环氧化三元乙丙橡胶增韧聚对苯二甲酸丁二酯的脆韧转变

环氧化的三元乙丙橡胶(eEPDM)与聚对苯二甲酸丁二酯(PBT)共混可以使PBT共混体的缺口冲击强度获得很大的提高.当eEPDM橡胶浓度为24wt%时,PBTeEPDM共混体的缺口冲击强度是纯PBT的12倍.随着eEPDM含量的增加,在室温下PBTeEPDM共混体出现了明显的脆韧转变,其脆韧转变的临界粒子间距为0.49μm.橡胶的加入及含量的增加使PBT体系的脆韧转变温度(TBD)向低温移动,且PBTuEPDM与PBTeEPDM共混体脆韧转变温度的差随橡胶含量的增加而逐渐增大.扫描电镜照片表明,在橡胶组成相同的情况下,PBT基体中分散的eEPDM粒子明显小于未环氧化的EPDM粒子.且eEPDM橡胶的粒子间距(ID)也明显地低于uEPDM橡胶粒子的ID,这导致PBTeEPDM共混体系在室温下出现脆韧转变.     

Effects of nucleating agents on microstructure and fracture toughness of poly(propylene)/ethylene‐propylene‐diene terpolymer blends

The effects of nucleating agents (NAs) on fracture toughness of injection‐molded isotactic poly(propylene)/ethylene‐propylene‐diene terpolymer (PP/EPDM) were studied in this work. Compared with PP/EPDM blends without any NA, PP/EPDM/NA blends show very small and homogeneous PP spherulites. As we expected, PP/EPDM blends nucleated with β‐phase NA aryl amides compound (TMB‐5) present not only a significant enhancement in toughness but also a promotion of brittle‐ductile transition. However, the addition of α‐phase NA 1,3:2,4‐bis(3,4‐dimethylbenzylidene) sorbitol (DMDBS) has no apparent effect on the toughness of the blends. The impact‐fractured surface morphologies of such samples were analyzed via scanning electronic microscope (SEM). More detail work about the toughening mechanisms of elastomer and NA based on elastomer particles size and matrix crystal structures were carried out. Our results suggest that, besides the crystal structures of matrix, the elastomer particles size and size distribution plays an important role in controlling the toughening effect of nucleated PP/elastomer blends. The smaller the elastomer particles size and lower the polydispersity, the more apparent the synergistic toughening effect of NA and elastomer is. This investigation provides a fresh insight into the understanding of toughening mechanism of elastomers in PP blends and facilitates to the design of super toughened PP materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 46–59, 2009     

Damage Studies of Brittle-Ductile Transition in PP EPDM Blends

Damage zones of brittle-ductile (B-D) transition in PP/EPDM blends are studied in this paper. The contribution of crazing and shear yielding zones in damage zones to energy dissipation of blends was measured with computer image analysis (CIA) and the transition of shear yielding zone (A_(sh)) with rubber volume fraction (V_f) was also manipulated. Results showed that the B-D transition of impact strength of blends corresponded to the fracture mechanism in PP/EPDM blends, from matrix crazing to matrix shear yielding. In addition, two new parameters, density of energy dissipation for crazing zone (F_(cz)) and for shear yielding zone (F_(sh)), are first obtained in this paper. The value of F_(sh) is about four times larger than that of F_(cz) for PP/EPDM blends, which confirmed that the matrix shear yielding is a more effective way of energy dissipation in blends.     

界面作用对HDPE/POEg/CaCO_3三元复合材料韧性的影响

通过界面改性,制备了以CaCO3为核,马来酸酐接枝乙烯-辛烯共聚物弹性体(POEg)为壳的高密度聚乙烯(HDPEg)/弹性体(POE)/CaCO3的三元复合材料.由于“核-壳”结构的形成,弹性体和CaCO3表现出协同的增韧作用.同未经表面处理的CaCO3复合材料相比,在相同的CaCO3含量的情况下,表面处理的CaCO3由于与弹性体形成更强的界面粘结,使得三元复合材料的“脆-韧”转变发生在较低的弹性体含量.     

