Effect of ultrasound on extrusion of polypropylene/ethylene–propylene–diene terpolymer blend: Processing and mechanical properties

The effects of ultrasonic irradiation on extrusion processing and mechanical properties of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends are examined. Results show that appropriate irradiation intensity can prominently decrease die pressure and apparent viscosity of the melt, increase output, as well as increase toughness of PP/EPDM blends without harming rigidity. In case the blends are extruded with ultrasonic irradiation twice, the impact strength of the blend rises sharply at 50–100 W ultrasonic intensity, and amounts to more than 900 J/m, 1.5 times as high as that of blend without ultrasonic irradiation. Scanning electron microscopy observation shows that with ultrasonic irradiation, morphology of uniform dispersed EPDM phase and good adhesion between EPDM and PP matrix was formed in PP/EPDM blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3519–3525, 2003     

PS/PMMA共混体系的挤出流变行为

利用单螺杆挤出机,配备特殊设计的狭缝模头,在不改变螺杆转速的情况下获得流经口模的不同流量,研究了聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)共混体系的挤出流变行为。结果表明,PS/PMMA共混物熔体的流变行为和其组分熔体的流变行为类似,都表现出假塑性流体的流动行为;在所研究的组成范围内,共混物熔体的非牛顿指数低于任一组分熔体。随着共混物黏度比的减小,其熔体的非牛顿指数呈下降的趋势;共混物熔体的黏度对加和性法则皆表现为负偏差,表明在界面处具有弱的相互作用。     

挤出反应温度与剪切应力对动态硫化PP/EPDM性能的影响

采用动态硫化的方法,在双螺杆挤出机中制备了聚丙烯(PP)/三元乙丙橡胶(EPDM)热塑性弹性体,研究了挤出反应温度与螺杆转速提供的剪切应力对动态硫化PP/EPDM热塑性弹性体性能的影响。结果表明,适当提高挤出反应温度或螺杆转速可提高PP/EPDM热塑性弹性体的拉伸强度、拉断伸长率和凝胶含量,当挤出反应温度为200℃、螺杆转速为600 r/min时,热塑性弹性体的综合拉伸性能最好,拉伸强度为19.87 MPa,拉断伸长率为527.3%,凝胶含量为54.69%。高螺杆转速提供的高剪切应力可在一定程度上提高PP/EPDM热塑性弹性体的熔融温度。     

剪切速率对动态硫化PP/EPDM热塑性弹性体相态结构及性能的影响

采用动态硫化法,在双螺杆挤出机中制备以聚丙烯(PP)/三元乙丙橡胶(EPDM)为基体材料的热塑性弹性体,研究螺杆转速对PP/EPDM热塑性弹性体相态结构及性能的影响;采用差示扫描量热(DSC)仪分析了PP/EPDM热塑性弹性体的结晶性能,通过扫描电子显微镜(SEM)分析PP/EPDM热塑性弹性体的微观相态结构,并用万能试验机等对其力学性能进行测试。结果表明,随着螺杆转速的增加,PP/EPDM热塑性弹性体的结晶温度降低,凝胶含量、拉伸强度和断裂伸长率先增大后减小,压缩永久变形先减小后增大,而螺杆转速对硬度的影响不明显。当螺杆转速为180 r/min时,PP/EPDM热塑性弹性体的凝胶含量、拉伸强度和断裂伸长率均达到最大值,分别为56.8%,15.9 MPa和634%,压缩永久变形和硬度(邵A)均达到最小值,分别为68.8%,88。     

Study on the thermoplastic vulcanizate using ultrasonically treated rubber powder

Nowadays, waste EPDM (ethylene propylene diene monomer) increasingly has been causing significant environmental problems with increasing numbers of vehicles. From the perspective of the environment and economics, recycling is the best method to treat waste materials. This study investigated waste EPDM/PP (polypropylene) blends with waste EPDM. Waste EPDM powders were treated ultrasonically, which physically modifies the rubber particles to confer good mechanical properties. Also investigated were the relevance of the mass percentage of the dispersed phase, the influence of the geometry and rotation speeds of the screw used in extrusion, and the melting temperature of PP materials on the morphology and mechanical properties of the blend. The purpose of this study was to develop a valuable thermoplastic elastomer from waste EPDM. This study concentrated on determining the optimum conditions for producing a blend by extrusion, including parameters of screw geometry, screw rotational speed, and operating temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2503–2507, 2003     

