Polymer–clay Nanocomposite Materials Research Articles

A benzimidazole-based conducting polymer and a PMMA–clay nanocomposite containing biosensor platform for glucose sensing

Development of materials composed of polymer–clay nanocomposites (PCN) and conducting polymers attracts great interest and preferred in various applications. Hereby, polymethylmethacrylate (PMMA) layered silicate nanocomposites were prepared by in-situ suspension polymerization by grafting PMMA with laponite using a suitable grafting agent. The properties of the as-synthesized PCN materials are characterized by differential scanning calorimetry (DSC), thermal gravimetry analysis (TGA) and gel permeation chromatography (GPC). A conducting polymer; poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-7-(2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)-2-benzyl-1H-benzo[d]imidazole) (poly(BIPE)) and a PMMA–clay nanocomposite with 2-(methacryloyloxy) ethyltrimethylammonium chloride (MTMA) modifier were examined as a platform for biomolecule deposition. Glucose oxidase (GOx, β-d-glucose: oxygen-1-oxidoreductase, EC 1.1.3.4) was chosen as the model enzyme to prepare a scaffold for glucose sensing. Three different sensing strategies; PCN/GOx, poly(BIPE)/GOx and PCN/poly(BIPE)/GOx were analyzed and their biosensor performances were discussed. Surface morphology of the modified electrodes was characterized by scanning electron microscopy (SEM) technique. Electrochemical responses of the enzyme electrodes were monitored at −0.7V vs. Ag reference electrode by monitoring oxygen consumption in the presence of glucose. After optimum conditions were determined, kinetic and analytical parameters; KMapp, Imax, LOD and sensitivity were investigated for each sensing platform.

Elastic modulus measurement of polymer matrix nano- composites reinforced by platelet nano-clays

Polymer-clay nano-composite materials, in which nano-meter thick layers of clay dispersed in polymer matrix, have generally higher mechanical properties than normal polymeric materials. A new threedimensional unit cell model has been developed for modeling three constituent phases including inclusion, interphase and matrix. The total elastic modulus of nano-composite is evaluated. Numerical results are in good agreement with the previous proposed theoretical modeling. Higher matrix and inclusion elastic modulus both can dramatically increase the total elastic modulus.

Properties of nanoclay PVA composites materials

Polyvinyl alcohol (PVA)/Na-rich Montmorillonite (MMT) nanocomposites were prepared using solution method to create polymer-clay nanocomposite (PCN) material. The PCN material was studied using X-ray diffraction (XRD), demonstrating polymer-clay intercalation that has a high d-spacing (lower diffraction angles) in the PCN XRD pattern, compared to the pure MMT clay XRD pattern, which has a low d-spacing (high diffraction angles). The nano-scanning electron microscope (NSEM) was used to study the morphological image of the PVA, MMT and PCN materials. The results showed that intercalation that took place between the PVA and MMT produced the PCN material. The mechanical properties of the pure PVA and the intercalated polymer material were studied. It was found that the small amount of MMT clay made the tensile modulus and percentage of the total elongation of the nano-composite significantly higher than the pure PVA polymer value, due to polymer-clay intercalation. The thermal stability of the intercalated pol...

Chiral poly(amide-imide)/organoclay nanocomposites derived from pyromellitoyl-bis-l-isoleucine and benzimidazole containing diamine: synthesis, nanostructure, and properties

