聚丙烯／轻质碳酸钙／三单体固相接枝物复合体系结构与性能的研究

将聚丙烯与马来酸酐、甲基丙烯酸甲酯、丙烯酸丁酯三种单体的固相接枝物应用于聚丙烯侥质碳酸钙复合体系，研究接枝物对复合体系力学性能、微观形态和耐热性等的影响。结果表明，在PP中加入CaCO3进行填充改性，在一定用量的三单体固相接枝物作用下，PP的力学性能及耐热性得到明显的提高。     

Toughening and reinforcement of HDPE/CaCO3 blends by interfacial modification—interfacial interaction

To improve the mechanical properties and structure of HDPE/CaCO₃ composites, a type of modifier, consisting mainly of carboxylated polyethylene (CPE), and a type of CaCO₃ grafted with acrylamide (CaCO₃(SINGLE BOND)A) were used. The carboxyl group content of CPE was from 1 to 10%. The amide group content on the surface of the modified CaCO₃ was from 0.2 to 1.8%. The interfacial structure and interaction of ternary blends of HDPE, CPE, and CaCO₃(SINGLE BOND)A were studied. The results indicate that the higher the amide group content and the carboxyl group content, the higher the tensile and impact strength. This behavior has been attributed to a series of chemical and physico-chemical interactions taking place between the two components during the blending process which were confirmed by FTIR and extraction experiments. The improvement of interfacial adhesion by the CPE and CaCO₃(SINGLE BOND)A was also clearly revealed in the SEM of the fracture surface. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1275–1281, 1997     

Assessment of efficacy of trivalent lanthanum complex as surface modifier of calcium carbonate

A complex of trivalent lanthanum stearate with stearin (REC) was used as a surface modifier to treat calcium carbonate, and its efficacy was assessed. The measurement of the viscosity of a CaCO₃/liquid paraffin suspension demonstrated that REC treatment could considerably improve the dispersion of filler in nonpolar media. The FTIR spectrum analysis revealed that the REC bonded to the CaCO₃ surface not only by physical absorption but also by a chemical reaction. The REC could change the surface properties of CaCO₃, resulting in greater hydrophobicity of the surface and enhanced compatibility with nonpolar matrices. The mechanical properties and melt flow rate (MFR) examination of polypropylene (PP)/CaCO₃ composites showed that REC treatment remarkably enhanced the toughness and MFR of composites at higher filler loading. The fractured surface observation with SEM showed improved filler dispersion and enhanced interfacial adhesion between the filler and matrix in PP composites filled with REC‐treated CaCO₃. All these improvements demonstrated that REC is an effective surface modifier of CaCO₃. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1339–1345, 2001     

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     

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     

Viscoelastic,thermal, and morphological analysis of HDPE/EVA/CaCO<Subscript>3</Subscript> ternary blends

High density polyethylene (HDPE), calcium carbonate (CaCO₃), and ethylene vinyl acetate (EVA) ternary reinforced blends were prepared by melt blend technique using a twin screw extruder. The thermal properties of these prepared ternary blends were investigated by differential scanning calorimetry. The effect of EVA loading on the melting temperature (T _m) and the crystallization temperature (T _C) was evaluated. It was found that the expected heterogeneous nucleating effect of CaCO₃ was hindered due to the presence of EVA. The melt viscosities of the ternary reinforced blends were affected by the % loading of CaCO₃, EVA, and vinyl acetate content. Viscoelastic analysis showed that there is a reduction of the storage modulus (G′) with increasing of EVA loading as compared to neat HDPE resin or to HDPE/CACO₃ blends only. The morphology of the composites was characterized by scanning electron microscopy (SEM). The dispersion and interfacial interaction between CaCO₃ with EVA and HDPE matrix were also investigated by SEM. We observed two main types of phase structures; encapsulation of the CaCO₃ by EVA and separate dispersion of the phases. Other properties of ternary HDPE/CaCO₃/EVA reinforced blends were investigated as well using thermal, rheological, and viscoelastic techniques.     

