Preparation and UV weathering of polyethylene nanocomposites

Polyethylene / montmorillonite (PE/MMT) nanocomposites films were prepared by blending in the molten state: Low-density polyethylene (LDPE), montmorillonite clay, and polyethylene grafted maleic anhydride (LDPE-g-MA) or zinc neutralized carboxylate ionomer (Surlyn B) as compatibilizers. A chemically modified clay Cloisite 20A has been used. Nanocomposites were prepared by melt blending in a twin-screw extruder by using two-step mixing. Characterization of the nanocomposites was performed by mechanical properties, X-ray diffraction, light transmittance, infrared spectroscopy (FTIR) and transmission electronic microscope (TEM) techniques. Changes in UV irradiated nanocomposites film samples were characterized by FTIR. The results were analyzed in terms of the effect of the compatibilizing agent in the clay dispersion, and UV degradation of the nanocomposite.     

Polystyrene–organoclay nanocomposites prepared by melt intercalation,in situ,and masterbatch methods

In this study, polystyrene (PS)/montmorillonite nanocomposites were prepared by melt intercalation, in situ polymerization, and masterbatch methods. In the masterbatch method, as the first step, a high clay content composite of PS–organoclay (masterbatch) was prepared by in situ polymerization, and then the prepared masterbatch was diluted to desired compositions with commercial PS in a twin‐screw extruder. The structure and mechanical properties of the nanocomposites were examined. X‐ray diffraction (XRD) analysis showed that the d‐spacing of the in situ formed nanocomposites increased from 32.9 Å for the organoclay powder to 36.3 and 36.8 Å respectively in nanocomposites containing 0.73 and 1.6 wt% organoclay, indicating intercalation. However, the d‐spacing of the other prepared materials remained nearly unchanged when compared with pure organoclay powder. Thus, at these low clay contents, in situ formed nanocomposites showed the best improvement in mechanical properties including tensile, impact strength, and Young's modulus. In situ polymerization method did not prove to be efficient at high clay loadings in terms of intercalation and mechanical properties. At high clay loadings, the effects of the three methods in promoting mechanical properties were not significantly different from each other. POLYM. COMPOS., 27:249–255, 2006. © 2006 Society of Plastics Engineers     

Effect of Ionomeric Compatibilizer on Clay Dispersion in Polyethylene/Clay Nanocomposites

Summary: Linear low‐density polyethylene (LLDPE)/clay nanocomposites are obtained and studied by using a zinc‐neutralized carboxylate ionomer as a compatibilizer. LLDPE‐g‐MA is used as a reference compatibilizer. Two different clays, natural montmorillonite (Closite Na⁺) and a chemically modified clay Closite 20A have been used. Nanocomposites are prepared by melt blending in a twin‐screw extruder using two mixing methods: two‐step mixing and one‐step mixing. The relative influence of each compatibilizer is determined by wide‐angle X‐ray diffraction structural analysis and mechanical properties. The results are analyzed in terms of the effect of the compatibilizing agent and incorporation method in the clay dispersion, and the mechanical properties of the nanocomposites. Experimental results confirm that the film samples with ionomer show a good mechanical performance only slightly below that of the samples with maleic anhydride (MA). The two‐step mixing conditions result in better dispersion and intercalation for the nanofillers than one‐step mixing. The exfoliation of clay platelets leads to an improved thermal stability of the composite. The oxygen permeability of the clay nanocomposites, using ionomer as a compatibilizer, is decreased by the addition of the clay.

TEM image of a PE/4 wt.‐% Closite 20A nanocomposite formed using ionomer.     

Effect of clay on mechanical and gas barrier properties of blown film LDPE/clay nanocomposites

Low density polyethylene (LDPE)/clay nanocomposites, which can be used in packaging industries, were prepared by melt‐mix organoclay with polymer matrix (LDPE) and compatibilizer, polyethylene grafted maleic anhydride (PEMA). The pristine clay was first modified with alkylammonium salt surfactant, before melt‐mixed in twin screw extruder attached to blown‐film set. D‐spacing of clay and thermal behavior of nanocomposites were characterized by Wide‐Angle X‐ray Diffraction (WAXD) and differential scanning calorimetry (DSC), respectively. WAXD pattern confirmed the increase in PEMA contents exhibited better dispersion of clay in nanocomposites. Moreover, DSC was reported the increased PEMA contents caused the decrease in degree of crystallinity. Mechanical properties of blown film specimens were tested in two directions of tensile tests: in transverse tests (TD tests) and in machine direction tests (MD tests). Tensile modulus and tensile strength at yield were improved when clay contents increased because of the reinforcing behavior of clay on both TD and MD tests. Tensile modulus of 7 wt % of clay in nanocomposite was 100% increasing from neat LDPE in TD tests and 17% increasing in MD tests. However, elongation at yield decreased when increased in clay loading. Oxygen permeability tests of LDPE/clay nanocomposites also decreased by 24% as the clay content increased to 7 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Dynamically vulcanized polypropylene/ethylene‐propylene diene monomer/organoclay nanocomposites: Effect of mixing sequence on structural,rheological, and mechanical properties