In this study, a series of polymer–clay nanocomposite materials, consisting of organosoluble poly(amide-imide) (PAI) matrix and dispersed nanolayers of inorganic montmorillonite clay, were successfully prepared by solution dispersion technique. At first, the reactive organoclay was prepared by using protonated l-isoleucine amino acid as a swelling agent for silicate layers of Cloisite Na+. Then, organosoluble PAI containing isoleucine amino acid was synthesized through step-growth polymerization reaction of N,N′-(pyromellitoyl)-bis-isoleucine diacid and 2-(3,5-diaminophenyl)-benzimidazole under green condition using molten tetrabutylammonium bromide. This polymer was end-capped with amine end groups near the completion of the reaction to interact chemically with acidic group of organoclay. Finally, PAI/organoclay nanocomposite films containing 2%, 5%, 10%, and 15% of organoclay were prepared via solution intercalation method through blending of organoclay with the PAI solution. Dispersion of the modified clay in the PAI matrix resulted in a nanostructured material containing intercalated polymer between the silicate layers. Structures of exfoliation were confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. Thermogravimetric analysis data indicated that the addition of organoclay into the PAI matrix increased the thermal decomposition temperatures of the obtained nanocomposites compared to the pure PAI.

On the overall elastic moduli of polymer–clay nanocomposite materials using a self-consistent approach. Part II: Experimental verification

Polyamide-6 (PA6) based nanocomposites were prepared using a modified montmorillonite (MMT) Cloisite 20A as nanofillers. The silicate weight fraction of the prepared nanocomposites, determined by burning off the PA6 matrix, was ranged from 0.2 wt% up to 7.5 wt%. The thermomechanical properties of both the neat PA6 and the PA6 filled with MMT nanoclay were measured by means of uniaxial tension tests and dynamic mechanical thermoanalysis, their crystallinity analyzed by differential scanning calorimetry and their morphology observed by transmission electron microscopy. The elastic stiffness of PA6–clay nanocomposites was examined under two moisture levels and was analyzed with the theory formulated in the Part I of this work. Predicted results are found in good agreement with our experiments. The model capabilities are also critically discussed by comparisons with both experiments issued from the literature and the Mori–Tanaka approach widely used in recent literature. It is demonstrated that the proposed micromechanical model is more efficient than the Mori–Tanaka approach. Moreover, the obtained results support the idea that the elastic stiffness of polymer–clay nanocomposites is governed by the same mechanisms as microcomposites, the effects of particle dimension or constrained region being of a second order.

On the overall elastic moduli of polymer–clay nanocomposite materials using a self-consistent approach. Part I: Theory

Although few investigations recently proposed to describe the overall elastic response of polymer–clay nanocomposite materials using micromechanical-based models, the applicability of such models for nanocomposites is far from being fully established. The main point of criticism to mention is the shelving of crucial physical phenomena, such as interactions and length scale effects, generally associated by material scientists, in addition to the nanofiller aspect ratio, to the remarkable mechanical property enhancement of polymer–clay nanocomposites. In this Part I of two-part paper, we present a micromechanical approach for the prediction of the overall moduli of polymer–clay nanocomposites using a self-consistent scheme based on the double-inclusion model. This approach is used to account for the inter-inclusion and inclusion–matrix interactions. Although neglected in the models presented in the literature, the active interaction between the nanofillers should play a key role in the reinforcing effect of nano-objects dispersed in a polymer matrix. The present micromechanical model incorporates the nanostructure of clay stacks, modeled as transversely isotropic spheroids, and the so-called constrained region, modeled as an interphase around reinforcements. This latter is linked to the interfacial interaction between matrix and reinforcements that forms a region where the polymer chain mobility is reduced. To account for length scale effects, interphase thickness and particle dimensions are taken as explicit model parameters. Instead of solving iteratively the basic homogenization equation of the self-consistent scheme, our formulation yields to a pair of equations that can be solved simultaneously for the overall elastic moduli of composite materials. When the interphase is disregarded for spheroids with zero aspect ratio, our formulation coincides with the Walpole solution (J Mech Phys Solids 1969;17:235–251). Using the proposed general form, a parametric study is presented to analyze the respective influence of aspect ratio, number of silicate layers, interlayer spacing and nanoscopic size of the transversely isotropic spheroids on the overall elastic moduli of nanocomposite materials.

