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     

Study of the morphology and granulometry of polyethylene–clay nanocomposite powders

Medium‐density polyethylene (MDPE) matrix nanocomposites reinforced with different clay contents were produced by using a planetary ball mill. The morphology of all the milled samples, including pure polyethylene and the polyethylene–clay nanocomposites, was examined by scanning electron microscopy. To investigate the effects of milling time and clay content on the particle size of polyethylene powder, sieve analysis was used. The results showed that during milling, the regular shape of pure polyethylene powder converts into flake shapes and the average particle size of the powder increases upon increasing the milling time because the welding mechanism is predominant. Also, the presence of the clay can increase the maximum‐particle size, and increasing the clay content can decrease the milling time required to reach the same maximum particle size. J. VINYL ADDIT. TECHNOL., 2010. © 2009 Society of Plastics Engineers     

Rheology,morphology, and thermal behavior of HDPE/clay nanocomposites

HDPE/Clay nanocomposites were prepared using laboratory made HDPE grafted maleic anhydride (HDPE‐g‐MA) as a compatibilizer. Rheology, morphology, and thermal behavior of nanocomposites were studied. The results showed that increasing the degree of grafted MA increased the intercalation of clay platelets leading to their exfoliation. The presence of free MA enhanced the clay dispersion via regrafting onto PE matrix. Although the presence of antioxidant improved the thermal stability of PE, it decreased the clay dispersion because of inhibition of regrafting of free MAs. The exfoliated nanocomposites exhibited higher viscosity and elasticity than those of intercalated nanocomposites. They displayed viscosity upturn and nonterminal behavior of elasticity at low frequency ranges, representative of the creation of three‐dimensional networks via the individual clay platelets and/or chain bridging between the platelets. The presence of such a network was evidenced by tan δ studies. Incorporation of clay remarkably increased the thermal stability of the PE. It was found that the effect of Hofmann elimination reaction can effectively be eliminated using the antioxidant. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

PE/clay nanocomposites produced via in situ polymerization by highly active clay-supported Ziegler–Natta catalyst

The synthesis of polyethylene/clay (PE/clay) nanocomposites by means of in situ polymerization was achieved using the clay/BOM/chloroform/EtOH/TiCl₄/TEA catalyst system where butyl octyl magnesium (BOM) and triethyl aluminum (TEA) were a modifier for the clay and cocatalyst, respectively. It was found that the catalyst had high activity in ethylene polymerization. The microstructure of the resulting PE/clay nanocomposites was characterized by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. The examinations evidenced the nanocomposite formation with exfoliated clay in the PE matrix. The thermal properties of the produced nanocomposites were studied by differential scanning calorimetry, oxidation induction time, and thermal gravimetric analysis. Furthermore, the mechanical properties of the nanocomposites were evaluated by the impact and tensile tests. The examinations indicated the improved thermal stability and mechanical properties. Meanwhile, a wide range of molecular weights were produced in the presence of hydrogen.     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Morphology,mechanical properties,and thermal stability of rigid PVC/clay nanocomposites

PVC/Poly(ε‐caprolactone) (PCL)/organophilic‐montmorillonite (OMMT) and PVC/Polylactide (PLA)/OMMT nanocomposites were prepared by a two‐step process. PCL/OMMT and PLA/OMMT master batches were prepared by melt blending using a two‐roller mill first, and then they were blended with PVC via extrusion. PVC/OMMT nanocomposites were also prepared using a two‐roller mill. Morphology, mechanical properties, and thermal stability were investigated. The formation of exfoliated or intercalated nanocomposites was confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Only the PVC/PCL/OMMT nanocomposite showed both higher tensile strength and stiffness than unfilled PVC. Atomic force microscopy (AFM) indicated dependency of this behavior not only on the clay dispersion, but also on the adhesion between the OMMT and the polymer matrix. Furthermore, scanning electron microscopy (SEM) showed that the large plastic deformation of the PVC/PCL matrix also contributed to the strength increase of the PVC nanocomposites. The effect of PCL/OMMT on the improvement of the thermal stability of PVC was remarkable while the effect of PLA/OMMT was moderate. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers.     

