Polypropylene-elastomer (TPO) nanocomposites: 2. Room temperature Izod impact strength and tensile properties

Room temperature Izod impact strength was determined for polypropylene (PP)/ethylene-co-octene elastomer (EOR) blends and nanocomposites, containing organoclays based on montmorillonite (MMT), at fixed elastomer content of 30 wt% and 0-7 wt% MMT. A ratio of maleated polypropylene, PP-g-MA to organoclay of unity was used as a compatibilizer in the nanocomposites. The organoclay serves to reduce the size of the EOR dispersed phase particles and facilitates toughening. The Izod impact strength is also influenced by the molecular weight of PP, elastomer octene content, elastomer MFI in addition to MMT content. Nanocomposites based on a low molecular weight polypropylene (L-PP) containing a higher octene content elastomer showed higher impact strength at lower MMT contents compared to those based on a low octene content elastomer. The effect of elastomer octene content on impact strength of high molecular weight polypropylene (H-PP) nanocomposites is not so significant. Elastomers having a melt flow index (MFI) in the range of 0.5-1.0 showed significant improvement in the impact strength of L-PP based nanocomposites. Most H-PP/EOR blends gave ‘super-tough’ materials without MMT and maintain this toughness in the presence of MMT. The critical elastomer particle size below which the toughness is observed is reduced by decreasing the octene content of the elastomer. For the similar elastomer particle sizes in nanocomposites, the impact strength varies as H-PP > M-PP > L-PP. The tensile modulus and yield strength improved with increasing MMT content; however, elongation at break was reduced. The extruder-made TPO showed a good-balance of properties in the presence of MMT compared to reactor-made TPO having similar modulus and elastomer content.     

Polypropylene-elastomer (TPO) nanocomposites: 3. Ductile-brittle transition temperature

Izod impact strength was determined as a function of temperature for polypropylene (PP)/ethylene-co-octene elastomer (EOR) blends and nanocomposites to determine the effect of PP molecular weight, elastomer MFI, EOR octene content and MMT content on the ductile-brittle (D-B) transition temperature. The D-B transition temperature decreases with increased molecular weight of the PP (H = high, M = medium and L = low) and the addition of MMT. The D-B transition temperature also decreases as the elastomer particle size is decreased, and at a fixed elastomer particle sizes, the D-B transition varies as H-PP< M-PP< L-PP. The H-PP based materials show a smaller decrease in the D-B transition temperature compared to L-PP based materials in the presence of MMT. Elastomers having a melt flow index (MFI) in the range of 0.5–1.0 showed a significant decrease in the D-B transition temperature for both L-PP and H-PP nanocomposites. The D-B transition temperature also decreases with increasing octene content of the elastomer.     

Effect of organoclay on the morphology, phase stability and mechanical properties of polypropylene/polystyrene blends

The effect of organically modified clay on the morphology, phase stability and mechanical properties of polypropylene (PP) and polystyrene (PS) blends was studied using three molecular weight grades of PP. Maleated polypropylene was used, at a PP-g-MA/organoclay ratio of 1, to preferentially promote dispersion of the organoclay in the PP matrix. The MMT content was fixed at 3 wt% based on the PP/PP-g-MA/MMT phase and the PS content was varied from 0-100 wt% in the blend. All blends were processed using a twin screw extruder. The organoclay resides in the PP phase and at the PP/PS interface. The dispersed PS particle size is significantly reduced by the presence of MMT, with maximum decrease observed for the low viscosity PP compared to its blend without MMT. The blends with MMT did not show any change in onset of co-continuity, though MMT shifts the phase inversion composition toward lower PS contents. The phase stability of the blend was significantly improved by the presence of MMT; for blends annealed at 210 °C for 2 h the dispersed phase particle size increased by as much as 10x without MMT with little change was noted with MMT present in the blend. The tensile modulus of blends improved with the addition of MMT at low PS contents. Blends based on the highest molecular weight grade PP showed increase in the tensile yield stress up to 40 wt% PS in the absence of MMT. The tensile strength at break for blend increased slightly with MMT while elongation at break and impact strength decreased in the presence of MMT. Surface energy analysis model was used to predict the orientation and equilibrium position of the clay platelet at the interface based on the surface energies.     

