Phase morphology and toughening mechanism of polyamide 6/EPDM-g-MA blends obtained via dynamic packing injection molding

One of the most important findings in polymer-toughening is known as the critical matrix ligament thickness (τ_c) theory, which is directly related to both rubber concentration and average size of particles. All these studies assume that rubber particles are spherical and randomly distributed in the matrix. Rubber particles may be stretched and oriented along the shear flow direction in real processing. In this paper the effect of stretched and oriented rubber particles on the impact strength of PA6/EPDM-g-MA blends have been studied via dynamic packing injection molding (DPIM). The impact strength of specimens obtained by DPIM was found substantially increase at all the blends investigated, compared with the one obtained via conventional injection molding. Particularly, more than 30 kJ m⁻² increase of the impact strength was observed for specimens with a higher rubber content (more than 15 wt%). SEM results showed a remarkably decrease of rubber particle size and more uniform dispersion of the dynamic molded specimens. This can be attributed to the shear induced reaction at the interface between polyamide 6 and EPDM-g-MA during the packing stage. The rubber particles were found stretched along the melt shear flow direction when it is content above 15 wt%. A master curve can be also constructed by plotting the impact strength versus the inter-particle distance, indicating that Wu's criterion still works for blends with stretched and oriented rubber particles when the crack propagation direction is perpendicular to the orientation direction of rubber particles. The observed higher impact strength in dynamic specimens could be due to, in part, the enhanced flexural stiffness, which will absorb more energy during impact process when the fracture of IZOD bars is incomplete, but more importantly due to the existence of the stretched and oriented rubber particles, which are more efficient in slowing the velocity of crack propagation and thus cause higher impact resistance when the fracture propagation direction is perpendicular to the rubber oriented direction.     

Orientation effects on the deformation and fracture properties of high‐density polyethylene/ethylene vinyl acetate (HDPE/EVA) blends

In this paper, the tensile deformation and fracture toughness of high‐density polyethylene (HDPE)/ethylene vinyl acetate (EVA) blends, obtained by dynamic packing injection moulding, have been comprehensively investigated in different directions of rectangle samples, including longitudinal, latitudinal and oblique directions relative to the flow direction. Two kinds of EVA were used with VA content 16 wt% (16EVA) and 33 wt% (33EVA) to control the interfacial interactions. The results indicate that molecular orientation and interfacial interaction play very important roles to determine the tensile behaviour and fracture toughness. Biaxial‐reinforcement of tensile strength was seen for HDPE/16EVA blends but only uniaxial‐reinforcement was observed for HDPE/33EVA blends. The difference is caused by the different interfacial interactions as highlighted by the peel test, scanning electron microscopy (SEM) observation as well as theoretical evaluation. Very high impact strength, decreasing with increasing EVA content, was observed when the fracture propagation is perpendicular to the shear flow direction, while a low impact strength, increasing slightly increasing with EVA content, was seen when the fracture propagation is parallel to the shear flow. The fracture of oblique samples is always along the flow direction instead of along the impact direction or tensile direction. The tensile behaviour and fracture toughness are discussed on the basis of the formation of transcrystalline zones, orientation of EVA particles and matrix toughness of HDPE in different directions. Copyright © 2004 Society of Chemical Industry     

动态保压注射成型技术对PA6/EPDM-g-MA 共混物相形态与力学性能的影响

采用动态保压注塑成型技术来控制分散相相形态和橡胶粒子在基体中的取向排列.纯尼龙,动态样与静态样具有相同的冲击强度.在加入橡胶后,动态样与静态样的冲击强度变化趋势基本一致,在橡胶含量为20%t时,体系完成脆韧转变冲击强度达到最大,在橡胶含量为30%和40%时冲击强度又下降.但与静态样相比,当橡胶含量为10%t时,动态样与静态样的冲击强度一致,而当橡胶含量超过10%时,动态样的冲击强度较静态样高.结合平行于熔体流动方向的SEM照片,在橡胶含量为10%时,动态样中的橡胶粒子与静态样一样并未被拉长与取向,而在橡胶含量超过10%时,动态样剪切层中的橡胶粒子被拉长且沿熔体流动方向取向.实验表明,在改善共混物界面相容性的基础上,适当的低剪切应力场能进一步提高橡胶分散相对冲击强度的贡献.     

