Effect of sodium montmorillonite nanoclay on the water absorbency and cationic dye removal of carrageenan-based nanocomposite superabsorbents

Nanocomposite superabsorbents were synthesized by simultaneously solution copolymerization of acrylamide (AAm) and sodium acrylate (Na-AA) in the presence of carrageenan biopolymer and sodium montmorillonite (Na-MMt) nanoclay. Potassium persulfate (KPS) and methylenebisacrylamide (MBA) were used as initiator and crosslinker, respectively. The structure and morphology of the nanocomposites were investigated using XRD, FTIR, scanning electron microscopy (SEM), and TEM techniques. The influence of nanoclay and carrageenan contents as well as monomer weight ratios on the degree of swelling of nanocomposites was studied. The optimum water absorbency was obtained at 10 wt% of clay, 10 wt% of carrageenan, and 1:1 of monomers weight ratio. The obtained nanocomposites were examined to remove of crystal violet (CV) cationic dye from water. The effect of carrageenan and clay content on the speed of dye adsorption revealed that while the rate of dye adsorption is enhanced by increasing the clay content up to 14 wt% of clay, it was decreased as the carrageenan increased in nanocomposite composition. The results showed that the pseudo-second-order adsorption kinetic was predominated for the adsorption of CV onto nanocomposites. The experimental equilibrated adsorption capacity of nanocomposites was analyzed using Freundlich and Langmuir isotherm models. The results corroborated that the experimental data fit the Freundlich isotherm the best.     

Microstructure,morphology, and mechanical properties of styrene‐butadiene rubber/organoclay nanocomposites

Composites based on styrene‐butadiene rubber containing organophilic montmorillonite were produced by melt compounding and conventional sulfur curing. The samples were characterized by X‐ray diffraction and both transmission and scanning electron microscopy. The dispersion of the clay and the spacing between the silicate layers revealed the presence of intercalated, aggregated, and partially exfoliated structures. Infrared spectroscopy also provided clear evidence for clay exfoliation and migration of zinc stearate to the surface of the samples. The crosslink density, evaluated through swelling in toluene, decreased with increasing organoclay content. This behavior could be justified by the partial absorption of the curatives on the filler surface. The mechanical properties of nanocomposites significantly increased when compared with those of unfilled rubber. These enhanced properties were attributed to the intercalation/exfoliation of the organoclay. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Thermomechanical behavior of polymer/layered silicate clay nanocomposites based on unmodified low density polyethylene

The purpose of this study was to investigate the effect of filler content and aspect ratio on the thermomechanical behavior of unmodified low density polyethylene (LDPE)‐based layered silicate clay nanocomposites. LDPE‐based nanocomposites, without any polymer modification and with two kinds of clays, one with low aspect ratio (i.e., synthetic laponite ‐Lp) and another with high aspect ratio (i.e., montmorillonite) were prepared and characterized using dynamic mechanical analysis (DMA). Organosilicates were added at 2, 5 and 10 wt%, respectively. X‐ray diffraction (XRD) analysis was performed on composites obtained by dispersing the organosilicates in unmodified LDPE. The LPDE reinforced with organo‐montmorillonite (OMt) had better performance in the whole temperature range than those with organo‐laponite (OLp). It was concluded that the relatively high aspect ratio OMt can induce superior dynamic mechanical properties to the LDPE polymer compared to lower aspect ratio OLp. This was linked to the higher active surface area and preferential orientation of longer platelets resulting in higher mechanical enhancement. This behavior was more pronounced up to filler contents of 5 wt%. Further increase of the filler content led to more conventional composites, which hindered the reinforcing ability of the silicates. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Preparation and characterization of polyurethane–organoclay nanocomposites