Rubber‐toughened polypropylene nanocomposite: Effect of polyethylene octene copolymer on mechanical properties and phase morphology

Rubber‐toughened polypropylene (PP)/org‐Montmorillonite (org‐MMT) nanocomposite with polyethylene octene (POE) copolymer were compounded in a twin‐screw extruder at 230°C and injection‐molded. The POE used had 25 wt % 1‐octene content and the weight fraction of POE in the blend was varied in the range of 0–20 wt %. X‐ray diffraction analysis (XRD) revealed that an intercalation org‐MMT silicate layer structure was formed in rubber‐toughened polypropylene nanocomposites (RTPPNC). Izod impact measurements indicated that the addition of POE led to a significant improvement in the impact strength of the RTPPNC, from 6.2 kJ/m² in untoughened PP nanocomposites to 17.8 kJ/m² in RTPPNC containing 20 wt % POE. This shows that the POE elastomer was very effective in converting brittle PP nanocomposites into tough nanocomposites. However, the Young's modulus, tensile strength, flexural modulus, and flexural strength of the blends decreased with respect to the PP nanocomposites, as the weight fraction of POE was increased to 20 wt %. Scanning electron microscopy (SEM) was used for the investigation of the phase morphology and rubber particles size. SEM study revealed a two‐phase morphology where POE, as droplets was dispersed finely and uniformly in the PP matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3441–3450, 2006     

Studies on rheology and morphology of POE/PP thermoplastic elastomer dynamically crosslinked by peroxide

An ethylene‐octene copolymer (POE)/polypropylene (PP) thermoplastic elastomer was prepared through dynamically crosslinking by 2,5‐dimethyl‐2,5‐dilbuty (Peroxy) hexane (DHBP). The effects of DHBP concentration, POE/PP ratio, melt flow index (MFI) of PP, and mixer rotation on rheology and morphology of the thermoplastic elastomer were studied. The results showed that with increasing DHBP concentration or POE content, the size of crosslinked particles as well as the melt viscosity increased. Furthermore, agglomerates or a network structure formed as the size of crosslinked particles increased. The melt viscosity also increased as MFI of PP decreased, while the size of crosslinked particles decreased under the same condition. Research on the morphology of dynamically crosslinked POE/PP thermoplastic elastomer flowing through a capillary rheometer at different shear rates show that the reprocessing had little effect on the morphology of dynamically crosslinked elastomer. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

Polypropylene/metallocene ethylene‐octene copolymer blends with a bimodal particle size distribution: Mechanical properties and their controlling factors

Blends of polypropylene homopolymer (PP) and metallocene produced ethylene‐octene copolymer (EOR) with a bimodal particle size distribution were investigated. The aim of the work was to study the influences of EOR characteristics and its concentration on the tensile and impact properties of the blends. The matrix ligament thickness between rubber particles was measured and compared to those predicted using the theoretical models. The relationships between blend morphology and impact property were reported. It was found that the content of comonomer and molecular weight of the EOR as well as its concentration in the blends were the major factors controlling the tensile and impact properties of the blends. These factors became ineffective to impact property when the ligament thickness of the matrix was larger than the critical value (T ～0.3–0.4 μm). To achieve blends of high impact strength, the ligament thickness between rubber particles should be smaller than the critical value, and for a certain ligament thickness, EOR with high octene content and high molecular weight was preferred. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2412–2418, 2002     

Phase Morphology and Mechanical Properties of Rubber-Toughened Polypropylene Nanocomposites: Effect of Elastomer Polarity

The objective of this work was to investigate the effect of elastomer polarity on phase structure and mechanical properties of PP nanocomposites. The nonpolar and polar elastomers studied were polyethylene octene (POE) and polyethylene octene grafted maleic anhydride (POEgMAH), respectively. The results from mechanical studies showed that the POEgMAH-toughened polypropylene nanocomposites have higher Izod impact strength but lower tensile and flexural properties than the unmaleated ones. X-ray diffraction (XRD) was used to characterize the formation of nanocomposites. XRD studies revealed that intercalated rubber-toughened PP nanocomposites (RTPPNC) had been successfully prepared where the macromolecule segments PP were intercalated into the interlayer space of organoclay. XRD also indicated that the incorporation of polar POEgMAH elastomers into PP nanocomposites contribute to a better intercalation effect and formed a more exfoliated combinations structure compared to POE. Scanning electron microscope (SEM) was used for the investigation of the phase morphology and rubber particle size and particle-size distribution. SEM study revealed a two-phase morphology where POE as droplets dispersed finely and uniformly in the PP matrix. The POEgMAH-toughened PP nanocomposites shows a much finer dispersion of elastomer particles than POE-toughened PP nanocomposites.     