Comparison of the mechanical properties and interfacial interactions between talc,kaolin, and calcium carbonate filled polypropylene composites

Three types of mineral fillers—talc, calcium carbonate (CaCO₃), and kaolin (10–40 wt % filler loadings)—were compounded with polypropylene (PP) with a twin‐screw extruder. The composites were injection‐molded, and the effects of the filler loading on the mechanical, flow, and thermal properties for the three different types of filled composites were investigated. The aim was to compare their properties and to deduce prospective filler combinations that would yield hybrid PP composites in following studies. The results showed that in most cases, the strength and stiffness of the talc‐filled PP composites was significantly higher than those of the CaCO₃‐ and kaolin‐filled PP composites. However, CaCO₃, being a nonreactive filler, increased the toughness of PP. The kaolin‐filled PP composites also showed some improvement in terms of strength and stiffness, although the increases in these properties were not as significant as those of the talc‐filled PP composites. The effects of interfacial interactions between the fillers and PP on the mechanical properties were also evaluated with semiempirical equations. The nucleating ability of all three fillers was studied with differential scanning calorimetry, and the strongest nucleating agent of the three was talc, followed by CaCO₃ and kaolin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3315–3326, 2004     

Morphology and properties of PP/EPDM binary blends and PP/EPDM/nano‐CaCO3 ternary blends

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     

Interfacial structures and mechanical properties of PVC composites reinforced by CaCO3 with different particle sizes and surface treatments

The effects of particle size and surface treatment of CaCO₃ particles on the microstructure and mechanical properties of poly(vinyl chloride) (PVC) composites filled with CaCO₃ particles via a melt blending method were studied by SEM, an AG‐2000 universal material testing machine and an XJU‐2.75 Izod impact strength machine. The tensile and impact strengths of CaCO₃/PVC greatly increased with decreasing CaCO₃ particle size, which was attributed to increased interfacial contact area and enhanced interfacial adhesion between CaCO₃ particles and PVC matrix. Titanate‐treated nano‐CaCO₃/PVC composites had superior tensile and impact strengths to untreated or sodium‐stearate‐treated CaCO₃/PVC composites. The impact strength of titanate‐treated nano‐CaCO₃/PVC composites was 26.3 ± 1.1 kJ m⁻², more than three times that of pure PVC materials. The interfacial adhesion between CaCO₃ particles and PVC matrix was characterized by the interfacial interaction parameter B and the debonding angle θ, both of which were calculated from the tensile strength of CaCO₃/PVC composites. Copyright © 2005 Society of Chemical Industry     

Mechanical properties and morphology of polypropylene‐calcium carbonate nanocomposites prepared by dynamic packing injection molding

In this article, dynamic packing injection molding (DPIM) technology was used to prepare injection samples of Polypropylene‐Calcium Carbonate (PP/CaCO₃) nanocomposites. Through DPIM, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding (CIM), the enhancement of the tensile strength and impact strength of the samples molded by DPIM was 39 and 144%, respectively. In addition, the tensile strength and impact strength of the PP/nano‐CaCO₃ composites molded by DPIM increase by 21 and 514%, respectively compared with those of pure PP through CIM. According to the SEM, WAXD, DSC measurement, it could be found that a much better dispersion of nano‐CaCO₃ in samples was achieved by DPIM. Moreover, γcrystal is found in the shear layer of the DPIM samples. The crystallinity of PP matrix in DPIM sample increases by 22.76% compared with that of conventional sample. The improvement of mechanical properties of PP/nano‐CaCO₃ composites prepared by DPIM attributes to the even distribution of nano‐CaCO₃ particles and the morphology change of PP matrix under the influence of dynamic shear stress. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical properties of modified biofiller‐polypropylene composites