Mechanical properties of polyamide-6/montmorillonite nanocomposites — Prepared by the twin-screw extruder mixed technique

In this paper, we present the effects of incorporated montmorillonite (MMT) on a surface and the bulk mechanical properties of as-synthesized PA6/MMT composites that are prepared using the twin-screw extruder mixed technique. The as-prepared polymer–clay nanocomposite (PCN) materials in the form of a pellet subsequently characterized using the powder X-ray diffraction (XRD) and the transmission electron microscopy (TEM). In this experiment, the surface mechanical property studies ( i.e., wear resistance and hardness) show that the integration of MMTs exhibited a distinct increase on shore hardness was up to 5 wt.% of MMTs loaded in composites. Moreover, the enhancement of wear resistance of as-prepared composites, compared to pure PA6, can be further identified by the Scanning Electron Microscopy (SEM) observation of the surface morphology after testing. On the other hand, for the bulk mechanical property studies ( i.e., tensile strength and flexural strength), we found that the composites containing 3 wt.% of MMTs in the PA6 matrix exhibited the best performance in tensile strength and flexural strength. It means that this composition of MMTs exhibits good compatibility with the PA6 matrix. Generally, PCN materials show an obvious enhancement of mechanical properties of neat polymer by an incorporated low loading of organophilic-clay platelets into a PA6 matrix used for the evaluation of the mechanical properties of the as-prepared samples. Furthermore, it was found that at higher MMT loading ( e.g. 5 wt.%), MMTs were to be aggregated in the polymer matrix, as observed in TEM. Also, the result leads to an obvious decrease in tensile and flexural strength tests.

Designing of fullers‐earth‐containing poly(vinyl alcohol)‐g‐poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) nanocomposites: Swelling and deswelling behaviors

AbstractIn this study, polymer–clay nanocomposites (PCNs) composed of poly(vinyl alcohol)s (PVAs), poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and fullers earth were prepared by the effective dispersal of inorganic nanoclays in the organic PVA matrix via in situ free‐radical polymerization with potassium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinker. The monomer, 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid, was grafted onto the PVA backbone, and at the same time, fullers earth layers were intercalated and exfoliated into the grafted copolymer, especially at a low or moderate loading of the fullers earth. The synthesized PCN materials were characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction techniques. The morphological features of the synthesized materials were studied by scanning electron microscopy; this revealed that the swelling ratio of this nanocomposite increased with increasing fullers earth content. The X‐ray diffraction results indicated that the fullers earth was exfoliated in the nanocomposite matrix, and its introduction into the polymer matrix enhanced the percentage crystallinity of the polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Mechanical properties of polystyrene‐montmorillonite nanocomposites—Prepared by melt intercalation

AbstractA series of polymer‐clay nanocomposite (PCN) materials, consisting of thermoplastic polystyrene (PS) sample and dispersing inorganic organoclay platelets, were successfully prepared. First, organoclay was prepared by performing cationic exchange reactions between the sodium ions existing in the interlayer region of the clay mineral and intercalation agent, followed by dispersing the organophilic clay into a PS basis through the melt intercalation approach performed by a twin‐screw mixing method. The as‐prepared PCN materials in the form of a pellet subsequently characterized using the powder X‐ray diffraction (XRD) and the transmission electron microscopy (TEM). In this study, it is found that the wear resistance of PS to be effectively enhanced by the incorporation of low loading organophilic clay platelets. The surface morphological image for the neat PS and PS‐clay after a wear resistance test has also been compared and identified by the scanning electron microscopy (SEM). Furthermore, the effect of organoclay on three other different measurement types of mechanical properties for as‐prepared PCN materials, e.g., flexural tests, impact tests, and micron‐nano indenter tests were performed and compared. Generally, PCN materials exhibited an obvious enhancement of mechanical properties of neat polymer by an incorporated low loading of organophilic clay platelets into a polystyrene matrix used for the evaluation of mechanical properties as‐prepared samples. For example, mechanical strength (excepting flexural strength) almost remain same beyond 3 wt % clay loading in PS, whereas much detrimental effect being observed in the wear loss in case of PCNs with 5 wt % clay than 3 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Acid Activation of Bentonites and Polymer-Clay Nanocomposites

