Optimization of mechanical properties of PP/Nanoclay/CaCO3 ternary nanocomposite using response surface methodology

Response surface method of experimental design was applied to optimize the mechanical properties of polypropylene (PP)/nanoclay/CaCO₃ hybrid ternary nanocomposite using three different levels of melt flow index (MFI) of PP, nanoclay, and CaCO₃ contents. The samples were prepared by melt mixing in a lab scale corotating twin screw extruder. The main effect of each parameter on the tensile modulus, tensile strength, and impact strength was extensively discussed. The structure of obtained nanocomposite was studied using X‐ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM) techniques. Tensile modulus and impact resistance of prepared ternary nanocomposite were correlated to considered parameters using a second‐order polynomial model. Also, the optimum values of studied variables were determined using contour plots. The obtained results show that increasing the nanoclay and CaCO₃ contents improve the tensile modulus up to 45%, whereas the optimum value of impact strength, about 54%, is achieved at low concentrations of nanoclay (2 wt %) and CaCO₃ (8 wt %). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology and mechanical property of binary and ternary polypropylene nanocomposites with nanoclay and CaCo3 particles

Inorganic nanofillers, CaCO₃ and nanoclay, are widely applied to improve the mechanical properties of polypropylene (PP). In general, the use of spherical CaCO₃ can enhance the impact strength while the use of layered nanoclay can enhance the modulus and yield stress. With the objective to simultaneously improve the stiffness, strength, and impact strength of PP, in this work a ternary nanocomposite, PP/CaCO₃/nanoclay (NCPP), was prepared and its morphology, crystallization, and mechanical behaviors were investigated with a comparison to the binary nanocomposites, PP/CaCO₃ (CPP) and PP/nanoclay (NPP). The results showed that in NCPP the nanoclay was extremely exfoliated with a much higher degree than that in NPP, which was possibly because the incorporation of CaCO₃ nanoparticles adjusted the matrix viscosity and thus provided a balance between shear stress and molecule diffusion. As a result of this highly exfoliated structure, a substantial increase in modulus and yield stress was attained in NCPP. However, its impact strength was less enhanced. The toughening effects of the CaCO₃ particles observed in CPP became ineffective. This difference was ascribed to the fact that in NCPP the crystallization behavior was dominated by the nanoclay and the formation of β‐phase crystallites induced by the CaCO₃ particles was inhibited. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Analysis of tensile modulus of PP/nanoclay/CaCO3 ternary nanocomposite using composite theories

The tensile modulus of PP/nanoclay/CaCO₃ hybrid ternary nanocomposite was analyzed using composite models. Rule of mixtures, inverse rule of mixtures, modified rule of mixtures (MROM), Guth, Paul, Counto, Hirsch, Halpin–Tsai, Takayanagi, and Kerner–Nielsen models were developed for three‐phase system containing two nanofillers. Among the studied models, inverse rule of mixtures, Hirsch, Halpin–Tsai, and Kerner–Nielsen models calculated the tensile modulus of PP/nanoclay/CaCO₃ ternary nanocomposite successfully compared with others. Furthermore, the Kerner–Nielsen model was simplified to predict the tensile modulus by volume fractions of nanofillers. Also, Takayanagi model was modified for the current ternary system. The developed Takayanagi model can predict the tensile modulus using Young's modulus and volume fractions of matrix and nanofillers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Investigation on preparation and property of nano‐CaCO3/PP masterbatch modified by reactive monomers

Nano‐CaCO₃/polypropylene (PP) masterbatch containing above 80 wt % nano‐CaCO₃ was prepared by nano‐CaCO₃ coated PP modified by reactive monomers. The chemical interaction, crystallization and melting behavior, thermal stability, morphology, and surface contact angle of masterbatch were investigated with IR, DSC, TEM, TGA, ESCA, and surface contact angle. The results indicated that nano‐CaCO₃ was coated by PP graft copolymers in the masterbatch modified by reactive monomers. The graft ratio and crystallization and melting behavior of PP in the masterbatch depended on the type and content of reactive monomer. The crystallization temperatures of masterbatch modified by reactive monomer is methyl methacrylate > butyl acrylate > methyl acrylate ≈ mixture of acrylic acid and styrene > unmodified ≈ maleic anhydride ≈ acrylic acid > styrene. Modification by reactive monomer increased the thermal stability and surface contact angle of masterbatch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3907–3914, 2006     

Crystallization and melting behavior of nano‐CaCO3/polypropylene composites modified by acrylic acid