Dynamically vulcanized thermoplastic elastomer (TPE) nanocomposites based on polypropylene (PP), ethylene‐propylene diene monomer (EPDM) and cloisite 15A were prepared via direct melt mixing in a co‐rotating twin‐screw extruder. The mixing process was carried out with optimized processing parameters (barrel temperature = 180°C; screw speed = 150 rpm; and feeding rate = 0.2 kg/hr). The formulation used to prepare the nanocomposites was fixed to 75/20/5 (PP/EPDM/Cloisite^©15A), expressed in mass fraction. Effect of mixing sequence on the properties of vulcanized and unvulcanized (TPE) nanocomposites prepared under similar conditions was investigated using X‐ray diffraction (XRD) and a tensile testing machine. Results showed that the sequence of mixing does affect the properties of final TPE nanocomposites. Accordingly, nanocomposite samples prepared through mixing the preblended PP/clay masterbatch with EPDM phase, show better clay dispersion within the polymer matrix. J. VINYL ADDIT. TECHNOL., 22:320–325, 2016. © 2014 Society of Plastics Engineers     

Preparation and mechanical properties of PP/PP-g-MA/Org-MMT nanocomposites with different MA content

Summary Polypropylene-clay nanocomposites were prepared by melt intercalation in a twin screw extruder using two mixing methods: two-step mixing and one-step mixing. The effect of using two different kinds of PP-g-MA (polypropylene-grafted maleic anhydride), with graft efficiencies of 0.1 and 1.0 wt% of MA and with different molecular weight, on clay dispersion and mechanical properties of nanocomposites was investigated. Three different clays, natural montmorillonite (Cloisite Na+) and chemically modified clays Cloisite 20A and Cloisite 30B were used. The relative influence of each factor was observed from structural analysis by WAXD, TEM, and mechanical properties. X-ray diffractometry (XRD) was used to investigate the intercalation effect in the nanocomposites. The results indicted that the intercalation effect and mechanical properties, specially modulus, tensile strength and impact strength, were enhanced by increasing the content of MA, using maleated PP with higher graft efficiency, and using the two step mixing conditions. Better dispersion and exfoliation were obtained when using clay 20A than 30B and natural Na+ montmorillonite. The results showed that clay dispersion and interfacial adhesion are greatly affected by the kind of maleated PP. The increase in content of polar groups gives as a result better interfacial adhesion and subsequent mechanical performance.     

Poly(lactic acid) and layered silicate nanocomposites prepared by melt mixing: Thermomechanical and morphological properties

Poly(lactic acid) (PLA) nanocomposites were prepared by melt mixing technique in a Haake batch mixer. The clay dispersion within the PLA matrix during melt mixing was well explained through the morphological characterization. Morphological characterizations were studied by X‐ray diffraction and transmission electron microscopy. The exfoliation/intercalation of the clay particles within the polymer matrix during melt mixing depends on the mixing torque generated during the preparation of nanocomposites. The significance of processing temperature and the mixing time in melt mixing were studied for PLA/C93A and PLA/C30B nanocomposites. The structure and properties of the nanocomposites were also characterized by differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and mechanical properties by standard tensile testing. The incorporation of nanoclays into the PLA matrix enhanced the mechanical properties and thermal stability of the PLA nanocomposites. This may be due to the reinforcing effect of nanoclays within the polymer matrix. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

The effect of clay type and of clay–masterbatch product in the preparation of polypropylene/clay nanocomposites