Modified bentonites are of widespread technological importance. Common modifications include acid activation and organic treatment. Acid activation has been used for decades to prepare bleaching earths for adsorbing impurities from edible and industrial oils. Organic treatment has sparked an explosive interest in a class of materials called polymer-clay nanocomposites (PCNs). The most commonly used clay mineral in PCNs is montmorillonite, which is the main constituent of bentonite. PCN materials are used for structural reinforcement and mechanical strength, for gas permeability barriers, as flame retardants, and to minimize surface erosion (ablation). Other specialty applications include use as conducting nanocomposites and bionanocomposites.

Preparation and characterization of poly(butylene terephthalate) nanocomposites with various organoclays

AbstractLayered‐silicate‐based polymer–clay nanocomposite materials were prepared depending on the surface modification of montmorillonite (MMT). Nanocomposites consisting of poly(butylene terephthalate) (PBT) as a matrix and dispersed inorganic clay modified with cetyl pyridinium chloride (CPC), benzyl dimethyl N‐hexadecyl ammonium chloride, and hexadecyl trimethyl ammonium bromide by direct melt intercalation were studied. The organoclay loading was varied from 1 to 5 wt %. The organoclays were characterized with X‐ray diffraction (XRD) to compute the crystallographic spacing and with thermogravimetric analysis to study the thermal stability. Detailed investigations of the mechanical and thermal properties as well as a dispersion study by XRD of the PBT/clay nanocomposites were conducted. X‐ray scattering showed that the layers of organoclay were intercalated with intercalating agents. According to the results of a differential scanning calorimetry analysis, clay acted as a nucleating agent, affecting the crystallization. The PBT nanocomposites containing clay treated with CPC showed good mechanical properties because of intercalation into the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Comparative studies for the effect of intercalating agent on the physical properties of epoxy resin-clay based nanocomposite materials

In this study, a series of comparative studies for the effect of intercalating agent on the physical properties of the epoxy resin-clay based nanocomposite materials were performed. First, the quaternary alkylphosphonium and alkylammonium salt were both used as the intercalating agents separately for the preparation of organophilic clay through the cationic exchange reactions with Na +-montmorillonite clay. Subsequently, the organophilic clay was blent into the epoxy resin through in-situ thermal ring-opening polymerizations to prepare a series of polymer-clay nanocomposite (PCN) materials. The as-synthesized PCN materials were subsequently characterized by Fourier-Transformation infrared (FTIR) spectroscopy, wide-angle powder X-ray diffraction (WXRD), and transmission electron microscopy (TEM). It should be noted that the quaternary alkylphosphonium salt (Φ 3P +-C 12)-modified clay was found to show better dispersion capability than that of quaternary alkylammonium salt (Me 3N +-C 16)-modified clay existed in the polymer matrix based on the studies of WXRD and TEM. The better dispersion of (Φ 3P +-C 12)-modified clay in epoxy resin was found to lead more effectively enhanced physical property such as corrosion protection, gas barrier, mechanical strength, thermal stability, and flame retardant properties of polymers than that of (Me 3N +-C 16)-modified clay, in the form of coating and membrane, based on the measurements of a series of electrochemical corrosion parameters, gas permeability analysis (GPA), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and limiting oxygen index (LOI), respectively. Effect of material composition on the physical properties of as-prepared materials was also investigated.

