Poly(vinyl alcohol) nanocomposites with different clays: Pristine clays and organoclays

Poly(vinyl alcohol) (PVA)/clay nanocomposites were synthesized using the solution intercalation method. Na ion‐exchanged clays [Na⁺–saponite (SPT) and Na⁺–montmorillonite (MMT)] and alkyl ammonium ion‐exchanged clays (C₁₂–MMT and C₁₂OOH–MMT) were used for the PVA nanocomposites. From the morphological studies, the Na ion‐exchanged clay is more easily dispersed in a PVA matrix than is the alkyl ammonium ion‐exchanged clay. Attempts were also made to improve both the thermal stabilities and the tensile properties of PVA/clay nanocomposite films, and it was found that the addition of only a small amount of clay was sufficient for that purpose. Both the ultimate tensile strength and the initial modulus for the nanocomposites increased gradually with clay loading up to 8 wt %. In C₁₂OOH–MMT, the maximum enhancement of the ultimate tensile strength and the initial modulus for the nanocomposites was observed for blends containing 6 wt % organoclay. Na ion‐exchanged clays have higher tensile strengths than those of organic alkyl‐exchanged clays in PVA nanocomposites films. On the other hand, organic alkyl‐exchanged clays have initial moduli that are better than those of Na ion‐exchanged clays. Overall, the content of clay particles in the polymer matrix affect both the thermal stability and the tensile properties of the polymer/clay nanocomposites. However, a change in thermal stability with clay was not significant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3208–3214, 2003     

Preparation and properties of montmorillonite‐based polyimide nanocomposites

Montmorillonite (MMT)‐based polyimide (PI) nanocomposites were prepared via two‐stage polymerization of PI using polyamic acid (PAA). The clay was organically modified using various alkylammonium ions to examine the effect of changes in alkyl length on the intercalation spacing of both the treated clays and their hybrids with PAA and PI. The intercalation behavior of clay in the PI matrix and its thermal and mechanical properties were investigated as a function of clay concentration. The d‐spacing of organically modified MMT (O‐MMT) increased with increasing length of the alkylammonium chain. PI/O‐MMT hybrids form exfoliated nanocomposites at clay concentrations below 2 wt%, while they form intercalated nanocomposites together with some exfoliated ones at clay contents exceeding 4 wt%. Young's modulus increased rapidly to a clay loading of 2 wt%, and leveled off with further increases in clay loading. The tensile strength at break increased rapidly up to a clay loading of 1 wt%, and then decreased sharply, while the strain at break showed a monotonic decrease with increasing clay loading from 0 to 8 wt%. The storage modulus, E′, in the temperature range below the glass transition temperature T_g, generally increased with increasing clay content, except at the highest clay content of 8 wt%. Copyright © 2004 Society of Chemical Industry     

Effect of shear rate on structural,mechanical, and barrier properties of chitosan/montmorillonite nanocomposite film

The dispersion of MMT‐Na⁺ (montmorillonite) layers in a chitosan polymer matrix, using the homogenization, was performed. The effect of shear rate was characterized on the mechanical, barrier, and structural properties of nanocomposites. Elongation at break (EAB) was unaffected by shear rate, which decreased after homogenization, increased above 13,000 rpm, however, tensile strength (TS) dramatically increased up to 59 MPa at 16,000 rpm. Water vapor permeability (WVP) and oxygen permeability (OP) of the homogenized nanocomposite decreased more than that of untreated nanocomposite and OP was not significantly changed above 16,000 rpm of shear rate. XRD result and TEM images indicated that three types of tactoids, exfoliation, and intercalation were generated and the largest distance of 18.87 Å between MMT‐Na⁺ layers was produced at 16,000 rpm. The results indicate that homogenization was a beneficial method for effectively dispersing MMT‐Na⁺ layers in a chitosan polymer matrix and that a shear rate of 16,000 rpm was the effective condition. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Surface‐modifiers of clay on mechanical properties of rigid polyurethane foams/organoclay nanocomposites