Clay containing polypropylene (PP) nanocomposites were prepared by direct melt mixing in a twin screw extruder using different types of organo‐modified montmorillonite (Cloisite 15 and Cloisite 20) and two masterbatch products, one based on pre‐exfoliated clays (Nanofil SE 3000) and another one based on clay–polyolefin resin (Nanomax‐PP). Maleic anhydride‐grafted polypropylene (PP‐g‐MA) was used as a coupling agent to improve the dispersability of organo‐modified clays. The effect of clay type and clay–masterbatch product on the clay exfoliation and nanocomposite properties was investigated. The effect of PP‐g‐MA concentration was also considered. Composite morphologies were characterized by X‐ray diffraction (XRD), field emission gun scanning electron microscopy (FEG‐SEM), and transmission electron microscopy (TEM). The degree of dispersion of organo‐modified clay increased with the PP‐g‐MA content. The thermal and mechanical properties were not affected by organo‐modified clay type, although the masterbatch products did have a significant influence on thermal and mechanical properties of nanocomposites. Intercalation/exfoliation was not achieved in the Nanofil SE 3000 composite. This masterbatch product has intercalants, whose initial decomposition temperature is lower than the processing temperature (T ～ 180°C), indicating that their stability decreased during the process. The Nanomax‐PP composite showed higher thermal and flexural properties than pure PP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of added ionomer on morphology and properties of PP/organoclay nanocomposites

Ethylene-methacrylic acid ionomer (Surlyn) with concentration up to 20 wt% based on total weight of polymer resin was added into polypropylene (PP)/organoclay hybrids. The microstructure, rheological properties, crystallization properties and mechanical properties of the obtained nanocomposites have been investigated. The addition of ionomer markedly enlarged interlayer spacing of the platelets and led to an improved degree of exfoliation. Moreover, clay silicates were found to selectively disperse either inside the ionomer phase or at the phase boundary. Compared to the binary immiscible blends, an improved interfacial adhesion was achieved for PP/Surlyn/OMMT hybrids. Unlike PP/Surlyn binary blends, the viscoelastic properties of the hybrids significantly increased with increasing Surlyn concentration, which could be attributed to the improved clay dispersion and the contribution of silicate layers at the interface between PP and Surlyn. A synergistic role between Surlyn and clay was also found to suppress the crystallization of PP matrix. In addition, PP/Surlyn/OMMT hybrids exhibited superior tensile strain compared to the corresponding PP/PP-g-MA/OMMT. Both tensile strength and elongation at break showed maximum at Surlyn concentration of 5 wt%. By comparing the experimental tensile yield strength with model prediction, it was suggested that the clay platelets localized at the interface could play a role of interfacial activation to some extent.     

Preparation and properties of chlorosulfonated polyethylene/organomontmorillonite nanocomposites

Chlorosulfonated polyethylene (CSPE)/organomontmorillonite (OMMT) nanocomposites were prepared by a melt intercalation method. The microstructure of the nanocomposites was characterized by transmission electron microscopy and X‐ray diffraction. The effects of the OMMT content on the mechanical properties and swelling behavior of the nanocomposites were investigated. The improvement in the thermal stability of the nanocomposites was determined by thermogravimetric analysis. Transmission electron microscopy and X‐ray diffraction showed that CSPE was intercalated into OMMT. When the OMMT content was lower than 12 wt %, the nanocomposites showed excellent tensile properties, which was attributed to nanometer‐scale dispersion. The introduction of a small amount of OMMT also improved the thermal stability and swelling behavior, which was attributed to the gas barrier action of the OMMT layers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphological evolution and mechanical property enhancement of natural rubber/polypropylene blend through compatibilization by nanoclay

Nanocomposites of natural rubber (NR)/polypropylene (PP) (80/20 wt %) blends filled with 5 phr pristine clay were prepared by melt‐mixing process. Effects of clay incorporation technique via conventional melt‐mixing (CV) and masterbatch mixing (MB) methods on nanostructure and properties of the blend nanocomposites were investigated. The XRD, SAXS, WAXD, and TEM results showed that the clays in the NR/PP blend nanocomposites were presented in different states of dispersion and were locally existed at the interface between NR and PP as well as dispersed in the NR matrix. The presence of clay caused unique morphological evolution such as fine fibrillar PP domains. The tensile strength was improved over the unfilled NR/PP blends by 53% and 224%, and the storage modulus at 25 °C was increased by 78% and 120% for the NR/PP/clay nanocomposites prepared by CV and MB methods, respectively. Significant improvement in both properties was particularly obtained from the MB method due to finer dispersion fibrillar PP phase in the NR matrix and stronger interfacial adhesion between NR and PP fibers, as suggested from DMA. The oil resistance of blend nanocomposites was also improved over that of the unfilled NR/PP blend, and this property was further progressed by the masterbatch mixing method. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44574.     