Effects of ultrasonic oscillations on rheological behavior and mechanical properties of novel propylene‐based plastomers

The effects of ultrasonic oscillations on the die pressure, productivity of extrusion, melt apparent viscosity, melt surface appearance, and die swell of novel propylene‐based plastomers were studied in a specially designed ultrasonic oscillations extrusion system developed in our laboratory. The effects of ultrasonic oscillations on molecular weights, tensile strength, and dynamic mechanical properties of extrudates were also studied. The experimental results showed that the presence of ultrasonic oscillations during extrusion could significantly increase the productivity of plastomers at the same die pressure, and reduce die swell and melt fracture such as sharkskin at a given screw rotation speed. The die pressure and apparent viscosity of plastomers remarkably decreased with increasing ultrasonic intensity. Introduction of ultrasonic oscillations into plastomer melts can improve their processibility. The possible mechanism for ultrasonic improvement of rheological behavior was also proposed in this article. Under certain conditions, ultrasound‐assisted extrusion could slightly decrease the glass transition temperature (T_g) and storage modulus of plastomers due to the minor reduction in molecular weights, but showed no significant impact on yield strength and strength at break. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Morphology and properties of PP/EPDM binary blends and PP/EPDM/nano‐CaCO3 ternary blends

In this article, the morphology, crystallization, and rheological behaviors of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) binary blend and PP/EPDM/calcium carbonate nanoparticles (nano‐CaCO₃) ternary blend were investigated. Two processing methods, i.e., direct extrusion and two‐step extrusion, were employed to prepare the PP/EPDM/CaCO₃ blend. The influence of EPDM and nano‐CaCO₃ respectively on phase morphology and properties of PP/EPDM blend and PP/EPDM/CaCO₃ blend were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and dynamic rheometer. The crystallinity and crystallization temperature of PP/EPDM blend were improved in comparison to pure PP due to addition of EPDM, but kept invariable with the increased EPDM loading. As the EPDM content was increased, the mobility of PP molecular chains was weakened. Compared with direct extruded blend, less and finer nano‐CaCO₃ was dispersed in matrix of two‐step extruded blend. Accordingly, the increased nano‐CaCO₃ in matrix gave rise to a weaker increment in crystallinity and crystallization temperature of two‐step extruded blend, and a later platform of tanδ curve. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Interfacial adhesion through maleic anhydride grafting of EPDM in PP/EPDM blend

This paper presents a study of interface modification effect through the use of maleic anhydride (MAH) grafting on one of the component polymers of the binary blend. The system used is binary blend of polypropylene (PP) and the elastomer EPDM (copolymer of ethylene–propylene–diene monomer). Two sets of the blend (i) PP/EPDM binary blend and (ii) PP/EPDM‐g‐MAH binary blend at constant degree of grafting (i.e., EPDM : MAH ratio) and at varying blending ratios were studied and compared for the properties and structure development. Results are discussed to illustrate the effect of interfacial modification due to presence of MAH by comparing the data of mechanical properties and crystallization behavior for the two sets of the binary blend at identical blending ratios, as well as to study the trends of variation of properties with blending ratio for each individual set of the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5528–5532, 2006     

Chemical modification of polymer blends by reactive processing: In situ reactions of interlinking agents in PS/EPDM blends

Polystyrene (PS) and the ethylene–propylene–ethylidene norbornene terpolymer (EPDM) were melt-processed in the presence of multifunctional interlinking agents, divinylbenzene (DVB) and trimethylolpropane triacrylate (TRIS), in an internal mixer to promote functionalization of the polymers and target in situ formation of the interpolymer product via coreaction of the functionalities. This approach leads to effective in situ compatibilization of the otherwise incompatible polymer components of the blends. The weight ratio of PS/EPDM and the concentration of the interlinking agents were kept constant at 70/30 and 5%, respectively. The effect of varying the concentration of the free-radical initiator (a peroxide) and the method of its addition during melt processing on the overall reaction outcome was also examined. Changes in torque during the melt-processing operation was monitored. Sequential extraction of the polymer blends was used to separate and characterize the insoluble fraction (interpolymer). Changes in the thermal behavior (shifts in glass transition temperatures) of both the polymer blends and their insoluble fractions was investigated together with an examination of the morphology and mechanical properties of the reactively processed blends. It was found that the use of mixed reactive interlinking agents in a one-step reactive blending process and the enhancement of PS reactivity via preinitiation before addition of the reactive agents led to an increase in the extent of the coupling reaction between the functionalized PS and EPDM. This results in the formation of an “across-phase” interpolymer with an optimum composition that is responsible for the significant changes observed in the morphology and associated improvements in the mechanical properties of the blend samples. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1933–1951, 1998     