Nano‐CaCO₃/polypropylene (PP) composites modified with polypropylene grafted with acrylic acid (PP‐g‐AA) or acrylic acid with and without dicumyl peroxide (DCP) were prepared by a twin‐screw extruder. The crystallization and melting behavior of PP in the composites were investigated by DSC. The experimental results showed that the crystallization temperature of PP in the composites increased with increasing nano‐CaCO₃ content. Addition of PP‐g‐AA further increased the crystallization temperatures of PP in the composites. It is suggested that PP‐g‐AA could improve the nucleation effect of nano‐CaCO₃. However, the improvement in the nucleation effect of nano‐CaCO₃ would be saturated when the PP‐g‐AA content of 5 phf (parts per hundred based on weight of filler) was used. The increase in the crystallization temperature of PP was observed by adding AA into the composites and the crystallization temperature of the composites increased with increasing AA content. It is suggested that the AA reacted with nano‐CaCO₃ and the formation of Ca(AA)₂ promoted the nucleation of PP. In the presence of DCP, the increment of the AA content had no significant influence on the crystallization temperature of PP in the composites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2443–2453, 2004     

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     

Effect of Dispersion Condition of Calcium Carbonate on the Crystallization and Melting Behavior of Polypropylene/CaCO3 Nanocomposites

Polypropylene/calcium carbonate (PP/CaCO₃) nanocomposites were prepared by melt compounding (C-1) and novel compounding process (C-2), respectively. Scanning electronic microscope (SEM) results illustrated that CaCO₃ nanoparticles were well dispersed at nanoscale in C-2, whereas the nanoparticles were mostly aggregate in C-1. Differential scanning calorimetry (DSC) measurements indicated the onset crystallization temperature was increased by 11.4°C and the supercooling wasdecreased by 13.68°C in C-2. A faster crystallization rate, a higher melting point, and a higher degree of crystallization in C-2 were also detected. Polarization light microscope (PLM) photographs showed the spherulites sizes of C-2 were 60 mm, whereas common spherulites with an average size of about 200 mm were observed in both pure PP and C-1. These phenomena demonstrated that the well-dispersed CaCO₃ nanoparticles could result in heterogeneous nucleation effect on PP even at quite low loading Q2 (1.5% wt.).     

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     

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.     

Extrusion foaming behavior of a polypropylene/nanoclay microcellular foam

With maleic anhydride grafted polypropylene (PP‐g‐MAH) as a compatibilizer, composites of block‐copolymerized polypropylene (B‐PP)/nanoclay were prepared. The effects of the PP‐g‐MAH and nanoclay content on the crystallization and rheological properties of B‐PP were investigated. The microcellular foaming behavior of the B‐PP/nanoclay composite material was studied with a single‐screw extruder foaming system with supercritical (SC) carbon dioxide (CO₂) as the foaming agent. The experimental results show that the addition of nanoclay and PP‐g‐MAH decreased the melt strength and complex viscosity of B‐PP. When 3 wt % SC CO₂ was injected as the foaming agent for the extrusion foaming process, the introduction of nanoclay and PP‐g‐MAH significantly increased the expansion ratio of the obtained foamed samples as compared with that of the pure B‐PP matrix, lowered the die pressure, and increased the cell population density of the foamed samples to some extent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44094.     

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.     

Effect of Nanoparticle Surface Treatment on Nonisothermal Crystallization Behavior of Polypropylene/Calcium Carbonate Nanocomposites

Polypropylene (PP)/CaCO₃ nanocomposites were prepared by melt-blending method using a Haake-90 mixer. The CaCO₃ nanoparticles were surface modified with a coupling agent before compounding. A fine dispersion of the modified nanoparticles in the nanocomposites was observed by transmission electron microscopy (TEM). Effects of surface treatment of CaCO₃ nanoparticles on the nonisothermal crystallization behavior and kinetics of PP/CaCO₃ nanocomposites were investigated by differential scanning calorimetry (DSC). Jeziorny and Mo methods were used to describe the nonisothermal crystallization process. It was shown that the crystallization temperature of the nanocomposites increased due to the heterogeneous nucleation of the surface-treated nanoparticles. It was found that the nanoparticles modified with a proper content range of coupling agent could facilitate the nonisothermal crystallization of the nanocomposites under certain conditions (the cooling rate and the relative degree of crystallinity). This may be a potential application for the crystallization controlling of composites in manufacturing. In addition, the activation energy of crystallization for the nanocomposites and the nucleation activity of the nanoparticle were estimated by using Kissinger and Dobreva's methods, respectively. It could be concluded that the surface-treated nanoparticles had a strong nucleating activity, which caused the decrease of the activation energy of the nanocomposites.     

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.     

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.     

Crystallization behavior of polypropylene filled with surface-modified calcium carbonate

Polypropylene (PP) and calcium carbonate (CaCO₃) were mixed in a two-roll mill. The mixed compounds were molded on the plate by using a compression press heater. To improve the affinity of the relation between CaCO₃ and the PP matrix, we modified the CaCO₃ surface through chemical reaction with alkyl dihydrogen phosphates. The CaCO₃ content and size modification affected the crystallization behavior of the filled PP composites. The crystallization temperature in the nonisothermal crystallization process increased with the increase of CaCO₃ content and the decrease of CaCO₃ size. The crystallization temperature revealed the function of log (1 + T_s) (T_s, total surface area of CaCO₃) irrespective of CaCO₃ content and size for modified and unmodified systems, respectively. The shoulder or double crystallization peak of PP composites is recognized for the unmodified system (particle sizes: 1.0 and 4.5 μm).     