Relationship between structure and rheological,mechanical and thermal properties of polylactide/Cloisite 30B nanocomposites

Melt‐state and solid state mechanical properties and thermal stability of polylactide layered silicate nanocomposites elaborated by melt intercalation were studied as a function of clay content. Wide angle X‐ray scattering results, transmission electron microscopy observations, and rheological measurements indicated that the clay was finely distributed in the polylactide matrix. Contrary to nonlinear mechanical properties, thermal and linear mechanical properties were shown to increase with increasing clay fraction. The nanoindentation measurements confirm the significant increase of linear mechanical properties previously observed by tensile tests. The good correlation of linear mechanical properties at the macrometric and nanometric scales is explained by the high dispersion degree of the nanofiller in the biodegradable polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Correlation of morphology,rheology, and performance improvement in gasoline tubes based on PA‐6 nanocomposites

PA‐6/organo‐modified layered silicate nanocompounds were prepared by the melt mixing of PA‐6 with different nanoclay loadings in a corotating twin‐screw extruder. Gasoline tubes based on these nanocompounds were produced at different silicate loadings. Thermal, mechanical, rheological, and barrier properties of the different samples were investigated and correlated to their morphology. Transmission electron microscopy, wide angle X‐ray scattering, and linear melt state viscoelastic measurements were used to characterize the different aspects of nanoclay dispersion in the nanocomposite samples. While tensile modulus, softening point, heat distortion temperature, and gasoline barrier properties of the prepared tubes were improved considerably by increasing the clay content, performance improvement with respect to clay content (after a certain value) decreased with increasing clay loading. It could be attributed to the re‐agglomeration of tactoids at higher concentrations. These findings were correlated with the rheological and morphological observations. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Blown films of nanocomposites prepared from low density polyethylene and a sodium ionomer of poly(ethylene-co-methacrylic acid)

A detailed study of the performance of blown films prepared from nanocomposites based on LDPE and a sodium ionomer of poly(ethylene-co-methacrylic acid) is reported. The organoclay content and film blowing conditions were varied to determine the effect of platelet concentration, exfoliation and orientation on film properties. Mechanical properties including stiffness, puncture resistance, and resistance to tear propagation were evaluated and compared to corresponding properties of unfilled polymer films. Permeability of the films to moisture and common atmospheric gases like oxygen, nitrogen, and carbon dioxide was also measured using standard testing methods.In general, films prepared from nanocomposites based on the ionomer exhibited greater improvements in mechanical and barrier properties over unfilled polymer compared to similar films prepared from nanocomposites based on LDPE. This is due to the greater degree of organoclay exfoliation achieved in the ionomer compared to LDPE. The addition of 3 wt% MMT to the ionomer increased the tensile modulus of blown films by an average of 50% without sacrificing much tear strength, puncture resistance or film extensibility. Gas permeability in these films was lowered by 40% and moisture transmission rate was reduced by 60%.     

Morphology and mechanical properties of polypropylene/organoclay nanocomposites

Polypropylene (PP) nanocomposites were prepared by melt intercalation in an intermeshing corotating twin‐screw extruder. The effect of molecular weight of PP‐MA (maleic anhydride‐ modified polypropylene) on clay dispersion and mechanical properties of nanocomposites was investigated. After injection molding, the tensile properties and impact strength were measured. The best overall mechanical properties were found for composites containing PP‐MA having the highest molecular weight. The basal spacing of clay in the composites was measured by X‐ray diffraction (XRD). Nanoscale morphology of the samples was observed by transmission electron microscopy (TEM). The crystallization kinetics was measured by differential scanning calorimetry (DSC) and optical microscopy at a fixed crystallization temperature. Increasing the clay content in PP‐ MA330k/clay, a well‐dispersed two‐component system, caused the impact strength to decrease while the crystallization kinetics and the spherulite size remained almost the same. On the other hand, PP/PP‐MA330k/clay, an intercalated three‐component system containing some dispersed clay as well as the clay tactoids, showed a much smaller size of spherulites and a slight increase in impact strength with increasing the clay content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1562–1570, 2002     

Compounding of nanocomposites by thermokinetic mixing

Nanocomposites have been prepared by melt mixing poly(propylene) (PP) and different levels of a premixed montmorillonite‐organoclay masterbatch (PP/clay concentrate). Melt mixing was achieved using a Gelimat, a high‐speed thermokinetic mixer. The Gelimat system is designed to handle difficult compounding and dispersion applications and can achieve mixing, heating, and compounding of products within a minute. Therefore, the thermal history of the compounded polymer is short, which limits degradation. The structure and properties of the nanocomposites prepared with a Gelimat were compared to ones prepared with a twin‐screw extruder. The structure and properties of PP/clay nanocomposites were compared by TEM, X‐ray diffraction, mechanical testing, and rheological analysis. Results indicate that a better dispersion of the clay can be achieved by thermokinetic mixing when compared to extrusion, resulting in better mechanical properties. Calculations, based on simplifying assumptions, showed that the shear rates generated in a Gelimat are at least one order higher than those generally generated in an extruder. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1557–1563, 2005     