Study on Morphology,Rheology and Mechanical Properties of Thermoplastic Elastomer Polyolefin (TPO)/Carbon Nanotube Nanocomposites with Reference to the Effect of Polypropylene-grafted-Maleic Anhydride (PP-g-MA) as a Compatibilizer

The structure–property relationships of polypropylene/ethylene-propylene-diene (PP/EPDM) (80/20) nanocomposites containing single-walled carbon nanotubes (SWCNTs) by melt-mixing process were investigated, the main focus being on the effect of SWCNTs concentration and compatilizer content. Morphological observations by scanning electron microscopy (SEM) are presented in conjunction with the mechanical, thermal, and rheological properties of these nanocomposites. The tensile modulus of nanocomposites was enhanced by increasing the SWCNTs concentration. A high level of toughness in the thermoplastic elastomer polyolefin (TPO)/SWCNTs nanocomposite was achieved with 0.5 wt% of SWCNTs and 1 wt% of polypropylene-grafted maleic anhydride (PP-g-MA). Differential scanning calorimetry (DSC) experiments confirmed the nucleation effect of nanotubes on the crystallization process of the TPO/SWCNTs composites. An appreciable viscosity upturn and a non-terminal low frequency storage modulus were observed in nanocomposites containing SWCNTs whose values increased in the presence of compatibilizer.     

Effect of Organomodified Ni-Al Layered Double Hydroxide (OLDH) on the Properties of Polypropylene (PP)/LDH Nanocomposites

This work addresses the effect of organomodified layer double hydroxide (OLDH) on the properties of PP/LDH nanocomposites prepared by melt intercalation method using a single screw extruder with maleic anhydride grafted polypropylene (PP-g-MA) as a compatibilizer. For this, Ni-Al LDH was first prepared by the co-precipitation method at constant pH using their nitrate salts. The above synthesized pristine LDH was organically modified using sodium dodecyl sulphate (SDS) by the regeneration method. The structural and thermal properties of LDH and PP nanocomposites were performed by X-ray diffraction (XRD), FTIR spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The influence of LDH loading on the mechanical and thermal properties of the nanocomposite was also investigated. The XRD results confirmed the formation of exfoliated PP/LDH nanocomposites. PP/LDH nanocomposites exhibited enhanced thermal stability relative to the pure PP. When 10% weight loss was selected as a point of comparison, the decomposition temperature of PP/LDH (5 wt%) nanocomposite was 15.3°C higher than that of pure PP. The DSC result indicated an increase in crystallization and melting temperature of the PP/LDH nanocomposites compared to pure PP. Overall, the mechanical properties of the PP/LDH nanocomposites increased with an increase in the LDH content. The maximum improvement of tensile strength, Young's modulus, flexural strength, and flexural modulus for the PP/LDH nanocomposite was found to be 11, 22.5, 28, and 22%, respectively, over neat PP. For comparison purposes, a nanocomposite with 5 wt% modified bentonite (PP/B5) was also prepared under the same operating condition and there was no significant improvement in mechanical properties (tensile strength and modulus).     

SBS nanocomposites as toughening agent for polypropylene

The toughening of polypropylene [PP] with styrene–butadiene–styrene rubber [SBS]/montmorillonite [MMT] nanocomposites was investigated with respect to morphological, thermal, and mechanical properties. The MMT/SBS nanocomposites were prepared in an internal mixer, using an epoxidized SBS [SBSe] to investigate its effect as a compatibilizer. The MMT/SBS nanocomposite was added to PP up to 10 wt%, aiming at material toughening. Transmission electron microscopy (TEM) revealed MMT induced dispersed-phase reductions when compared to typical PP/SBS blends. In addition, changes in the PP crystallization process were observed in the presence of the nanocomposite. Surprisingly, the use of nanofiller, combined with SBSe compatibilizer agent, increased the PP impact strength by about 60%, with no reduction in the tensile module.     