High‐performance polyimide–clay nanocomposite materials based on a dual intercalating agent system

AbstractBACKGROUND: Polymer–clay nanocomposites (PCNs) have attracted considerable interest in recent years owing to their unique physical and chemical properties that lead to a wide range of applications. A series of PCN materials consisting of polyimide and layered montmorillonite (MMT) clay were successfully prepared by in situ polymerization.RESULTS: Silicate layers are better dispersed in polymer matrices when dual intercalating agents (hexadecyltrimethylammonium bromide–4,4′‐oxydianiline) are applied for MMT modification according to wide‐angle X‐ray diffraction and transmission electron microscopy studies. Effects of single and dual intercalating agents on thermal stability, mechanical strength and the molecular barrier of PCN materials consisting of organo‐modified MMT were studied by means of thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analyses, gas permeability analysis and vapor permeability analysis.CONCLUSION: Improved thermal and mechanical stabilities, as well as barrier properties were observed for the PCN materials containing dual intercalating agent‐modified MMT. Copyright © 2008 Society of Chemical Industry

Adsorption of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and related compounds onto montmorillonite clay

Sodium montmorillonite clay (Na-MMT) was modified using 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS). The objective of this study was to determine which chemical group is the ‘driving force’ leading to the adsorption of AMPS inside the clay galleries. AMPS has been reported to be a good candidate as a clay modifier for the preparation of polymer–clay nanocomposites by in situ free radical polymerization in emulsion. However, the way in which AMPS interacts with the surface of MMT has not yet been studied. The type of interaction between organic modifiers and clay plays a determining role in the successful preparation of polymer–clay nanocomposite materials. The adsorption ability of three other organic compounds similar to AMPS, namely sodium 1-allyloxy-2-hydroxypropyl sulfonate (Cops), N-isopropylacrylamide (NIPA) and methacryloyloxyundecan-1-yl sulfate (MET), was also evaluated. These selected compounds also have functional groups potentially able to interact with the clay surface (i.e., a sulfonate group, an amido group, or a sulfate group, respectively). Results of FT-IR, TGA and SAXS analyses showed that AMPS, NIPA, Cops and MET all interacted with clay, but to various extents.

Effect of organoclay on the thermal stability, mechanical strength, and surface wettability of injection‐molded ABS–clay nanocomposite materials prepared by melt intercalation

AbstractIn this article, a series of polymer–clay nanocomposite (PCN) materials consisted of commercial thermoplastic ABS matrix and dispersing inorganic organoclay platelets were successfully prepared by melt intercalation through the twin‐roller mixer. The as‐prepared materials in the form of pellet were then shaped by injection‐molding machine and the as‐molded specimens were subsequently examined by chemical characterizations, through Fourier transformation infrared (FTIR) spectroscopy, powder X‐ray diffraction (XRD), and transmission electron microscopy (TEM). Effect of the organoclay on thermal stability, mechanical strength, and surface wettability of PCN materials, in both the form of standard dumbbell shape and pellet, was studied using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), tensile test, hardness test, and contact‐angle measurements, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99; 1576–1582, 2006

Siloxane-modified epoxy resin–clay nanocomposite coatings with advanced anticorrosive properties prepared by a solution dispersion approach

A series of polymer–clay nanocomposite (PCN) materials that consist of siloxane-modified epoxy resin and inorganic nanolayers of montmorillonite (MMT) clay has been prepared through a thermal ring opening polymerization using 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane as a curing agent. These PCN materials at low clay concentration in the form of coating on cold-rolled steel (CRS) were found to be much superior in corrosion protection over those of pure epoxy resin when tested for performance in a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current, and impedance spectroscopy in 5 wt.% aqueous NaCl electrolyte. The as-prepared materials were characterized by infrared spectroscopy, wide-angle X-ray diffraction, and transmission electron microscopy. After measurements, we found advanced protection against corrosion on CRS coupon compared to bulk epoxy resin. Molecular (e.g., O2, N2, and H2O) permeability of epoxy resin–clay nanocomposite membranes was found to be lower than that of bulk epoxy resin along with the loading of nanoclay based on the studies of gas and vapor permeability analysis. Moreover, the epoxy resin–clay nanocomposite materials have significant advantages over standard epoxy resins such as lower water absorption, lower cure shrinkage, moderate glass transition temperature (Tg), and higher tensile strength.