Three-dimensional phase morphologies in HDPE/EVA blends obtained via dynamic injection packing molding

The formation of phase morphology of injection molded HDPE/EVA blends, under the effect of shear stress, has been investigated in detail. The shear stress was induced by dynamic packing injection molding, by which a specimen is forced to move repeatedly in the model by two pistons that move reversibly with the same frequency during cooling. Two kinds of EVA with VA content 16 wt% (16EVA) and 33 wt% (33EVA) were used to investigate the effect of interfacial tension. The phase morphology was viewed both parallel and perpendicular to the shear flow direction, so one can get an overall three-dimensional phase morphology. Low shear stress provided by the pistons has a substantial effect on the phase morphology along the flow direction but is insignificant in the direction perpendicular to the flow direction. Generally, a much elongated and layer-like structure is formed along the flow direction, and spherical droplet-like morphology is formed perpendicular to the flow direction, and the degree of deformation of rubber particles also depends upon their size and elasticity as well as on the interfacial properties between matrix and dispersed phase. For static samples of HDPE/16EVA blends (without shearing), only droplet morphology is formed as 16EVA content increases from10 to 40 wt%. However, under the effect of shear stress (dynamic samples), both droplet and cylinder morphologies can be formed depending on the volume ratio. For static samples of HDPE/33EVA blends, not only droplet, but also cylinder and co-continuous morphology (perpendicular to flow direction) can be formed depending on the volume ratio. For dynamic samples of HDPE/33EVA blends, droplet, cylinder and co-continuous network (co-continuous in both parallel and perpendicular to flow direction) can be formed under the effect of shear stress. The formation of phase morphology is discussed based on interfacial interaction, viscosity ratio, shear stress, and phase inversion.     

Fracture behavior of polypropylene/ ethylene- diene-terpolymer blends : Effect of temperatures,notch radius and rubber content

The mechanical fracture and ductile-brittle transition (DBT) behavior, hysteresis phenomenon and the plastic zone size of polypropylene (PP) / ethylene-propylene-diene terpolymer (PP/EPDM) blends were investigated by varying EPDM content and notch radius under different temperatures. An increase in test temperature or rubber content in the PP/EPDM blend results in lower yield stress and Young's modulus. The ductile-brittle transition temperature (DBTT) of the notched impact strength decreases with the increase of the EPDM content. However, the DBTT is fairly independent of the notch radius. SEM morphologies of the fracture surfaces indicate that two separate modes, localized and mass shear yielding, work simultaneously in these blends. The plane-strain localized shear yielding dominates the brittle failure at lower temperatures, whereas the plane stress mass shear yielding dominates the ductile fracture at higher temperatures. The presence of EPDM rubber decreases the yield stress of the PP/EPDM blend due to the overlapping stress fields of adjacent particles, resulting in higher hysteresis energy. The relationships among the test temperature, hysteresis loss energy and the size of plastic zone are discussed in detail.     

Study on the phase structures and toughening mechanism in PP/EPDM/SiO2 ternary composites

In this paper, EPDM rubber and nano-SiO₂ particles were employed to modify PP simultaneously. Our goal was to control the distribution and dispersion of EPDM and nano-SiO₂ particles in PP matrix by using an appropriate processing method and adjusting the wettability of nano-SiO₂ particles toward PP and EPDM, so as to achieve a simultaneous enhancement of toughness and modulus of PP. With regard to this, two kinds of nano-SiO₂ particles (with hydrophilic or hydrophobic) as well as two processing methods (one-step or two-step) were employed to prepare PP/EPDM/SiO₂ ternary composites. A unique structure with the majority of EPDM particles surrounded by SiO₂ particles was first observed by using hydrophilic SiO₂ and two-step processing method, resulting in a dramatically increase of Izod impact strength as the rubber content in the range of brittle-ductile transition (15-20 wt%). The observation that poor adhesion and poor compatibility between particles and PP matrix could result in a significant increase in Izod impact strength was unusual and needed further investigation. This could be tentatively understood as a consequence of the overlap of the ‘stress volume’ between EPDM and SiO₂ particles due to the formation of the unique structure. Our work provided a deep understanding of the toughening mechanism and a new way for the preparation of high performance polymer composites.     

