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     

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     

Mechanical and thermal properties of talc and calcium carbonate filled polypropylene hybrid composites

The main aim of this work was to study and compare the mechanical and thermal properties of hybrid polypropylene (PP) composites and single‐filler PP composites. With two main types of mineral fillers—calcium carbonate (CaCO₃) and talc—PP composites of different filler weight ratios (talc/CaCO₃) were compounded with a twin‐screw extruder and then injection‐molded into dumbbell specimens with an injection‐molding machine. Tensile, flexural, and impact tests were performed to determine and compare the mechanical properties of the hybrid and single‐filler PP composites. A synergistic hybridization effect was successfully achieved; the flexural strength and impact strength were highest among the hybrids when the PP/talc/CaCO₃ weight ratio was 70:15:15. The nucleating ability of the fillers and its effects on the mechanical properties were also studied with differential scanning calorimetry. Because of the influence of talc as the main nucleating agent, the hybrid fillers showed significant improvements in terms of the nucleating ability, and this contributed to the increase in or retention of the mechanical properties of the hybrid composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3327–3336, 2004     

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     

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     

Study on isotactic polypropylene/zinc‐neutralized sulfonated ethylene propylene diene monomer rubber/CaCO3 ternary blends

The morphological structure and mechanical properties of isotactic polypropylene (PP)/zinc‐neutralized sulfonated ethylene propylene diene monomer rubber (Zn? SEPDM)/CaCO₃ blends were studied. PP/Zn? SEPDM/CaCO₃ blends were prepared through two different sequences. A: Blending PP with Zn? SEPDM, then adding CaCO₃; B: Blending Zn? SEPDM with CaCO₃, then adding PP. The blending sequence has substantial influence on the mechanical properties. SEM micrographs and X‐ray photoelectron spectrometry indicate that the CaCO₃ filler is encapsulated by Zn? SEPDM in those blends prepared through sequence B, which caused an extra increase of impact strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1635–1640, 2004     

Influence of Elastomer Modification on Impact Strength of PP/Elastomer/CaCO3 Composite

Polypropylene (PP)/elastomer/fine filler particle ternary composite was prepared using polystyrene-block-poly(ethylene-butene)-block-polystyrene triblock copolymer (SEBS) or carboxylated SEBS (C-SEBS) as elastomer and calcium carbonate (CaCO₃) having mean size about 160 nm as filler. First, SEBS (or C-SEBS) and CaCO₃ particles were mixed to form master batch. Second, the prepared master batch and PP matrix were kneaded. In the PP/SEBS/CaCO₃ ternary composite, CaCO₃ particles and SEBS particles were dispersed in the PP matrix separately. In the PP/C-SEBS/CaCO₃ ternary composite, CaCO₃ particles were encapsulated in C-SEBS and formed a core–shell structure at lower CaCO₃ concentration; however, some CaCO₃ particles were dispersed in PP matrix at higher CaCO₃ concentration. In the PP/SEBS/CaCO₃ composite, the impact strength increased with the amount of incorporated CaCO₃ particles. Whereas, in the PP/C-SEBS/CaCO₃ composite, the impact strength increased with the amount of CaCO₃ particles dispersed in PP matrix. The master-batch method was found to be useful for improving the dispersibility of CaCO₃ particles than the commonly used single-batch method.     

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     

Improved mechanical properties and structure of PP/nano‐CaCO3 blends prepared by low‐frequency vibration injection molding