Synthesis and characterization of polypropylene/clay nanocomposites

Polypropylene/clay (PP/clay) nanocomposites were synthesized via intercalative polymerization. The nanostructure of the composites was investigated by wide‐angle X‐ray diffractometry (WAXD) and transmission electron microscopy (TEM). The WAXD patterns of the PP/clay nanocomposites indicated that the characteristic diffraction peak of the clay disappeared. The TEM image showed the clay was exfoliated into nanometer size and dispersed uniformly in the PP matrix. The composites exhibited much higher storage modulus compared to that of pure PP. At temperatures higher than T_g, the storage modulus of the PP/clay nanocomposites with 8.1 wt % clay content increased three times that of the pure PP. Additionally, the thermal stability of the nanocomposites significantly increased. The maximum decomposition temperature was increased by 44°C with the introduction of about 10 wt % clay. The heat‐distortion temperatures (HDTs) of the nanocomposites also increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3611–3617, 2001     

Effect of clay on properties of polyimide‐clay nanocomposites

Effect of clay on mechanical, thermal, moisture absorption, and dielectric properties of polyimide‐clay nanocomposites was investigated. Nanocomposites of polyimide (ODA‐BSAA) hybridized with two modified clay (PK‐802 and PK‐805) were synthesized for comparison. The silicate layers in the polymer matrix were intercalated/exfoliated as confirmed by wide‐angle X‐ray diffraction and transmission electron microscopy. Thermal stability, moisture absorption, and storage modulus for these nanocomposites are improved as hybridized clay increases. Reduced dielectric constants due to the hybridization of layered silicates are observed at frequencies of 1 kHz–1 MHz and temperatures of 35–150°C. The tetrahedrally substituted smectite (PK‐805) resulted in higher mechanical strength and dielectric constants than those of octahedrally substituted smectite (PK‐802), which could be attributed to their stronger ionic bonding between clay layer and polymer matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 318–324, 2007     

Effects of clay dispersion and content on the rheological,mechanical properties,and flame retardance of HDPE/clay nanocomposites

Full exfoliation of clay/high density polyethylene (HDPE) nanocomposites was successfully achieved with the aid of maleated HDPE (PE‐g‐MAn), by melt blending in a twin‐screw extruder employing a long residence time configuration. The morphology of the composites was determined using wide‐angle X‐ray diffraction and transmission electron microscopy. The effects of clay content and state of clay dispersion on the rheological, tensile properties, and flame retardancy of nanocomposites containing very small amounts of clay, in the range of 0.05–1.0 wt %, were investigated in this study. It was demonstrated that achieving a higher degree of exfoliation for nanosized clay particles is key to enhancing the rheological, mechanical, and flame retarding properties even when small amounts of clay (less than 1%) are used. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

PVC‐clay nanocomposites: Preparation,thermal and mechanical properties

PVC‐clay nanocomposites were prepared by melt blending of the polymer with an organically modified clay, both in the presence and in the absence of di(2‐ethylhexyl) phthalate (DOP). The clay can serve as a plasticizer for PVC in the absence of DOP. The nanocomposites were characterized by using X‐ray diffraction and transmission electron microscopy, and the materials were found to be largely intercalated. Thermal properties were evaluated by using thermogravimetric analysis, and the thermal stability was determined to be variable, depending upon the amounts of clay and DOP that were present. The fraction of polymer that remained at 600°C was significantly reduced in the presence of the clay, a result indicating that the clay had an effect on the course of the degradation of the PVC. The tensile strength of the nanocomposites increased as the fraction of clay increased, and the addition of a small amount of clay increased the elongation, but when additional clay was added, the elongation decreased.     

Enhancement of radiation‐resistant effect in ethylene–vinyl acetate copolymers by the formation of ethylene–vinyl acetate copolymers/clay nanocomposites

Ethylene–vinyl acetate (EVA) copolymers/clay nanocomposites, prepared by using nonreactive organophilic clay and reactive organophilic clay, were characterized by X‐ray diffraction and by high‐resolution transmission electron microscopy. The influence of gamma irradiation on the structure and properties of the pure EVA and EVA/clay nanocomposites was systematically investigated. In the presence of gamma radiation, the clay can effectively restrain the increase of the storage modulus of EVA/clay nanocomposites, which was supported by dynamical mechanical analysis. Gamma irradiation had almost no effect on the thermal properties of EVA/clay nanocomposites by using nonreactive organophilic clay, but it obviously improved the thermal stability of EVA/clay nanocomposites by using reactive organophilic clay. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2532–2538, 2005     

Electrolytic admicellar polymerization of pyrrole on natural rubber/clay nanocomposites

Organic–inorganic composites consisting of natural rubber (NR), polypyrrole (PPy), and sodium montmorillonite (Na‐MMT) were synthesized via electrolytic admicellar polymerization. A constant potential of 9 volts was chosen for the synthesis. The PPy concentration was fixed at 100 mM, and the clay contents were varied from 1 to 7 parts per hundred of rubber (phr). The synthesized nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy (TEM), together with thermal stability (TGA), mechanical properties, and electrical conductivity (σ_dc) studies. The FTIR spectra indicated the characteristic peaks of both PPy and MMT clay and also evidenced a slight interaction between the PPy chain and the clay layers, verifying the success of electrolytic admicellar polymerization. XRD and TEM results pointed out the good dispersion of clay platelets in the polymer matrix, suggesting an exfoliated structure. The morphology of the nanocomposites was greatly dependent on the amount of MMT clay, especially at a 7 phr loading. The initial modulus and tensile strength of the nanocomposites containing the 7 phr loading were about four and two times higher, compared with unfilled NR/PPy, respectively. Thermal stability studies revealed a slight improvement in the decomposition temperature for the PPy component by the clay layers, whereas the opposite trend was found for the NR component. More interestingly, the electrical conductivity of the admicelled rubber increased significantly (～ 19–32 times) with increasing clay contents from 1 to 7 phr, in comparison with unfilled NR/PPy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and material properties of syndiotactic polystyrene/organophilic clay nanocomposites

Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were fabricated by direct‐melt intercalation method. To overcome the thermal instability of organophilic clay at high‐melt processing temperatures of sPS, an organophilic clay modified by alkyl phosphonium was adopted, which is known to be thermally stable. By using the newly synthesized clay, we could fabricate sPS intercalated nanocomposites. The microstructures of nanocomposites were confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The crystallization rate of nanocomposites investigated by differential scanning calorimetry (DSC) does not increase despite the presence of clay, which may be due to the physical hindrance of organic modifiers in the clay dispersion. Nanocomposites exhibited enhanced mechanical properties such as strength and stiffness relative to the virgin polymer. In addition, thermal stability was confirmed to be improved by thermogravimetric analysis (TGA). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2144–2150, 2004     

Synthesis and properties of BCDA‐based polyimide–clay nanocomposites

Bicyclo[2.2.2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BCDA)‐based polyimide–clay nanocomposites were prepared from their precursor, namely polyamic acid, by a solution‐casting method. The organoclay was prepared by treating sodium montmorillonite (Kunipia F) clay with dodecyltrimethylammonium bromide at 80 °C. Polyamic acid solutions containing various weight percentages of organoclay were prepared from 4,4′‐(4,4′‐isopropylidenediphenyl‐1,1′‐diyldioxy)‐dianiline and BCDA in N‐methyl‐2‐pyrrolidone containing dispersed particles of organoclay at 20 °C. These solutions were cast on a glass plate using a Doctor's blade and then heated subsequently to obtain nanocomposite films. The nanocomposites were characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal mechanical analysis, dynamic mechanical analysis, polarizing microscopy, scanning electron microscopy, transmission electron microscopy, wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis. The glass transition temperature of the nanocomposites was found to be higher than that of pristine polymer. The coefficient of thermal expansion of the nanocomposites decreased with increasing organoclay content. WAXD studies indicated that the extent of silicate layer separation in the nanocomposite films depended upon the organoclay content. Tensile strength and modulus of the nanocomposite containing 1% organoclay were significantly higher when compared to pristine polymer and other nanocomposites. The thermal stability of the nanocomposites was found to be higher than that of pristine polymer in air and nitrogen atmosphere. Copyright © 2007 Society of Chemical Industry     

Preparation and characteristics of nitrile rubber (NBR) nanocomposites based on organophilic layered clay

The effect of clay modification on organo‐montmorillonite/NBR nanocomposites has been studied. Organo‐montmorillonite/NBR nanocomposites were prepared through a melt intercalation process. NBR nanocomposites were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and a universal testing machine (UTM). XRD showed that the basal spacing in the clay increased, which means that the NBR matrix was intercalated in the clay layer galleries. On TEM images, organo‐montmorillonite (MMT) particles were clearly observed, having been exfoliated into nanoscale layers of about 10–20 nm thickness from their original 40 µm particle size. These layers were uniformly dispersed in the NBR matrix. The DMTA test showed that for these nanocomposites the plateau modulus and glass transition temperature (T_g) increased with respect to the corresponding values of pure NBR (without clay). UTM test showed that the nanocomposites had superior mechanical properties, ie strength and modulus. These improved properties are due to the nanoscale effects and strong interactions between the NBR matrix and the clay interface. Copyright © 2003 Society of Chemical Industry     

Effects of clay dispersion on the foam morphology of LDPE/clay nanocomposites

Intercalated and exfoliated low‐density polyethylene (LDPE)/clay nanocomposites were prepared by melt blending with and without a maleated polyethylene (PE‐g‐MAn) as the coupling agent. Their morphology was examined and confirmed by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of clay content and dispersion on the cell morphology of nanocomposite foams during extrusion foaming process were also thoroughly investigated, especially with a small amount of clay of 0.05–1.0 wt%. This research shows the optimum clay content for achieving microcellular PE/clay nanocomposite foams blown with supercritical CO₂. It is found that < 0.1 wt% of clay addition can produce the microcellular foam structure with a cell density of > 10⁹ cells/cm³ and a cell size of ～ 5 μm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2129–2134, 2007     

