased from 2 up to 40-50 kJ/m². The stearic acid coating on the particle surface showed a large positive effect on the impact strength. This was mainly due to the improved dispersion of the CaCO₃ particles. Aggregates of particles clearly had a detrimental effect on the impact behaviour of the composites. The smaller particle sizes (<0.7 μm) showed coarse morphologies and this lowered the toughening efficiency. The molecular weight of the polypropylene matrix had a profound effect on the toughening properties. A higher molecular mass shifted the brittle-to-ductile transition towards lower temperatures. At the higher filler loads (>20 vol%), however, still problems seem to occur with dispersion, lowering the toughening efficiency. Of all particle types used in this study the stearic acid treated particles of 0.7 μm were found to give the best combination of properties. From the study of the micro-toughening mechanism it was shown that at low strain the particles remain attached to the matrix polymer. At higher strain the particles debond and this leads to a change in stress state at the particle size level. This prevents crazing of the matrix polymer and allows extensive plastic deformation, resulting in large quantities of fracture energy.     

Processability,morphology, thermal,and mechanical properties of rigid PVC composites with liquid macromolecular modifier‐coated CaCO3

Rigid poly(vinyl chloride) (PVC)/CaCO₃ and PVC/liquid macromolecular modifier (LMM) coated CaCO₃ (PVC/LCC) composites were both fabricated by melt mixing. The processability, micro‐structure, dynamic mechanical behavior and mechanical properties of PVC/CaCO₃ and PVC/LCC composites were studied by using torque rheometer, scanning electron microscope (SEM), dynamic mechanical analysis (DMA), and universal mechanical testing machine. The results showed that the synergistic effect of LMM and CaCO₃ particles accelerated the plasticization of PVC resins. The processability of PVC/LCC composites was improved. The dispersion of LCC in PVC matrix was improved by the modification of CaCO₃ particles with LMM. The T_gs of PVC/LCC composites were enhanced by filling with LCC. Because of the synergistic toughening of LMM and CaCO₃ particles, the PVC/LCC composites exhibited excellent notched impact properties at the optimum value of LCC particles content. POLYM. COMPOS., 36:1286–1292, 2015. © 2014 Society of Plastics Engineers     

Mechanical properties and morphologies of polypropylene/single‐filler or hybrid‐filler calcium carbonate composites

Three types of polypropylene (PP) with different intrinsic toughness were used to study the mechanical properties and morphologies of the PP composites filled with single‐filler and hybrid‐filler of calcium carbonate particles. The calcium carbonate particles used were with average particle sizes of 25 μm (CC25), and 0.07 μm (CC0.07), respectively. A hybrid‐filler CaCO₃ named CC25/CC0.07 was used as a mixture of CC25 and CC0.07 (CC25/CC0.07 weight ratio = 1:1). It was found that the type of PP and the particle size of inorganic filler were the two important factors for the determination of mechanical properties of the composites. And the general mechanical properties of the composites filled with hybrid‐filler CaCO₃ were better than those of the composites filled with single‐filler CaCO₃, but the synergistic hybridization effect of the hybrid‐filler CaCO₃ did not exist. The major toughening mechanism of the PP/CC25 composites was the cavitation of the matrix caused by CC25, and the major toughening mechanism of the PP/CC0.07 composites was the pinning effect introduced by CC0.07. For the PP/CC25/CC0.07 composites, the cavitation of the matrix caused by CC25 and the pinning effect introduced by CC0.07 existed simultaneously. And when the intrinsic toughness of the matrix was large enough, the major factor to toughen PP was the pinning effect introduced by CC0.07, otherwise the major factor to toughen PP was the cavitation of the matrix caused by CC25. POLYM. ENG. SCI., 47:95–102, 2007. © 2007 Society of Plastics Engineers     

Phase structure and mechanical properties of PP/EPR/CaCO3 nanocomposites: Effect of particle's size and treatment

Calcium carbonate (CaCO₃) reinforced polypropylene/ethylene propylene rubber (PP/EPR) copolymer composites for automotive use were developed by means of extrusion and injection molding process. Three kinds of CaCO₃ (stearic acid treated and untreated) nanoparticles and microparticles were used as fillers. The influence of stearic acid, particle size, and filler content on the state distribution and morphology were investigated by SEM and rheological measurements. Two different morphologies were observed: EPR and CaCO₃ dispersed in the PP matrix and a core shell structure, depending on the interactions between EPR and CaCO₃. Toughening mechanisms and mechanical properties of the different systems were investigated. Significant improvement in tensile modulus is observed in all composites, depending on filler content. Elongation and notched impact strength were drastically decreased, especially for composites with nano CaCO₃. Better impact properties were obtained with low content of treated particles, showing the importance of filler treatment. POLYM. ENG. SCI., 55:2859–2868, 2015. © 2015 Society of Plastics Engineers     

Rigid particle toughening of aliphatic polyketone

The influence of precipitated calcium carbonate particles on the toughening behaviour of aliphatic polyketone has been studied. The calcium carbonate particles had a particle size of 0.7 μm and a stearic acid coating (1%). Composites of 0-31.5 vol% CaCO₃ content have been compounded and injection moulded. Studied are the morphology of the composites, the modulus, yield strength, the notch Izod impact strength and the temperature development in the deformation zone by infrared thermography.The thermal properties of the matrix remained unchanged upon addition of CaCO₃. With increasing particle content the modulus increased and the yield strength decreased. This decrease in yield strength is due to the debonding of the particles and was similar as with rubber particles. With increasing particle content the notched impact resistance increased strongly. The notched impact energy at room temperature was increased from 10 to 80 kJ/m² and the brittle-to-ductile transition temperature was lowered to 80 °C. At calcium carbonate contents higher that 16 vol% no further impact improvement was observed. The calcium carbonate particles seemed to debond quite well despite the expected thermal contraction of the matrix polymer. The temperature development in the deformation zone was strong, as strong as with rubber particles. The toughening mechanism with these rigid particles is discussed.     

Study on mechanical and flow properties of acrylonitrile‐butadiene‐styrene/poly(methyl methacrylate)/nano‐calcium carbonate composites

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     

Novel Comb-Like Copolymer Dispersant for Polypropylene/CaCO3 Composites and Its Influence on Dispersion,Crystallization, Mechanical,and Thermal Properties

A novel comb-like copolymer with carboxyl group as an anchoring group and polycaprolactone as a solvent chain was first used as the dispersant of CaCO₃ particles in polypropylene (PP). The dispersion of CaCO₃ particles in PP matrix was significantly improved in the presence of comb-like copolymer dispersant because of the strong repulsive force caused by steric hindrance effect. The influences of the coating amount of comb-like copolymer dispersant on crystallization behaviors, mechanical properties, and thermal stabilities were systematically investigated. The crystallization temperature, crystallinity, and crystallization rate of PP/CaCO₃ composites prepared with monolayer-coated CaCO₃ were all improved, where the monolayer comb-like copolymer coating remained as a rigid layer and provided a noticeable nucleating effect. The PP/CaCO₃ composites coated with monolayer SP comb-like copolymer also had the best mechanical properties, including tensile strength, Young’s modulus, flexural modulus, and impact strength because of the good dispersion of CaCO₃ particles in PP matrix. The thermal stability of PP/CaCO₃ composites were measured by thermogravimetric analysis. The results showed that SP comb-like copolymer dispersant treated CaCO₃ filled composites had excellent thermal stability than untreated and neat PP, especially for the composite prepared with monolayer-coated CaCO₃.