BACKGROUD: Melt vibration technology was used to prepare injection samples of polypropylene (PP)/nano‐CaCO₃ blends. It is well known that nano‐CaCO₃ particles are easy to agglomerate owing to their large surface energy. Improving the distribution of nano‐CaCO₃ particles in PP/nano‐CaCO₃ blends is very important for enhancing the mechanical properties. In this work, low‐frequency vibration was imposed on the process of injection molding of PP/nano‐CaCO₃ blends. The aim of importing a vibration field was to change the crystal structure of PP as we studied previously and improve the distribution of nano‐CaCO₃ particles. Furthermore, the mechanical properties were improved. RESULTS: Through melt vibration, the mechanical properties of PP/nano‐CaCO₃ samples were improved significantly. Compared with conventional injection molding, the enhancement of the tensile strength and impact strength of the samples molded by vibration injection molding was 17.68 and 175.96%, respectively. According to scanning electron microscopy, wide‐angle X‐ray diffraction and differential scanning calorimetry measurements, it was found that a much better dispersion of nano‐CaCO₃ in samples was achieved by vibration injection molding. Moreover, the crystal structure of PP in PP/CaCO₃ vibration samples changed. The γ crystal form was achieved at the shear layer of vibration samples. Moreover, the degree of crystallinity of PP in vibration samples increased 6% compared with conventional samples. CONCLUSION: Concerning the microstructure, melt vibration could effectively change the crystal structure and increase the degree of crystallinity of PP besides improving the distribution of nano‐CaCO₃ particles. Concerning the macrostructure, melt vibration could enhance the mechanical properties. The improvement of mechanical properties of PP/nano‐CaCO₃ blends prepared by low‐frequency vibration injection molding should be attributed to the even distribution of nano‐CaCO₃ particles and the formation of γ‐PP and the increase of the degree of cystallinity. Copyright © 2007 Society of Chemical Industry     

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     

Thermomechanical properties of virgin and recycled polypropylene impact copolymer/CaCO3 nanocomposites

The effect of successive injection moldings on the thermal, rheological, and mechanical properties of a polypropylene impact copolymer (PP) was investigated. The crystal content decreased as the molecular weight decreased due to chain scission with repeated injection molding. The Young modulus and the yield stress remained constant, despite a drop in the strain to break. Virgin and recycled PP matrix were filled with nanosized calcium carbonate (CaCO₃) particles. The effect of morphology on the thermal and mechanical properties of nanocomposites of virgin and recycled PP filled with nanosized CaCO₃ particles was also studied. The mechanical properties of the nanocomposites were strongly influenced by the intrinsic toughness of the matrix and the concentration and dispersion of the filler. The yield strength and strain of virgin PP decreased gradually, while its Young's modulus increased slightly with increasing CaCO₃ loading. These phenomena were less pronounced for the recycled matrix. Incorporation of nanoparticles to virgin matrix produced an increase in tensile stiffness and ductility, when good dispersion of the filler was achieved. However, the impact strength dropped dramatically for high filler contents. A significant increase in impact strength was observed for the recycled PP. POLYM. ENG. SCI., 50:1904–1913, 2010. © 2010 Society of Plastics Engineers     

Comparative Characterization of PP Nano‐ and Microcomposites by In‐Mold Shrinkage Measurements and Structural Characteristics

Poly(propylene)‐clay nanocomposites and poly(propylene) containing conventional inorganic fillers such as calcium carbonate (CaCO₃) and glass fiber were used in a comparative study focusing on dimensional stability, structure, mechanical and thermal properties. Micro‐ and nanocomposites were prepared by melt blending in a twin‐screw extruder. The relative influence of each filler was observed from dimensional stability measurements and structural analysis by WAXD, TEM, and thermal and mechanical properties. At equal filler loadings, PP/clay nanocomposites exhibit an improvement in dimensional stability and were the only composites capable of reduced shrinkage in both in‐flow and cross‐flow directions. The flexural modulus of PP increased nearly 20% by compounding with 4% organoclay, as compared to a similar performance obtained by compounding with 10 wt.‐% of CaCO₃ or approximately 6 wt.‐% of glass fiber. The HDT and thermal stability of PP were enhanced by using nanoclay as filler.

     

Effects of calcium carbonate and its purity on crystallization and melting behavior,mechanical properties,and processability of syndiotactic polypropylene

Calcium carbonate‐filled syndiotactic poly(propylene) (CaCO₃‐filled s‐PP) was prepared in a self‐wiping, co‐rotating twin‐screw extruder. The effects of CaCO₃ of varying particle size (1.9, 2.8 and 10.5 μm), content (0–40 wt %), and type of surface modification (uncoated, stearic acid‐coated, and paraffin‐coated) on the crystallization and melting behavior, mechanical properties, and processability of CaCO₃‐filled s‐PP were investigated. Non‐isothermal crystallization studies indicate that CaCO₃ acts as a good nucleating agent for s‐PP. The nucleating efficiency of CaCO₃ for s‐PP was found to depend strongly on its purity, type of surface treatment, and average particle size. Tensile strength was found to decrease, while Young's modulus increased, with increasing CaCO₃ content. Both types of surface treatment on CaCO₃ particles reduced tensile strength and Young's modulus, but improved impact resistance. Scanning electron microscopy (SEM) observations of the fracture surfaces for selected CaCO₃‐filled s‐PP samples revealed an improvement in CaCO₃ dispersion as a result of surface treatment. Finally, steady‐state shear viscosity of CaCO₃‐filled s‐PP was found to increase with increasing CaCO₃ content and decreasing particle size. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 201–212, 2004     