Three different surface modifiers, octadecyl trimethyl ammonium (ODTMA), octadecyl primary ammonium (ODPA), and decanediamine (DDA) were used to modify Na⁺? montmorillonite (MMT), and the resultant organoclays were coded as ODTMA‐MMT, ODPA‐MMT, DDA‐MMT, respectively. Rigid PU foams/organoclay composites were prepared by directly using organoclay as the blowing agent without the addition of water. Investigation shows that the morphology of the nanocomposites is greatly dependent on the surface modifiers of clay used in the composites. In detail, DDA‐MMT is partially exfoliated in the PU matrix with the smallest cell size, while two others are intercalated in the PU matrices with smaller cell sizes. The sequence of their cell sizes is pristine PU foams > rigid PU foams/ODTMA‐MMT > rigid PU foams/ODPA‐MMT > rigid PU foams/DDA‐MMT, and the average cell size of rigid PU foams/DDA‐MMT composites decreases evidently from 0.30 to 0.07 mm. Moreover, all rigid PU foams/organoclay composites show remarkable enhanced compressive and tensile strengths as well as dynamic properties than those of PU foams, and the enhancement degree coincides well with the relative extent of internal hydrogen bonding of materials and gallery spacing of organoclay. For example, in the case of rigid PU foams/DDA‐MMT composite, 214% increase in compressive strength and 148% increase in tensile strength compared with those of pure PU foams were observed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

Chitosan/clay nanocomposite film preparation and characterization

Nanocomposites of chitosan and nanoclays (MMT‐Na⁺ and Cloisite 30B) were prepared by solvent casting. The structural properties, thermal behaviors, and mechanical properties were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy, differential scanning calorimetry, thermogravimetry analyses, and an Instron universal testing machine. XRD and TEM results indicated that an exfoliated structure was formed with addition of small amounts of MMT‐Na⁺ to the chitosan matrix. Intercalation along with some exfoliation occurred with up to 5 wt % MMT‐Na⁺. Micro‐scale composite (tactoids) formed when Cloisite 30B was added to the chitosan matrix. Surface roughness increased with addition of a small amount of clay. Tensile strength of a chitosan film was enhanced and elongation‐at‐break decreased with addition of clay into the chitosan matrix. Melt behavior and thermal stability did not change significantly with addition of clays. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1684–1691, 2006     

Rigid PVC/(layered silicate) nanocomposites produced through a novel melt‐blending approach

On the basis of the fusion behavior of poly(vinyl chloride) (PVC), the influence of compounding route on the properties of PVC/(layered silicate) nanocomposites was studied. Four different compounding addition sequences were examined during the melt compounding of PVC with montmorillonite (MMT) clay, including (a) a direct dry mixing of PVC and nanoclay, (b) an addition of nanoclay at compaction, (c) an addition of nanoclay at the onset of fusion, and (d) an addition of nanoclay at equilibrium torque. Both unmodified sodium montmorillonite (Na⁺‐MMT) and organically modified montmorillonite (Org.‐MMT) clays were used, and the effect of the addition sequence of the clay during compounding on its dispersion in the matrix was evaluated by X‐ray diffraction and transmission electron miscroscopy. The surface color change, dynamic mechanical analysis, and flexural and tensile properties of PVC/clay nanocomposites were also studied. The experimental results indicated that both the extent of property improvement and the dispersion of nanoparticles in PVC/(layered silicate) nanocomposites are strongly influenced by the degree of gelation achieved in PVC compounds during processing. The addition of nanoclay to PVC must be accomplished at the onset of fusion, when PVC particles are reduced in size, in order to produce nanocomposites with better nanodispersion and enhanced mechanical properties. Overall, rigid PVC nanocomposites with unmodified clay (Na⁺‐MMT) were more thermally stable and exhibited better mechanical properties than their counterparts with organically modified clay (Org.‐MMT). J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Morphology and properties of PVC/clay nanocomposites via in situ emulsion polymerization

PVC/Na⁺–montmorillonite (MMT) nanocomposites were prepared via a simple technique of emulsion polymerization at several different MMT clay concentrations. X‐ray diffraction and transmission electron microscopy studies revealed the formation of a mixture of intercalated and exfoliated nanostructure. Tensile testing results showed that the tensile modulus of the nanocomposites increased with the addition of clay, while the tensile strength decreased little. The notched impact strength of the nanocomposites was also improved. For systems containing clay in the range of 2.1 to 3.5 wt %, the impact strength was almost two times as large as that of pure PVC. However, those mechanical properties began to decrease with the continuously increasing amount of clay. The fracture surface of pure PVC and the nanocomposites was observed by scanning electron microscope. Thermal properties of the nanocomposites were found to increase as a result of clay incorporation. The glass transition temperatures of the PVC/clay nanocomposites were nearly identical to that of pure PVC. The Vicat softening points exhibited a progressively increasing trend with the clay content added. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 277–286, 2004     

Ethylene propylene diene terpolymer/ethylene vinyl acetate/layered silicate ternary nanocomposite by solution method

