EPDM/纳米CaCO3预混料动态力学性能及其对聚丙烯基三元复合材料韧性的影响

采用熔融法分别制备了三元乙丙橡胶(EPDM) /纳米碳酸钙（CaCO3）二元预混料及其与聚丙烯（PP）共混的三元复合材料。利用动态力学分析仪研究了纳米CaCO3含量和共混时间对EPDM /纳米CaCO3二元预混料的动态力学性能的影响,利用扫描电子显微镜分析了分散相纳米CaCO3和EPDM在PP基体中的形态。结果表明,常温下,纳米CaCO3含量为70 %（质量分数,下同）、共混时间为15 min时,EPDM/纳米CaCO3二元预混料的储能模量、损耗模量和损耗角正切达到最高值;纳米CaCO3与EPDM组成的二元共混物分散于PP基体中,通过纳米CaCO3团聚体及EPDM协同变形、界面脱黏成纤及诱导剪切带的形成耗散外界作用能,显著提高了PP/EPDM/纳米CaCO3三元复合材料的冲击强度。     

Largely improved toughness of PP/EPDM blends by adding nano-SiO2 particles

As a part of long-term project aimed at super polyolefin blends, in this work, we report the toughness and phase morphology of polypropylene (PP)/EPDM/SiO₂ ternary composites. Two processing methods were employed to prepare PP/elastomer/filler ternary composites. One was called one-step processing method, in which the elastomer and the filler directly melt blended with PP matrix. Another one was called two-step processing method, in which the elastomer and the filler were mixed first, and then melt blended with pure PP. Two kinds of PP (grafted without or with maleic anhydride (PP-g-MA)) and SiO₂ (treated with or without coupling agent) were used to control the interfacial interaction among the components. The dependence of the phase morphology on interfacial interaction and processing method was investigated. It was found that the formation of filler-network structure could be a key for a simultaneous enhancement of toughness and modulus of PP and its formation seemed to be dependent on the work of adhesion (W_AB) and processing method. As the W_AB of PP/EPDM interface was much lower than that of PP/SiO₂ and EPDM/SiO₂, and the two-step processing method was used, the formation of filler-network structure was favorable. In this case, a super toughened PP ternary composite with the Izod impact strength 2-3 times higher than PP/EPDM binary blend and 15-20 times higher than pure PP could be achieved.     

Morphology prediction and the effect of core‐shell structure on the rheological behavior of PP/EPDM/HDPE ternary blends

In this work, the morphologies of polypropylene (PP)/ethylene‐propylene‐diene (EPDM) rubber/high density polyethylene (HDPE) 70/20/10 blends were studied and compared with the predictions of the spreading coefficient and minimum free energy models. The interfacial tension of PP/HDPE, PP/EPDM, and HDPE/EPDM blends were obtained by fitting the experimental dynamic storage modulus data to Palierne's theory. The prediction results showed core‐shell morphology (core of HDPE and shell of EPDM) in PP matrix. The PP/EPDM/HDPE blends were respectively prepared by direct extrusion and lateral injection method. Core‐shell morphology (core of HDPE and shell of EPDM) could be obtained with direct extrusion corresponding to the predicted morphology. The morphology of PP/EPDM/HDPE blends could be effectively controlled by lateral injection method. For PP/EPDM/HDPE blend prepared by lateral injection method, HDPE and EPDM phase were dispersed independently in PP matrix. It was found that the different morphology of PP/EPDM/HDPE blends prepared by two methods showed different rheological behavior. When the core‐shell morphology (core of HDPE and shell of EPDM) appeared, the EPDM shell could confine the deformation of HDPE core significantly, so the interfacial energy contribution of dispersed phase on the storage modulus of blends would be weaken in the low frequency region. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Lignin‐Reinforced Ethylene‐Propylene‐Diene Copolymer Elastomer via Hydrogen Bonding Interactions

It is still a great challenge to prepare lignin/polyolefin composites with good strength and toughness. Inspired by the energy sacrificial mechanism from biomaterials, dynamic hydrogen bonds (H‐bonds) are incorporated into the lignin/ethylene‐propylene‐diene monomer (EPDM) composite system to improve the interfacial interactions between lignin and EPDM. Such H‐bonding interactions are demonstrated to be able to simultaneously improve the modulus, strength, and toughness of lignin/EPDM composites without sacrificing the extensibility. This work provides a facile method for the high‐valued utilization of lignin in the preparation of high‐performance elastomer composites using bio‐renewable resources as reinforcing agent.     

