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.     

A comparative study on some properties of wood plastic composites using canola stalk,Paulownia, and nanoclay

In this research, the reinforcing effect of fillers including canola stalk, paulownia and nanoclay, in polypropylene (PP) has been investigated. In the sample preparation, 50 wt% of lignocellulosic materials and 0, 3, and 5 wt% of nanoclay particles were used. The results showed that while flexural and tensile properties were moderately enhanced by the addition of nanoclay in the matrix, notched Izod impact strengths decreased dramatically. However, with increase in the nanoclay content (5 wt%), the flexural and tensile properties decreased considerably. The mechanical properties of composites filled with paulownia are generally greater than canola stalk composites, due to the higher aspect ratio. The thickness swelling and water absorption of the composites significantly decreased with the increase in nanoclay loading. Except tensile modulus, the differences between the type of fibrous materials and nanoclay contents had significant influence on physicomechanical properties. Morphologies of the composites were analyzed using transmission electron microscopy (TEM) and X‐ray diffraction (XRD), and the results showed increased d‐spacing of clay layers indicating enhanced compatibility among PP, clay, and lignocellulosic material. TEM micrographs also confirmed that the composites containing 3 wt% nanoclay had uniform dispersion and distribution of clay layers in the polymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and characterization of EVA/clay Nanocomposites with improved barrier performance

Poly (ethylene‐co‐vinyl acetate) (EVA)/clay nanocomposites containing two different organoclays with different clay loadings were prepared. The transport of gases (oxygen and nitrogen) through the composite membranes was investigated and the results were compared. These studies revealed that the incorporation of nanoclays in the polymer increased the efficiency of the membranes toward barrier properties. It was also found that the barrier properties of the membranes decreased with clay loadings. This is mainly due to the aggregation of clay at higher loadings. The morphology of the nanocomposites was studied by scanning electron microscopy, transmission electron microscopy and X‐ray scattering. Small angle X‐ray scattering results showed significant intercalation of the polymer chains between the organo‐modified silicate layers in all cases. Better dispersed silicate layer stacking and more homogeneous membranes were obtained for Cloisite® 25A based nanocomposites compared with Cloisite® 20A samples. Microscopic observations (SEM and TEM) were coherent with those results. The dispersion of clay platelets seemed to be maximized for 3 wt % of clay and agglomeration increased with higher clay loading. Wide angle X‐ray scattering results showed no significant modifications in the crystalline structure of the EVA matrix because of the presence of the clays. The effect of free volume on the transport behavior was studied using positron annihilation spectroscopy. The permeability results have been correlated with various permeation models. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of polyimide nanocomposites with different organo‐montmorillonites

Poly(amic acid) nanocomposites were synthesized from a dimethylacetamide (DMAc) solution with two organophilic montmorillonites (organo‐MMTs). It was then heated at various temperatures under vacuum, yielding 15–20 um thick films of polyimide/organo‐MMT hybrid with different clay contents (1–8 wt%). Dodecy‐lamine (C₁₂‐) and hexadecylamine (C₁₆‐) were used as aliphatic alkylamines in organo‐MMT. The ultimate strength monotonically increased with increasing clay content in the polymer matrix. Maximum enhancement in the initial modulus was observed for the blends containing 2 wt% clay with two kinds of organo‐clays, and values did not alter significantly with further increases in clay content. Additions of only 2 wt% C₁₂‐ and C₁₆‐MMT to the polyimide were shown to cause 94%‐95% reduction in oxygen gas permeability. This is caused by the barrier properties of the clay layers dispersed in the composite. In general, C₁₆‐MMT is more effective than C₁₂‐MMT in increasing both the tensile property and the gas barrier in a polyimide matrix. Intercalations of the polymer chains in clay were examined through wide‐angle X‐ray diffraction (XRD) and electron microscopies (SEM and TEM).     