This article reports the mechanical, thermal, and morphological properties of polypropylene (PP)‐chicken eggshell (ES) composites. Mechanical properties like tensile strength, tensile modulus, izod impact strength, flexural modulus of PP composites with normal (unmodified) eggshell and chemically treated ES [modified ES (MES) with isophthalic acid] have been investigated. PP–calcium carbonate (CaCO₃) composites, at the same filler loadings, were also prepared and used as reference. The results showed that PP composites with chemically MES had better mechanical properties compared to the unmodified ES and CaCO₃ composites. An increase of about 3–18% in tensile modulus, 4–44% in izod impact strength and 1.5–26% in flexural modulus at different filler loading was observed in MES composites as compared to unmodified ES composites. Scanning electron microscopy (SEM) micrographs of fractured tensile specimens confirmed better interfacial adhesion of MES with polymer matrix resulting into lower voids and plastic deformation resulting in improved mechanicals of the composites. TEM micrographs showed acicular needle shaped morphology for modified ES and have contributed to better dispersion which is the prime reason for enhancement of all the mechanical properties. At higher filler loading, the modulus of MES composite was found to be higher by 5% as compared to commercial CaCO₃ composites. POLYM. COMPOS., 35:708–714, 2014. © 2013 Society of Plastics Engineers     

An investigation on the mechanical and dynamic rheological properties of single and hybrid filler/polypropylene composites based on talc and calcium carbonate

Some results of experiments on the mechanical and rheological properties of mineral filled polypropylene were presented. Single filler and hybrid filler composites of talc and calcium carbonate (CaCO₃) were prepared in a co‐rotating twin‐screw extruder. The effect of filler type, filler content, and coupling agent on the mechanical and rheological properties of the polypropylene were studied. The coupling agent was maleic anhydride‐grafted polypropylene (PP‐g‐MA). It was found that the mechanical properties are affected by filler type, filler concentration, and the interaction between filler and matrix. The tensile strength of the composite is more affected by the talc while the impact strength is influenced mostly by CaCO₃ content. The elongation at break of PP/CaCO₃ composites was higher than that of PP/talc composites. The incorporation of coupling agent into PP/mineral filler composites increased the mechanical properties. Rheological properties indicated that the complex viscosity and storage modulus of talc filled samples were higher than those of calcium carbonate filled samples while the tan δ was lower. The rheological properties of hybrid‐filler filled sample were more affected by the talc than calcium carbonate. The PP‐g‐MA increased the complex viscosity and storage modulus of both single and hybrid composites. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Toughening and Reinforcement of HDPE/CaCO3 Blends by Interfacial Modification. I. Mechanical Properties and Morphology

To improve the mechanical properties and interfacial structure of HDPE/CaCO₃ composites, a kind of modifier, consisting mainly of carboxylated polyethylene (CPE), and a kind of CaCO₃ grafted with acrylamide (CaCO₃-A) are used. The carboxyl group content of CPE is from 1% to 10%. The amide group content on the surface of modified CaCO₃ is from 0.2% to 1.8%. The results indicate that the CPE improves compatibility partially, and the application of CaCO₃-A results in more ductile material with good impact and tensile strength. The higher the amide group content and carboxyl group content, the higher the tensile and impact strength. The improvement of interfacial adhesion by CPE and CaCO₃-A is clearly revealed by SEM and solvent extracting experiment.     

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     

Influence of m‐isopropenyl‐α,α‐dimethylbenzyl isocyanate grafted polypropylene on the interfacial interaction of wood‐flour/polypropylene composites

In this article, the effects of m‐isopropenyl‐α,α‐dimethylbenzyl isocyanate grafted polypropylene (m‐TMI‐PP) on the interfacial interaction of wood‐flour/polypropylene (WF/PP) were investigated by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermogravimetry, dynamic rheological analysis, and mechanical properties tests. The experimental results demonstrated that m‐TMI‐PP greatly improved the interfacial interaction between WF and PP. According to the DSC results, m‐TMI‐PP made the crystallization temperature and the crystallization degree of PP in WF/m‐TMI‐PP/PP decrease when compared with WF/PP composite without m‐TMI‐PP, but it was still higher than pure PP. These results demonstrated that WF presented the nucleate effect for the crystallization of PP and m‐TMI‐PP improved the interfacial adhesive, which restrained the mobility of PP chain. The rheological analysis indicated that the complex viscosity, storage, and loss modular of WF/PP composite increased, and the tan δ decreased with the addition of m‐TMI‐PP. This was attributed to the strong improvement effects of m‐TMI‐PP on the interfacial interaction of the composites, and was further confirmed by the mechanical properties tests and SEM analysis of the composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of Filler Size on Impact Properties of PP/Elastomer/Filler Ternary Composites