Transparent low‐density polyethylene/starch nanocomposite films

Low‐density polyethylene (LDPE)/starch nanocomposite films were prepared by melt extrusion process. The first step includes the preparation of starch–clay nanocomposite by solution intercalation method. The resultant product was then melt mixed with the main matrix, which is LDPE. Maleic anhydride‐grafted polyethylene (MAgPE), produced by reactive extrusion, was used as a compatibilizer between starch and LDPE phases. The effects of using compatibilizer, clay, and plasticizers on physico‐mechanical properties were investigated. The results indicated that the initial intercalation reaction of clay layers with starch molecules, the conversion of starch into thermoplastic starch (TPS) by plasticizers, and using MAgPE as a compatibilizer provided uniform distribution of both starch particles and clay layers, without any need of alkyl ammonium treatment, in LDPE matrix. The nanocomposite films exhibited better tensile properties compared to clay‐free ones. In addition, the transparency of LDPE film did not significantly change in the presence of TPS and clay particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties of layered silicate/starch polycaprolactone blend nanocomposites

The mechanical behavior of layered silicate/starch polycaprolactone blend nanocomposites was evaluated. Three different clays (Cloisite Na⁺, Cloisite 30B and Cloisite 10A) were used as reinforcement. Nanocomposites were prepared by melt intercalation followed by compression molding. These nanocomposites were characterized using X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis and tensile testing. X‐ray diffraction results showed that most of the clays were intercalated within the polymeric chains. In all cases, mechanical properties were improved with clay incorporation and the improvement was better as the clay content was increased. The best properties were achieved with Cloisite 10A due to their greatest compatibility with the matrix. A mechanical model, which takes into account the effective parameters of the clay, was used in order to estimate the dispersion of clay within the polymer. The highest dispersion was obtained for Cloisite 10A, which is in accordance with the experimental mechanical properties. Although dynamical‐mechanical properties improved with clay incorporation, the glass transition temperature was not affected. Copyright © 2006 Society of Chemical Industry     

Colorless polyimide nanocomposite films with pristine clay: Thermal behavior,mechanical property,morphology, and optical transparency

Polyimide (PI)/clay hybrids were synthesized using the in situ solution intercalation method via poly(amic acid). The Na ion‐exchanged clays Na⁺‐saponite (SPT), Na⁺‐mica (Mica), and Na⁺‐montmorillonite (MMT) were used for the intercalation of PI polymer chains. Our dispersion results show that pristine SPT is more easily dispersed in a PI matrix than MMT or Mica. PI nanocomposites were prepared with various SPT contents to examine the variations with SPT content in the range 0–1 wt% of the thermomechanical properties, morphology, and optical transparency of the nanocomposites. The PI films have excellent optical transparencies, and are almost colorless. However, the optical transparency of the PI hybrid films decreases slightly with increases in the clay content. We also examined the relationship between the properties and clay content of the PI hybrid films using wide‐angle X‐ray diffraction (XRD) measurements, electronic microscopy (SEM and TEM), and universal tensile machine (UTM). The color intensities of the PI films were evaluated with a spectrophotometer. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Barrier and mechanical properties of montmorillonite/polyesteramide nanocomposites

The barrier and mechanical properties of biodegradable melt‐mixed polyesteramide/octadecylamine‐treated montmorillonite clay (filler) have been studied. Extruded films containing 5 and 13 wt% filler were prepared by melt‐mixing. Samples compression molded after extrusion was also studied. Oxygen and water transmission rates were measured. X‐ray diffraction was used to assess the periodic distance of the clay layers and transmission electron microscopy was used to assess the composite morphology. An increase of the periodic distance from 23.7 Å for pure filler to 32–36 Å for the processed composites was observed. This suggested that the collapsed stacks of clay particle of the first order X‐ray reflection became intercalated upon extrusion. A decrease in the intensity with increasing rotation speed was observed, which suggested that higher shear rates promoted delamination, especially in composites with higher filler content. Transmission electron microscopy indicated that a sizable portion of the clay stacks were delaminated into smaller aggregates, containing generally one to three clay sheets. Density measurements indicated that shear‐induced voids were formed in the nanocomposite, and these were, according to transmission electron microscopy, almost exclusively located between the clay sheets. The presence of voids limited the improvement in barrier properties with increasing filler content. However, the very large improvement in stiffness and strength with filler content indicated that these properties were unaffected by these voids.