Microstructure‐properties correlations in dynamically vulcanized nanocomposite thermoplastic elastomers based on PP/EPDM

Thermoplastic vulcanized (TPV) nanocomposites were prepared in a laboratory mixer using EPDM, polypropylene of different viscosities, maleic anhydride modified polypropylene, an organo‐clay, and a sulfur‐based curing system. Based on the obtained results from X‐ray diffraction, transmission electron microscopy (TEM), scanning electron microscopy (SEM), differential scanning calorimeter, and mechanical properties, the microstructure of the prepared nanocomposites was found to be sensitive to the viscosity difference between the two phases and the clay content. X‐ray diffraction and TEM images of the TPV nanocomposites showed that clay was nearly exfoliated and randomly distributed into the polypropylene phase. The SEM photomicrographs of the dynamically vulcanized thermoplastic elastomer samples showed that the rubber particles were dispersed through the polypropylene in form of aggregates and their size increased with the introduction of clay. The nanoscale dimensions of the dispersed clay resulted in a significant improvement of the tensile modulus of the TPV nanocomposite samples, from 20 to 90% depending on clay content and the viscosity ratio of PP/EPDM. In the PP nanocomposites, the clay layers act as nucleating agents, resulting in higher crystallization temperature and reduced degree of crystallinity. Moreover, the oxygen permeability in the TPV nanocomposites was found to be lower than in unfilled but otherwise similar materials. POLYM. ENG. SCI., 47:207–217, 2007. © 2007 Society of Plastics Engineers.     

Preparation and characterization of chitosan/montmorillonite‐K10 nanocomposites films for food packaging applications

Chitosan (CS)/montmorillonite‐K10 (MMTK‐10) clay composite films with different amounts of the clay MMTK‐10 (0.5, 1, 2.5, and 5%) were prepared using a solution‐casting method, and their properties were determined. The objective of this study is to prepare CS/clay nanocomposites and then to investigate the effects of clay content on mechanical, barrier, and thermal properties of these nanocomposites. The prepared films were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction analysis, transmission electron microscopy, and scanning electron microscopy. Barrier properties (oxygen and water permeability), mechanical properties (tensile strength and elongation), and thermal behaviors (thermogravimetric analysis) were investigated and compared. The water vapor and gas permeability values of the composite films decreased significantly with increasing filler concentration. Tensile strength of the composites increased significantly with the addition of clay, and elongation at break decreased with increasing clay concentration. The tensile strength of nanocomposites is up to 34.82 MPa for 5 wt% clay content, and the tensile modulus shows a 74.63% higher value than that of neat CS. The resulting films had an opaque appearance, which depended on the amount of MMTK‐10 added. The oxygen permeability decreased with the increase in MMTK‐10. The minimum oxygen permeability (1.54 cm³/m² day atm) was recorded for film with 5% MMTK‐10. The water permeability of the composite films decreased significantly between 13 and 22% when clay was added. The dispersed clay improves the thermal stability and enhances the hardness and elastic modulus of the matrix systematically with the increased loading of clay. POLYM. COMPOS., 33:1874–1882, 2012. © 2012 Society of Plastics Engineers     

Poly(vinyl alcohol) nanocomposite films: Thermooptical properties,morphology, and gas permeability

Poly(vinyl alcohol) (PVA)/saponite nanocomposites were prepared with various clay concentrations with the solution intercalation method. The intercalations of the polymer chains in the clay were examined with wide‐angle X‐ray diffraction and transmission electron microscopy. The variations of the dispersion, morphology, thermal properties, and gas permeability of the nanocomposites with clay concentrations in the range of 0–10 wt % were examined. Up to a 5 wt % clay loading, the clay particles were highly dispersed in the PVA matrix without any agglomeration of particles. However, some agglomerated structures formed in the polymer matrix above a 7 wt % clay concentration. The thermal stability of the hybrids increased linearly with increases in the clay loading up to 10 wt %. To measure the oxygen permeability and optical properties of the PVA hybrid films, the PVA hybrid solutions were coated onto both biaxially oriented polypropylene and poly(ethylene terephthalate) films, which were used as polymer substrates. The oxygen permeability values monotonically decreased with increases in the clay loading in the range of 0–10 wt %. The optical properties, such as the haze and gloss of the hybrid films when coated onto the matrix films, were nearly constant, that is, independent of the clay loading. These improvements arose because of the largely nanometer‐scale dispersion of the clay layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 591–596, 2006     

Transparent copolyester/organoclay nanocomposites prepared by in situ intercalation polymerization: Synthesis,characterization, and properties