A new ternary nanocomposite has been developed using ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA‐45) copolymer, and organically modified layered silicate (16 Me‐MMT) from sodium montmorillonite (Na⁺‐MMT). Wide angle X‐ray diffraction and transmission electron microscopic analysis confirmed the intercalation of the polymer chains in between the organosilicate layers and the nanoscale distribution of 16 Me‐MMT in polymer matrix, respectively. The measurement of mechanical properties for 2–8 wt% of 16 Me‐MMT loadings showed a significant increase in tensile strength, elongation at break, and modulus at different elongations. Such an improvement in mechanical properties has been correlated based on the fracture behavior of nanocomposite by SEM analysis. Thermal stability of EPDM/EVA/layered silicate ternary nanocomposites also showed substantial improvements compared with the neat EPDM/EVA blend, confirming thereby the formation of a high performance nanocomposite. POLYM. ENG. SCI., 46:437–843, 2006. © 2006 Society of Plastics Engineers     

Synthesis of Na+‐montmorillonite/amphiphilic polyurethane nanocomposite via bulk and coalescence emulsion polymerization

Polyurethane/clay nanocomposites have been synthesized using Na⁺‐montmorillonite (Na⁺‐MMT)/amphiphilic urethane precursor (APU) chains that have hydrophilic polyethylene oxide (PEO) chains and hydrophobic segments at the same molecules. Nanocomposites were synthesized through two different crosslinking polymerization methods. One is UV curing of melt mixed APU/Na⁺‐MMT mixtures; the other is coalescence polymerization of APU/Na⁺‐MMT emulsions. These two kinds of composites had intercalated silicate layers of Na⁺‐montmorillonite by insertion of PEO chains in APU chains, which was confirmed by X‐ray diffraction measurement and transmission electron microscopy. These composite films also showed improved mechanical properties compared to pristine APU films. Although the two kinds of nanocomposites exhibited the same degree of intercalation and were synthesized based on the same precursor chains, these nanocomposite films had the different mechanical properties. Nanocomposites synthesized using APU/Na⁺‐MMT emulsions, having microphase‐separated structure, had greater tensile strength than those prepared with melt‐mixed APU/Na⁺‐MMT mixtures. Location of intercalated Na⁺‐MMT by PEO chains at the oil–water interface also could be confirmed by rheological behavior of the APU/Na⁺‐MMT/water mixture. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3130–3136, 2003     

Synthesis and characterization of epoxy based nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of the content and type of different clays on the structure and mechanical properties of the nanocomposites. Diglycidyl ether of bisphenol‐A (epoxy) was reinforced by 0.5–11 wt % natural (Cloisite Na⁺) and organically modified (Cloisite 30B) types of montmorillonite. SEM results showed that as the clay content increased, larger agglomerates of clay were present. Nanocomposites with Cloisite 30B exhibited better dispersion and a lower degree of agglomeration than nanocomposites with Cloisite Na⁺. X‐ray results indicated that in nanocomposites with 3 wt % Cloisite 30B, d‐spacing expanded from 18.4 Å (the initial value of the pure clay) to 38.2 Å. The glass transition temperature increased from 73°C, in the unfilled epoxy resin, to 83.5°C in the nanocomposite with 9 wt % Cloisite 30B. The tensile strength exhibited a maximum at 1 wt % modified clay loading. Addition of 0.5 wt % organically modified clay improved the impact strength of the epoxy resin by 137%; in contrast, addition of 0.5 wt % unmodified clay improved the impact strength by 72%. Tensile modulus increased with increasing clay loading in both types of nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1081–1086, 2005     

Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

Electrical conductivity behavior of epoxy matrix nanocomposites with simultaneous dispersion of carbon nanotubes and clays

In this work, nanocomposites with simultaneous dispersion of multiwalled carbon nanotubes (MWCNT) and montmorillonite clays in an epoxy matrix were prepared by in situ polymerization. A high energy sonication was employed as the dispersion method, without the aid of solvents in the process. The simultaneous dispersion of clays with carbon nanotubes (CNT) in different polymeric matrices has shown a synergic potential of increasing mechanical properties and electrical conductivity. Two different montmorillonite clays were used: a natural (MMT‐Na⁺) and an organoclay (MMT‐30B). The nanocomposites had their electrical conductivity (σ) and dielectric constant (ε_r) measured by impedance spectroscopy. The sharp increase in electrical conductivity was found between 0.10 and 0.25 wt% of the MWCNTs. Transmission electron microscopy (TEM) of the samples showed a lower tendency of MWCNT segregation on the MMT‐30B clay surface, which is connected to intercalation/exfoliation in the matrix, that generates less free volume available for MWCNTs in the epoxy matrix. Data from electrical measurement showed that simultaneously adding organoclay reduces the electrical conduction in the nanocomposite. Moreover, conductivity and permittivity dispersion in low frequency suggest agglomeration of nanotubes surrounding the natural clay (MMT‐Na⁺) particles, which is confirmed by TEM. POLYM. COMPOS., 37:1603–1611, 2016. © 2014 Society of Plastics Engineers     