The Effect of Spray-Freeze Drying of Montmorillonite on the Morphology,Dispersion, and Crystallization in Polypropylene Nanocomposites

The spray-freeze drying (SFD) technique was applied to sonicated aqueous suspensions of spray-dried montmorillonite clay (MMT) to produce highly porous agglomerates (SFD-MMT). Both MMT (used as a reference) and SFD-MMT were subsequently incorporated in polypropylene (PP) via melt compounding to produce 2 wt % nanocomposites with and without maleic anhydride grafted polypropylene (PP-g-MA). Polypropylene nanocomposites containing SFD-MMT exhibited thinner silicate flake layers compared to large agglomerates in PP/MMT nanocomposites. SFD-MMT particles became even more finer in the presence of PP-g-MA (i.e., in PP/PP-g-MA /SFD-MMT) where it hindered PP crystallization instead of serving as nucleation sites for the PP crystallization during rapid cooling. SFD-MMT improved the thermal stability of PP/PP-g-MA by 30°C compared to only 5–8°C for MMT/nanocomposites. MMT acts as a heterogeneous nucleating agent in the nucleation-controlled PP nanocomposites, but the hindrance effect was observed for the PP/PP-g-MA with SFD-MMT. PP/PP-g-MA/SFD-MMT exhibited twice the edge surface energy as compared to PP/PP-g-MA/MMT. The incorporation of both types of MMT raised the tensile moduli of PP and PP/PP-g-MA, with no improvement in their tensile strength and a decrease in the elongation at break. The PP/PP-g-MA/SFD-MMT showed brittle failure. POLYM. ENG. SCI., 60:168–179, 2020. © 2019 Society of Plastics Engineers     

Evaluation of amine functionalized polypropylenes as compatibilizers for polypropylene nanocomposites

The compatibilization effects provided by amine functionalized polypropylenes versus those of a maleated polypropylene, PP-g-MA, for forming polypropylene-based nanocomposites were compared. Amine functionalized polypropylenes were prepared by reaction of maleated polypropylene, PP-g-MA, with 1,12-diaminododecane in the melt to form PP-g-NH₂ which was subsequently protonated to form PP-g-NH₃⁺. Nanocomposites were prepared by melt processing using a DSM microcompounder (residence time of 10 min) by blending polypropylene and these functionalized materials with sodium montmorillonite, Na-MMT, and with an organoclay. X-ray and transmission electron microscopy plus tensile modulus tests were used to characterize those nanocomposites. Composites based on Na-MMT as the filler showed almost no improvement of tensile modulus compared to the polymer matrix using any of these functionalized polypropylenes, which indicated that almost no exfoliation was achieved. All the compatibilized nanocomposites using an organoclay, based on quaternary ammonium surfactant modified MMT, as the filler had better clay exfoliation compared to the uncompatibilized PP nanocomposites. Binary and ternary nanocomposites using amine functionalized polypropylenes had good clay exfoliation, but no advantage over those using PP-g-MA. The PP-g-MA/organoclay and PP/PP-g-MA/organoclay nanocomposites showed the most substantial improvements in terms of both mechanical properties and clay exfoliation.     

Polypropylene/organically modified Sabah montmorillonite nanocomposites: Surface modification and nanocomposites characterization

The aim of the work is to extract, purify, and organically modify montmorillonite (MMT) of Lahad Datu, Sabah bentonite. The octadecylamine treated Sabah MMT (S‐OMMT) (2–8 wt%) was then melt blended with polypropylene (PP) and maleated polypropylene (PPgMAH) (10 wt%) via single screw nanomixer extruder followed by injection molding into test samples to examine the mechanical, thermal, and morphological properties of PP/S‐OMMT nanocomposites. Unmodified Sabah MMT (S‐MMT) and commercial grade MMT (Nanomer 1.30P) filled PP nanocomposites were also characterized for comparison purpose. X‐ray diffraction results showed that the interlayer spacing of S‐MMT increased after organic modification as Fourier transform infra‐red and elemental analysis evidenced the presence of octadecylamine. PP/S‐OMMT nanocomposites showed a better dispersion and strength compared to PP/Nanomer 1.30P nanocomposites due to its smaller MMT platelet size. differential scanning calorimetry and Thermogravimetry analysis revealed that the thermal stability and crystallinity of neat PP improved with the addition of all types of MMT. Dynamic mechanical analyzer showed that PP nanocomposites have higher storage modulus (E′) values than the neat PP over the whole temperature range. The new PP/S‐OMMT nanocomposites showed a comparable performance with PP/Nanomer 1.30P nanocomposites exhibiting promising future applications of S‐MMT in polymer/MMT nanocomposites. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

