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.     

Toughening of isotactic polypropylene with CaCO3 particles

The mechanisms of deformation and fracture of isotactic polypropylene filled with CaCO₃ particles were studied. Three types of particles with average diameters of 0.07, 0.7, and 3.5 μm were used at filler volume fraction from 0.05 to 0.30. The experiments included slow tensile tests, notched Izod impact tests with varying notch depths, and fracture resistance tests using double-cantilever-beam sample configurations. In slow tension, addition of fillers increased the modulus and decreased the yield stress independently of filler type. The strain at break increased with initial incorporation of fillers but decreased at higher loadings. The 0.7 μm diameter particles improved Izod impact energy up to four times that of the unfilled matrix. The other particles had either adverse or no effect on the impact toughness. The toughening mechanisms at work were plastic deformation of interparticle ligaments following particle-matrix debonding with additional contribution coming from crack deflection toughening. The failure of the 0.07 and 3.5 μm diameter particles to toughen the matrix was attributed to poor dispersion.     

Interfacial interactions in calcium carbonate–polypropylene composites. 2: Effect of compounding on the dispersion and the impact properties of surface-modified composites

This study was carried out to investigate the influences of compounding process and surface treatment on calcium carbonate (CaCO₃) filled polypropylene. The compounding process is discussed with reference to a twin-screw extruder and an internal mixer. The calcium carbonate filler was surface-treated with a liquid titanate coupling agent (LICA 12) and stearic acid. Composites of different weight fractions were prepared by both compounding processes, and their impact properties were evaluated. The notched Izod impact strength increased with CaCO₃ content up to a maximum at about 10 vol%, and then decreased. Surface treatment of CaCO₃ filler generally yielded composites of higher impact strength than untreated system. Though LICA 12 was more effective than stearic acid in modifying the filler, the low-cost stearic acid proved to be more effective when dealing with the impact properties of composites. Moreover, the composites from a Brabender Plasti-corder exhibited better gross uniformity than that from the twin-screw extruder. However, good filler dispersion and uniform microscopic morphology, as revealed by SEM microscopy, was observed in the samples from the twin-screw extruder. Polym. Compos. 25:451–460, 2004. © 2004 Society of Plastics Engineers.     

Filler toughening of plastics. Part 1—The effect of surface interactions on physico-mechanical properties and rheological behaviour of ultrafine CaCO3/HDPE nanocomposites

Precipitated CaCO₃ (PCC)/High Density Polyethylene (HDPE) composites were prepared on a twin screw mixer-single screw extruder with a particle content of 10 vol%. The average particle size was 70 nm. The influence of surface treatment of the particles, with and without stearic acid (SA), on the physico-mechanical and rheological properties was studied. The experiments included tensile tests, impact tests, differential scanning calorimetry (DSC), microscopy and rheology experiments. The addition of 10 vol% calcium carbonate to HDPE causes a rise in Young's modulus and yield stress of its composites and is accompanied by a sharp drop in impact strength. The addition of SA has the effect of slightly decreasing both Young's modulus and yield stress of the composites compared to the uncoated PCC composites, while the impact strength progressively increases.During the tensile test filled HDPE composites showed stress whitening zones appear and develop along the gauge length. Volume measurements during tensile tests showed an increase in volume strain with deformation, due to the matrix-particle debonding phenomenon, while pure HDPE showed actually a decrease in volume with elongation. At constant deformation, for the composites with coated PCC, it can be observed that an increase in the SA content leads to a slight decrease in volume change. The microscopical evaluation showed cavities and voids due to debonding and deformation bands in the stress whitened areas.DSC experiments have shown that uncoated PCC particles have a very small nucleating effect on HDPE.     

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.     