Organo-soluble polyimde (ODA-BSAA)/montmorillonite nanocomposite materials prepared by solution dispersion technique

A series of polymer–clay nanocomposite materials, consisting of organo-soluble polyimide (ODA-BSAA) matrix and dispersed nanolayers of inorganic montmorillonite clay, were successfully prepared by solution dispersion technique and subsequently characterized by FTIR, powder X-ray diffraction patterns, transmission electron microscopy, and atomic force microscopy. 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, impedance spectroscopy), gas permeability analysis, and UV–visible transmission spectroscopy, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1082–1090, 2005

Influence of fillers on free volume and gas barrier properties in styrene-butadiene rubber studied by positrons

The measurements of free-volume hole property by positron annihilation lifetime spectroscopy (PALS) have been carried out for polymer–clay nanocomposite materials that consist of styrene–butadiene rubber (SBR) and layered silicate clay of rectorite and conventional composite materials N326 (carbon black) /SBR. The PALS and differential scanning calorimeter (DSC) results show layered rectorite has a stronger effect on restraining polymer chain mobility which results in the decrease of fraction free volume and gas permeation than carbon black. The dispersion of nanoscale rectorite clay in SBR largely enhances gas barrier property in contrast to results obtained in N326/SBR system. Experimental results reveal that gas permeability in rectorite/SBR nanocomposite is mainly influenced by fractional free volume and tortuous diffusional path effects attributed to the clay plateletlike morphology.

Comparative studies of the properties of poly(methyl methacrylate)–clay nanocomposite materials prepared by in situ emulsion polymerization and solution dispersion

AbstractA series of polymer–clay nanocomposite (PCN) materials consisting of organic poly(methyl methacrylate) (PMMA) and inorganic montmorillonite (MMT) clay platelets were prepared successfully by the effective dispersion of nanolayers of the MMT clay in the PMMA framework through both in situ emulsion polymerization and solution dispersion. The as‐prepared PCN materials obtained with both approaches were subsequently characterized with wide‐angle powder X‐ray diffraction and transmission electron microscopy. For a comparison of the anticorrosion performance, a PCN material (e.g., 3 wt % clay loading) prepared by in situ emulsion polymerization, showing better dispersion of the clay platelets in the polymer matrix, exhibited better corrosion protection in the form of a coating on a cold‐rolled steel coupon than that prepared by solution dispersion, which showed a poor dispersion of the clay nanolayers according to a series of electrochemical corrosion measurements. Comparative studies of the optical clarity, molecular barrier properties, and thermal stability of samples prepared in both ways, as membranes and fine powders, were also performed with ultraviolet–visible transmission spectroscopy, molecular permeability analysis, thermogravimetric analysis, and differential scanning calorimetry. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1936–1946, 2004

Poly(vinylidene fluoride-hexafluoropropylene)/organo-montmorillonite clays nanocomposite lithium polymer electrolytes

Polymer-clay nanocomposite (PCN) materials were prepared by intercalation of an alkyl-ammonium ion spacing/coupling agent and a polymer between the planar layers of a swellable-layered material, such as montmorillonite (MMT). The nanocomposite lithium polymer electrolytes comprising such PCN materials and/or a dielectric solution (propylene carbonate) were prepared and discussed. The chemical composition of the nanocomposite materials was determined with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy, which revealed that the alkyl-ammonium ion successfully intercalated the layer of MMT clay, and thus copolymer poly(vinylidene fluoride-hexafluoropropylene) entered the galleries of montmorillonite clay. Cyclic voltammetry and electrochemical impedance spectroscopy (EIS) were used to investigate the electrochemical properties of the lithium polymer electrolyte. Equivalent circuits were proposed to fit the EIS data successfully, and the significant contribution from MMT was thus identified. The resulting polymer electrolytes show high ionic conductivity up to 10 −3 S cm −1 after gelling with propylene carbonate. The PCN materials exhibit good electrochemical stability and could be potentially used in lithium secondary battery.