Preparation of dynamically vulcanized thermoplastic elastomer nanocomposites based on LLDPE/reclaimed rubber

Dynamically vulcanized thermoplastic elastomers nanocomposites (TPV nanocomposites) based on linear low density polyethylene (LLDPE)/reclaimed rubber/organoclay were prepared via one‐step melt blending process. Maleic anhydride grafted polyethylene (PE‐g‐MA) was used as a compatibilizing agent. The effects of reclaimed rubber content (10, 30, and 50 wt %), nanoclay content (3, 5, and 7 wt %), and PE‐g‐MA on the microstructure, thermal behavior, mechanical properties, and rheological behavior of the nanocomposites were studied. The TPV nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, scanning electron microscopy (SEM), differential scanning calorimeter, mechanical properties, and rheometry in small amplitude oscillatory shear. SEM photomicrographs of the etched samples showed that the elastomer particles were dispersed homogeneously throughout the polyethylene matrix and the size of rubber particles was reduced with introduction of the organoclay particles and compatibilizer. The effects of different nanoclay contents, different rubber contents, and compatibilizer on mechanical properties were investigated. Increasing the amount of nanoclay content and adding the compatibilizer result in an improvement of the tensile modulus of the TPV nanocomposite samples. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of reactive melt mixing on the morphology and thermal behavior of linear low-density polyethylene/rubber blends

Linear low-density polyethylene (LLDPE)/polybutadiene (PB) and LLDPE/poly(styrene-b-butadiene-b-styrene) (SBS) binary blends were prepared by simple melt mixing or by reactive blending in the presence of a free-radical initiator, and for comparison, pure LLDPE was treated under the same conditions with a comparable free-radical initiator concentration. The effect of the reactive melt mixing on the morphology of the blends was studied with transmission electron microscopy, and the corresponding particle size distributions were analyzed and compared to highlight the effects of the crosslinking and grafting phenomena. Thermal properties of the obtained materials were investigated with differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA). In particular, the effect of the reactive mixing parameters on the amorphous phase mobility was investigated. The influence of the chemical modification on the crystallization behavior of LLDPE, neat and blended with PB and SBS, was also studied with dynamic and isothermal differential scanning calorimetry tests, and the isothermal thermograms were analyzed in light of the Avrami equation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

POE/硅橡胶热塑性弹性体的力学性能及加工性能研究

采用动态硫化方法制备了乙烯-丙烯共聚物(POE)/硅橡胶热塑性弹性体。考察了共混比和交联剂含量对POE/硅橡胶热塑性弹性体的力学性能以及流变加工特性的影响。结果表明,m(硅橡胶)/m(POE)为60/40,交联剂质量分数为2.5%时表现出优越的力学性能,拉伸强度达到9.8MPa,断裂伸长率达到740%。制备出的POE/硅橡胶在流变测试中表现出优越的流变性能,具有高剪切粘度低,低剪切粘度高的特点。     

共混型聚丙烯/超细粉末丁苯橡胶全硫化热塑性弹性体的制备及其结构与性能

以全硫化超细粉末丁苯橡胶(PSBR)与聚丙烯(PP)为原料,采用双螺杆挤出机共混方法制备PP/PSBR全硫化热塑性弹性体。通过透射电镜观测,发现PP/PSBR全硫化热塑性弹性体具有和动态硫化方法制备的热塑性弹性体相似的微观形态,PSBR粒子作为分散相分散在连续相PP中;所制备的热塑性弹性体的力学性能与PP的相对分子质量、共聚与否、PSBR含量及其交联度有关;通过流变行为研究,发现此类全硫化热塑性弹性体为假塑性流体,且橡胶的含量对热塑性弹性体的黏度影响很小;采用差示扫描量热法对PP/PSBR全硫化热塑性弹性体中连续相PP的结晶行为进行了研究,发现连续相PP的结晶温度提高,表明PSBR对PP有异相成核作用。     