羟基不饱和脂肪酸改性纳米碳酸钙对聚丙烯微观形态和流变性能的影响

采用羟基不饱和脂肪酸,通过固相法对硬脂酸改性的工业纳米碳酸钙CCR进行表面改性制备了R-CCR,红外光谱(FTIR)显示改性剂已结合在碳酸钙表面.通过熔融共混法制备了聚丙烯(PP)/乙丙橡胶(EPDM)/纳米碳酸钙二元和三元复合材料.并利用扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察复合材料的微观形态,发现R-CCR的加入,使PP复合材料的拉伸断面出现明显的拉丝状结构和大面积的屈服变形,与PP/EPDM/CCR相比,PP/EPDM/R-CCR冲击断面的空穴明显增加并细化,R-CCR在PP基体中分散均匀,且界面模糊,与基体的相容性明显优于CCR.复合材料流变行为的研究表明R-CCR的加入,体系储存模量G′和损耗模量G″随频率的增加而增加,对损耗因子和复数粘度的影响不大;但PP/EPDM/R-CCR复合材料的表观粘度,明显低于PP/EPDM/CCR和纯PP,同时,剪切速率的增加可有效降低体系的表观粘度.力学性能表明,R-CCR对PP同时起到增韧和增强的效果.且R-CCR和EPDM对PP具有协同增韧的效果.在保持聚丙烯的模量和强度基本不变的前提下,大幅度的改善聚丙烯的韧性,同时加工性能保持不变.     

Effect of dispersed phase composition on morphological and mechanical properties of PET/EVA/PP ternary blends

Immiscible ternary blends of PET/EVA/PP (PET as the matrix and (PP/EVA) composition ratio = 1/1) were prepared by melt mixing. Scanning electron microscope results showed core‐shell type morphology for this ternary blend. Binary blends of PET/PP and PET/EVA were also prepared as control samples. Two grades of EVA with various viscosities, one higher and the other one lower than that of PP, were used to investigate the effect of components' viscosity on the droplet size of disperse phase. The effect of interfacial tension, elasticity, and viscosity on the disperse phase size of both binary and ternary blends was investigated. Variation of tensile modulus of both binary and ternary blends with dispersed phase content was also studied. Experimental results obtained for modulus of PET/EVA binary blends, showed no significant deviations from Takayanagi model, where considerable deviations were observed for PET/PP binary blends. Here, this model that has been originally proposed for binary blends was improved to become applicable for the prediction of the tensile modulus of ternary blends. The new modified model showed good agreement with the experimental data obtained in this study. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 251–259, 2010     

Compatibilized PP/EPDM/PA6 ternary blends: extended morphological studies

Polypropylene (PP)/polyamide6 (PA6)/ethylene propylene diene monomer (EPDM) (70/15/15) ternary polymer blends compatibilized with maleic‐anhydride‐grafted EPDM (EPDM‐g‐MA) were prepared by melt blending using a twin‐screw extruder (TSE) in different processing conditions (barrel temperature profile, screw speed, and mixing sequence). The microstructures of prepared ternary blends were studied and compared to the predictions of spreading coefficient, minimum relative interfacial energy (RIE), and dynamic interfacial energy phenomenological models. The observed morphologies were somehow different from the model predictions. Copyright © 2011 John Wiley & Sons, Ltd.     

iPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为

用DSC、~(13)C-NMR、SEM和WAXD等方法研究了IPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为。实验结果表明,EPDM与PE组分的相容性优于与PP组分的相容性,多数EPDM分子链段能够分布在PE组分中;EPDM含量为15％时,共混物相容性最好,SEM照片呈现晶体微区的互连或网络状结构;随EPDM含量增加,总结晶度X_c减小,其中PE组分结晶度X_(cE)有较大幅度地降低,PP组分结晶度X_(cp)基本没有变化,这可以根据EPDM和PE、PP之间相容性的差异以及PE、PP两组分在冷却过程中不同的结晶行为来解释。     

PP/EPDM/CaCO3三元复合材料的相结构及力学性能研究

采用以化学键合方式在CaCO3表面包覆上聚丙烯蜡和将改性后的CaCO3先与EPDM复合、再与PP复合的工艺,制备PP/EPDM/CaCO3三元复合材料,以期在PP基体材料中得到EPDM包裹CaCO3的相结构.通过测量三元复合体系中各组分的表面张力,计算各可能组分对之间的界面张力和黏结功,分析三元复合体系中可能的相结构.热力学计算结果表明,三元复合体系中既存在以EPDM为壳、CaCO3为核的"核壳结构",又存在CaCO3与EPDM各自独立分散在PP基体中的结构.电镜照片进一步揭示,在PP/EPDM/改性CaCO3三元复合体系与PP/EPDM/未改性CaCO3三元复合体系中,这两种相结构的比例是不同的,在前者中以核壳结构为主.CaCO3表面性质的不同是产生这一差别的原因.由于这一结构差别的存在,PP/EPDM/改性CaCO3三元复合体系比PP/EPDM/未改性CaCO3三元复合体系具有更好的力学性能.当EPDM用量为8 phr、改性CaCO3用量为15 phr时,三元复合体系的冲击强度达14.25 kJ/m2,是纯PP的3.17倍.     