Mechanical properties of wood-fiber/toughened isotactic polypropylene composites

This study investigates the mechanical properties of wood-fiber/toughened PP composite modified by physical blending with an EPDM rubber to improve impact toughness. Wood-fiber thermoplastic composites were prepared with a modified PP matrix resin, employing high shear thermokinetic compounding aided with maleated PP for the fiber dispersion. The addition of EPDM improved the impact toughness, while it reduced stiffness and strength properties. To compensate the non-plane strain fracture toughness, the specimen strength ratio (R_sb) was adopted as a comparative measure of fracture toughness. The strength ratio increased with the addition of EPDM, while it decreased with increasing wood-fiber concentration. The work of fracture increased with EPDM level except at large wood-fiber concentration. The effectiveness of the impact modification was assessed with the balance between tensile modulus and unnotched impact energy as a function of wood-fiber concentration. EPDM rubber modification was moderately effective for wood-fiber PP composites. The examination of fracture surfaces showed twisted fibers, fiber breakage, and fiber pull-out from the matrix resin.     

Effect of dynamic crosslinking on impact strength and other mechanical properties of polypropylene/ethylene‐propylene‐diene rubber blends

The deformation and fracture behavior of several dynamic vulcanizate blends of isotactic polypropylene with ethylene‐propylene‐diene rubber (EPDM) was examined and compared with those of uncrosslinked blends of PP/EPDM. These blends were prepared by melt mixing in an internal mixer at 190°C in a composition range of 10–40 wt % EPDM rubber. The variation in yield stress, the strength of fibrils of the craze, and the number density of the EPDM rubber domains (morphology fixation) that are dominant factors for enhancing interfacial adhesion and toughness in dynamic vulcanizate blends were evaluated. The ductility and toughness of these materials were explained in light of the composition between crack formation and the degree of plastic deformation through crazing and shear yielding. The physicomechanical properties including the hardness, yield stress, Young's modulus, percentage elongation, impact strength, flexural strength, and flexural modulus of dynamic vulcanized blends were found to be consistent and displayed higher values compared with uncrosslinked blends. The nucleation effect of the crosslinked particles and the decrease of crystallinity of the EPDM rubber were also considered to contribute to the improvement in the impact strength. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2089–2103, 2000     

Skin-Core morphology and failure of injection-molded specimens of impact-modified polypropylene blends

The structure-property relationship as well as the failure phenomena of injection molded polypropylene (PP) blends modified with ethylene/propylene/diene terpolymer (EPDM) and thermoplastic polyolefinic rubber (TPO) were investigated. Single and double-gated tensile bars were injection molded by different Injection speeds. Microscopic studies on the failure behavior of knit lines were carried out using microtomed sections taken from the doublegated specimens. It was found that during injection molding, a skin-core morphology is formed in both the continuous PP matrix as well as in the modified PP blends containing rubber particles of various deformation. The characteristics of the latter are in agreement with those described by the Tadmor flow model. The skin consists of a thin pure PP layer, whereas the subsurface layer contains more or less elongated rubbery particles due to the elongational flow at the wall. The deformation of the rubbery particles decreases, but their concentration increases with increasing distance from the skin towards the core. The deformed particles are oriented tengentionally to the flow front profile. Failure during tensile and tensile impact loading is initiated in the shear zone along the skin-core boundary. This zone has a transcrystalline character and favors the formation of crazing. Final fracture of the bars depends, however, on how crazing and shear yielding simultaneously interact. Their interaction is a function of the average particle size of the dispersed phase. Above an average particle size of 0.6 μm, crazing is prevented by shear bands. For injection molding of PP/rubber blends a moderate injection speed is recommended, if the melt viscosities of the components are closely matched. In this way a pronounced dispersion gradient of the rubber particles across the plaque thickness is avoided. However, for the blends modified with rubber of high viscosity ratio and greater melt elasticity, use of higher injection speed is advantageous. Here, the higher shear stress field decreases the average particle size taken into the direction perpen dicular to the lead, since the cross section of the stronger deformed particle decreases.     

