Effect of nanofiller on fibril formation in melt‐drawn HDPE/PA6 microfibrillar composite

Effect of layered silicates on structure of microfibrillar composites (MFCs) with reinforcing PA6 fibrils formed in situ by melt drawing was studied. Clay was added to HDPE/PA6 MFC using different mixing protocols including simultaneous addition, application of pre‐made masterbatches with both constituents and their combinations. In all cases, majority of nanofiller (NF) was contained inside PA6 fibrils. On the other hand, fibrils dimensions were significantly affected by the clay addition protocol; their marked increase in the case of simultaneous addition of all components and application of HDPE/C30 nanocomposite indicate important effect of NF migration to the PA6 phase in the course of mixing and melt drawing. The effect of properties of PA6 and HDPE phases and NF migration on the morphology evolution is discussed. It is shown that the fiber shape and volume after sample drawing are controlled by the interplay between the dispersed fibril extension and coalescence. POLYM. ENG. SCI., 55:2133–2139, 2015. © 2015 Society of Plastics Engineers     

Nano-modified HDPE/PA6 microfibrillar composites: Effect of aminated graphite platelets coupling

Modification of microfibrillar composites (MFCs) by nanofillers shows important effects of its localization on performance. This work deals with control of migration/localization of amine-modified graphite nanoplatelets (GNPAs) in the HDPE/PA6 system through their in situ coupling. GNPA/HDPE linking also leads to complex morphology of PA6 fibers. Although such control of GNPA localization and migration in MFC is limited, marked variations of properties, including decrease with high draw ratio, occurs. This is in spite of the fact that structure and crystallinity are comparable with that of the polymer/GNPA adduct. The reason is a more pronounced negative effect of presence of the GNP adducts in the fiber surface layer on HDPE crystallinity, in comparison with neat GNP, that is, formation of “soft” interface. The negative effects were markedly eliminated by pre-blending and coupling of GNPA in both polymer phases. Results confirm more effective control of MFC performance by in situ coupling of GNPA with polymer components in comparison with a nonreactive system. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47660.     

Morphology and mechanical properties of polypropylene/polyamide 6 nanocomposites prepared by a two‐step melt‐compounding process

Polypropylene/polyamide 6 blends and their nanocomposites with layered silicates or talc were prepared in a melt‐compounding process to explore their mechanical performance. The thermomechanical behavior, crystallization effects, rheology, and morphology of these materials were studied with a wide range of experimental techniques. In all cases, the inorganic filler was enriched in the polyamide phase and resulted in a phase coarsening of the polypropylene/polyamide nanocomposite in comparison with the nonfilled polypropylene/polyamide blend. The mechanical properties of these nanoblends were consequently only slightly better than those of the pure polymers with respect to the modulus, whereas the impact level was below that of the pure polymers, reflecting the heterogeneity of the nanoblend. Polymer‐specific organic modification of the nanoclays did not result in a better phase distribution, which would be required for better overall performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 283–291, 2006     

Processing‐induced degradation of nanoclay organic modifier in melt‐mixed PET/PE blends during twin screw extrusion at industrial scale: Effect on morphology and mechanical behavior

Immiscible PET/PE blends (80/20 wt %) were prepared on an industrial twin‐screw extruder with and without different types of commercially available montmorillonites (Cloisite® C15A, C10A, and 30B), containing organic surfactants differing by their polarities and their thermal stability). XRD and TEM observations evidence an intercalated structure, C15A leading to a better dispersion compared to C30B and C10A. The size of the PE dispersed phase decreases upon addition of organoclays (OMMT), suggesting an efficient compatibilization. The most efficient compatibilizing effect is observed in the case of C15A (smallest droplet size and narrowest size distribution). Nevertheless, elongation at break in tension and impact strength of PET/PE blends drastically decrease upon addition of OMMT, whatever the organoclay added, due to a possible degradation of the clay surfactant during melt compounding, which counteracts the nanofiller compatibilization effect. Furthermore, similar PET/PE/OMMT blends prepared at a lab scale using a microcompounder are ductile contrary to those compounded in the industrial extruder, which show a brittle behavior. This difference was ascribed to the extrusion residence time (much higher in an industrial extruder than in a lab micro‐compounder), which appeared to be a key parameter in controlling the clay surfactant degradation and thus the end‐use properties of such immiscible blends. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39712.     