具有“沙袋”结构的PP/EPDM/CB导电复合材料的形态构建及性能研究

提出通过构建类似拳击训练沙袋的硬核-软壳分散相结构来同时实现导电高分子复合材料的高电导率和高韧性这一设想,并通过两步熔融共混法构建了这种具有“沙袋”分散相结构的聚丙烯（PP）/三元乙丙橡胶（EPDM）/炭黑（CB）导电复合材料,其中,CB粒子选择性分布于EPDM分散相中。通过定量计算发现,无论从热力学角度还是动力学角度,CB粒子均倾向于选择性分布在EPDM中,这也阐明了“沙袋”分散相结构的形成机理。此外,性能测试表明,这种具有“沙袋”分散相结构的导电复合材料的体积电导率和缺口冲击强度随炭黑含量的增加呈现反常的同步增长。     

Processability,morphology and mechanical properties of wood flour reinforced high density polyethylene composites

Abstract

Wood flour reinforced high density polyethylene (HDPE) composites have been prepared and their rheological properties measured. The melt viscosity decreased as the processing temperature increased and the wood flour content decreased. A power law model was used to describe the pseudoplasticity of these melts. Adding wood flour to HDPE produced an increase in tensile strength and modulus. Composites compounded in a twin screw extruder and treated with a coupling agent (vinyltrimethoxysilane) or a compatibliser (HDPE grafted with maleic anhydride) exhibited better mechanical properties than the corresponding unmodified composites because of improved dispersion and good adhesion between the wood fibre and the polyalkene matrix. Scanning electron microscopy of the fracture surfaces of these composites showed that both the coupling agent and compatibiliser gave superior interfacial strength between the wood fibre and the polyalkene matrix.     

Improvement of interfacial adhesion of poly(m‐phenylene isophthalamide) short fiber–thermoplastic elastomer (SEBS) composites by N‐alkylation on fiber surface

A composite of short‐fiber, poly(m‐phenylene isophthalamide), and thermoplastic elastomer styrene (ethylene–butylene) styrene (SEBS), was investigated. The fiber surface was modified by N‐alkylation (heptylation and dodecylation) to improve their compatibility with a less polar SEBS matrix. Observation of fiber‐surface morphology by SEM revealed surface roughness after N‐alkylation. Nearly complete coating of the polymer matrix on the fiber was observed on a fractured surface of the composite, which is evidence for the improvement of fiber–matrix adhesion. It was found that the modulus of the composites grew with increasing fiber loading to approximately the same extent for both unmodified and modified fiber composites. Tensile strength of the modified fiber composites was found to improve significantly over that of the unmodified fiber composite. This suggests that the presence of the alkyl group on the fiber surface is responsible for an improvement of interfacial adhesion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2414–2422, 1999     

Preparation and properties of nano‐Al2O3 particles/polyester/epoxy resin ternary composites

This article presents the results of an experimental study on the preparation and properties of new ternary composites composed of nano‐Al₂O₃ particles, polyester, and epoxy resin. The ternary composites were prepared by the addition of the nano‐Al₂O₃ particles in a binary matrix, with elevated viscosity, of the epoxy resin modified by the polyester. The nano‐Al₂O₃ particles were previously located and dispersed in the polyester phase. The study showed that the ternary system was a type of nanoscale dispersed composite with high strength and toughness as well as modulus, combined with excellent dielectric and heat‐resistance properties. All related properties of the composites were remarkably superior to those of both the binary matrix and the unmodified epoxy resin. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 70–77, 2002     

Effect of EPDM‐g‐MAH on the morphology and properties of PA6/EPDM/HDPE ternary blends

The formation of core‐shell morphology within the dispersed phase was studied for composite droplet polymer‐blend systems comprising a polyamide‐6 matrix, ethylene‐propylene‐diene terpolymer (EPDM) shell and high density polyethylene (HDPE) core. In this article, the effect of EPDM with different molecular weights on the morphology and properties of the blends were studied. To improve the compatibility of the ternary blends, EPDM was modified by grafting with maleic anhydride (EPDM‐g‐MAH). It was found that core‐shell morphology with EPDM‐g‐MAH as shell and HDPE as core and separated dispersion morphology of EPDM‐g‐MAH and HDPE phase were obtained separately in PA6 matrix with different molecular weights of EPDM‐g‐MAH in the blends. DSC measurement indicated that there may be some co‐crystals in the blends due to the formation of core‐shell structure. Mechanical tests showed that PA6/EPDM‐g‐MAH/HDPE ternary blends with the core‐shell morphology exhibited a remarkable rise in the elongation at break. With more perfect core‐shell composite droplets and co‐crystals, the impact strength of the ternary blends could be greatly increased to 51.38 kJ m^?2, almost 10 times higher than that of pure PA6 (5.50 kJ m^?2). POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synergetic toughness and morphology of poly(propylene)/nylon 11/maleated ethylene‐propylene diene copolymer blends

