Polypropylene nanocomposites prepared with natural and ODTABr‐modified montmorillonite

In this study, the main goal is to obtain montmorillonite nanocomposites of polypropylene (PP). To achieve this goal, a two‐phase study was performed. In the first part of the work, organomodified clay (OMMT) was synthesized and characterized. Octadecyltrimethylammonium bromide (ODTABr) cationic surfactant was added to the clay (Na‐activated montmorillonite, MMT) dispersions in different concentrations in the range of 5 × 10^?5–1 × 10^?2 mol/L. Rheologic, electrokinetic, and spectral analyses indicated that ODTABr has interacted with MMT at optimum conditions when the concentration was 1 × 10^?2 mol/L. In the second part, modified (OMMT) and unmodified (MMT) montmorillonite were used to obtain PP nanocomposites (OMMT/PP and MMT/PP, respectively). The nanocomposites were prepared by melt intercalation where the montmorillonite contents were 1 or 5% (w/w) for each case. The thermal analyses showed that the thermal properties of OMMT/PP nanocomposites were better than MMT/PP, and both of them were also better than pure polymer. Increase in the concentration of MMT (or OMMT) decreased the thermal resistance. Based on the IR absorption intensity changes of regularity and conformational bands, it is found that the content of the helical structure of macromolecular chains has increased with increasing concentrations of both MMT and OMMT in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nanocomposite alkyd coatings

Organophilic montmorillonite intercalants were prepared by a cation‐exchange process between Na⁺ ions of montmorillonite and ammonium salt of octadecylamine. Fourier transform infrared (FTIR) spectrometry and X‐ray diffraction analyses of the compounds were carried out. The layer spacings of both modified and unmodified montmorillonites were calculated with Bragg's law. FTIR and X‐ray profiles showed organophilic characteristics for the modified montmorillonite, the layer spacing of which increased by two orders of magnitude with respect to that of the unmodified montmorillonite. The prepared organoclay was incorporated into an alkyd‐based clear coating, and X‐ray profiles showed an exfoliated structure for the organoclay alkyd coating. The application of the prepared organoclay to alkyd‐based clear coatings showed a significant enhancement of the hardness and impact strength of the coating film compared with those of unmodified montmorillonite equally incorporated into the coating formulations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2639–2642, 2006     

Improvement of compression set property of ethylene vinyl acetate copolymer/ethylene‐1‐butene copolymer/organoclay nanocomposite foams

To chemically bond polymer and organoclay, low molecular weight trimethoxysilyl‐modified polybutadiene (Silane) was used in this study. When Silane was added, ethylene‐vinyl acetate copolymer (EVA)/ethylene‐1‐butene copolymer (EtBC)/methyl tallow bis‐2‐hydroxyethyl quaternary ammonium‐modified montmorillonite (OH‐MMT)/Silane foams with and without maleic anhydride grafted EtBC (EtBC‐g‐MAH) display lower compression set than EVA/EtBC foams. According to the compression set result, OH‐MMT is more effective in improvement of compression set than dimethyl dihydrogenated tallow quaternary ammonium‐modified montmorillonite (DM‐MMT) because in addition of OH groups in the organoclay surface, the OH groups of the alkylammonium ion existed in interlayer of OH‐MMT may react with silanol group of Silane. The possible chemical reactions between Silanol groups of Silane and the hydroxyl groups of OH‐MMT and DM‐MMT were proved by ATR‐FTIR experiments. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Synthesis of bismaleimide‐modified novolac resin/clay nanocomposites using p‐phenylenediamine as swelling agent

Sodium montmorillonite (Na–MMT) was swollen with protonated p‐phenylenediamine, and the latter was converted to maleamic acid. Intercalation of the swelling agents was confirmed by FTIR, XRD, and TGA data. Exfoliation of the organoclay took place easily in the melt of the Bismaleimide‐modified allylated novolac resin. It is remarkable that, as a result of layer delamination, introduction of 2 phr organoclay MAA–MMT brought in a rise in steady shear viscosity for over two orders of magnitude at low shear rates. Major improvement in thermal stability, flexural strength, and modulus was achieved by incorporation of the exfoliated clay layers, in contrast to the composite using pristine Na–MMT as reinforcement. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 466–474, 2005     