Comparison of the influence of different compatibilizers on the structure and properties of ethylene vinyl acetate copolymer/modified clay nanocomposites

Nanocomposites of an ethylene vinyl acetate copolymer and clay were prepared by melt blending and extrusion. Two different compatibilizers, ethylene glycidyl methacrylate (EGMA) and maleic anhydride grafted polypropylene (MAPP), were used in these nanocomposites. The structural properties of the composites were characterized with X‐ray diffraction and transmission electron microscopy. The surface morphology was characterized with polarized optical microscopy. The tensile and permeability properties were studied. The thermal stability of the nanocomposites was characterized through thermogravimetric analysis. MAPP‐compatibilized nanocomposites had intercalated and partially exfoliated structures, whereas EGMA‐compatibilized nanocomposites had completely exfoliated structures. The EGMA‐compatibilized nanocomposites were thermally more stable than the MAPP‐compatibilized nanocomposites. The mechanical and permeability properties of the EGMA‐compatibilized nanocomposites were better than those of the MAPP‐compatibilized nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Thermal degradation mechanism of polycarbonate/organically modified montmorillonite nanocomposites

There were contradictory results about the effect of clay on polycarbonate (PC) thermal stability in previous reported papers. For ascertainment of the actual role of clay, PC nanocomposites were prepared by direct melt‐mixing PC with hexadecyl trimethyl ammonium chloride modified montmorillonite (OMT). The results of X‐ray diffractometry, transmission electron microscopy, and high‐resolution electron microscopy experiments present the formation of uniformly intercalated structure. Thermogravimetric analyses show the onset decomposition temperature of PC/OMT nanocomposites is earlier 65°C than neat PC. The mechanism of PC thermal decomposition effected by OMT was discussed in detail. It reveals that OMT can catalyze thermal degradation of PC macromolecular chains and decrease thermal stability of the nanocomposites. POLYM. COMPOS., 37:2301–2305, 2016. © 2015 Society of Plastics Engineers     

Modifying montmorillonite clay via silane grafting and interfacial polycondensation for melt compounding of nylon‐66 nanocomposite

A trifunctional organo alkoxysilane (3‐aminopropyl)triethoxysilane (γ‐APS) has been used as reagent for the chemical modification of montmorillonite clay. Silane grafting was taken place in dry and hydrolyzing conditions. Silane grafted and pristine clay took part in interfacial polycondensation process to deposit a layer of nylon‐66 onto the clay lamellae and therefore, enhance their affinity with nylon‐66 matrix. Evidence of presence of grafted silane molecules and deposition of nylon‐66 on clay particles were provided by Fourier transform‐infrared, thermogravimetric analysis (TGA), and X‐ray diffraction (XRD). Such modified clays and pristine clays were melt compounded with nylon‐66. The structures of the resulting nylon composites were characterized using XRD and transmission electron microscopy and the results showed presence of both intercalation and exfoliation. TGA thermograms of nanocomposites indicated improved thermal stability upon the incorporation of silane grafted montmorillonite. Furthermore, differential scanning calorimetry scans showed that silane modified clays promoted crystallization in nanocomposites. Increase of storage modulus and depression of tan δ peak in nanocomposites in dynamical mechanical thermal analysis were observed. The rheological properties of nylon‐66 and nanocomposites were also evaluated and differences in values of complex viscosity of samples were noticed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of different kinds of clay and different vinyl acetate content on the morphology and properties of EVA/clay nanocomposites

A series of EVA/clay nanocomposites and microcomposites have been prepared via melt-blending. Using four kinds of EVA with different vinyl acetate (VA) contents: 28, 40, 50 and 80 wt%, and four kinds of clay: three are organophilic clay (OMMT) and one unfunctionalized clay (Na-MMT), the effects of different VA content of EVA and the kinds of the clay on the morphology and properties of EVA/clay nanocomposites were systematically investigated. In previous studies, there are only two distinct nanostructures to distinguish polymer/clay nanocomposites: the intercalated and the exfoliated. But in this paper, we proposed a new nanostructure—‘the wedged’ to describe the dispersion degree of clay in nanocomposites, it means the sheets of clay were partly wedged by the chains of polymer. The wedged, the intercalated and the partially exfoliated structures of EVA/clay nanocomposites were characterized by X-ray diffraction (XRD) and by high-resolution transmission electron microscopy (HRTEM). The enhanced storage modulus of EVA/clay nanocomposites was characterized by dynamic mechanical thermal analysis (DMTA). The enhanced degree in the storage modulus of the OMMT on EVA/clay nanocomposites with the partially exfoliated and intercalated structure is much higher than that with wedged structure, and that with the higher VA content is higher than that with the lower. The thermal stabilities of EVA/clay nanocomposites were also studied by thermal gravimetric analysis (TGA).