PVC/NBR热塑性弹性体加工流变性能研究

采用反应挤出动态硫化法制备了聚氯乙烯／丁腈橡胶(PVC／NBR)热塑性弹性体，用锥板流变仪、毛细管流变仪和转矩流变仪研究了动态硫化的PVC／NBR热塑性弹性体的流交性能和塑化性能。实验结果表明，动态硫化的PVC／NBR热塑性弹性体的熔体属于剪切稀化的假塑性流体，具有良好的返炼性能，综合性能超过国外同类产品。     

动态硫化溴化丁基橡胶/聚丙烯热塑性弹性体制备及性能的影响因素

采用密炼工艺制备了动态硫化溴化丁基橡胶(BIIR)/聚丙烯(PP)热塑性弹性体(TPV),考察了加工温度、硫化时间对TPV力学性能、微观相态结构、交联密度和流动性的影响。结果表明,当加工温度为180℃时,TPV的力学性能较好,且橡胶相粒子均匀分散于树脂相中。在TPV制备过程中,当硫化时间为10～12min时,胶料的交联密度趋于稳定,胶料达到完全硫化;在硫化3min时,共混物完成了以BIIR和PP为双连续相到以BIIR为分散相、PP为连续相的转变;随着硫化时间的延长,TPV的流动性逐渐增加。     

乙烯-乙酸乙烯酯共聚物/聚乙烯热塑性硫化胶的形态结构及流变性能

使用双转子密炼技术制备了具有双连续相结构的乙烯-乙酸乙烯酯共聚物(EVA)/聚乙烯(PE)的热塑性聚烯烃(EVA/PE-TPO)和热塑性硫化胶(EVA/PE-TPV)材料,并利用扫描电子显微镜、Han曲线和vGP曲线对二者的相形貌进行了分析和表征。动态流变行为的结果表明,在低频区,EVA含量对EVA/PE-TPO材料体系的储能模量(G′)和复数黏度的影响均大于EVA/PE-TPV体系;在高频区,组成相同的两种体系的G′相近。当两相的组成比例相同时,时温等效原理适用于210℃以下的EVA/PE-TPV体系。修正Palierne模型对双连续相结构EVA/PE-TPV材料的线性黏弹性的拟合程度不高。     

Ternary elastomer nanocomposites based on NR/BR/SBR: Effect of nanoclay composition

Elastomer nanocomposites based on natural rubber (NR), butadiene rubber (BR), and styrene butadiene rubber (SBR) containing Cloisite 15A were prepared using a two‐roll mill. Mechanical, morphological, and rheological characterization of the prepared nanocomposites was carried out in order to study the effect of different nanoclay compositions, i.e., 1, 3, 5, 7, and 10 wt %. Intercalation of the elastomer chains into the silicate layers was evidenced by d‐spacing values calculated according to the results of the X‐ray diffraction (XRD) patterns. This was directly confirmed by transmission and scanning electron microscopy (TEM and SEM). The results depict a decreasing trend in the optimum cure time (t₉₀) and scorch time (t₅) values of the nanocomposite samples with increasing nanoclay loading; where the elastic modulus (G′) and complex viscosity (η*) of the samples considerably increased. The mechanical properties of the nanocomposites show a considerable increase in the tensile modulus of NR/BR/SBR/Cloisite 15A nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties and morphology of high-density polyethylene/linear low-density polyethylene blend

The binary blend of high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE) in the range of composition from 100% HDPE to 100% LLDPE has been investigated for tensile and flexural properties and the morphology in the deformed state on tensile fracture. Tensile properties (initial modulus, yield stress, and elongation-at-yield, ultimate tensile strength and elongation-at-break, and work of yield and work of rupture) and flexural properties (flexural modulus and flexural yield stress) are studied as a function of blend composition. Behavior, in terms of these properties, is distinguishable in three zones of blend composition, viz. (i) HDPE-rich blend, (ii) LLDPE-rich blend, and (iii) the middle zone. In zones (i) and (ii), the variations of these properties are more or less linear, whereas in the middle region [i.e., zone (iii)], there is a reversal of trends in variation or sometimes a behavior opposite to the expected one. The results are explained on the basis of the effects of cocrystallization and the presence of octene-containing segments in the amorphous phase. Scanning electron micrographs of the tensile fracture surfaces are presented to illustrate the occurrence of transverse bands interconnecting the fibrils.     