Polypropylene (PP)/nylon 11/maleated ethylene‐propylene‐diene rubber (EPDM‐g‐MAH) ternary polymer blends were prepared via melt blending in a corotating twin‐screw extruder. The effect of nylon 11 and EPDM‐g‐MAH on the phase morphology and mechanical properties was investigated. Scanning electron microscopy observation revealed that there was apparent phase separation for PP/EPDM‐g‐MAH binary blends at the level of 10 wt % maleated elastomer. For the PP/nylon 11/EPDM‐g‐MAH ternary blends, the dispersed phase morphology of the maleated elastomer was hardly affected by the addition of nylon 11, whereas the reduced dispersed phase domains of nylon 11 were observed with the increasing maleated elastomer loading. Furthermore, a core‐shell structure, in which nylon 11 as a rigid core was surrounded by a soft EPDM‐g‐MAH shell, was formed in the case of 10 wt % nylon 11 and higher EPDM‐g‐MAH concentration. In general, the results of mechanical property measurement showed that the ternary blends exhibited inferior tensile strength in comparison with the PP matrix, but superior toughness. Especially low‐temperature impact strength was obtained. The toughening mechanism was discussed with reference to the phase morphology. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of the interface structure of different surface‐modified nano‐SiO2 on the mechanical properties of nylon 66 composites

The nylon 66‐based nanocomposites containing two different surface‐modified and unmodified SiO₂ nanoparticles were prepared by melt compounding. The interface structure formed in different composite system and their influences on material mechanical properties were investigated. The results indicated that the interfacial interactions differed between composite systems. The strong interfacial adhesion helped to increase tensile strength and elastic modulus of composites; whereas, the presence of modification layer in silica surface could enhance the toughness of composites, but the improvement of final material toughness was also correlated with the density of the adhered nylon 66 chains around silica nanoparticles. In addition, the results also indicated that the addition of surface‐modified silica nanoparticles has a distinct influence on the nonisothermal crystallization behavior of the nylon 66 matrix when compared with the unmodified silica nanoparticle. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improvement in impact property of continuous glass mat reinforced polypropylene composites

The toughened polypropylene (PP) was obtained by the blending of PP with ethylene‐propylene diene monomer (EPDM). The impact property of continuous glass mat‐reinforced polypropylene was adjusted through three ways: different toughness PPs and their blends were used as matrices, the functionalized polypropylene was added into the matrix to control the interfacial adhesion; the ductile interlayer was introduced at the fiber/matrix interphase by the grafting and crosslinking of rubber chains on fiber surface. The effect of PP toughness, interfacial adhesion, and ductile interlayer on the mechanical properties of composite systems was studied. The impact toughness of GMT increased with increasing the matrix toughness, whereas the flexural strength and modulus decreased. The good interfacial adhesion resulted in the low impact toughness. However, GMT composite with high strength, modulus, and impact toughness could be obtained by the introduction of a ductile interlayer at fiber/matrix interphase. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2680–2688, 2002     

Glass fiber reinforced polypropylene/EPDM blends. II. Mechanical properties and morphology

Tensile and impact properties of the ternary system polypropylene (PP)/ethylene propylene diene elastomer (EPDM)/glass fiber (GF) and the corresponding binary systems PP/EPDM blend and PP/GF composite are studied. Results are presented and analyzed as functions of compositional variables, viz., (i) matrix PP/EPDM blending ratio at constant GF loadings and (ii) GF loading at constant matrix blending ratios for the ternary system and (iii) EPDM content for PP/EPDM binary system and (iv) GF content for the binary system PP/GF, respectively. The role of individual components EPDM and GF in these mechanical properties is discussed and their combined effects are inspected at certain composition ranges. Theoretical analysis of tensile data is presented which reveals the effect of EPDM on the reinforcing effect of GF. Unlike the conventional role of an elastomer, increase of EPDM content in the presence of GF increases the modulus of the ternary system. Impact strength of the ternary system increases with increasing GF content both in the presence and absence of EPDM, showing a distinct minimum at matrix blending ratio PP/EPDM 90/10. Scanning electron micrographs of impact-fractured surfaces are presented to illustrate the dispersion of the two phases of the polyblend matrix, fiber alignment, and the fiber interface.     