Composite droplets with core/shell morphologies prepared from HDPE/PS/PMMA ternary blends by twin‐screw extrusion

Ternary blends of PS and PMMA in a PE matrix were prepared by twin‐screw extrusion to investigate the core/shell encapsulation phenomenon in the composite droplet. The PS was found to encapsulate the PMMA to form composite droplets within the PE matrix as expected from the spreading coefficient theory. The effects of dispersed phase concentration, viscosity ratio, feeding sequence and twin‐screw operating conditions were investigated. The blend morphology was observed by scanning electron microscopy after selective extraction of either PS or PMMA, and average core and composite droplet diameters were determined by image analysis. Although it is known that the structure of composite droplet blends can be substantially altered through control of the volume fraction of the components in the dispersed phase, this study demonstrates that blends with a 1:1 composite droplet volume fraction are relatively stable to large variations in the minor phase viscosities and processing conditions. Twin‐screw extrusion thus provides a highly robust technique for the melt processing of blends possessing composite droplet morphologies. Polym. Eng. Sci. 44:749–759, 2004. © 2004 Society of Plastics Engineers.     

Effect of dynamic cross‐linking on melt rheological properties of polypropylene/ethylene‐propylene‐diene rubber blends

Study of melts rheological properties of unvulcanized and dynamically vulcanized polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, at blending ratios 10–40 wt %, EPDM, are reported. Blends were prepared by melt mixing in an internal mixer at 190°C and rheological parameters have been evaluated at 220°C by single screw capillary rheometer. Vulcanization was performed with dimethylol phenolic resin. The effects of (i) blend composition; (ii) shear rate or shear stress on melt viscosity; (iii) shear sensitivity and flow characteristics at processing shear; (iv) melt elasticity of the extrudate; and (v) dynamic cross‐linking effect on the processing characteristics of the blends were studied. The melt viscosity increases with increasing EPDM concentration and decreased with increasing intensity of the shear mixing for all compositions. In comparison to the unvulcanized blends, dynamically vulcanized blends display highly pseudoplastic behavior provides unique processing characteristics that enable to perform well in both injection molding and extusion. The high viscosity at low shear rate provides the integrity of the extrudate during extrusion, and the low viscosity at high shear rate enables low injection pressure and less injection time. The low die‐swell characteristics of vulcanizate blends also give high precision for dimensional control during extrusion. The property differences for vulcanizate blends have also been explained in the light of differences in the morphology developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1488–1505, 2000     

Ultrasonic improvement of rheological behavior of polystyrene

The effects of ultrasonic oscillation on die pressure, productivity of extrusion, melt viscosity, and melt oscillating flow of polystyrene (PS) as well as their mechanism were studied in a special ultrasonic oscillations extrusion system developed in our lab. The experimental results show that in the presence of ultrasonic oscillations, the PS melt oscillating flow or surface distortion of PS extrudate is inhibited or disappears. The surface appearance of PS extrudate gets greatly improved. The die pressure, melt viscosity, flow activation energy, and consistency efficiency of PS decreased and the productivity of PS extrudate increased in the presence of ultrasonic oscillation. The shear sensitivity of PS melt viscosity is decreased because of the increase of its power law index in the presence of ultrasonic oscillation. Introduction of ultrasonic oscillation into PS melt can greatly improve the processibility of PS. Their possible mechanism is also proposed in this article. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2451–2460, 2002     