Super polyolefin blends achieved via dynamic packing injection molding: the morphology and mechanical properties of HDPE/EVA blends

As a part of long-term project aimed at super polyolefin blends, in this work, we report the mechanical reinforcement and phase morphology of the blends of high-density polyethylene (HDPE) and ethylene vinyl acetate (EVA) achieved by dynamic packing injection molding. The shear stress (achieved by dynamic packing injection molding) and interfacial interaction (obtained by using EVA with different VA content) have a great effect on phase morphology and thus mechanical properties. The super HDPE/EVA blends having high modulus (1.9–2.2 GPa), high tensile strength (100–120 MPa) and high impact strength (six times as that of pure HDPE) have been prepared by controlling the phase separation, molecular orientation and crystal morphology of the blends. The phase inversion was also found to shift towards lower EVA content under shear stress. The enhancement of tensile strength and modulus originates from the formation of oriented layer, while the high impact strength is related to shear induced phase morphology. DSC studies indicated that the shish kebab crystal structure that also contributes to the enhancement of tensile strength is formed in the oriented layer. The dramatic improvement of impact strength may result from the formation of microfibers and elongated EVA particles along the flow direction. Wu's toughening theory was found non-applicable for the elongated and oriented rubber particles, and a brittle–ductile–brittle transition was observed with increasing EVA content.     

Influence of nanoclay on adhesion of EPDM vulcanizate

The influence of unmodified clay, Cloisite Na⁺ on adhesion between prevulcanized EPDM rubber and unvulcanized EPDM rubber containing nanoclay was investigated using 180° peel test. The rubber showed improvement in peel strength with increasing clay concentration up to 4 phr, beyond which it decreased. A maximum of 51% improvement in peel strength was obtained for 4 phr Cloisite Na⁺. This was attributed to enhanced tensile strength, monomer friction coefficient, marginal improvement of polarity and micro-roughness of the clay filled rubber. At higher clay loading (8 phr), the peel strength reduced due to formation of boundary layer of Zn-stearate, accelerators and clay on the outermost surface, diffusion of the fewer rubber chains, agglomeration of the clay particles and increased modulus of the rubber.     

PP/EPDM/纳米弹性体粒子三元共混体系的脆韧转变

研究了PP／EPDM／纳米弹性体粒子(ENP)三元共混体系的脆韧转变行为。结果表明，与PP／EPDM二元共混物相比，三元共混物的脆韧转变可以在EPDM质量分数较低的情况下发生；在橡胶总质量分数相同的情况下，三元共混物有更高的冲击强度，拉伸强度有一定提高。从脆断样条的扫描电镜照片观察到，在相同EPDM质量分数下，PP／EPDM／ENP三元共混物中的EPDM粒子明显细化，分布均一，粒子间距减小，这是脆韧转变提前的原因。     

Evaluation of the role of devulcanized rubber on the thermomechanical properties of expanded ethylene-propylene diene monomers composites

Various amounts of both devulcanized (DR) and non-devulcanized (NDR) recycled rubber were melt compounded with a virgin ethylene-propylene diene monomer (EPDM) rubber. The resulting compounds were then expanded by using azodicarbonamide. The role played by the presence of DR or NDR on the thermomechanical properties of the obtained materials was evaluated. Electron scanning microscope micrographs highlighted that DR particles were better encapsulated within the EPDM matrix with respect to the corresponding NDR ones. Moreover, a better interfacial adhesion was observed with DR, probably due the re-vulcanization process in which the free crosslinking sites that typically characterize DR could form linkages with the EPDM matrix. Tensile impact behavior of expanded EPDM/recycled rubber blends highlighted a strong improvement of the normalized total absorbed energy, of the normalized impact strength and of the elongation at break with respect to the neat expanded EPDM for all the investigated compositions, and especially with a DR content of 20 wt%. The preparation of expanded EPDM containing considerable amounts of devulcanized rubber was, therefore, demonstrated to be a practical route to reduce the costs and improve the properties and the environmental sustainability of rubber products.     