Novel ternary blends of natural rubber/linear low-density polyethylene/thermoplastic starch: influence of epoxide level of epoxidized natural rubber on blend properties

Novel degradable materials based on ternary blends of natural rubber (NR)/linear low-density polyethylene (LLDPE)/thermoplastic starch (TPS) were prepared via simple blending technique using three different types of natural rubber (i.e., unmodified natural rubber (RSS#3) and ENR with 25 and 50 mol% epoxide). The evolution of co-continuous phase morphology was first clarified for 50/50: NR/LLDPE blend. Then, 10 wt% of TPS was added to form 50/40/10: NR/LLDPE/TPS ternary blend, where TPS was the particulate dispersed phase in the NR/LLDPE matrix. The smallest TPS particles were observed in the ENR-50/LLDPE blend. This might be attributed to the chemical interactions of polar functional groups in ENR and TPS that enhanced their interfacial adhesion. We found that ternary blend of ENR-50/LLDPE/TPS exhibited higher 100 % modulus, tensile strength, hardness, storage modulus, complex viscosity and thermal properties compared with those of ENR-25/LLDPE/TPS and RSS#3/LLDPE/TPS ternary blends. Furthermore, lower melting temperature (T _m) and heat of crystallization of LLDPE (?H) were observed in ternary blend of ENR-50/LLDPE/TPS compared to the other ternary blends. Also, neat TPS exhibited the fastest biodegradation by weight loss during burial in soil for 2 or 6 months, while the ternary blends of NR/LLDPE/TPS exhibited higher weight loss compared to the neat NR and LLDPE. The lower weight loss of the ternary blends with ENR was likely due to the stronger chemical interfacial interactions. This proved that the blend with ENR had lower biodegradability than the blend with unmodified NR.     

(Re)processing effects on linear low-density polyethylene/silica nanocomposites

A linear low density polyethylene matrix was melt compounded with a given amount (2 vol.%) of both untreated (hydrophilic) and surface treated (hydrophobic) fumed silica nanoparticles with the aim to investigate the influence of the time under processing conditions on the microstructure and thermo-mechanical properties of the resulting materials. Crosslinking reactions induced by thermal processing caused a remarkable increase of the melt viscosity, as revealed by the melt flow index values of both neat matrix and nanocomposites. Thermal oxidation of the matrix was slightly reduced by the introduction of fumed silica nanoparticles, especially for long compounding times. Differential scanning calorimetry evidenced how silica nanoparticles had a nucleating effect on the matrix, while both the melting temperature and the relative crystallinity were decreased by the compounding process. Nanosilica addition promoted a general improvement of the tensile properties, that progressively decreased with the processing time.     

Mechanical and rheological properties,and morphology of polyamide-6/organoclay/elastomer nanocomposites

The effects of ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and three types of organoclays (Cloisite^® 15A, 25A, and 30B) on mechanical and rheological properties, and morphology of impact modified polyamide-6/montmorillonite ternary nanocomposites were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), parallel disk rheometry, melt flow index measurements, and tensile and impact tests. The materials were prepared by melt blending using a co-rotating twin-screw extruder. XRD and TEM analyses showed that exfoliated-intercalated nanocomposites were formed in both polyamide-6/Cloisite^® 25A and Cloisite^® 30B binary nanocomposites and in ternary systems. SEM micrographs showed that rubber domain sizes were larger in the nanocomposites than in their corresponding polyamide-6/elastomer blends. Generally, tensile strength, Young's modulus, and elongation at break decreased with the addition of elastomer to polyamide-6/organoclay binary nanocomposites. In the melt state, liquid-like behavior of polyamide-6 slightly turned to pseudo solid-like in the binary and ternary nanocomposites. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improvement in volume resistivity and morphology of a blend of polyolefin elastomer with linear low-density polyethylene