In situ compatibilization of PP/EPDM blends during ultrasound aided extrusion

Blends of isotactic polypropylene (iPP) and uncured ethylene-propylene diene rubber (EPDM) of various concentrations were treated by high power ultrasonic waves during extrusion. Die pressure and power consumption were measured. The effects of different gap sizes, blend ratios and number of ultrasonic horns were investigated. The rheological properties, morphology and mechanical properties of the blends with and without ultrasonic treatment were studied. In situ compatibilization of the blends was observed as evident by their more stable morphology after annealing, improved mechanical properties and IR spectra. The obtained results indicated that ultrasonic treatment induced the thermo-mechanical degradations and led to the possibility of enhanced molecular transport and chemical reactions at the interfaces. Processing conditions were established for enhanced in situ compatibilization of the PP/EPDM blends.     

Influence of poly(ethylene glycol)‐containing additives on extrusion of ultrahigh molecular weight polyethylene/polypropylene blend

The influence of poly(ethylene glycol) (PEG)‐containing additives on the extrusion behavior of ultrahigh molecular weight polyethylene/polypropylene (UHMWPE/PP) blend was studied. It was found that the addition of small amounts of PEG to UHMWPE/PP blend resulted in significant reduction of die pressure and melt viscosity, and obvious increase of the flow rate at a given die pressure, while PEG/diatomite binary additives enhanced the improvement in the processability of UHMWPE/PP blend. When pure HDPE was extruded with the die through which UHMWPE/PP/PEG blend was previously extruded, the extrusion pressure of HDPE increased with the extrusion time gradually. This meant that PEG might migrate to the die wall surface and coat it in the extrusion of UHMWPE/PP/PEG blend. FTIR spectra and SEM micrographs of the UHMWPE/PP/PEG extrudates indicated that PEG located not only at the surface but also in the interior of the extrudates. So, the external lubrication at the die wall, combined with the internal lubrication to induce interphase slippage of the blend, was proposed to be responsible for the reduction of die pressure and viscosity. In addition, an ultrahigh molecular weight polysiloxane and a fluoropolymer processing aid were used as processing aids in the extrusion of UHMWPE/PP as control, and the results showed that only minor reduction effects in die pressure and melt viscosity were achieved at their suggested loading level. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1282–1288, 2006     

Dynamic behavior of a single screw plasticating extruder part I: Experimental study

The dynamic responses of a 2–1/2 inch single screw plasticating extruder and extrusion line were investigated. Step changes in screw speed, take-up speed, back pressure, and processing materials were used to determine the transient responses of barrel pressures, die pressure, melt temperature, and extrudate thickness. Dynamic responses of the entire extrusion line can be explained by the flow mechanism of the extruder and the logical properties of the polymer used. A capillary rheometer was also used to determine if it could simulate pressure responses in the extruder for screw speed changes. Results showed that capillary rheometer was helpful in estimating the short term pressure responses in the die.     

PS/EPDM blends prepared by in situ polymerization of styrene

PS/EPDM blends formed by in situ polymerization of styrene in the presence of EPDM were prepared. EPDM has excellent resistance to factors such as weather, ozone and oxidation and it could be a good alternative for substituting polybutadiene‐based rubbers in PS toughening. The PS/EPDM blends present two phases, an EPDM elastomeric phase dispersed into a rigid matrix. The blends show higher thermal stability than polystyrene homopolymer due to the stabilizing effect of EPDM incorporation. The mechanical properties of in situ polymerized PS/EPDM blends with different compositions were evaluated before and after accelerated photoaging and compared with the properties of HIPS submitted to the same aging conditions. The blend containing 17 wt % of EPDM presents an increase in the impact resistance of 210% in comparison with the value of PS. Although the initial mechanical properties of HIPS are superior, a pronounced drop was observed after an exposure time. For example, after the aging period, all PS/EPDM blends showed higher strain at break than HIPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of ultrasound on extrusion of PP/EPDM blends: Structure and mechanical properties

The effects of ultrasonic irradiation on the mechanical properties, morphology, and crystal structure of polypropylene (PP)/ethylene‐propylene‐diene terpolymer (EPDM) blends were examined. Results show that appropriate irradiation intensity can noticeably increase the toughness of the PP/EPDM blends without reducing rigidity. Scanning electron microscopic (SEM) observation shows that with ultrasonic irradiation, the morphology of a well‐dispersed EPDM phase is formed in the PP/EPDM blend. The glass transition temperatures of PP and EPDM phase approach each other as a result of ultrasonic irradiation. Differential Scanning Calorimetric (DSC) analysis indicates that the crystallinities of the PP and EPDM phases increase with ultrasonic irradiation, and β crystals of PP form in the PP/EPDM blend with ultrasonic irradiation, which is proven by wide angle X‐ray diffraction (WAXD) analysis. Polym. Eng. Sci. 44:1509–1513, 2004. © 2004 Society of Plastics Engineers.     