In this study, amorphous poly(ethylene terephthalate‐co‐1,3/1,4‐cyclohexylenedimethylene terephthalate) (PETG)/organoclay nanocomposites was synthesized by the in situ intercalation polymerization of terephthalic acid, ethylene glycol, 1,3/1,4‐cyclohexanedimethanol, and organoclay. The organoclay was obtained by modifying sodium montmorillonite (clay) with hexadecyl triphenylphosphonium bromide. The thermal, mechanical, optical, and gas barrier properties of these PETG nanocomposites with various organoclay contents (0–3 wt%) were discussed. The differential scanning calorimetry and X‐ray analyses revealed that all of the nanocomposites were amorphous. X‐ray diffraction and transmission electron micrographs showed that the organoclay was well dispersed in the polymer matrix, although some parts of the agglomerated layers remained on the scale of several hundreds of nanometers. The thermal stability and the mechanical property of the nanocomposites increased with organoclay content. The optical transmittances of nanocomposites that contained 0.5, 1, and 3 wt% of organoclay were 86.8%, 84.4%, and 77.4%, respectively. The oxygen transmission rate of the nanocomposite that contained 3 wt% of organoclay was about 50% of the PETG base polymer. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Processing of transmission electron microscope images for quantification of the layer dispersion degree in polymer‐clay nanocomposites

Quantification of the layered silicates dispersion level is necessary to more accurately evaluate the performance in polymer/clay nanocomposites. In this article, a new approach is developed to quantify the degree of exfoliation, intercalation, and immiscibility of layered silicates in polymer matrix, based on bright‐dark pixel measurement (BDPM) in transmission electron microscope (TEM) images. Several examples of exfoliated, intercalated, and immiscible composites with different polymer and clay systems were examined. The method is capable of estimating the percent contribution of all morphologies present in the image. Comparing with X‐ray diffraction (XRD) evidences, it is indicated that as a rule of thumb, the exfoliated structure is dominant whenever the exfoliation percent calculated by BDPM methodology is over 65%, no matter what kind of clay or polymer matrix is used. The intercalated structure can be ascribed to the images with exfoliation level less than 65%, but with the intercalation degree over 28%. Application of this method can facilitate the modeling or correlation of various nanocomposite properties with respect to exfoliation degree. A quantified relation is also possible between XRD and TEM using this approach. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Effect of bilayered stearate ion‐modified Mg?Al layered double hydroxide on the thermal and mechanical properties of silicone rubber nanocomposites

The homogeneous dispersion of nanofillers in polymer matrices to form polymer nanocomposites remains a challenge in the development of high‐performance polymer materials for various applications. In the work reported, a stearate ion‐modified Mg? Al layered double hydroxide (St‐LDH) as nanofiller was incorporated in a silicone rubber (SR) matrix by solution intercalation and subsequently characterized. X‐ray diffraction and transmission electron microscopy studies confirm the formation of a predominantly exfoliated dispersion of St‐LDH layers of 75–100 nm in width and about 1–2 nm in thickness in the SR. Thermogravimetric analysis shows that the thermal degradation temperature of the exfoliated SR/St‐LDH (1 wt%) nanocomposites is about 80 °C higher than that of pure SR. Differential scanning calorimetric studies indicate that the melting and crystallization temperatures are higher by 4 and 10 °C for 5 and 8 wt% St‐LDH‐loaded SR nanocomposites compared to neat SR. A significant improvement of 97% in tensile strength and 714% in storage modulus and a reduction of 82% in oxygen permeability have been achieved at 3 wt% St‐LDH loading in SR. Copyright © 2011 Society of Chemical Industry     

Effect of crosslinker and nanoclay on jute fabric reinforced soy flour green composite

Bio‐based composites were prepared by using soy flour, jute, glutaraldehyde (GA), nanoclay, and glycerol. An optimum concentration of glycerol was used as a plasticizer. The synthesized composites were characterized by various techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The exfoliation of clay layers was detected both by XRD and TEM study. FTIR study showed an interaction between clay, jute, and soy flour. The percentage content of GA and nanoclay was found to have profound influence on various physical properties of the composites. The increase in the concentration of GA and nanoclay improved the thermal stability, flame retardancy, dimensional stability, and most importantly the mechanical properties of the prepared composite. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Evaluation of polymethacrylic ionomer as compatibilizers for MCPA6/clay composites