Effect of core‐shell morphology evolution on the rheology,crystallization, and mechanical properties of PA6/EPDM‐g‐MA/HDPE ternary blend

In this article, polyamide 6 (PA6), maleic anhydride grafted ethylene‐propylene‐diene monomer (EPDM‐g‐MA), high‐density polyethylene (HDPE) were simultaneously added into an internal mixer to melt‐mixing for different periods. The relationship between morphology and rheological behaviors, crystallization, mechanical properties of PA6/EPDM‐g‐MA/HDPE blends were studied. The phase morphology observation revealed that PA6/EPDM‐g‐MA/HDPE (70/15/15 wt %) blend is constituted from PA6 matrix in which is dispersed core‐shell droplets of HDPE core encapsulated by EPDM‐g‐MA phase and indicated that the mixing time played a crucial role on the evolution of the core‐shell morphology. Rheological measurement manifested that the complex viscosity and storage modulus of ternary blends were notable higher than the pure polymer blends and binary blends which ascribed different phase morphology. Moreover, the maximum notched impact strength of PA6/EPDM‐g‐MA/HDPE blend was 80.7 KJ/m² and this value was 10–11 times higher than that of pure PA6. Particularly, differential scanning calorimetry results indicated that the bulk crystallization temperature of HDPE (114.6°C) was partly weakened and a new crystallization peak appeared at a lower temperature of around 102.2°C as a result of co‐crystal of HDPE and EPDM‐g‐MA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of layered silicates on fibril formation and properties of PCL/PLA microfibrillar composites

The study deals with improvement of poly(?‐caprolactone) (PCL) parameters by in situ forming of poly(lactic acid) (PLA) fibrils. This structure is achieved by preparation of the melt‐drawn microfibrillar composite (MFC) from the PCL/PLA 80/20 blend containing the organophilized montmorillonite (oMMT) added using various mixing protocols. Improved mechanical behavior corresponds to the micron‐sized fibrils formation and reinforcement of both polymer components by oMMT, and to increased crystalline phase content in the fibrillar PLA phase. Effective melt drawing is only possible after the rheological parameters of the polymer components have been modified by oMMT where the clay addition method and content are of primary importance. From the results obtained, it follows that the role of oMMT in MFC is quite complex, numerous clay‐induced effects may be contradictory and must be harmonized to achieve PCL‐based biodegradable MFCs with improved parameters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43061.     

Effect of hydrocarbon resin on the morphology and mechanical properties of isotactic polypropylene/clay composites

The article reports an investigation of the effect of a hydrocarbon resin, Necirés TR100, on the structure, morphology, and properties of two isotactic polypropylene/clay composites. The clays are Dellite HPS, a purified montmorillonite, and Dellite 67G, a purified and modified montmorillonite with a high content of quaternary ammonium salt. Necirés TR100 contains hydroxyl and acid groups, which were expected to interact during the melt mixing with the polar surface of the clays to have intercalation with Dellite HPS and/or exfoliation of Dellite 67G, which is already intercalated by the quaternary ammonium salt. The morphological results indicate that the composite isotactic polypropylene/Dellite HPS presents large and coarse clay domains, whereas the composite isotactic polypropylene/Dellite 67G presents a better distribution of the clay clusters, although the presence of some clay domains of a few μm are also detected. Although results from Wide Angle X‐ray Diffraction have indicated that Necirés TR100 has no effect on the layers distance of Dellite HPS and Dellite 67G its addition produces composites with clay particles homogenously distributed in the polyolefin matrix, better tensile properties (higher values of Young's modululs and elongation to break) and decrease of permeability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

High shear melt‐processing of fiberglass‐reinforced poly(trimethylene) terephthalate composites

As the demand for polymer‐matrix composites (PMC) expands in order to replace traditional materials, processing of the PMC is increasingly vital, as the morphology and properties are processing dependent. Typically, thermoplastic PMCs are processed in at least two heat‐intensive steps, including a pre‐compounding step in order to achieve good mixing followed by a part fabrication step. The key aim of this study is to prepare a fiberglass‐reinforced poly (trimethylene terephthalate) (FG‐PTT) composite using a one‐step, high shear melt‐processing method that achieves both compounding and part fabrication. The morphology, thermal properties, and mechanical properties are characterized to determine the effect of FG reinforcement on this renewable biopolymer. This novel method produces a FG‐PTT composite with superior mixing and tensile strength, as well as enhanced toughness, in one processing step, reducing polymer degradation and fiber attrition, as well as, time, energy, and cost requirements. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42714.     