Montmorillonite‐reinforced sulfonated poly(phthalazinone ether sulfone ketone) nanocomposite proton exchange membranes for direct methanol fuel cells

To produce a composite membrane with high conductivity and low permeability, SPPESK with a degree of sulfonation of 101% was carefully selected for the preparation of montmorillonite (MMT)‐reinforced SPPESK using solution intercalation. The fundamental characteristics such as water uptake, swelling ratio, proton conductivity, methanol permeability, and mechanical properties of the composite membranes were studied. Water uptake is improved when organic MMT (OMMT) loading increase. The composite membranes with CTAB‐MMT loading of 4–0.5% show 0.143–0.150 S cm^?1 proton conductivity at 80°C, which approaches the value of Nafion112. In addition, methanol permeability was decreased to 6.29 × 10^?8 cm² s^?1 by the addition of 6 wt % OMMT. As a result, the SPPESK‐MMT composite membrane is a good candidate for use in direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39852.     

Interaction of functional groups of gelatin and montmorillonite in nanocomposite

As an amphoteric polyelectrolyte, gelatin could intercalate into the galleries of montmorillonite (MMT). In this paper, sodium laurate/MMT composites and sodium laurate/dehydroxylated MMT composites were introduced as low molecular simulation to investigate the interaction functional groups of gelatin and MMT. The composites were characterized by X‐ray diffraction (XRD), Fourier transform infrared spectra (FTIR), thermogravimetric analysis (TGA) and ¹³C nuclear magnetic resonance (¹³C NMR). Furthermore, the effect of interaction between gelatin and MMT on the mechanical properties of the composites was investigated. The results indicated that ? COO^?, not ? COOH, in gelatin chains could interact strongly with the MMT sheets. The reactive sites on MMT were hydroxyl groups, which could interact with ? COO^? in gelatin chains by forming hydrogen bonds. The gelatin/MMT composites prepared in alkalic media have better mechanical properties due to stronger interaction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1556–1561, 2006     

Novel organic modification of montmorillonite in hydrocarbon solvent using ionic liquid‐type surfactant for the preparation of polyolefin–clay nanocomposites

The possibility of organic modification of montmorillonite (MMT) in hydrocarbon solvents by employing ionic liquid‐type surfactants was investigated. As a first example, 1‐methyl‐3‐tetradecylimidazolium chloride ([C₁₄mim]⁺Cl^?) was used to treat pristine MMT in xylene. The dispersion of MMT in xylene was significantly improved, the collected organifically modified MMT displayed a sufficiently enlarged interlayer spacing. The novel art of MMT organic modification is specifically advantageous to the preparation of polyolefin‐based nanocomposites. A polypropylene/MMT nanocomposite was exemplarily prepared by directly dissolving polypropylene in the MMT modification system and found to possess an excellent thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4314–4320, 2006     

Polyaniline–organoclay nanocomposites as curing agent for epoxy: Preparation and characterization

Polyaniline (PANI)–organoclay/Epoxy (EP) nanocomposites were prepared. PANI–organoclay nanocomposites were used as curing agent for EP. Organoclay was prepared by an ion exchange process between sodium cations in MMT and NH₃⁺ groups in polyoxypropylene (D₂₃₀). PANI–organoclay nanocomposite was synthesized by in situ polymerization of aniline in (14 wt%) organoclay. Infrared spectra and differential scanning calorimetry confirm the curing of EP. The absence of d₀₀₁ diffraction band of organoclay in the nanocomposites was observed by X‐ray diffraction. The structure argument was further supported by scanning electron microscopy and transmission electron microscopy. Electrical conductivity of the nanocomposites within the range 2.1 × 10⁻⁷–3.2 × 10⁻⁷ S/cm depending on the concentration of the PANI/D₂₃₀‐MMT. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Enhanced swelling and methylene blue adsorption of polyacrylamide‐based superabsorbents using alginate modified montmorillonite