The compatibilization effects provided by polymethacrylic ionomer (PMMA ionomer) on monomer‐casting polyamide6 (MCPA6)/clay (pristine sodium montmorillonite) composites were studied in this work. The PMMA ionomer used in this study was sodium polymethacrylate ionomer (PMMA Na⁺‐ionomer), which is a copolymer of methyl methacrylate and sodium methacrylate, prepared using emulsion polymerization. MCPA6/clay/PMMA Na⁺‐ionomer composites were prepared by in situ anionic ring‐opening polymerization (AROP) of ε‐caprolactam (CLA). X‐ray diffraction (XRD) and transmission electron microscopy (TEM) plus rheological measurement were used to characterize those composites. The results indicated that PMMA Na⁺‐ionomer is a good compatibilizer for this system. With increasing PMMA Na⁺‐ionomer content, a better dispersion of clay layers was successfully achieved in the MCPA6 matrix. Furthermore, differential scanning calorimetry (DSC) and XRD results indicated that well dispersed silicate layers limit the mobility of the MCPA6 molecule chains to crystallize, reduce the degree crystalline, and favor the formation of the γ‐crystalline form of the MCPA6 matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Epoxy‐clay nanocomposites: Influence of the clay surface modification on structure

In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Properties of poly(vinyl alcohol)—Bentonite clay nanocomposite films in relation to polymer–clay interactions

This study describes an effective way for the preparation of well‐dispersed, high‐loaded PVA/bentonite nanocomposites with improved properties, based on nanoscale interactions. To this end, a series of Poly(vinyl alcohol)—bentonite clay nanocomposites have been prepared via solvent casting technique and their properties were thoroughly investigated by atomic force microscopy, transmission electron microscopy, X‐Ray diffraction, oxygen and water permeability, water sorption along with mechanical and thermal studies. Microscopic and XRD techniques revealed highly organized regions. Clay content up to 10% led to nanocomposites with high degree of exfoliation. In addition samples with increased filler content (20%) demonstrated also, apart from the delaminated, well‐organized intercalated regions. The nanocomposites exhibited increased mechanical, thermal and gas barrier properties, though they retained their optical clarity. Thus, the Young's modulus of the sample containing 20% clay was increased by 193 times, while the oxygen permeability was decreased about seven times, in regard to the corresponding values of the neat polymer. The obtained results were explored on the basis of nanoscale phenomena and it was concluded that the organized structures and intercalated regions observed on highly loaded samples are attributed to the competitive effect between weaker polymer–polymer interactions in relation to stronger polymer–clay ones. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

In situ polymerization of polyethylene/clay nanocomposites using a novel clay‐supported Ziegler‐Natta catalyst

Polyethylene/clay nanocomposites (PECNC) were synthesized via in situ Ziegler‐Natta catalyst polymerization. Activated catalyst for polymerization of ethylene monomer has been prepared at first by supporting of the cocatalyst on the montmorillonite (MMT) smectite type clay and then active complex for polymerization formed by reaction of TiCl₄ and aluminum oxide compound on the clay. Acid wash treatment has been used for increasing hydroxyl group and porosity of the clay and subsequently activity of the catalyst. The nanostructure of composites was investigated by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Obtained results show that silica layers of the mineral clay in these polyethylene/nanocomposites were exfoliated, intercalated, and uniformly dispersed in the polyethylene matrix even at very high concentration of the clay. Thermogravimetric analysis (TGA) shows good thermal stability of the PECNCs. Differential scanning calorimeter (DSC) results reveal considerable decrease in the crystalline phase of the PECNC samples. Results of permeability analysis show an increase in barrier properties of PECNC films. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

The effects of clay dispersion on the mechanical,physical, and flame‐retarding properties of wood fiber/polyethylene/clay nanocomposites