EPDM rubber reclaim from devulcanized EPDM

Two types of ethylene–propylene–diene monomer (EPDM) rubbers, namely an efficient vulcanized (EV) and a semiefficient vulcanized (SEV), have been used to produce devulcanizates in a continuous setup. The devulcanizates are re‐cured using the same recipes as for the virgin rubber. The influence of mixing it with virgin rubber compound, the addition of extra sulfur, the operating devulcanization conditions, and the excess of devulcanizing agent on the mechanical properties (hardness, tensile strength, and compression set) of the reclaim rubbers are studied. Most of the reclaims produced show slightly inferior mechanical properties compared to the virgin rubber. Surface imperfection was observed on the devulcanizate with high devulcanizing agent content. Excellent mechanical properties (all above the standards) of the reclaim were found when the devulcanized profile material was used (EV‐EPDM) to replace the virgin one for application as a roofing sheet material (SEV‐EPDM). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5948–5957, 2006     

A die rotating system for moderations of extrusion load and pressure drop profiles for molten PP and wood/polypropylene composites in extrusion processes

A die‐rotating system was proposed in this work for moderations of extrusion forces and entrance pressure drop for molten polypropylene (PP) and wood/polypropylene (WPP) composites in a capillary rheometer and a single screw extruder. The effects of processing conditions and wood loading in PP were of our interests. The extrusion force and entrance pressure drop with and without the die rotating system were monitored in real‐time. This was the first time that the die‐rotating system was used for processing of highly viscous wood/polymer composite materials. It was found that the flow properties of the molten PP and WPP composites obeyed pseudoplastic non‐Newtonian behavior. The behavior was more obvious at wood contents of above 6 wt % and in the capillary rheometer. The rotation of the die could moderate the extrusion load by 60% and entrance pressure drop by 20% in the capillary rheometer, and the entrance pressure drop by 30% in the single screw extruder, especially at the conditions where the viscosities of the WPP and the extrusion rate were high. Greater fluctuations in entrance pressure drop caused by die rotation were observed in the single screw extruder. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120:1006–1016, 2011     

Functionalization of ethylene–propylene–diene monomer rubber with maleic anhydride in the melt state through high‐shear stress‐induced initiation

The functionalization reactions of ethylene–propylene–diene monomer rubber (EPDM) with maleic anhydride (MAH) in melt state through high‐shear‐stress‐induced initiation by an increase in the screw rotation speed of the twin‐screw extruder and through compounded initiation by the addition of some initiator and an increase in the screw rotation speed were investigated. The results show that, with increasing screw rotation speed and reaction temperature, the percentage grafting and melt flow rate of the functionalized products (EPDM‐g‐MAH) were noticeably increased, and the viscosity‐average molecular weight decreased, which implied that the grafting reaction consisted of the chain scission and grafting reaction of the produced macroradicals with MAH. In the presence of a certain peroxide initiator, the crosslinking reaction during melt extrusion was suppressed by an increase in the screw rotation speed. The percentage grafting of EPDM‐g‐MAH amounted to 1.1%, its melt flow rate was between 0.3 and 4.0 g/10 min, and its gel content was less than 1.0%, depending on the screw rotation speed and reaction temperature. Impact testing and scanning electron microscopy showed that the functionalized product prepared through the high shear stress‐induced initiation had a higher blocking activity with the amide terminated of PA66 than that prepared through the peroxide initiation or through the compound initiation, and the impact strength of the PA66/EPDM blends, improved by the high‐shear‐stress‐induced product was noticeably higher than those of the peroxide‐initiated product or the compound‐initiated one. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009