Influence of filler size on impact properties for polypropylene (PP)/elastomer/filler ternary composites was investigated. Calcium carbonate (CaCO₃) particles with a diameter in the range from 120 to 1200 nm were used as a filler and polystyrene-block-poly(ethylene-butene)-block-polystyrene triblock copolymer (SEBS) was used as an elastomer. In the PP/SEBS/CaCO₃ ternary composite, CaCO₃ particles and SEBS particles were dispersed in the PP matrix separately. In the case that SEBS elastomer volume fraction was below 0.12, the impact strength improved gradually with a decrease of CaCO₃ mean diameter from 1200 to 160 nm. In the case that SEBS volume fraction was above 0.17, the impact strength improved significantly by the incorporation of CaCO₃ particles with a mean diameter in the range from 120 to 900 nm. However, the impact strength hardly improved by the incorporation of CaCO₃ particles with a mean diameter of 1200 nm.     

Preparation and characterization of composites: EPDM‐g‐AA/CaCO3

In this study a new method was applied to form crosslinking networks in the ethylene‐propylene‐diene terpolymer (EPDM) matrix with calcium carbonate (CaCO₃) particles, which were chemically treated with acrylic acid (AA). The tensile test showed that the tensile strength and the elongation at break of the composites were improved significantly, and that when the content of CaCO₃ was about 20 wt% in the composites the maximum tensile properties were achieved. The results of swell and solution tests showed that the composites had an evident crosslinking structure. The results of ATR‐FTIR spectrum proved that the acid–base reaction between CaCO₃ and AA had occurred. The SEM photos show that an interfacial adhesion between CaCO₃ and copolymer was good. The TGA curves show that the composites had a new change in mass between 650°C and 750°C, which might be the decomposition temperature of calcium acrylic acid. POLYM. COMPOS., 26:587–592, 2005. © 2005 Society of Plastics Engineers     

Preparation and characterization of composites: Ethylene–propylene–diene terpolymer‐graft‐maleic anhydride/CaCO3

In this paper, a new method was applied to form crosslinking networks in the ethylene–propylene–diene terpolymer (EPDM) matrix with calcium carbonate(CaCO₃) particles, which were chemically treated by maleic anhydride (MAH). The tensile test showed that the tensile strength and the elongation at break of the composites were improved significantly, and when the content of CaCO₃ was about 20 wt % in the composites, the maximum tensile properties were achieved. The results of swell and solution text showed that the composites had evident crosslinking structure. The results of attenuated transmission reflectance‐Fourier transform infrared (ATR‐FTIR) spectrum proved that the Acid‐Base reaction between CaCO₃ and MAH had happened. SEM micrographs showed that the interfacial adhesion between CaCO₃ and copolymer was well. The thermogravimetric analysis curves showed that the composites had a new change in mass between 655 and 700°C, which might be the decomposition temperature of calcium maleicate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1810–1815, 2006     

Plasticization of nano‐CaCO3 in polystyrene/nano‐CaCO3 composites

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     

Characterization of polyethylene/kaolin composites by polymerization filling with Cp2ZrCl2/MAO catalyst system

In this work, the preparation and characterization of metallocene‐catalyzed polyethylene (PE)/kaolin composites were presented. The composites was prepared by the so‐called polymerization‐filling method in which the PE matrix was formed directly on the kaolin surface by ethylene polymerization with the prefixed Cp₂ZrCl₂/methylaluminoxane (MAO) catalyst system on the kaolin surface. SEM, FTIR, and DMA were carried out to characterize the composites. The experimental results showed the new composites had homogeneous distribution of kaolin particles in the PE matrix and strong interfacial interaction between the PE matrix and kaolin particles. At the molecular level, the interfacial interaction caused the decrease of the mobility of PE molecular chains. In addition rheological testing showed that the introduction of kaolin by polymerization filling could improve the rheological behavior of prepared composites. The relationship between the rheological behaviors and the interfacial conditions were discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2913–2921, 2002