In this study, nanosized clay particles were introduced into wood fiber/plastic composites (WPCs) to improve their mechanical properties and flame retardancy, which are especially important in various automotive and construction applications. A high degree of exfoliation for nanoclay in the wood fiber/high density polyethylene (HDPE) composites was successfully achieved with the aid of maleated HDPE (PE‐g‐MAn), through a melt blending masterbatch process. The structures and morphologies of the composites were determined using X‐ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. This article presents the effects of clay content and degree of clay dispersion on the mechanical and physical properties and flame retardancy of wood fiber/HDPE composites that contained a small amount of clay, in the range of 3–5 wt %. We concluded that achieving a higher degree of dispersion for the nanosized clay particles is critical to enhance the mechanical properties and the flame retardancy of WPCs when small amounts of clay are used. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Some important aspects in designing high molecular weight poly(L‐lactic acid)–clay nanocomposites with desired properties

BACKGROUND: The main aim of the work reported here was to investigate the effect of clay aspect ratio and functional edge group on the dispersion, degree of order of clays and interfacial strength of high molecular weight poly(L ‐lactic acid) (PLLA)–clay amorphous nanocomposites and consequently their properties. Three kinds of clays (two montmorillonites (SMMTC18 and NMMTC18) and one fluoro‐mica (MC18) with the same surfactant) were used to synthesize three amorphous nanocomposites. Thermomechanical properties, permeability, etc., were compared among composites and with pure PLLA. RESULTS: From X‐ray diffraction and transmission electron microscopy, both MMTs with lower aspect ratio showed better dispersion and greater degree of disorder, which led to stronger interfacial strength and consequently higher storage modulus than MC18‐based composites. All composites showed better properties than pure PLLA. The oxygen barrier efficiencies of SMMTC18‐ and NMMTC18‐based composites were higher than that of the MC18‐based composites. Due to the highest exposed area and probably stronger interactions, SMMTC18 had the highest nucleating efficiency. CONCLUSIONS: Along with aspect ratio, dispersion and degree of intercalation, the interfacial strength of composites and degree of order of clays are also important issues for property development. Compared to reported results in the literature, our amorphous composites showed less of an improvement of thermomechanical properties as real reinforcement was solely from clays. Copyright © 2008 Society of Chemical Industry     

Polymer–organoclay hybrids by polymerization into montmorillonite‐vinyl monomer interlayers

A different series of polymer–clay hybrid materials have been prepared by modification of the clay with different vinyl monomers, followed by polymerization of different ratios of vinyl monomers–clay with the monomers, such as methyl methacrylate, hydroxyethyl methacrylate, and styrene‐maleic anhydride. The materials were investigated by IR, which confirmed the intercalation of vinyl‐cation within the clay interlayers, and by TGA, which illustrated that phosphonium cation has high thermal stability than ammonium cation. Swelling studies of these materials in different organic solvents showed that the swelling degree increases as clay ratio decrease, and also showed higher swelling relative to vinyl–clay. X‐ray diffraction illustrated that the nanocomposites were exfoliated up to a 25 wt % content of organoclay relative to the amount of polymer. SEM and TEM examined the micrograph, which showed a good dispersion of the polymers into clay galleries, and formation of nanosize particles ranged 150–300 Å. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Comparative studies on corrosion protection properties of polyimide‐silica and polyimide‐clay composite materials

Comparative studies on corrosion protection properties of polyimide‐silica‐clay composites were studied in this article. A series of polyimide‐silica (PIS), polyimide‐clay (PIC), and polyimide‐silica‐clay composites (PISC) materials, consisting of an organo‐soluble polyimide (ODA‐BSAA) matrix, inorganic silica particles prepared through the sol–gel reaction of tetraethyl orthosilicate (TEOS) and dispersed nanolayers of inorganic montmorillonite clay, were successfully prepared by solution dispersion technique. Then, all samples were characterized by FTIR, powder X‐ray diffraction patterns, transmission electron microscopy, and ²⁹Si solid‐state NMR. The main focus of this article is the comparison of the corrosion protection properties of PIS, PIC, and PISC composite materials. Normally, the aspect ratio of clay is higher than silica. Superior dispersion of clay platelets into a polymer matrix may effectively increase the length of diffusion pathways for oxygen and water. The effects of the materials composition on the corrosion protection performance, gas barrier, and optical properties, in the form of both coating and film, were also studied by electrochemical corrosion measurements (e.g., corrosion potential, polarization resistance, corrosion current, and impedance spectroscopy), gas permeability analysis, and UV‐visible transmission spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011