Polyacrylamide/sodium alginate modified montmorillonite (PAM/SA‐MMT) superabsorbent composites were synthesized by free‐radical polymerization under normal atmospheric conditions. They were characterized by X‐ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy (FTIR). Their water absorbency and methylene blue (MB) adsorption behaviors were studied. Compared with PAM/MMT composites, PAM/SA‐MMT composites demonstrated greater water absorbency (863 g g^?1 in distilled water and 101 g g^?1 in 0.9 wt % NaCl solution) and higher adsorption capacity of 2639 mg g^?1 for MB. The adsorption behaviors of the composites showed that the isotherms and adsorption kinetics were in good agreement with the Langmuir equation and pseudo‐second‐order equation, respectively. FTIR analysis suggested that the MB adsorption of PAM/SA‐MMT composites via a mechanism combined electrostatic, H‐bonding and hydrophobic interaction. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40013.     

Effect of nanofillers as reinforcement agents for lignin composite fibers

Biobased nanocomposites and composite fibers were prepared from organosolv lignin/organoclay mixtures by mechanical mixing and subsequent melt intercalation. Two organically‐modified montmorillonite (MMT) clays with different ammonium cations were used. The effect of organoclay varying from 1 to 10 wt % on the mechanical and thermal properties of the nanocomposites was studied. Thermal analysis revealed an increased in T_g for the nanocomposites as compared with the original organosolv lignin. For both organoclays, lignin intercalation into the silicate layers was observed using X‐ray diffraction (XRD). The intercalated hybrids exhibited a substantial increase in tensile strength and melt processability. In the case of organoclay Cloisite 30B, X‐ray analysis indicates the possibility of complete exfoliation at 1 wt % organoclay loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Technological and processing properties of natural rubber layered silicate‐nanocomposites by melt intercalation process

Natural rubber nanocomposites were produced by melt‐mixing of natural rubber with organically modified silicates. For comparison, a pristine‐layered silicate and a nonlayered version [English Indian clay (EIC)] were also included in the study. The layered silicate used was sodium bentonite (BNT) and organoclays used were octadecylamine‐ modified montmorillonite (MMT‐ODA) and methyltallow bis‐2‐hydroxyethyl ammonium‐modified montmorillonite (MMT‐ TMDA). Accelerated sulfur system was used for the vulcanization of the nanocomposites. The dispersion of these silicates was studied by X‐ray diffraction and transmission electron microscopy. The organoclay‐incorporated composites exhibited faster curing and improved mechanical properties. The improvement in the mechanical properties of the composites followed the order MMT‐ODA > MMT‐TMDA > EIC > BNT. The property improvement was attributed to the intercalation/exfoliation of the organically modified silicates because of their high initial interlayer distance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2537–2543, 2006     

Morphological characterization and electrochemical/electrical properties of poly(N‐vinyl carbazole)/montmorillonite composites

A series of poly(N‐vinyl carbazole) (PNVCz)/sodium montmorillonite (Na⁺MMT) and PNVCz/organo‐MMT composite materials have been successfully prepared by in situ free radical polymerization with cerium ammonium nitrate (CAN) as initiator in the presence of inorganic nanolayers of hydrophilic Na⁺MMT or organophilic organo‐MMTs, modified with octadecylamine (ODA) and trimethyl stearyl ammonium (TMSA). The synthesized materials were subsequently characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The distribution of MMT layers in the PNVCz matrix was also studied through polarized optical microscope (POM). Their electrochemical and electrical properties were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results showed that the type of intercalation agent and mixing method was affected on the structures and properties of composite materials. Both the interlayer spacing of clays and glass transition temperature of PNVCz was increased nearly from 1.18 nm to 3.53 nm and from 140°C to 185°, respectively. Their conductivities also increased relatively to that of the PNVCz homopolymer (10⁻¹¹–10⁻¹⁵ S/cm) and varied in the range of 10⁻¹⁰–10⁻⁵ S/cm, inversely dependent on the amount of MMT loading. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Novel high-strength montmorillonite/polyvinyl alcohol composite film enhanced by chitin nanowhiskers