Characterization of carbon black‐filled immiscible polypropylene/polystyrene blends

The electrical and rheological behaviors of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) blends were investigated. The compounding sequence influences the phase morphology of the ternary CB/PP/PS composites and the distribution of CB aggregates. Simultaneous measurements of resistance and dynamic modulus were carried out to monitor the phase coalescence of the ternary composites and CB migration and agglomeration in the PS phase during annealing at temperatures above the melting point of PP. The variation of resistivity is mainly attributed to CB agglomeration in the PS phase and the interfacial region, while the variation of dynamic modulus is regarded as the superimposition of the phase coalescence and CB agglomeration in the PS phase. The ternary composites with the majority of CB particles distributed in the interfacial region show the lowest conductive percolation threshold and the most stable resistivity–temperature performance during heating–cooling cycles. Copyright © 2011 Society of Chemical Industry     

Polypropylene composites. II: Structure-property relationships in two- and three-component polypropylene composites

Two- and three-component polypropylene (PP) blends and composites were prepared to study their structure/property relationships. Butadiene-styrene (BDS) copolymers of low compatibility formed large particles of poor adhesion in PP resulting in inferior mechanical properties. Better miscibility of ethylene-propylene-diene (EPDM) elastomer results in more finely dispersed particles and the experimental results indicate a transition to an interpenetrating network (IPN)– like structure with increasing elastomer content. Effective impact modification can be achieved only with EPDM elastomers of sufficient miscibility. Mutual wettability and adhesion of the components determine the structure and properties in PP/elastomer/filler systems. Modification of PP by acrylic acid grafting promotes PP/filler adhesion which, in turn, results in the separate dispersion of the components. In an unmodified PP matrix, a significant amount of the filler is encapsulated by the elastomer. At low filler content, better low temperature impact strength is achieved in the case of separately dispersed components, while encapsulation is more advantageous at high filling grades.     

Microstructural characteristics of glass bead‐ and wollastonite‐filled isotactic‐polypropylene composites modified with thermoplastic elastomers

Microstructural characteristics of isotactic‐polypropylene/glass bead (iPP/GB) and iPP/wollastonite (iPP/W) composites modified with thermoplastic elastomers, poly(styrene‐b‐ethylene‐co‐butylene‐b‐styrene) copolymer (SEBS) and corresponding block copolymer grafted with maleic anhydride (SEBS‐g‐MA), were investigated. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and dynamic mechanical analyses (DMA) showed that the iPP/SEBS and iPP/SEBS‐g‐MA blends were partially compatible two‐phase systems. Well‐dispersed spherical GB and acicular W particles without evidence of interfacial adhesion were observed in the iPP/GB and iPP/W binary composites respectively. Contrary to the blends, melt flow rates of the iPP/GB and PP/W composites decreased more with SEBS‐g‐MA than with SEBS because of enhanced interfacial adhesion with SEBS‐g‐MA elastomer. The SEM analyses showed that the ternary composites containing SEBS exhibited separate dispersion of the rigid filler and elastomer particles (i.e., separate microstructure). However, SEBS‐g‐MA elastomer not only encapsulated the spherical GB and acicular W particles completely with strong interfacial adhesion (i.e., core‐shell microstructure) but also dispersed separately throughout iPP matrix. In accordance with the SEM observations, the DSC and DMA revealed quantitatively that the rigid filler and SEBS particles in iPP matrix acted individually, whereas the rigid filler particles in the ternary composites containing SEBS‐g‐MA acted like elastomer particles because of the thick elastomer interlayer around the filler particles. The Fourier transform infrared analyses revealed an esterification reaction inducing the strong interfacial adhesion between the SEBS‐g‐MA phase and the filler particles. POLYM. COMPOS., 31:1265–1284, 2010. © 2009 Society of Plastics Engineers     

Effect of morphology on the electric conductivity of binary polymer blends filled with carbon black