Nanocomposite polyurethane (PU)–organoclay materials have been synthesized via in‐situ polymerization. The organoclay is first prepared by intercalation of tyramine into montmorillonite (MMT)‐clay through ion exchange process. The syntheses of polyurethane–organoclay hybrid films containing different ratios of clay were carried out by swelling the organoclay into diol and diamine followed by addition of diisocyanate and then cured. The nanocomposites with dispersed and exfoliated structure of MMT were obtained as evidenced by X‐ray diffraction and scanning electron microscope. X‐ray diffraction showed that there is no peak corresponding to d₀₀₁ spacing in organoclay with the ratios up to 20 wt%. SEM images confirmed the dispersion of nanometer silicate layers in the polyurethane matrix. Also, it was found that the presence of organoclay leads to improvement in the mechanical properties. The tensile strength was increased with increasing the organoclay contents to 20 wt% by 221% in comparision to the PU with 0% organoclay. POLYM. COMPOS. 28:108–115, 2007. © 2007 Society of Plastics Engineers     

Thermal and mechanical properties of melt processed intercalated poly(methyl methacrylate)–organoclay nanocomposites over a wide range of filler loading

BACKGROUND: Poly(methyl methacrylate) (PMMA)–organoclay nanocomposites with octadecylammonium ion‐modified montmorillonite, prepared via melt processing, over a wide range of filler loading (2–16 wt%) were investigated in detail. These hybrids were characterized for their dispersion structure, and thermal and mechanical properties, such as tensile modulus (E), break stress (σ_brk), percent break strain (ε_brk) and ductility (J), using wide‐angle X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and tensile and impact tests. RESULTS: Intercalated nanocomposites were formed even in the presence of 16 wt% clay (high loading) in PMMA matrix. PMMA intercalated into the galleries of the organically modified clay, with a change in d‐spacing in the range 11–16 Å. TGA results showed improved thermal stability of the nanocomposites. The glass transition temperature (T_g) of the nanocomposites, from DSC measurements, was 2–3 °C higher than that of PMMA. The ultimate tensile strength and impact strength decreased with increasing clay fraction. Tensile modulus for the nanocomposites increased by a significant amount (113%) at the highest level of clay fraction (16 wt%) studied. CONCLUSION: We show for the first time the formation of intercalated PMMA nanocomposites with alkylammonium‐modified clays at high clay loadings (>15 wt%). Tensile modulus increases linearly with clay fraction, and the enhancement in modulus is significant. A linear correlation between tensile strength and strain‐at‐break is shown. Thermal properties are not affected appreciably. Organoclay can be dispersed well even at high clay fractions to form nanocomposites with superior bulk properties of practical interest. Copyright © 2007 Society of Chemical Industry     

Chlorosulfonated polypropylene: preparation and its application as a coupling agent in polypropylene-clay nanocomposites

Polypropylene nanocomposites containing organophilic layered silicate were prepared by melt mixing. In order to increase polypropylene polarity, Cl and SO₂Cl groups were introduced by reaction with sulfuryl chloride under UV irradiation. Chlorosulfonated polypropylene was subsequently melt-compounded with organophilized montmorillonite clay to produce a masterbatch. The masterbatch was then blended with commercial isotactic polypropylene. An organophilized silicate (Cloisite 15A) and three chlorosulfonated polypropylenes with different degrees of functionalization were used in this study. The effect of various processing procedures was examined as well. The morphology of nanocomposites obtained was examined using TEM and X-ray diffraction. It has been shown that the presence of polar groups leads to an increased gallery distance and partial exfoliation. Nevertheless, full exfoliation of clay platelets has not been achieved. The observed morphologies affected the resulting tensile mechanical behaviour: both stiffness and strength significantly increased.     

Biodegradable polyester layered silicate nanocomposites based on poly(ϵ‐caprolactone)

Nanocomposites based on biodegradable poly(?‐caprolactone) (PCL) and layered silicates (montmorillonite, MMT) were prepared either by melt interaction with PCL or by in situ ring‐opening polymerization of ?‐caprolactone as promoted by the so‐called coordination‐insertion mechanism. Both non‐modified clays (Na⁺ ‐MMT) and silicates modified by various alkylammonium cations were studied. Mechanical and thermal properties were examined by tensile testing and thermogravimetric analysis. Even at a filler content as low as 3 wt% of inorganic layered silicate, the PCL‐layered silicate nanocomposites exhibited improved mechanical properties (higher Young's modulus) and increased thermal stability as well as enhanced flame retardant characteristics as a result of a charring effect. It was shown that the formation of PCL‐based nanocomposites depended not only on the nature of the ammonium cation and related functionality but also on the selected synthetic route, melt intercalation vs. in situ intercalative polymerization. Interestingly enough, when the intercalative polymerization of ?‐caprolactone was carried out in the presence of MMT organo‐modified with ammonium cations bearing hydroxyl functions, nanocomposites with much improved mechanical properties were recovered. Those hybrid polyester layered silicate nanocomposites were characterized by a covalent bonding between the polyester chains and the clay organo‐surface as a result of the polymerization mechanism, which was actually initiated from the surface hydroxyl functions adequately activated by selected tin (II) or tin (IV) catalysts.     