Influence of the clay modification and compatibilizer on the structure and mechanical properties of ethylene–propylene–diene rubber/montmorillonite composites

Ethylene–propylene–diene rubber (EPDM)/montmorillonite (MMT) composites were prepared through a melt process, and three kinds of surfactants with different ammonium cations were used to modify MMT and affect the morphology of the composites. The morphology of the composites depended on the alkyl ammonium salt length, that is, the hydrophobicity of the organic surfactants. Organophilic montmorillonite (OMMT), modified by octadecyltrimethyl ammonium salt and distearyldimethyl ammonium salt, was intercalated and partially exfoliated in the EPDM matrix, whereas OMMT modified by hexadecyltrimethyl ammonium chloride exhibited a morphology in which OMMT existed as a common filler. Ethylene–propylene–diene rubber grafted with maleic anhydride (MAH‐g‐EPDM) was used as a compatibilizer and greatly affected the dispersion of OMMT. When OMMTs were modified by octadecyltrimethyl ammonium chloride and distearydimethyl ammonium chloride, the EPDM/OMMT/MAH‐g‐EPDM composites (100/15/5) had an exfoliated structure, and they showed good mechanical properties and high dynamic moduli. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 638–646, 2004     

Effects of compatibilizer,compounding method,extrusion parameters,and nanofiller loading in clay‐reinforced recycled HDPE/PET nanocomposites

Nanocomposites based on recycled high density polyethylene (rHDPE), recycled polyethylene terephthalate (rPET), and organoclay (C10A) were made using twin screw extruder followed by hot pressing. The independent effects of polymer/clay compatibility, preparation method, extrusion parameters, and clay loadings were investigated. Ethylene‐glycidyl methacrylate could effectively improve the compatibilization of immiscible rHDPE/rPET blend with clay, which confirmed by the good polymers‐clay adherence and domain size reduction obtained in scanning electron microscopy images. Although intercalated structures were observed in the composites made by one‐step compounding, in the composites prepared by two‐step extrusion method, enhanced dispersion of clay in polymer blend was found from X‐ray diffraction results. Higher extrusion temperature and intermediate speed of rotation (90 rpm) appeared to increase the mechanical properties due to improvement of nanofiller dispersion in matrix. Results showed that the stiffness increased whereas tensile and impact strength decreased with clay content. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42287.     

Preparation and properties of melt‐blended polylactic acid/polyethylene glycol‐modified silica nanocomposites

One commercial type of fumed silica modified with methoxy polyethylene glycol (mPEG) plasticizer was incorporated into polylactic acid (PLA) biobased polymer to improve its performance. The modification on silica was confirmed through Fourier transform infrared spectra, nuclear magnetic resonance, and TGA assessments. The grafting percentage of mPEG onto silica was about 19.8 wt %. Transmission electron microscope revealed a similar degree of dispersion for control silica and modified silica‐filled PLA nanocomposites. Not much difference in the glass transition temperatures at various silica contents was found for PLA/control silica systems from the differential scanning calorimetry measurement, but the glass transition temperature of PLA/modified silica nanocomposite at 10 phr of modified silica showed up to 11°C decrement. It was suggested that the mPEG plasticizer efficiently plasticized the PLA matrix through the enhanced segmental mobility of PLA chains. Young's modulus of PLA was about 2133 ± 53 MPa, and the value for the nanocomposite increased to 2547 ± 54 MPa at 10 of phr control silica mainly due to the reinforcing effect from nanoparticles. For modified silica, Young's modulus decreased at various silica contents. The elongation at break for modified silica‐filled cases was higher than that of control silica‐filled cases. These results were attributed to the plasticizing effect of surface modifier. Optical transmittance for pristine PLA was generally in a similar order as PLA/control silica and modified silica cases at various silica contents. The results agreed with the morphology observation as well. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

高密度聚乙烯/聚对苯二甲酸乙二醇酯原位成纤增强复合材料的形态与力学性能

用挤出-拉伸-注塑法制得了高密度聚乙烯/聚对苯二甲酸乙二醇酯(HDPE/PET)原位成纤增强复合材料,研究了PET质量分数对PET成纤性和材料拉伸强度及模量的影响及其作用机制。熔体拉伸时分散相液滴的聚结-形变成纤对PET相形态随PET质量分数的变化起关键作用,分散相对基体增强效应和两相界面缺陷效应相互竞争是决定拉伸强度随PET质量分数变化的重要因素,纤维对基体增刚作用受纤维数量和细度的双重控制是决定材料拉伸模量与PET质量分数关系的支配因素。     