Several carbon black (CB)‐filled binary polymer blends were prepared in Haake rheometer. Distribution states of CB and effect of morphology on the electric conductivity of different ternary composites were investigated. Under our experimental condition CB particles located preferentially at the interface between polymethyl methacrylate (PMMA) and polypropylene (PP) in PMMA/PP/CB composites, in high‐density polyethylene (HDPE) phase in PP/HDPE/CB composites, and in Nylon6 (PA6) phase in polystyrene (PS)/PA6/CB, PP/PA6/CB, PMMA/PA6/CB, and polyacrylonitrile (PAN)/PA6/CB composites; the ternary composites in which CB particles locate at the interface of two polymer components have the highest electric conductivity when the mass ratio of the two polymers is near to 1 : 1. The ternary composites in which CB particles located preferentially in one polymer have the highest electric conductivity usually when the amount of the polymer component having CB particles is comparatively less than the amount of the polymer component not having CB particles; if the formulations of PS/PA6/CB, PP/PA6/CB, and PMMA/PA6/CB composites equaled and PA6/CB in them is in dispersed phase, PS/PA6/CB composites have the highest electric conductivity and PP/PA6/CB composites have the lowest electric conductivity; suitable amount of PS or PAN in PA6/CB composites increase the electric conductivity due in the formation of a parallel electrocircuit for electrons to transmit. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Factors influencing encapsulation behavior in composite droplet-type polymer blends

In this study the influence of the molecular weight of the dispersed phase components on encapsulation effects in the composite droplet phase was examined for high density polyethylene (HDPE)/PS/PMMA ternary blends. Three different blends composed of various PS and PMMA materials dispersed in an HDPE matrix were prepared using an internal mixer. The morphology was studied by light and electron microscopy. Current models used for predicting encapsulation effects and composite droplet formation in ternary systems (based on static interfacial tension) predict in all cases that PS will encapsulate the PMMA. However, in one case, an unexpected encapsulation of PS by PMMA was observed. It was found that arguments based on the effect of viscosity ratio or the absolute viscosity of the different dispersed phases do not explain that discrepancy. In addition, the reversal of that latter composite droplet morphology from PMMA encapsulating PS to PS encapsulating PMMA was observed upon annealing treatment. Considering all the above, a conceptual model was developed to predict encapsulation effects in composite droplet type systems based on the use of a dynamic interfacial tension (i.e. taking into account the elasticity of the polymer components). Calculations based on the dynamic interfacial tension model, using elasticities based on constant shear stress, were able to account for all of the observed encapsulation effects in this study.     

Study on the effect of woven sisal fiber mat on mechanical and viscoelastic properties of petroleum based epoxy and bioresin modified toughened epoxy network

Sisal fiber reinforced biocomposites are developed using both unmodified petrol based epoxy and bioresin modified epoxy as base matrix. Two bioresins, epoxidized soybean oil and epoxy methyl soyate (EMS) are used to modify the epoxy matrix for effective toughening and subsequently two layers of sisal fiber mat are incorporated to improve the mechanical and thermomechanical properties. Higher strength and modulus of the EMS modified epoxy composites reveals good interfacial bonding of matrix with the fibers. Fracture toughness parameters K_IC and G_IC are determined and found to be enhanced significantly. Notched impact strength is found to be higher for unmodified epoxy composite, whereas elongation at break is found to be much higher for modified epoxy blend. Dynamic mechanical analysis shows an improvement in the storage modulus for bioresin toughened composites on the account stiffness imparted by fibers. Loss modulus is found to be higher for EMS modified epoxy composite because of strong fiber–matrix interfacial bonding. Loss tangent curves show a strong influence of bioresin on damping behavior of epoxy composite. Strong fiber–matrix interface is found in modified epoxy composite by scanning electron microscopic analysis. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42699.     

Influence of maleated elastomer on filler dispersion,mechanical and antimicrobial properties of hybrid HDPE/clay/silver nanocomposites

This work analyses the effect of using ethylene-propylene-diene-monomer-grafted maleic anhydride (EPDM-g-MA) as compatibilizer to improve the interfacial properties and toughness of high-density polyethylene–organoclay–silver (HDPE/clay/silver) nanocomposites. EPDM-g-MA was reacted using ultrasound with a solution of AgNO₃ 0.04 M and ethylene glycol using ammonium hydroxide to obtain the silver ammonium complex. This silver-coated maleated EPDM was then melt mixed with HDPE and organoclay (Nanomer I28E) using a twin-screw extruder. Transmission electron microscopy (STEM) and X-ray diffraction (XRD) results confirmed the filler dispersion of both organoclay and silver nanoparticles into HDPE matrix when maleated EPDM was used. Both fillers were better dispersed and exfoliated by using this compatibilizer. The thermal stability enhancement of nanocomposites was confirmed using thermogravimetric analysis. Mechanical and antimicrobial properties demonstrated that better dispersed filler obtained with maleated EPDM enhanced the toughness and antimicrobial behaviour of HDPE/clay/silver hybrid nanocomposites. This confirmed that maleated EPDM was an efficient compatibilizer to obtain hybrid nanocomposites with enhanced properties to be used for several HDPE applications.