A silane moisture-cured polyolefin elastomer/linear low-density polyethylene (LLDPE) blend was prepared through a two-step silane-grafting method (Sioplas Process) in an industrial scale twin-screw extruder. The silane-grafted compound was used to make wire and cable coatings. In this work, the effect of some interactive parameters on quality of the products prepared by the above method has been studied, while so far, there have been less experimental investigations. The volume resistivity of cross-linked compound was changed from 2.96 × 10¹⁴ to 7.41 × 10¹⁴ Ω cm with increasing LLDPE component by maximum 10 wt%. Surface morphology of the product was corrected with reduction in benzoyl peroxide (BPO) concentration from 0.2 wt% to 0.13 wt%. BPO at this level acted as an initiator in grafting reaction of vinyl trimethoxysilane. The curing condition and specimen preparation method by injection molding and/or extrusion were factors which influenced the hot-set test results at 200 °C. The results of tensile and elongation studies showed a maximum value of 9 MPa and 397% for the tests, after 6 h curing. With increases in curing time at a specified temperature, the gel content of the cross-linked compound was increased and reached its maximum value. The maximum gel content values were found to be approximately 60%, 80%, and 82% at temperatures of 25, 60, and 85 °C, respectively. The hardness, density, and tear strength of the samples did not vary significantly with the curing temperature.

     

Preparation and linear rheological behavior of polypropylene/MMT nanocomposites

Maleic anhydride grafted low isotactic homopolypropylene elastomer (LiPP‐g‐MAH) is used as a compatibilizer in the melting mixing of polypropylene (PP) and clay. The microstructures of the composites of PP/clay (PPCN) are investigated using a wide‐angle X‐ray diffractometer (WAXD) and transmission electron microscope (TEM) as well as parallel rheometer, which show that PPCN with different phase morphologies have been obtained. It is found that the weight ratio of LiPP‐g‐MAH to clay and the weight content of LiPP‐g‐MAH in PPCN have a strong effect on the final dispersibility of the clay. The rheological response to small amplitude oscillatory shear (SAOS) shows that the storage modulus (G′) at the low frequencies is greatly sensitive to the microstructures in comparison with WAXD measurements. The investigation further indicates that the virgin clay particles, intercalated silicate crystallites, and exfoliated layers may coexist in the matrix at the same time, resulting in the great enhancement of G′ plateau at low frequency region.     

Nanostructure morphology and dynamic rheological properties of nanocomposites based on thermoplastic polyurethane and organically modified montmorillonite

Thermoplastic polyurethane (TPU) nanocomposites based on organophilic-layered silicates were prepared via melt blending. Wide angle X-ray diffraction (WAXD) and transmission electron microscope (TEM) were employed to investigate the state and mechanism of exfoliation of the layered silicate within TPU matrix. The TPU nanocomposites were found to have a partially exfoliated morphology at lower clay loading, whereas the morphology changed to an intercalated nanostructure at higher clay loadings. The effect of the state of dispersion of organoclay on rheological properties of the nanocomposites were carried out by rubber process analyzer (RPA), which exhibited more pronounced shear thinning behavior, and increased storage and loss modulus with the increase in organoclay content. The pseudo-plastic like behavior was observed due to change in liquid-like to solid-like behavior of nanoclay-filled systems.     

Preparation and characterization of thermoplastic polyurethane/organoclay nanocomposites by melt intercalation technique: Effect of nanoclay on morphology,mechanical, thermal,and rheological properties

Nanocomposites based on thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) were prepared by melt blending. Organically modified nanoclay was added to the TPU matrix in order to study the influence of the organoclay on nanophase morphology and materials properties. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. Morphological characterization of the nanocomposites was carried out using X‐ray diffraction, transmission electron microscopy, and scanning electron microscopy techniques. The results showed that melt mixing is an effective process for dispersing OMMT throughout the TPU matrix. Nanocomposites exhibit higher mechanical and thermal properties than pristine TPU. All these properties showed an increasing trend with the increase in OMMT content. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of nanocomposites significantly. Differential scanning calorimetry was used to measure the melting point and the glass transition temperature (T_g) of soft segments, which was found to shift toward higher temperature with the inclusion of organoclays. From dynamic mechanical thermal analysis, it is seen that addition of OMMT strongly influenced the storage and loss modulus of the TPU matrix. Dynamic viscoelastic properties of the nanocomposites were explored using rubber process analyzer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanochemical devulcanization and gamma irradiation of devulcanized waste rubber/high density polyethylene thermoplastic elastomer