Effect of graphite nanoplatelets on fracture behavior of HDPE/PA66 microfibrillar composites

Effect of in situ formation of PA66 fibrils and modification with graphite nanoplatelets (GNP) on fracture behavior of the high‐density polyethylene (HDPE)‐matrix microfibrillar composites (MFC) has been evaluated using tensile impact strength (TIS) and J‐integral methods. According to J‐integral, the main mechanism of failure is unstable crack growth; dissimilar layout of both methods causes different contribution of reinforcement with GNP and PA66 fibrils to fracture process evaluated. More marked orientation and parallel loading lead to increase in impact energy by both GNP and fibrils in TIS; on the other hand, much lower contribution of fibres and even negative effect of GNP pre‐blended in HDPE was found for J‐integral as a consequence of load acting in perpendicular direction. The fact that lower addition of GNP pre‐blended in PA66 does not deteriorate impact behavior indicates that such modification of MFC is an efficient way to get materials with enhanced, well‐balanced parameters. POLYM. ENG. SCI., 59:382–388, 2019. © 2018 Society of Plastics Engineers     

Preparation of HDPE/SEBS‐g‐MAH and its effect on mechanical properties of HDPE/wood flour composites

In this article, high density polyethylene/styrene‐ethylene‐butylene‐styrene block copolymer blends (HDPE/SEBS) grafted by maleic anhydride (HDPE/SEBS‐g‐MAH), which is an effective compatibilizer for HDPE/wood flour composites was prepared by means of torque rheometer with different contents of maleic anhydride (MAH). The experimental results indicated that MAH indeed grafted on HDPE/SEBS by FTIR analysis and the torque increased with increasing the content of maleic anhydride and dicumyl peroxide (DCP). Styrene may increase the graft reaction rate of MAH and HDPE/SEBS. When HDPE/SEBS MAH was added to HDPE/wood flour composites, tensile strength and flexural strength of composites can reach 25.9 and 34.8 MPa in comparison of 16.5 and 23.8 MPa (without HDPE/SEBS‐g‐MAH), increasing by 157 and 146%, respectively. Due to incorporation of thermoplastic elastomer in HDPE/SEBS‐g‐MAH, the Notched Izod impact strength reached 5.08 kJ m^?2, increasing by 145% in comparison of system without compatibilizer. That HDPE/SEBS‐g‐MAH improved the compatibility was also conformed by dynamic mechanical measurement. Scanning electron micrographs provided evidence for strong adhesion between wood flour and HDPE matrix with addition of HDPE/SEBS‐g‐MAH. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Structural,rheological, and mechanical properties of PA6/SAN/SEBS ternary blend/organoclay nanocomposites

The aim of this study was to investigate the effect of nanoclay addition on the morphological and mechanical properties of PA6/SAN/SEBS ternary blend. Two different nanoclays with different modifiers and two different mixing sequences were used to investigate the role of thermodynamic and kinetic, respectively, in the nanoclays localization. XRD, SEM, TEM, melt rheology, tensile and Izod impact tests were used to characterize the nanocomposites. Results of characterization of nanocomposites showed that clay localization is a very influential parameter to determine the type of morphology and, consequently, mechanical properties of ternary/clay nanocomposites. It was demonstrated that presence of nanoclay in the matrix results in the increase of stiffness, while localization of nanoclay at the interface improves the toughness and tensile strength. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41969.     

Investigation into the morphology and mechanical properties of melt‐drawn filaments from uncompatibilized blends of polystyrene and high‐density polyethylene

Uncompatibilized immiscible blends of polystyrene (PS) and high‐density polyethylene (HDPE) were melt‐processed in a single‐screw extruder fitted with a fine screen mesh and capillary die and were further drawn into filaments to produce near‐nanoscale immiscible domains. The resultant morphologies and mechanical properties were studied for these structures in which load transfer is achieved solely by mechanical linkages between blend domains. The morphology of the blends revealed co‐continuity approximately in the range of 45–47 volume percent PS. The development of a three‐dimensional co‐continuous network in 45 vol% PS, as revealed by morphology observations, was also related to a decrease in extruder output rate in this region, an indicator of the melt interaction of the two phases as co‐continuity is achieved. Image analysis revealed submicron fibrillar structures near the phase inversion composition where domain sizes ranged from 6–220 nm with an average domain size of 90 nm. Tensile modulus increased with increasing PS content (E = 2.7 GPa at 47% PS) over the entire blend range with values greater than the rule of mixtures up to 50% PS. Strain to failure did not seem to be influenced by co‐continuous morphologies and the fine dispersion of PS domains appears to constrain the fundamentally high strain of HDPE. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1616–1625, 2007     