不同工艺制备的PP/蒙脱土纳米复合材料的性能

选择一种新型有机蒙脱土（MMT）,分别通过直接注塑法和挤出一注射法（简称挤出法）将聚丙烯（PP）与有机MMT复合,制备出高抗冲PP／MMT纳米复合材料。透射电子显微镜观察表明。挤出法制备的复合材料为全插层型结构,MMT分散均匀,尺寸小;而直接注塑法制备的复合材料为部分插层型结构．MMT明显分散不均匀,尺寸较大,且有少量团聚产生。力学性能测试表明,随着MMT的增加．2种试样的缺口冲击强度都有显著提高,均在ω（MMT）为4％时达到极大值。此时,挤出法试样缺口冲击强度比纯PP提高102％。屈服拉伸强度、弹性模量也略有提高;直接注塑法试样的缺口冲击强度比纯PP提高82．6％,但屈服拉伸强度、弹性模量都明显降低。     

聚丙烯／蒙脱土纳米复合材料的制备与性能

用烷基季铵盐对钠基蒙脱土进行有机化处理,使其成为有机蒙脱土。X射线衍射（XRD）表明有机阳离子已同钠离子发生离子交换作用,导致层间距扩大。用熔融插层法制备聚丙烯／蒙脱土纳米复合材料,测试了力学性能。通过XRD、DSC等手段研究了其结构与结晶行为,并与聚丙烯进行了对比。实验表明,通过熔融插层可使聚丙烯插层于蒙脱土片层之中,且所得聚合物的冲击强度有所提高。     

Morphology and mechanical properties of impact modified polypropylene blends

Isotactic polypropylene (PP) has been reactively blended with various grades of an ethylene–octene copolymer (EOC) in a twin‐screw extruder. Free radical polymerization of styrene and a multifunctional acrylate during melt extrusion has resulted in an enhancement of mechanical properties over the binary blend. The reactive blend exhibits a notched Izod impact strength over 12 times that of pure polypropylene and greater than double the performance of the binary blend. Electron microscopy shows that by grafting onto the polymers, elastomer particle size and interparticle distance decrease, while particle shape becomes less spherical. The acrylate is crucial to achieve superior performance, as infrared spectra correlate an increase in graft yield to improvements in stress–strain behavior and impact strength. In addition, melt flow index (MFI) and melt strength data indicate a reduction in unwanted side reactions of polypropylene and the presence of long‐chain branching. Dynamic‐mechanical analysis reveals that the reaction promotes miscibility between polypropylene and the EOC and reduces molecular mobility at their glass‐transition temperatures. Mechanical properties, graft yield, and MFI are shown to be highly dependent upon the elastomer's concentration, density, and molecular weight, initiator and monomer concentration, as well as processing temperature. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

聚丙烯/蒙脱土纳米复合材料的制备与性能研究

以马来酸酐接枝低分子量聚丙烯为相容剂,采用双螺杆挤出机熔融挤出法,制备插层型聚丙烯/有机钠基蒙脱土、聚丙烯/酸化有机化钠基蒙脱土、聚丙烯/钠基蒙脱土3种纳米复合材料,发现有机钠基蒙脱土、酸化有机化钠基蒙脱土和钠基蒙脱土对PP力学性能和燃烧性能均有一定程度的提高。经X射线衍射(XRD)和扫描电子显微镜(SEM)观察,发现有机钠基蒙脱土片层间距增幅最大,复合材料的燃烧性能也有很大提高。     