Studies on crystal morphology and crystallization kinetics of polypropylene filled with CaCO3 of different size and size distribution

Changes in the crystal morphology, crystallinity, and the melting temperature of thermoplastics resulted in significant changes in the mechanical behavior of composites containing them. For this reason, the research of crystal morphology and crystallization kinetics in thermoplastic composites became an important requirement. The thermoplastic filled with the filler of different size gradation was a new method for improving processability of thermoplastic composites. We have previously reported that the melt viscosity of polypropylene (PP) composites, which were filled with 30 wt % CaCO₃ of effective size gradation, could be evidently declined. In this study, two sizes of CaCO₃, 325 meshes and 1500 meshes, were blended by different proportions and filled into PP matrix with 30 wt %. Crystal morphology and isothermal crystallization kinetics of a series of composites were characterized by differential scanning calorimeter (DSC) and polarizing microscope. The results showed that composites filled with CaCO₃ of effective size gradation leaded to a well‐crystalline order and a large crystal size, while their isothermal crystallization kinetics and crystallization rate constant (k) were declined, and their Avrami exponents (n) and crystallization half‐life (t_1/2) were increased compared with the composites filled with single size CaCO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2437–2444, 2006     

Tuning the nano/micro‐structure and properties of melt‐processed ternary composites of polypropylene/ethylene vinyl acetate blend and nanoclay: The influence of kinetic and thermodynamic parameters

The present study reports the dependence of the nano/micro‐structure and properties of polypropylene (PP)/ethylene vinyl acetate (EVA)/nanoclay ternary composites on the kinetics and thermodynamics of the melt‐mixing process. The size of dispersed EVA particles in the blends increased in the presence of the nanoclay particles, whereas in the ternary blend composites the size of the EVA dispersions decreased with increasing processing time. Intercalation and exfoliation were achieved more efficiently in ternary composites prepared with a longer EVA processing time. Moreover, the incorporation of the nanoclay particles within the EVA phase and interphase, as well as a long processing time stabilized the morphology. The degree of crystallinity, melting behavior, and crystallization temperature of PP in the ternary composites were not influenced by the presence of the nanoclay particles or by the duration of the melt‐mixing process. The thermal stability of the ternary composites improved with increasing melt‐mixing time. The rheological and thermomechanical properties were found to be dependent on the processing time and on the resulting structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45585.     

Crystallization kinetics of polypropylene composites filled with nano calcium carbonate modified with maleic anhydride

The subject of this study was the crystallization behavior and thermal properties of polypropylene (PP)/maleic anhydride (MAH) modified nano calcium carbonate (nano‐CaCO₃) composites. In this study, 5 wt % nano‐CaCO₃ modified with different contents of MAH was filled into a PP matrix. X‐ray diffraction and differential scanning calorimetry were used to characterize the crystal morphology and crystallization kinetics of a series of composites. The results demonstrate that the nano‐CaCO₃ modified with MAH had an important effect on the thermal and morphological properties of the nanocomposites. The Avrami exponent of the pure PP was an integer, but those of the composites were not integers, but the crystallization rate constant decreased as the content of MAH in the nano‐CaCO₃ filler increased in isothermal crystallization. In nonisothermal crystallization, the kinetic parameter F(T) and the degree of crystallinity of pure PP were compared with those of the PP composites filled with nano‐CaCO₃. We suggest that heterogeneous nucleation existed in the PP composites and that the transformation and retention of the β‐form crystal into the α‐form crystal took place in the composite system and the β‐form crystal had a higher nucleation rate and growth process than the α‐form crystal in the PP composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Crystallization behavior and melting characteristics of PP nucleated by a novel supported β-nucleating agent

The β-nucleated PP with high β-PP content was prepared by a novel supported β-nucleating agent, which was prepared with pimelic acid supported on nano-CaCO₃ as support. The influences of the content of the support and supported β-nucleating agent, pre-melting temperature (T_melt) and scan rates on crystallization behavior and melting characteristics, and the β-PP content of β-nucleated PP were determined by Differential Scanning Calorimeter (DSC) and Wide-Angle X-ray Diffraction (WAXD). The results indicated that the addition of supported β-nucleating agent markedly increased the crystallization temperature (T_c) of PP. Increasing the content of supported β-nucleating agent slightly increased the T_c, but had no influence on the melting temperatures (T_m) of β-nucleated PP. The T_c and T_m of β-nucleated PP decreased slightly with increasing the content of the support nano-CaCO₃. The effects of scan rates and multiple scans with different T_melt on the crystallization and melting behavior of PP nucleated by supported β-nucleating agent are similar to that of PP nucleated by calcium pimelate (CaHA). The β-PP content above 90 percent was obtained in PP nucleated by supported β-nucleating agent and was not influenced by the content of nano-CaCO₃. The supported β-nucleating agent prepared by supporting pimelic acid on nano-CaCO₃ is a β-nucleating agent with high efficiency and selectivity, and low cost.