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     

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     

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     

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     

Polypropylene-elastomer (TPO) nanocomposites: 2. Room temperature Izod impact strength and tensile properties

Room temperature Izod impact strength was determined for polypropylene (PP)/ethylene-co-octene elastomer (EOR) blends and nanocomposites, containing organoclays based on montmorillonite (MMT), at fixed elastomer content of 30 wt% and 0-7 wt% MMT. A ratio of maleated polypropylene, PP-g-MA to organoclay of unity was used as a compatibilizer in the nanocomposites. The organoclay serves to reduce the size of the EOR dispersed phase particles and facilitates toughening. The Izod impact strength is also influenced by the molecular weight of PP, elastomer octene content, elastomer MFI in addition to MMT content. Nanocomposites based on a low molecular weight polypropylene (L-PP) containing a higher octene content elastomer showed higher impact strength at lower MMT contents compared to those based on a low octene content elastomer. The effect of elastomer octene content on impact strength of high molecular weight polypropylene (H-PP) nanocomposites is not so significant. Elastomers having a melt flow index (MFI) in the range of 0.5-1.0 showed significant improvement in the impact strength of L-PP based nanocomposites. Most H-PP/EOR blends gave ‘super-tough’ materials without MMT and maintain this toughness in the presence of MMT. The critical elastomer particle size below which the toughness is observed is reduced by decreasing the octene content of the elastomer. For the similar elastomer particle sizes in nanocomposites, the impact strength varies as H-PP > M-PP > L-PP. The tensile modulus and yield strength improved with increasing MMT content; however, elongation at break was reduced. The extruder-made TPO showed a good-balance of properties in the presence of MMT compared to reactor-made TPO having similar modulus and elastomer content.     

Toughening of polypropylene combined with nanosized CaCO3 and styrene–butadiene–styrene

Nanocomposites of nanosized CaCO₃/SBS/PP were prepared by using twin‐screw and single‐screw extruder. By adding nanosized CaCO₃ particles into SBS/PP blend, the notched impact strength, flexural modulus, and tensile strength of the composites can be improved, whereas, by adding microsized CaCO₃ particles into SBS/PP blend, the notched impact strength of the composite is decreased markedly. At nanosized CaCO₃ content of 16 phr (parts per hundred PP resin by weight), the impact strength of nanosized CaCO₃/SBS/PP composite reaches 56.55 KJ/m², which is 1.27 times that of SBS/PP blend. At nanosized CaCO₃ content of 4 phr, the tensile strength of the composites reaches 31.3 MPa, which is 1.23 times that of SBS/PP blend. The maximum and balanced torque of the composites improves significantly by the addition of CaCO₃ nanoparticles. The increased shear force during compounding continuously breaks down SBS particles, resulting in the reduction of the SBS particles size, and improving the dispersion of SBS particles in PP matrix. Thus the toughening effect of SBS on matrix was improved. Simultaneously, the existence of SBS provides the matrix with a good intrinsic toughness, satisfying the condition that nanosized inorganic particle of CaCO₃ efficiently toughens polymer matrix. The synergistic toughening function of nanosized CaCO₃ and SBS on PP matrix was exhibited. POLYM. ENG. SCI. 47:201–206, 2007. © 2007 Society of Plastics Engineers     

Effect of surface modifiers and surface modification methods on properties of acrylonitrile–butadiene–styrene/poly(methyl methacrylate)/nano‐calcium carbonate composites

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

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     

Investigation on microstructures,melting and crystallization behaviors,mechanical and processing properties of <Emphasis Type="Italic">β</Emphasis>-isotactic polypropylene /CaCO<Subscript>3</Subscript> toughening masterbatch composites

In this study, β-isotactic polypropylene (β-iPP)/CaCO₃ toughening masterbatch (CTM) composites were compounded in a single screw extruder. The microstructures and properties of the composites were investigated. It was shown that CTM influenced the crystallinity and crystallization temperature of β-iPP. The flexural modulus and storage modulus (E’) at 23 °C increased with the increasing CTM content, implying the increased stiffness of the composites. The improved miscibility between β-iPP and CTM was demonstrated by the decreased glass transition temperatures of the composites. The Izod notched impact strength at 23 °C of the composites was directly related to the CTM content because of the competition between the morphological feature of β-iPP and the content of inorganic rigid toughening particles. The critical ligament thickness (τ _c = 1.47 μm) at 40% CTM content was calculated according to the modified Wu’s equation. The morphologies of impact fractured surfaces were observed and the massive shear deformation was related to the debonding of CaCO₃ particles. The presence of CTM also improved the melt flowability and dimensional stability but it was detrimental to heat deflection temperature (HDT) of the composites.     