Role of nanoclay distribution on morphology and mechanical behavior of rubber‐modified polyolefins

Polyolefin blends have attracted great attention for years because of their improved physical and mechanical properties; especially when micro/nanofillers are present in the compound. Previous investigations have proven that incorporation of small amounts of nanoclay can enhance physical and mechanical properties of the polymer. This research has focused on the role of clay distribution on morphology and mechanical properties of ternary nanocomposites containing a rubbery phase. High‐density polyethylene/ethylene vinyl acetate/clay (HDPE/EVA/clay) is opted as a typical model for this purpose. EVA is selected to act as both compatibilizer, because of having polar vinyl groups, and rubber‐modifier, because of its elastomeric properties, in this ternary blend. Nanocomposite preparation was performed via one‐ and two‐step mixing routes to achieve two different desired morphologies. Tensile and Izod impact tests, and different microscopic techniques, were used to evaluate nanostructure and mechanical performance of blends. Results of the study proved two distinct morphologies forming as a result of different incorporated processing techniques. Mixing components simultaneously leaded to a structure in which, clay platelets are located at the HDPE/EVA interface, whereas in the two‐step processing route, most of the clay platelets are encapsulated by the EVA second phase particles. According to the results of the current study, encapsulation of the nanofillers by the second rubbery phase harms mechanical properties of the blend and should be avoided. On the other hand, much better mechanical performance is obtained when the clay platelets are located at the matrix/rubber interface. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41993.     

Effect of titanate coupling agent on the mechanical properties of clay‐filled polybutadiene rubber

Clays belong to an economic class of fillers, which are used extensively in rubbers and plastics. Being nonreinforcing in nature, there are limitations upon its use. If the properties of filler are modified, it will get a higher value as a filler. To achieve this modification of surface properties is one of the avenues. In the present work, the effect of treatment of the coupling agent on clay has been studied, with polybutadiene as a matrix. Composites were made with a varying proportion of untreated and treated clay. A two‐roll mill was used for dispersing the filler in the rubber, and a compression‐molding technique was used to cure the compounded in sheet forms. Tensile properties were measured on a computerized UTM using the ASTM procedure. Comparison of properties of composites filled with treated and untreated clay established that treatment of clay imparts better reinforcing properties. The properties under consideration were tensile strength, modulus at 100 and 400%, Young's modulus, hardness, etc. Tensile strength was improved by 52%, while modulus at 400% was improved by 150%. Similarly Young's modulus also was improved by 27%. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1299–1304, 2004     

Influence of nanofiller dimensionality on the crystallization behavior of HDPE/carbon nanocomposites

The isothermal and nonisothermal crystallization behavior of high density polyethylene (HDPE) containing various zero, one, and two dimensional (0‐D, 1‐D, and 2‐D) carbon nanofillers were investigated by means of differential scanning calorimetry. For a given temperature, the isothermal crystallization incubation time of HDPE became longer with the addition of lower dimensional carbon nanofillers, and the isothermal crystallization rate got slower. The values of Avrami and Tobin exponents indicated that the isothermal crystallization of HDPE followed two‐dimensional crystal growth in the presence of 2‐D and 1‐D carbon nanofillers, while exhibited three‐dimensional heterogeneous crystal growth in the presence of 0‐D carbon nanofillers. Contrary to the isothermal study, the nonisothermal crystallization of HDPE was accelerated in the presence of lower dimensional nanofillers. The nonisothermal crystallization data were finally analyzed using Ozawa and Mo methods. It was observed that only Mo approach could successfully describe the nonisothermal crystallization process of HDPE and HDPE/carbon nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of HDPE/EPDM‐g‐TMEVS nanocomposites with enhanced electrical and flame properties

Nanoclay reinforced HDPE/silane grafted EPDM composites have been developed using an epoxy functionalized HDPE as compatibilizer.The nanoclay has been varied from 0% to 10% in the composites along with the incorporation of compatibilizer and without compatibilizer in a brabender plasticorder.The dielectric and fire retardant properties of these nanocomposites have been examined. Addition of nanoclay enhanced char formation with increased values of limiting oxygen index. Electrical properties such as volume and surface Resistivity improved with addition of nanoclay and compatibilizer. The values of tan δ increased with increase in grafted EPDM and silanated nanoclay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013