Waste rubber (WR) powder was introduced in a two-roll mill in the presence of various ratios of curatives to develop sheets of devulcanized waste rubber (DWR). The product has been investigated by FTIR, TGA and SEM. A thermoplastic elastomer (TPE) was prepared by blending the obtained DWR with high density polyethylene (HDPE) at different feed ratios under conditions of gamma irradiation, 25, 50, 100, and 150 kGy. The mechanical parameters of the blend: tensile strength, elongation at break, and hardness (Shore D) were studied. In addition, blend characterization using FTIR spectra, gel fraction, TGA and SEM was discussed.     

Linear low-density polyethylene/poly(ethylene-ran-butene) elastomer blends: Miscibility and crystallization behavior

The phase and crystallization behavior of the blends consisting of LLDPE (0.7 mol% hexene copolymer) and PEB (26 mol% butene copolymer) have been investigated using optical microscopy (OM), differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). The blends exhibited an upper critical solution temperature of 162°C. The solubility parameter analysis showed that the solubility parameter of LLDPE decreased more rapidly than that of PEB with temperature. However, due to the slow kinetics of phase separation, at lower crystallization temperatures, the crystallization and melting behavior of LLDPE mainly reflected the miscibility between LLDPE and PEB. Crystallization from the two-phase state could present two crystallization peaks. PEB didnt change the crystal cell unit and crystallinity of LLDPE, but changed its distribution of lamellar thickness or crystal perfection. The dilute effect of PEB also changed the overall nature of the nucleation and growth process of LLDPE. The equilibrium melting temperature in this blend could be obtained by the Hoffman-Weeks method, and comparing with that of the pure LLDPE, it was reduced and kept relatively constant in the bi-phase state. The phase diagram made up of the LLPS boundary, equilibrium melting temperatures and melting temperatures observed may be better to indicate the phase and crystallization behavior of LLDPE/PEB blends.     

Effect of organoclay on the morphology,mechanical, thermal,and rheological properties of organophilic montmorillonite nanoclay based thermoplastic polyurethane nanocomposites prepared by melt blending

Polymer nanocomposites based on the thermoplastic polyurethane (TPU) and organically modified montmorillonite (OMMT) was prepared by melt intercalation technique using a laboratory internal batch mixer followed by compression molding. Varying amount of organically modified nanoclays (1, 3, 5, 7, and 9 wt%) was added to the TPU matrix to examine the influence of organoclay on nanophase morphology and structure–property relationships. The interaction between TPU matrix and nanofiller was studied by infrared spectroscopy. The morphology of nanocomposites was studied by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy that shows melt mixing by a batch mixer is an effective method for dispersing OMMT throughout the TPU matrix. Thermogravimetric analysis revealed that incorporation of organoclay enhances the thermal stability of the nanocomposites significantly. Differential scanning calorimetry was employed to measure the melting point and glass transition temperature (T_g) of soft segments. The reinforcing effect of the organoclay was determined by dynamic mechanical analysis and physico–mechanical testing. The effects of nanoclay concentration and processing parameters on the dynamic viscoelastic properties of the nanocomposites were studied by a rubber process analyzer using frequency sweep. A significant increase in the viscosity and storage modulus of the nanocomposites was found with the increasing clay content. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Shear viscosity of rubber modified thermoplastics: Dynamically vulcanized thermoplastic elastomers and ABS resins at very low stress

The shear viscosity of PP-EPDM dynamically vulcanized thermoplastic elastomers and ABS resins were investigated using (a) a constant shear stress creep instrument, (b) a rotational rheometer, and (c) a capillary extrusion rheometer. It was found that stresses exist for some of these materials below which they exhibit only finite deformations. This indicates they exhibit yield values. Much attention was given to measurements of creep at low stresses especially in the neighborhood of yield values. The magnitudes of the yield stresses obtained from these low stress measurements are significantly lower than those obtained using standard extrapolation to zero shear rate of higher stresses from rotational instruments. We also observed a high shear viscosity (～10⁹ PA s) plateau in the materials of high rubber content. We contrasted our results to those found in the literature.