Shear-induced crystallization in phase-separated blends of isotactic polypropylene with ethylene-propylene-diene terpolymer

The compatibility between isotactic polypropylene(i PP) and ethylene-propylene-diene terpolymer(EPDM) in the blends was studied. SAXS analysis indicates that i PP and EPDM phases in the binary blend are incompatible. Isothermal crystallization behaviors of i PP in phase-separated i PP/EPDM were studied by in situ POM equipped with a Linkam shear hot stage. It was found that typical spherulites of i PP were formed both in neat i PP and in i PP/EPDM blends. The radial growth rate(d R/dt) of spherulites of i PP in the blend was not influenced by EPDM phases. Further investigations on isothermal crystallization of i PP in i PP/EPDM after shear with a fixed shear time showed that the crystallization rate of i PP in the blends increased with increasing shear rates, whereas, the crystallization rate was much lower than that of neat i PP. WAXD results showed that ?-crystal i PP was formed in neat i PP as well as in i PP/EPDM blends after shearing and the percentage of ?-crystal bore a relationship to the applied shear rate. The presence of EPDM resulted in lower percentage of ?-crystal in the blends than that in neat i PP under the same constant shear conditions. SAXS experiments revealed that shear flow could induce formation of oriented lamellae in i PP and i PP in the blends, and the presence of EPDM led to a reduced fraction of oriented lamellae.     

iPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为

 用DSC、¹³C-NMR、SEM和WAXD等方法研究了IPP/HDPE/EPDM三元共混体系的组分分布、相容性和结晶行为。实验结果表明,EPDM与PE组分的相容性优于与PP组分的相容性,多数EPDM分子链段能够分布在PE组分中;EPDM含量为15％时,共混物相容性最好,SEM照片呈现晶体微区的互连或网络状结构;随EPDM含量增加,总结晶度X_c减小,其中PE组分结晶度X_cE有较大幅度地降低,PP组分结晶度X_cp基本没有变化,这可以根据EPDM和PE、PP之间相容性的差异以及PE、PP两组分在冷却过程中不同的结晶行为来解释。     

Ductile–brittle‐transition phenomenon in polypropylene/ethylene‐propylene‐diene rubber blends obtained by dynamic packing injection molding: A new understanding of the rubber‐toughening mechanism

For a more complete understanding of the toughening mechanism of polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, dynamic packing injection molding was used to control the phase morphology and rubber particle orientation in the matrix. The relative impact strength of the blends increased at low EPDM contents, and then a definite ductile–brittle (D–B) transition was observed when the EPDM content reached 25 wt %, at which point blends should fail in the ductile mode with conventional molding. Wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to investigate the shear‐induced crystal structure, morphology, orientation, and phase separation of the blends. WAXD results showed that the observed D–B transition took place mainly for a constant crystal structure (α form). Also, no remarkable changes in the crystallinity and melting point of PP were observed by DSC. The highly oriented and elongated rubber particles were seen via SEM at high EPDM contents. Our results suggest that Wu's criterion is no longer valid when dispersed rubber particles are elongated and oriented. The possible fracture mechanism is discussed on the basis of the stress concentration in a filler‐dispersed matrix. It can be concluded that not only the interparticle distance but also the stress fields around individual particles play an important role in polymer toughening. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2086–2097, 2002     

相容剂对PP/POE共混体系脆韧转变行为的影响

采用熔融挤出法制备了不同相容剂含量的PP/POE共混体系,测试了不同体系的脆韧转变温度、热性能和力学性能.结果表明,乙烯-丙烯多嵌段共聚物相容剂的加入降低了PP/POE共混物的脆韧转变温度,提高了共混物的韧性.AFM和STEM照片显示相容剂的加入减小了橡胶分散相的临界粒子间距,PP和POE在两相界面结合处相互扩散或渗透,实现了POE弹性体在PP树脂中合适的尺度分布以及良好的形态分散.当相容剂含量达到10％时,POE分散相尺寸细小均匀,分散相粒子粒径为0.54μm,粒子间距为0.1 μm,PP结晶链段更多地插入到弹性体内部,弹性体POE分散相形成明显的“硬核-软壳”结构.DSC曲线中结晶峰和熔融峰的变化说明适量的相容剂对于材料结晶度的提高具有一定的促进作用.力学性能测试结果可以看出相容剂的加入在提高材料韧性,降低其脆韧转变温度的同时也保持了材料的刚性性能.     