Shrinkage and mechanical properties of unsaturated polyester reinforced with clay and core–shell rubber

Glassy unsaturated polyester (UP) resin was reinforced using an organically modified montmorillonite (OMMT) and toughened with core?Cshell rubber (CSR) particles. The nanostructure, morphology, and deformation mechanism of composite specimens were studied by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and reflected optical microscopy (ROM). An intercalated nanostructure with partial exfoliation was observed in the UP reinforced by various amounts of OMMT. Locally clustered but globally good CSR particle dispersion in the UP matrix was evident in UP toughened with 5 and 10 wt% CSR particles. Simultaneous presence of OMMT and CSR particles in UP/OMMT/CSR hybrid composites was found to cause partial phase separation with bigger rubber particle agglomerates and lower clay-intergallery height increase. The effects of OMMT and CSR contents on volume shrinkage, impact fracture energy, fracture toughness, and compressive yield strength of UP were investigated. The introduction of OMMT of up to 3?wt% into the UP matrix lowered volume shrinkage to some extent, while further addition increased the shrinkage slightly. In the hybrid nanocomposites, the volume shrinkage decreased to a minimum level of 5.2?% with increases in OMMT level. The impact fracture energy of UP improved with increasing the OMMT level of up to 3?wt%, whereas its further addition decreased the impact fracture energy slightly due to the clay particle agglomeration. The hybrid composites with OMMT level below 3?wt% showed higher impact fracture energy compared to the reinforced UP specimens with the same OMMT levels. Interestingly, a synergism in the fracture toughness (K _IC) was observed in the hybrid composite containing 1?wt% OMMT and 10?wt% CSR particles. The presence of OMMT as reinforcement in the hybrid composites could compensate the lowering of the compressive yield strength caused by low-modulus CSR particles. The clay?Crubber particle interaction in the hybrid systems seems to increase the threshold of shear deformation of the UP matrix to some extent.     

基体性质对聚丙烯力学性能的影响

采用过氧化二异丙苯(DCP)作为降解剂,以聚丙烯(PP)为基体,以三元乙丙橡胶(EPDM)为增韧剂,研究了EPDM对降解PP/EPDM共混物力学性能的影响,并利用扫描电子显微镜(SEM)对共混体系微观形貌进行了表征。熔体质量流动速率结果表明:随着EPDM质量分数从10%增加到30%时,对应共混物的熔体质量流动速率明显下降,从14.8 g/10 min下降到10.8 g/10 min。随着EPDM用量的增加,共混物的冲击强度明显增大,从30.06J/m增长到90.26 J/m,拉伸强度有所减小。SEM照片显示,随着EPDM用量的增加,共混物中分散相的尺寸明显增大。因为EPDM含量的增加,导致分散的橡胶粒子产生"聚并",从而分散相的相区尺寸增大。     

Mechanical properties of polyketone terpolymer/rubber blends

Blends of aliphatic polyketone terpolymer and a core-shell rubber (CSR) were melt processed with varying CSR concentration of 0-40 wt%. The obtained morphology was of finely dispersed CSR particles in the polyketone matrix. The thermal properties of the matrix polymer remained unaffected by the addition of the CSR phase. The crystallinity remained constant at 35 wt% and the melting temperature was not changed. The tensile modulus and yield stress were decreased by the addition of the rubber phase to the aliphatic polyketone polymer. The deformation was strongly delocalised with increasing CSR content. The temperature development during fracture was also strongly reduced with increasing rubber concentration. The CSR phase was found to toughen the aliphatic polyketone matrix very effectively, the brittle to ductile transition temperature was lowered from 90 to −40 °C with the highest rubber concentration (40 wt%). Cavitation experiments revealed that the macroscopic cavitation strain remained constant with increasing rubber content. A study of the deformation zone below the fracture surface showed that voids were produced by cavitation of the rubber phase. The voids were strongly deformed by the plastic deformation of the matrix polymer. At high strain rates a relaxation layer was found below the fracture surface, where the voids were no longer present. This relaxation zone was found to be due to the adiabatic temperature rise of the material during fracture at high strain rates.     

Adding EPDM Rubber Makes Poly(propylene) Brittle

To better understand the mechanism of polymer‐toughing with rubber and the critical matrix ligament thickness theory developed by Wu, the rubber particle shape was controlled as elongated and oriented instead of spherical in PP/EPDM blends via dynamic packing injection molding. For the first time, the brittle‐ductile‐brittle transition was observed with increasing rubber content. This result clearly indicates that Wu's theory applies only for cubic or spherical particles but not for elongated and oriented particles. The higher stress concentration will be expected at the tip, which causes blends to fail in brittle mode. More work is needed to verify this expectation.     