The toughening mechanism of polypropylene/calcium carbonate nanocomposites

The toughening mechanism of polypropylene (PP) filled with calcium carbonate (CaCO₃) nanoparticles is described. In a previous study (Macromolecule 2008;41:9204), we observed that intensive ligament-stretching following debonding of nanoparticles was responsible for the significant improvement in the impact toughness of the annealed PP/CaCO₃ nanocomposites. Furthermore, we hypothesized that strong ligaments, which have high fracture stresses, are needed to stabilize the crack-initiation process and to increase the energy dissipation in the crack-initiation stage. In this study, we used a high-molecular-weight PP to test this hypothesis because strong ligaments could be created from this high-molecular-weight PP. The notched Izod impact strength of the nanocomposites containing the high-molecular-weight PP and 20 wt% CaCO₃ nanoparticles with a monolayer coating of stearic acid was measured to be about 370 J/m, whereas the impact strength of the unfilled PP was 50 J/m. The size of the plastic deformation zone was found to be dependent on the molecular weight of the PP matrix because the strong ligaments of the high-molecular-weight PP enabled the expansion of the plastic deformation zone, leading to a considerable increase in the impact strength. The synergic effect of the high-molecular-weight PP and the monolayer-coated nanoparticles produced nanocomposites with high impact strength, which is much greater than the inherent impact strength of the unfilled polymer. In addition, the effect of the high-molecular-weight PP on the dispersion of the nanoparticles was investigated.     

Toughening of dimethacrylate resins by addition of ultra high molecular weight polyethylene (UHMWPE) particles

The effects of the addition of UHMWPE particles, of nominal 〈80 μm〉 size, on the fracture toughness, flexural modulus and strength of composites made with dimethacrylate resins (60/40 wt/wt BisGMA-TEGMA) were investigated as a function of volume fraction of UHMWPE (0-60 vol%) and particle surface treatment. Interfacial shear strengths (τ) were measured via microbond shear strength tests using Spectra900™ (UHMWPE) fibers and BisGMA-TEGMA beads. τ increased by a factor of 4 compared with untreated UHMWPE, and surface treated particles improved the mechanical properties of the composite. Fracture toughness (K_IC) and flexural modulus (E) increased with increased volume fraction of UHMWPE, with maximum K_IC/E increases (at 60 vol%) of 238%/25% compared with the neat resin. SEM images showed debonding as well as yielding and fibrillation of the UHMWPE particles, suggesting that these were significant toughening mechanisms.     

Selective particle distribution and mechanical properties of nano‐CaCO3/ethylene‐propylene‐diene terpolymer/polypropylene composites with high content of nano‐CaCO3

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

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     

Mechanical properties of i-PP/CaCO3 composites

Tensile and impact behavior of CaCO₃-filled polypropylene was studied in the composition range 0–60 wt % filler. Tensile modulus increased while tensile strength and breaking elongation decreased with increase in CaCO₃ content. The modulus increase and elongation decrease were attributed to increased filler–polymer interaction resulting in reduction in molecular mobility, while increased amorphization and obstruction to stress transfer accounted for the tensile strength decrease. Analysis of tensile strength data showed introduction of stress concentration in the composites. Izod impact strength at first increased up to a critical CaCO₃ content, beyond which the value decreased. Surface treatment of CaCO₃ with a titanate coupling agent LICA 12 enhances the adhesion of the filler and polymer, which further modifies the strength properties. Scanning electron microscopic studies indicated better dispersion of CaCO₃ particles upon surface treatment, which effected the changes in the strength properties of the composites.