聚氨酯/蒙脱土纳米复合材

聚氨酯／蒙脱土(PU／MMT)纳米复合材料主要是采用插层聚合法合成的1种综合性能优越的新型材料。广角X-射线(WAXD)和透射电镜(TEM)分析结果表明蒙脱土以3～4nm的层间距分散在聚氨酯基体中，因此获得非常有序的插层结构。当PU中加入质量分数为8％的有机蒙脱土(OMMT)时，其拉伸强度提高1．5倍以上，伸长率则提高1．2倍以上；其吸水性随着有机蒙脱土含量的增加而下降，并具有较好的阻隔性。同时热失重分析(TGA)表明，PU／MMT纳米复合材料的热稳定性略有提高。因此，PU／MMT纳米复合材料具有广泛的工业应用前景。     

Evaluation of the structure of polypropylene/montmorillonite nanocomposite by in‐line light extinction and color measurements during multiple extrusions

This work extends the method to follow in real time the reduction of the clay particle size by light extinction measurements (turbidity), obtained via an in‐line optical detector fitted at the extruder die exit, to monitor multiple extrusions of PP/MMT nanocomposites. The optical detector was calibrated and showed to follow the Mie Theory. This theory states that the transmitted light intensity decreases for suspension of particles smaller than 500 nm. Corroborating with these results, off‐line color measurements has shown that the luminosity decrease and the yellow color increases during multiple extrusions of the nanocomposites. In addition, the color difference and the yellowness indexes of the nanocomposites using organic modified montmorillonite (MMT) are higher then the MMT Na⁺ (sodium MMT) after multiple extrusions. The addition of clay to a PP matrix produced an increase in the opacity. Results from X‐ray do follow the same trend as those obtained from the in‐line light extinction measurements. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Properties of water‐soluble acrylic copolymer/montmorillonite nanocomposites for warp sizing

Acrylic copolymer/montmorillonite (MMT) nanocomposites for warp sizing were prepared in the presence of Na⁺‐MMT by the in situ intercalative polymerization of acrylic acid, acrylamide, and methyl acrylate in water solution. The properties of the solution and cast film were tested according to an application in sizing process of the nanocomposite size with various MMT contents. The results indicate that, for an exfoliated structure corresponding to the MMT content increasing to 7 wt %, the performance parameters of solution viscosity, glass‐transition temperature, and tensile strength of the film increased and the moisture sorption, abrasion loss, and elongation at break of the film decreased. When the intercalated structure of MMT was 9 wt %, the gathered MMT layers acted as a common inorganic filler in the copolymer matrix, with limited contribution to the properties of the composite. The adhesion work of the nanocomposite solution was calculated by use of the Young–Dupre relation, which showed maximum values at an MMT content of 3 wt % on the surfaces of both the polyester and cellulose films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of organic modifiers and silicate type on filler dispersion,thermal, and mechanical properties of ABS‐clay nanocomposites

Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. T_g of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd₀₀₁) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of transparent poly(methyl methacrylate)/Na+‐MMT nanocomposite films by solution casting

Films of poly(methyl methacrylate) (PMMA)/sodium montmorillonite (Na⁺‐MMT) nanocomposites have been successfully prepared utilizing Na⁺‐MMT by N,N‐dimethylformamide solution casting. The nanocomposite films show high transparency, enhanced thermal resistance, and mechanical properties in comparison with the neat polymer film. The transparency of the films was investigated by UV‐vis spectra. The exfoliated dispersion of Na⁺‐MMT platelets in nanocomposites were investigated by X‐ray diffraction and transmission electron microscopy. The enhanced thermal resistance and mechanical properties of PMMA were studied by thermal gravimetric analysis and dynamic mechanical analysis, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and Properties of Biodegradable Thermoplastic Starch/Clay Hybrids

Biodegradable thermoplastic starch (TPS)/clay hybrids were prepared by melt intercalation. Three organically modified montmorillonite (MMT) with different ammonium cations and one unmodified Na⁺ MMT (Cloisite Na⁺) were used. Cloisite Na⁺ showed the best dispersion in the TPS matrix. It was observed that the TPS/Cloisite Na⁺ hybrid showed an intercalation of TPS in the silicate layer due to the matching of the surface polarity and interactions of the Cloisite Na⁺ and the TPS, which gives higher tensile strength and better barrier properties to water vapor as compared to the other TPS/organoclay hybrids as well as the pristine TPS. It was found that the dynamic mechanical properties of the TPS/clay hybrids were also affected by the polar interactions.