Rheological properties of ground tyre rubber based thermoplastic elastomeric blends

This work analyses the rheological behaviour of thermoplastic elastomeric blends (TPE) based on ground tyre rubber (GTR), more specifically the rheological behaviour of binary and ternary polypropylene (PP) based blends with different rubber materials: an ethylene propylene diene monomer (EPDM), an ethylene propylene rubber (EPR) and GTR. The study was developed under steady-shear rate conditions by capillary rheometry at three different temperatures. Time–Temperature Superposition Principle (TTSP) was applied to the viscosity curves using a temperature dependent shift factor, allowing the construction of master curves for the analysed blends. The Cross-WLF model was used to predict the rheological parameters, giving numerical results for viscosity similar to the experimental data. GTR increased the blends viscosity. EPR showed rheological behaviour similar to PP, and EPDM presented higher power law behaviour. Pseudoplastic behaviour was observed for all the analysed blends. Incorporation of GTR in TPE blends for injection moulding purposes was found to be a feasible strategy to upcycle this type of potentially wasted material.     

Interaction of two phases in PP/EPDM polymer blend probed by positron annihilation: CONTIN analysis

Positron annihilation lifetime measurements were performed on pure polypropylene (PP), ethylene-propylene-diene monomer (EPDM) rubber, and their blends PP/EPDM with a series of EPDM volume fraction ϕ (= 10–40%). A numerical Laplace inversion technique (i.e., CONTIN algorithm), was employed to obtain the probability distribution functions (PDF) of free-volume radius. We observed that, first, the average free-volume radius in PP/EPDM blends is generally same as that in PP and is much smaller than that in EPDM. Second, the standard deviation σ_R or the width of the free-volume radius PDF in the blend decreases with ϕ in the region of ϕ = 10ndash;30%, and it increases when ϕ increases from 30% to 40%. The difference in the σ_R of the blend and the calculated value σ^c _R according to the simple-mixing rule of PP and EPDM is interpreted by the existence of the two-phase interaction (i.e., the residual thermal pressure and shear stress between PP and EPDM phases in the PP/EPDM blends). The correlation between σ_R, which indicates the interaction of two phases, and the impact strength of PP/EPDM blends was found and discussed. © 1996 John Wiley & Sons, Inc.     

Preparation of fully cross‐linked CNBR/PP‐g‐GMA and CNBR/PP/PP‐g‐GMA thermoplastic elastomers and their morphology,structure and properties

Binary CNBR/PP‐g‐GMA and ternary CNBR/PP/PP‐g‐GMA thermoplastic elastomers were prepared by reactive blending carboxy nitrile rubber (CNBR) powder with nanometer dimension and polypropylene functionalized with glycidyl methacrylate (PP‐g‐GMA). Morphology observation by using an atomic force microscope (AFM) and TEM revealed that the size of CNBR dispersed phase in CNBR/PP‐g‐GMA binary blends was much smaller than that of the corresponding CNBR/PP binary blends. Thermal behavior of CNBR/PP‐g‐GMA and CNBR/PP blends was studied by DSC. Comparing with the plain PP‐g‐GMA, T_c of PP‐g‐GMA in CNBR/PP‐g‐GMA blends increased about 10 °C. Both thermodynamic and kinetic effects would influence the crystallization behavior of PP‐g‐GMA in CNBR/PP‐g‐GMA blends. At a fixed content of CNBR, the apparent viscosity of the blending system increased with increasing the content of PP‐g‐GMA. FTIR spectrum verified that the improvement of miscibility of CNBR and PP‐g‐GMA was originated from the reaction between carboxy end groups of CNBR and epoxy groups of GMA grafted onto PP molecular chains. Comparing with CNBR/PP blends, the tensile strength, stress at 100% strain, and elongation at break of CNBR/PP‐g‐GMA blends were greatly improved. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1042–1052, 2004     

Morphology development and phase inversion during dynamic vulcanisation of EPDM/PP blends