Structure-property relations of 55 nm particle-toughened epoxy

55-nm rubber particles significantly toughened two epoxy systems without loss of Young’s modulus, tensile strength and glass transition temperature. Transmission Electron Microscopy (TEM) showed that the nanoparticles are uniformly dispersed in matrix and have blurred interface with epoxy. 5 wt% rubber nanoparticles increased the critical strain energy release rate (G_1c) of Jeffamine D230 (J230)-cured epoxy from 175 J/m² to 1710 J/m², while the 10 wt% increased G_1c of diaminodiphenyl sulfone (DDS)-cured epoxy from 73 J/m² to 696 J/m². This is explained by comparing the surface-surface interparticle distance and total particle surface of nanocomposites with those of composites. The higher the matrix stiffness, the more nanoparticles needed for toughening. Although the 10 wt% J230-cured nanocomposite showed a 50% larger size of stress-whitened zone than the 5 wt% J230-cured nanocomposite, the 5 wt% nanocomposite showed a higher toughness. These nanoparticles were found to pose barriers to the vibration of crosslinked matrix molecules, leading to higher glass transition temperatures. While the matrix shear banding caused by nanoparticle expansion and growth is the major toughening mechanism for the J230-cured nanocomposites, the matrix plastic void growth and deformation are most probably the major mechanisms for the DDS-cured system. Under tensile loading, the nanoparticles in the DDS-cured epoxy created fibrils of 100-200 nm in diameter and 3-5 μm in length. TEM analysis in front of a subcritically propagated crack tip showed a number of voids of 30-500 nm in diameter in the vicinity of the crack, implying that rubber nanoparticles expanded, grew and deformed under loading. Unlike conventional epoxy/rubber composites in which all of the rubber particles in the crack front cavitated under loading, only a portion of the nanoparticles in this study expanded to create voids. Huang and Kinloch’s model developed from composites was found not fit well into these nanocomposites.     

Synthesis and characterization of ABS resin using in situ transferring from emulsion to suspension polymerization

A novel approach based on an emulsion in situ suspension polymerization process for synthesizing poly(acrylonitrile–butadiene–styrene) (ABS) resin is reported. Experimental results show that the reaction system can be transformed from an emulsion state to a suspension polymerization state steadily with the content of polybutadiene (PB) in the range 0–15 wt% in ABS resin. When PB is replaced by poly(styrene‐co‐butadiene) with the content of rubber particles being kept below 20 wt%, the emulsion system can be easily transferred to the suspension polymerization state through a process of latex coagulation in the forward direction, which means that the emulsion solution was dripped slowly into the suspension reaction system in the presence of coagulating agent. The dispersion status of the rubber particles in the ABS resin was studied using transmission electron microscopy, which indicated that the rubber particles were in a dispersed state in a continuous matrix of poly(styrene‐co‐acrylonitrile) when the content of rubber particles was below 20 wt%. The mechanical properties of the ABS resins obtained are as follows: elongation at break, 9.4–45.7%; yield tensile strength, 35.1–42.2 MPa; impact strength, 98.2–116.3 J m^?1. Copyright © 2006 Society of Chemical Industry     

Influence of sample thickness on fracture behaviour of a polyketone and a polyketone-rubber blend

The influence of sample thickness on the fracture behaviour of an aliphatic polyketone and a blend of this polymer and 10 wt% core-shell rubber was studied. The sample thickness was varied from 0.1 to 8 mm. The skin morphology was studied by SEM. The fracture behaviour was studied on single edge notch specimen at a high strain rate (30 s⁻¹) in the temperature range of −40 to 120 °C. The fracture stress, fracture strain and fracture energies were determined. The temperature development in the notch area was followed with an Infra Red camera. The cavitation of the rubber particles was studied on tensile bars with a laser setup.With decreasing specimen thickness the fracture energies increased strongly and the brittle-ductile transition shifted to lower temperatures this both for the aliphatic polyketone and the polyketone-rubber blend. The deformation in these materials in accompanied with a strong temperature increase in the deformation zone. The addition of rubber particles decreases the sensitivity towards the thickness. However, in very thin samples the cavitation of the rubber particles is more difficult and the rubber toughening effect decreases. The strong thickness effects on the fracture toughness indicate for both the homo polymer and the blend indicate that data from a standard test with 4 mm thick samples are not representative for thin walled applications.