Synthesis of bio‐based polymeric nanocomposites from acrylated epoxidized soybean oil and montmorillonite clay in the presence of a bio‐based intercalant

Polymeric nanocomposites were synthesized from functionalized soybean‐oil‐based polymer matrix and montmorillonite (MMT) clay using an in situ free radical polymerization reaction. Acrylated epoxidized soybean oil combined with styrene was used as the monomer. Organophilic MMT (OrgMMT) was obtained using a quaternized derivative of methyl oleate, which was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized using X‐ray diffraction and atomic force microscopy. The effect of increased nanofiller loading on the thermal and mechanical properties of the nanocomposites was investigated using thermogravimetric analysis and dynamic mechanical analysis. It was found that the desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt%, whereas a partially exfoliated or intercalated nanocomposite was obtained for 3 wt% loading. All the nanocomposites were found to have improved thermal and mechanical properties as compared with virgin acrylated epoxidized soybean‐oil‐based polymer matrix. The nanocomposite containing 2 wt% OrgMMT clay was found to have the highest thermal stability and best dynamic mechanical performance. Copyright © 2010 Society of Chemical Industry     

New aramid‐based nanocomposites: Synthesis and characterization

New type of nanocomposites containing various proportions of montmorillonite in aromatic polyamide was prepared via solution intercalation method. Aramid chains were synthesized by reacting 4,4′‐oxydianiline with isophthaloyl chloride in N,N′‐dimethyl acetamide. Dodecylamine was used as swelling agent to change the hydrophilic nature of montmorillonite into organophilic. Appropriate amounts of organoclay were mixed in the polymer solution using high‐speed mixer for complete dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterized by XRD, TEM, mechanical, thermal, and water absorption measurements. The structure and morphology of the nanocomposites determined by XRD and TEM revealed the formation of exfoliated and intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus of the nanocomposites with clay loading up to 6 wt%. The glass transition temperature increased up to 12 wt% clay content and thermal stability amplified with increasing clay loading. The water absorption reduced gradually as a function of organoclay and approached to zero with 20 wt% organoclay in the aramid. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of nano clay on the constrained polymer volume of chlorobutyl rubber nanocomposites

The dynamic mechanical properties of chlorobutyl rubber nanocomposites containing different varieties of clay have been investigated. The clay moieties have been chosen so that they vary in their organic modification, modifier concentration, and d spacing. The viscoelastic properties such as storage modulus, damping behavior, and loss modulus of polymer composites depends on matrix filler interaction, crystallinity, and extent of crosslinking. The prepared composites were characterized by X Ray Diffraction, and the extend of exfoliation/intercalation was studied. It has been observed that the storage modulus of the composites increased with the addition of filler due to the enhancement in stiffness of the material. The damping behavior was found to decrease with the addition of filler and this was attributed to the restricted movement of the polymer segments. The higher surface area to volume ratio of the layered silicate resulted in the better interaction between the polymer matrix and filler. The variation of loss as well as storage modulus of the nanocomposites were evaluated as a function of filler loading, and a comparison of the properties of the rubber nanocomposites containing different organic clay was also carried out. Finally, a calculation of constrained volume of polymer chains was done in the nanocomposites. POLYM. COMPOS., 36:2135–2139, 2015. © 2014 Society of Plastics Engineer     

Preparation of exfoliated high‐impact polystyrene/MMT nanocomposites via in situ polymerization under controlling viscosity of the reaction medium