TPO based nanocomposites. Part 1. Morphology and mechanical properties

The relationship between morphology and the mechanical properties of thermoplastic olefin (TPO) materials that are reinforced with organoclay fillers and prepared by melt processing is reported. Nanocomposites based on blends of polypropylene and elastomer and using an organoclay masterbatch were prepared in a twin-screw extruder. Transmission electron microscopy, atomic force microscopy and wide-angle X-ray scattering were employed to carry out a detailed particle analysis of the morphology of the dispersed clay and elastomer phases for these nanocomposites. The improvement in mechanical properties, e.g. stiffness enhancement as evaluated by stress-strain analysis and impact strength obtained from notched Izod impact tests, were successfully explained in terms of morphological changes induced by the presence of the clay and elastomer particles. Quantitative analyses of TEM micrographs and AFM images revealed a decrease in the aspect ratio of the clay particles and a reduction in the size of elastomer particles with increasing clay content. In addition, WAXD scans indicated a skin-core effect for the injection molded specimens in terms of both polypropylene crystal orientation and clay filler orientation. This information is essential for the understanding of the mechanism of mechanical property enhancement in nanocomposite materials.     

Tuning the functionalization chemistry of polypropylene for polypropylene/clay nanocomposites

New polypropylene (PP)-graft-maleic anhydride (PP-g-MA) samples have been successfully synthesized by adding N-bromosuccinimide (NBS) during the reactive extrusion process. These NBS-mediated PP-g-MAs possess higher graft content than classic PP-g-MAs (i.e. without NBS) while they keep acceptable molar masses. NBS-mediated PP-g-MAs were used as matrices in model PP-g-MA/organoclay nanocomposites and compared with commercial and home-made classic PP-g-MAs in order to evaluate their ability to disperse the clay. Significantly better degrees of clay delamination and dispersion were reached using NBS-mediated PP-g-MAs than with classic PP-g-MAs. As expected, PP-g-MAs having high graft content showed the best clay dispersion. Within the examined range of molar masses, the PP-g-MA molar mass had no influence on the clay dispersion. However PP-g-MAs exhibiting important reduction of crystallinity lead to poor clay dispersion whatever the graft content. The PP-g-MA/organoclay nanocomposite prepared using the selected “optimized” NBS-mediated PP-g-MA exhibited the best improvement of thermal properties and one of the best clay dispersions. PP/PP-g-MA blends were prepared to evaluate the miscibility between PP and selected PP-g-MAs. No problem of miscibility between the selected NBS-mediated PP-g-MA and PP was noticed. Finally the PP/organoclay prepared using the selected NBS-mediated PP-g-MA as compatibilizer showed much better clay dispersion and thermal stability than the one prepared with the corresponding classic PP-g-MA, thus establishing the interest to use such new NBS-mediated PP-g-MAs as compatibilizers.     

Evaluation of toughening mechanisms of polypropylene/ethylene–octene copolymer/maleic anhydride‐grafted poly(ethylene‐co‐octene)/clay nanocomposite

The toughness of a polypropylene (PP)/ethylene‐octene copolymer (EOC)/maleic anhydride‐grafted poly(ethylene‐co‐octene) (EOC‐g‐MA)/clay nanocomposite and blends of PP/EOC and PP/EOC/EOC‐g‐MA was investigated using Charpy impact and single‐edge‐notch tensile (SENT) tests. In order to understand the toughening mechanisms, impact fracture surfaces and damage zones of single‐edge‐notch samples were studied with scanning electron microscopy and transmission optical microscopy, respectively. It was observed that the addition of EOC‐g‐MA to PP/EOC blend led to improvements in both impact strength and fracture energy of SENT tests because of the enhanced compatibility of the blend, which resulted from reduced EOC particle size and improved interfacial adhesion, and the decreased crystallinity of PP. The incorporation of clay to PP/EOC/EOC‐g‐MA blend caused a further increase of the toughness, owing to the greater decrease in the size of elastomer particles, to the presence of clay tactoids inside the elastomer phase and presumably to debonding of clay layers during the low‐speed SENT tests. The results of microscopic observations showed that the main toughening mechanism in PP/EOC/EOC‐g‐MA blend and PP/EOC/EOC‐g‐MA/clay nanocomposite is crazing. Copyright © 2012 Society of Chemical Industry