Nanomaterials can be used as reinforcement phase to improve the performance of polymers. A simple method to prepare a composite film with super high tensile strength was used in this study. The properties of montmorillonite (MMT)/polyvinyl alcohol (PVA) films reinforced by chitin nanowhisker (CNW) have been evaluated. The structures and properties of films were analyzed by atomic force microscope (AFM), Fourier transforms infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile testing. The results of FTIR and XRD showed that no chemical interaction occurred among MMT, PVA, and CNW. The SEM and AFM images suggested that the obtained composite films with the three substances had a relatively uniform layered structure and relatively smooth. The temperature at the onset of decomposition of the composite films was increased from 262.0 to 282.3°C by the addition of CNW. The tensile strength of the MMT/PVA/CNW film was reached 263.5 MPa, which was increased approximately 382% compared with the MMT/PVA film. According to these results, the composite film could be potentially used in packaging materials.     

Electrospinning fabrication and characterization of poly(vinyl alcohol)/montmorillonite nanofiber mats

Poly(vinyl alcohol) (PVA)/montmorillonite clay (MMT) nanofiber mats have been fabricated by the electrospinning technique. The PVA/MMT nanofiber mats were characterized by X‐ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and mechanical measurements. The study showed that the introduction of MMT results in improvement in tensile strength, and thermal stability of the PVA matrix. XRD patterns and SEM micrographs suggest the coexistence of exfoliated MMT layers over the studied MMT contents. FTIR revealed that there might be possible interaction occurred between the MMT clay and PVA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electron beam synthesis and characterization of poly(vinyl alcohol)/montmorillonite nanocomposites

Poly(vinyl alcohol) (PVA)/montmorillonite clay (MMT) nanocomposites in the form of films were prepared under the effect of electron beam irradiation. The PVA/MMT nanocomposites gels were characterized by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and mechanical measurements. The study showed that the appropriate dose of electron beam irradiation to achieve homogeneous nanocomposites films and highest gel formation was 20 kGy. The introduction of MMT (up to 4 wt %) results in improvement in tensile strength, elongation at break, and thermal stability of the PVA matrix. In addition, the intercalation of PVA with the MMT clay leads to an impressive improved water resistance, indicating that the clay is well dispersed within the polymer matrix. Meanwhile, it was proved that the intercalation has no effect on the metal uptake capability of PVA as determined by a method based on the color measurements. XRD patterns and SEM micrographs suggest the coexistence of exfoliated intercalated MMT layers over the studied MMT contents. The DSC thermograms showed clearly that the intercalation of PVA polymer with these levels of MMT has no influence on the melting transitions; however, the glass transition temperature (T_g) for PVA was completely disappeared, even at low levels of MMT clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1129–1138, 2006     

Preparation and evaluation of nanocomposites of polyfuran with Al2O3 and montmorillonite clay

High yield oxidative polymerization of furan was accomplished in CHCl₃ solvent at 0 °C. A nanocomposite of polyfuran (PF)–Al₂O₃ was prepared through polymerization of furan in a suspension of nanodimensional Al₂O₃ in CHCl₃ at 0 °C. High yield polymerization of furan was also achieved in montmorillonite clay (MMT) without any extraneous oxidant. The formation of PF was confirmed by FTIR and elemental analysis. Thermogravimetric analyses revealed the following trends in thermal stability: PF < PF–Al₂O₃ < Al₂O₃ and PF < PF–MMT < MMT. Scanning electron microscopy showed the average particles sizes to be ca 51 nm and ca 40 nm for PF–Al₂O₃ and PF–MMT composites, respectively. The occurrence of a peak at 19.84 Å in the X‐ray diffraction pattern of the PF–MMT composite was indicative of the intercalation of PF in MMT lamellae. Transmission electron microscopic analyses for the PF–MMT composite also showed incorporation of PF moieties in‐between the MMT layers. The dc conductivity values (S cm^?1) of PF–FeCl₃, PF–Al₂O₃–FeCl₃, PF–MMT and PF–MMT–FeCl₃ systems were in the order of 10^?6, 10^?7, 10^?8 and 10^?7, respectively, and the values were significantly enhanced compared to the dc conductivity value of PF homopolymers (10^?11). Copyright © 2004 Society of Chemical Industry     

Effects of co‐plasticization of acetyl tributyl citrate and glycerol on the properties of starch/PVA films