Morphology development and phase inversion were investigated during dynamic vulcanisation of ethylene–propylene–diene terpolymer (EPDM)/polypropylene (PP) blends. The effects of viscosity ratio and cross-linking reactions were also addressed. EPDM/PP blends were dynamically vulcanised in a Haake batch mixer using resole and SnCl₂ as cross-linking agents. The morphology development and cross-linking degree with reaction time were followed by morphology analysis (SEM and TEM) and measurement of EPDM gel content, respectively. For the same reaction time, it was found that the EPDM gel content decreased when the low-molecular-weight EPDM was used. As a result, the morphological development was delayed and the phase-inversion point was shifted to higher reaction times, allowing us to monitor morphological development during a thermoplastic vulcanisate (TPV) preparation. Using the low-molecular-weight EPDM and increasing the PP viscosity accelerated the morphological development, shifting phase-inversion to lower reaction times. While blend composition influenced final TPV morphology, it had a minor effect on the mechanism of morphological development. A correlation between cross-linking degree and morphology development was established. The results obtained allowed to propose a mechanism of morphology development during dynamic vulcanisation of the EPDM/PP blends, including phase inversion.     

Rheology and phase structure of PP/EPDM/SiO2 ternary composites

In this article, the rheological properties of polypropylene (PP)/ethylene-propylene-diene terpolymer (EPDM)/silicon dioxide (SiO₂) ternary composites were systematically investigated. Two kinds of nano-SiO₂ particles (with hydrophobic (denoted as A-SiO₂) or hydrophilic (denoted as B-SiO₂)) as well as two processing methods (one-step or two-step) were first employed to prepare PP/EPDM/SiO₂ ternary composites. Then the deep mixing and morphology evolution of polymer composite with mixing time were assessed by rheological method, on the focus of formation of filler-network, and compared with scanning electron microscopy (SEM) observations. Linear viscoelastic behavior was observed for PP/EPDM and PP/SiO₂ binary system, showing no evidence of the formation of filler-network structure. However, a solid-like rheological behavior, which was attributed to the formation of the filler-network structure as confirmed by SEM observation, could be observed in some PP/EPDM/SiO₂ ternary systems, depending on the SiO₂ surface property, processing method and EPDM content. It seemed that SiO₂ with hydrophilic surface was necessary for the formation of filler-network in PP/EPDM/SiO₂ ternary system. Besides, two-step processing method made the solid-like behavior occurred at an earlier stage compared with that of a one-step processing method, also, the higher elastomer content facilitated the formation of the filler-network structure. The results were in good agreement with those reported in our previous publications [Yang H, Zhang Q, Guo M, Wang C, Du R, Fu Q. Polymer 2006;47:2106] [Yang H, Zhang X, Qu C, Li B, Zhang L, Zhang Q, et al. Polymer 2007;48:860].     

A New Criterion for Brittle-Ductile Transition of Polymer Blends

The T_c criterion was first used by S. Wu for characterizing the brittleductile (B-D) transition of N6/EPDM blends. But in this paper, a new criterion which is based on the stress analysis of blends is proposed to characterize the B-D transitions of blends, namely, A criterionV_(fc) and d_c are the critical volume fractions and particle size of dispersed particles in blends, respectively. For given blends, A is independent of the morphology of dispersed phase and is only the characteristic parameter of matrix. The B-D transitions of different blends, including polar N6/EPDM blends, nonpolar PP/EPDM blends and PE/CaCO_3 composites, were manipulated with A criterion and satisfactory results were obtained. In addition, a new master curve for the impact strength of PP/EPDM blends versus V_f~2/d was obtained. The results showed that A criterion is more suitable than T_c criterion for characterizing the B-D transition of blends.     

Investigation of phase morphology of incompatible polyethylene/nylon 6 blends containing EPDM-based functionalized compatibilizers

Graft copolymer and graft terpolymer were prepared by solution grafting of maleic anhydride (MAH) or acrylonitrile (AN) alone and mixture of MAH and AN on to ethylene–propylene–diene terpolymer (EPDM) using benzoyl peroxide (BPO) as an initiator. The resulting EPDM-g-MAH, EPDM-g-AN and EPDM-g-(MAH-co-AN) have been used to obtain a binary blend of Nylon 6/functionalized EPDM and a ternary blend of polyethylene/Nylon 6/functionalized EPDM by melt blending. The effects of the nature and the amount of the grafted species on the phase morphology, crystallization behavior and mechanical properties of the blends were characterized through scanning electron microscopy, optical microscopy, infrared spectroscopy and using a dynamic mechanical analyzer. From the morphological study, it can clearly be seen that the presence of the functionalized EPDMs in these blends resulted in an improvement of the dispersion degree in incompatible polyethylene/Nylon 6 blends.