Exfoliated high‐impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization of styrene in the presence of polybutadiene, using an intercalated cationic radical initiator‐MMT hybrid (organoclay). In the solution polymerization in toluene, the silicate layers of the clay were well exfoliated, due to the low extra‐gallery viscosity that can facilitate the diffusion of styrene monomers into the clay layers during the polymerization. The exfoliated HIPS/MMT nanocomposites were also successfully prepared by controlling the viscosity of the reaction medium with prolong swelling of the organoclay in styrene, prior to bulk polymerization. The HIPS/MMT nanocomposites, obtained from bulk polymerization, exhibited a significant improvement in thermal stability, compared to those obtained from solution polymerization as well as the pure polymer counterparts. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Effect of Nanoclay on the Mechanical,Thermal, and Water Absorption Properties of an UP-toughened Epoxy Network

Unsaturated polyester (UP)-toughened epoxy nanocomposites were prepared, and their effective mechanical and thermal properties were studied. Two types of organo-modified montmorillonite (OMMT) clays were used to prepare the nanocomposites. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis showed the formation of exfoliated silicate layers in the UP-toughened epoxy matrix. Mechanical tests revealed that nanocomposites (containing 1 wt% OMMT clay) showed an increase in tensile strength to 13.8%, flexural strength to 10%, and impact strength to 4% compared with an UP-toughened epoxy blend. The effect of different heating rates on the curing behavior of UP-toughened epoxy nanocomposites was investigated using non-isothermal differential scanning calorimetry. The data were interpreted using the Kissinger and Flynn–Wall–Ozawa models to find the curing reaction parameter. The water uptake behavior for nanocomposites increased with the addition of OMMTs. Scanning electron microscopy micrographs indicated morphological changes in the impact fractured samples of UP-toughened epoxy nanocomposites.     

PP/clay nanocomposite: optimization of mixing conditions with respect to mechanical properties

Polypropylene/clay nanocomposites were studied with focus on optimization of mixing conditions. Two different types of commercial nanofillers Dellite^® were used (Dellite^® 72T and Dellite^® 67G). Effect of various concentrations of fillers on morphology and mechanical properties was investigated. Conditions of preparation were varied with respect to mixing time and speed of rotation of kneaders. Results of morphology study showed that nanocomposites contained agglomerates of nanofillers. The comparison of the filler types revealed that better dispersion and distribution was found for nanocomposites containing Dellite 72T which had also better tensile strength. Optimum mixing time was 30 min. 3D graphical analysis showed that the optimum speed of rotation was 60 rpm and with increasing clay content (2–10 wt%) the tensile strength increased.     

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.     

Enhanced dyeability of poly(ethylene terephthalate)/organoclay nanocomposite filaments

This study deals with the generation of poly(ethylene terephthalate)/organoclay nanocomposite filaments by the melt‐spinning method and with the investigation of their morphological and dyeing properties. Different montmorillonite types of clay (Resadiye and Rockwood) were modified using different intercalating agents, and poly(ethylene terephthalate) nanocomposite filaments containing 0.5 and 1 wt% organoclays were prepared. Afterwards, the filaments were dyed with two disperse dyes (Setapers Red P2G and Setapers Blue TFBL‐NEW) at different temperatures (100, 110, and 120 °C) in the absence/presence of a carrier. Organoclays and poly(ethylene terephthalate)/organoclay nanocomposites showed an increased d‐spacing between clay layers. Irrespective of clay and surfactant type, poly(ethylene terephthalate)/organoclay nanocomposite filaments dyed at 120 °C in the presence of only a very small amount of carrier showed appreciable dyeability in comparison with neat poly(ethylene terephthalate). The dyeability of the organoclay‐containing poly(ethylene terephthalate) samples was found to be better in spite of having increased degrees of crystallinity. Moreover, the colour fastness properties of the clay‐containing samples were not affected adversely.     