Starch/polyvinyl alcohol (PVA) nanocomposite films by film blowing process were successfully obtained. Starch (1700 g), PVA (300 g), and organically modified montmorillonite (OMMT, 200 g) were blended and plasticized with acetyl tributyl citrate (ATBC) and glycerol (GLY) at weight ratios of 0/100, 5/95, 10/90, 15/85, 20/80, and 25/75. The structural, morphology, barrier, mechanical, and thermal properties of the films, as well as molecular interactions in the nanocomposites were analyzed. The 3.98 nm d‐spacing was the highest in starch/PVA nanocomposite films plasticized with ATBC/GLY ratio of 10/90. The film with ATBC/GLY (5/95) had the lowest WVP (3.01 × 10^?10 g m^?1 s^?1 Pa^?1). The longitudinal tensile strength (TS) of starch/PVA nanocomposite films gradually increased from 4.46 to 6.81 MPa with the increase of ATBC/GLY ratios. The T_g steadily increased from 49.2°C to 55.2°C and the ΔH of the nanocomposite films decreased from 81.77 to 51.43 J/g at the presence of ATBC. The addition of ATBC into GLY plasticized starch/PVA/OMMT system enhanced the intermolecular interaction in the nanocomposites. This study proved that ATBC was an excellent compatibilizer in the preparation of starch/PVA/OMMT nanocomposite films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42544.     

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     

Proton‐conducting blend membranes of crosslinked poly(vinyl alcohol)–sulfosuccinic acid ester and poly(1‐vinyl‐1,2,4‐triazole) for high temperature fuel cells

New type of composite membranes were synthesized by crosslinking of poly(vinyl alcohol) (PVA) with sulfosuccinic acid (SSA) and intercalating poly(1‐vinyl‐1,2,4‐triazole) (PVTri) into the resulting matrix. The complexed structure of the membranes was confirmed by Fourier transform infrared (FTIR) spectroscopy. The resulting hybrid membranes were transparent, flexible, and showed good thermal stability up to ～200°C. The proton conductivities of the membranes were investigated as a function of PVTri and SSA and operating temperature. The water/methanol uptake was measured and the results showed that solvent absorption of the materials increased with increasing PVTri content in the matrix. The proton conductivity of the membranes continuously increased with increasing SO₃H content, PVTri content, and the temperature. In the anhydrous state, the maximum proton conductivity is 7.7 × 10^?5 S/cm for PVA–SSA–PVTri‐1 and for PVA–SSA–PVTri‐3 is 1.6 × 10^?5 S/cm at 150°C. After humidification (RH = 100%), PVA–SSA–PVTri‐4 showed a maximum proton conductivity of 0.0028 S/cm at 60°C. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Comparative study of gamma and ion beam irradiation of polymeric nanocomposite on electrical conductivity

Poly(vinyl alcohol) (PVA) was used to prepare nanocomposites of multi‐wall carbon nanotubes (MWCNT) and functionalized carbon nanotubes (MWCNT‐NH₂) in existence of 2‐carboxyethyl acrylate oligomers (CEA). Radiation‐induced crosslinking of the prepared matrix was carried out via gamma and ion beam irradiation. A comparative study of gamma and ion beam irradiation effect on the electrical conductivity of nanocomposite was conducted. The gelation of the gamma irradiated matrix outperforms the ion beam irradiated matrix. The order of gelation is PVA > (PVA/CEA) > (PVA/CEA)‐MWCNT > (PVA/CEA)‐MWCNT‐NH₂. There is a significant reduction in the swelling of the nanocomposite. The formation of nanocomposites was confirmed by scanning electron microscopy, energy‐dispersive X‐ray (EDX) and FTIR examinations. The direct current electrical properties of PVA/nanocomposites are examined at room temperature by applying electric voltage from 1 to 20 V. The results revealed that the electrical conductivity is increased by adding the carbon nanotubes and irradiation by gamma and ion beam. At an applied electric voltage 20 V, in the electrical conductivity of the unirradiated PVA was from 9.20 × 10^?8 S cm^?1. After adding MWCNT an increase up to 4.70 × 10^?5 S cm^?1 was observed. While after ion beam irradiation, a further increase up to 9.30 × 10^?5 S cm^?1 was noticed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46146.