Composites of high density polyethylene and different grades of calcium carbonate: Mechanical,rheological, thermal,and morphological properties

Calcium carbonate (CaCO₃)/high density polyethylene (HDPE) composites were prepared in a HAAKE twin screw extruder, using the experimental conditions defined by the factorial experimental design presented in a prior study. In this study, the effect of different grades (Ca₁ and Ca₂) and CaCO₃ content (varying from 0 to 15 wt %) on the mechanical, rheological, thermal, and morphological properties was evaluated. The results showed that the addition of the filler provoked a decrease on the impact strength, stress at break, and yield stress properties in relation to the pure HDPE. A consequent increase on the modulus of elasticity, indicating an increase on the rigidity of the composite, was observed. It was also verified a tendency to increase the toughness and the viscosity of the composites as CaCO₃ was added. Scanning electron micrographs showed that as the filler was incorporated to HDPE matrix, CaCO₃ particles tended to agglomerate, especially that grade constituted of particles of smaller size. The thermal analysis showed that the addition of mineral filler caused a decrease on the crystallinity degree. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2559–2564, 2006     

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     

Fractal analysis of polypropylene composite filled with nano‐calcium carbonate

Polypropylene (PP) and nano‐calcium carbonate (CaCO₃) composites were prepared by melt mixing in a corotating twin‐screw extruder. Transmission electron microscopy study and particle size analysis revealed the dispersion and the size distribution of CaCO₃ in PP. With the increase of loading of filler, CaCO₃ nanoparticles densely aggregated together and the dispersion of filler became bad. The fractal dimensions of the composites were determined using fractal concept. The fractal dimensions of D and D_k described the irregularities of the shape of an object and the distributions of particle populations, respectively. The D and D_k values were influenced by the content of filler, i.e., the D values increased, and the D_k values decreased with the increase of loading of filler. When the loading of filler was low, the values of D and D_k of PP composites differ slightly than the counterparts of PP/PP‐g‐MA (50 wt %) blend. For 20 wt %, they were almost identical. This fact showed that the fractal dimension was correlated with the dispersion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of isotactic polypropylene and stearic acid-modified calcium carbonate composite: a promising material for microwavable packaging

Isotactic polypropylene (PP) composite films were developed, with incorporation of CaCO₃ particles as active filler. Stearic acid was used for the surface treatment of CaCO₃ to provide composite films having improved mechanical, thermal and barrier properties against oxygen as well as water vapor, in comparison to neat PP films. The filler was melt mixed with PP in a twin-screw extruder, and the films produced through melt blowing. A slight reduction in T _g values of the filled PP films was observed, along with an increase in the overall crystallization extent relative to neat PP films. X-ray diffraction data confirmed that the CaCO₃ particles served as a β-nucleating agent capable of promoting the formation of the β-crystalline phase of PP and reducing the spherulite size, with stearic acid-coated CaCO₃ being most effective in promoting these features. Exposing the films to microwave radiation altered their properties; at low irradiation power, the T _g values and the degree of β-crystallization were enhanced, and barrier properties against oxygen and water vapor showed improvements. In contrast, no significant changes in the appearance of the film surface were evident highlighting the potential of these PP-based composite films in microwave packaging applications.     

Toughening and reinforcing polypropylene with core–shell structured fillers

An elastomer/rigid particle filler with core–shell structure was prepared by twin‐screw extruder according to an encapulation model. It was used to toughen and reinforce polypropylene (PP). An original idea of a one‐step processing method was adopted in creating PP/polyoctene–ethylene/talc ternary composites. The rheological behavior of PP was changed and the mechanical properties were improved. SEM observation showed that the core–shell structured filler dispersed better in copolypropylene than in homopolypropylene. Two reasons were proposed and proved by the rheology test and SEM observation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2397–2403, 1999     

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.     

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.