A Study on Structure and Mechanical Properties of Polyurethane/Organic-Montmorillonite Nanocomposites

The intercalated nanocomposites of polyurethane (PU) with organic-montmorillonite (OMMT) treated by cetryltrimethyl ammonium bromide was prepared. The interlayer spacing of PU/OMMT nanocomposites was 3–4 nm. The interface interaction of PU/OMMT nanocomposites was improved compared to that of PU/montmorillonite (MMT) composites. The orderly arrangement of the PU chains was hindered because of strong interface interaction between the silicate layers dispersed in the nanometer and PU chains. By adding 2 wt% OMMT to PU, tensile strength and tear strength of the PU/OMMT composites were increased from 10.5 MPa and 36.4 KN/m to 13.8 MPa and 42.2 KN/m, respectively. The tensile strength and tear strength increased with OMMT content firstly, reaching its maximum when the OMMT content was 8 wt%. After that, the tensile strength and tear strength decreased with the further increase of the OMMT content. Compared to that of PU, the elongation at break of the PU/OMMT nanocomposites increased, indicating that the stretch of PU/OMMT nanocomposites increased.     

Deformation and fracture behavior of polyamide nanocomposites: The effect of clay dispersion

This study describes the effect of the clay content and its dispersion on deformation and fracture behavior of polyamide nanocomposites. Two nanocomposite systems, intercalated and exfoliated nanocomposites containing layered silicate, were compared. They were prepared by melt‐compounding of polyamide with sodium montmorillonite or organophilized montmorillonite. It has been shown that while the exfoliated structure imparts to the nanocomposite higher stiffness and strength, the toughness is inferior to the intercalated nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ethylene vinyl acetate/layered silicate nanocomposites prepared by a surfactant-free method: Enhanced flame retardant and mechanical properties

Exfoliated EVA/layered silicate nanocomposites were prepared by a masterbatch process using polymer-modified layered silicate instead of small molecule surfactant-modified clays. The nanocomposites exhibited improved mechanical properties and flame retardancy. Microscale flammability test showed that the heat release capacity (HRC) and total heat release (THR) were reduced by 21-24% and 16%, respectively. Radiant gasification studies revealed that the exfoliated EVA nanocomposites exhibited better improvements in flame retardant properties of EVA than did the corresponding intercalated nanocomposites. The peak mass loss rate of the exfoliated EVA nanocomposite containing about 5 wt% clay was reduced by 80% and the mass loss rate plot was spread over a much longer period of time. The mechanical and flammability tests revealed that the observed improvements in all the desirable properties were due to the presence of both the incorporated polymeric surfactant and the nanoclay.     

Structure and properties of poly(vinyl chloride)/montmorillonite composites produced from plastisols

Poly(vinyl chloride) (PVC)/montmorillonite nanocomposites were prepared from plastisols. The concentrations of plasticizer and montmorillonite were varied. The composites were characterized by both X‐ray diffraction and transmission electron microscopy, which indicated that intercalated nanocomposites were prepared, but that the distribution of clay was not uniform on the nanoscale. Plasticizer migration was found to decrease with increasing concentration of clay and could be reduced by 25% when 3 wt% of Cloisite 30B was added in formulations containing 100 phr (parts by weight per hundred parts of resin) of plasticizer. Montmorillonite was found to reduce the tensile properties of PVC, especially when the plasticizer concentration was low, i.e., 50 phr. J. VINYL ADDIT. TECHNOL., 22:140–145, 2016. © 2014 Society of Plastics Engineers     

Investigation of the influence of processing conditions on the thermal,rheological and mechanical behavior of polypropylene nanocomposites

The use of polypropylene (PP)‐layered silicate nanocomposite has attracted great interest in the polymer industry over the last years. On one hand, PP is widely used in many fields of applications because of good performance and cost. On the other hand, the major advantage of layered silicate nanofiller in the polymer matrix is the small amount of filler (<5 wt%) needed to enhance various properties such as Young's modulus. The most commonly used layered silicates are organomodified montmorillonite (MMT). In this study, a PP/organoclay nanocomposite, filled with layered silicate Nanofil SE3010 (1 and 5 wt%), provided by Rockwood Additives, USA, was used. The polymer nanocomposites were prepared via melt intercalation in a laboratory kneader. The compatibilizer (PP grafted with maleic acid anhydride) admixture content relative to the organoclay content (1 and 5 wt%) was chosen at a ratio of 1:1 (clay:compatibilizer). The influence of different processing conditions (rotation speed and residence time) on the thermal, rheological, and mechanical properties and the interlayer distance was investigated. It was the target to determine whether a short and intensive or a long and soft process performs better. Different properties prefer different states of dispersion of MMT in the polymer matrix. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers