Effect Of Clay Modification Research Articles

The effect of clay modification on the structure, dielectric behaviour and mechanical properties of PVDF/PMMA/CTAMag polymer nanocomposites as potential flexible performance materials

Abstract In this approach, nanocomposites of PVDF/PMMA/CTAMag films have been successfully synthesized. Modified Maghnite was used as inorganic reinforcement. In this study, nanocomposite polymers were developed based on a mixed matrix of poly(vinylidene fluoride) (PVDF) and poly(methyl methacrylate) (PMMA) of composition (80/20 w/w) in dispersion containing 0, 1, 3, 5 and 7 wt % fillers of organomodified montmorillonite nanoclay (CTAMag) in the melt state. The results obtained by scanning electron microscopy (SEM), XRD traces and FTIR spectra highlighted the homogeneous flexible character of the PVDF/PMMA/CTAMag films and their intercalated and intercalated/exfoliated surface morphology, in addition to the presence of PVDF α, β and γ phase crystallites in these complex films. The increased presence of the modified clay in the host matrix of the PVDF/PMMA blend significantly influenced the melting temperature and the degree of crystallinity of the PVDF crystallites. The scattering of the dielectric spectra, which covers a wide range of frequencies from 20 Hz to 1 GHz, indicates the presence of the phenomenon of interfacial polarization associated with the dielectric capacitance complex at lower frequencies in these composites at 27 °C. The mechanical properties of these composites were evaluated as a function of the load and the mixed matrix of these composites.

The effect of montmorillonite modification and the use of coupling agent on mechanical properties of polypropylene–clay nanocomposites

In this work, polypropylene (PP)–clay nanocomposites obtained by melt blending were investigated. Different commercial montmorillonites (MMTs), such as unmodified MMT, octadecyl ammonium-modified MMT, and dimethyl dialkyl ammonium-modified MMT, have been used. Maleic anhydride–polypropylene (MAPP) copolymer has been used as a coupling agent, and the effect of clay modification as well as MMT: MAPP ratio on final nanocomposites performance was studied. The transmission electron microscopy was used to evaluate the incorporation of clays into the PP matrix. The isothermal crystallization behavior of neat PP and different nanocomposites was studied by differential scanning calorimetry and polarized optical microscopy. Only nanocomposites based on organically modified MMT showed mechanical performance improvements. Nanocomposite reinforced with 5 wt% of organically modified MMT without MAPP showed modulus and strength values of 871 and 29.3 MPa, respectively, these values being higher, around 23% and 4.6%, respectively, than modulus and strength values of neat PP. The incorporation of MMT into the PP matrix produced an increment on the crystallinity rate with respect to neat PP. The half crystallization time of nanocomposites without MAPP was, at least, two times faster than for a neat PP system.

PHB/Bentonite Compounds. Effect of Clay Modification and Thermal Aging on Properties

Poly(3-hydroxybutyrate) (PHB) was compounded with three different Bentonite clays: natural, purified by ultrasound/sonicated and organically modified with hexadecyltrimethylammonium bromide. PHB/Bentonite masterbatches with 30% clay were prepared in a laboratory internal mixer and letdown with pure matrix to 1% and 3% w/w clay. Test samples were injection molded and characterized by x-ray diffraction (XRD), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Increase in Bentonite hydrophobic character was evinced by FTIR for organoclays. XRD of composites showed increase in clay interlayer distance and peak broadening, suggesting formation of intercalated nanocomposites. DSC showed increase in crystallinity and crystallization rate for compounds, especially for PHB/organoclay formulations. Thermal aging was conducted by exposing specimens at 115oC for up to 120 hours, and mechanical properties were measured according to ASTM standards. Elastic modulus increased and impact strength decreased with time and clay content; clay purification had little effect on the tensile properties. Tensile strength of thermal aged samples showed little variation, except for the organoclay nanocomposites, for which it significantly decreased with exposure time. SEM images displayed a whitened honeycomb structure and detachment of PHB/Bentonite layers which may be connected to cold crystallization and degradation processes taking place during thermal aging.Keywords:

Effect of clay modification on structure–property relationships and thermal degradation kinetics of β-polypropylene/clay composite materials

The influence of neat and organically modified montmorillonite on the structure–property relationships of a β-nucleated polypropylene matrix has been thoroughly investigated. High-angle annular dark field scanning transmission electron microscopy revealed that the organic modification of clay facilitated the dispersion of the clay, while X-ray diffractograms showed the α-nucleating effect of the clays on the β-nucleated matrix. The results from tensile tests showed that the organic modification of MMT affected profoundly only the tensile strength at yield and at break. The effect of the organic modification of the clay on the thermal stability of the composites was finally evaluated by thermogravimetric analysis, where the samples filled with oMMT decomposed faster than the ones filled with neat MMT, due to the decomposition of the organic salts that were initially used for the modification of MMT. A kinetics study of the thermal degradation of the composites was also performed, in order to export additional conclusions on the activation energy of the samples.

Effect of clay modification on the structure and properties of sulfonated poly(ether ether ketone)/clay nanocomposites

Sulfonated poly(ether ether ketone) (SPEEK)/clay hybrid membranes were prepared using three types of commercially available clays, the sodium montmorillonite (IC), hydrophobic organo-clay with long alkyl chains (OC), and organo-clay with carboxylic acid end groups (HC). It was found that the SPEEK/HC hybrid membranes achieved the best clay dispersion, with the exfoliation of the clay nano-platelets when the filler loading was < 10 wt%. The incorporation of the carboxylic acid groups in clay layers also improved the connectivity between the ionic clusters in the membrane, resulting in higher proton conductivity without compromising the dimensional stability of membranes. The selectivity higher than the pristine SPEEK membranes was obtained for the SPEEK/HC hybrid membranes at low filler loading (<10 wt%), with higher proton conductivity and similar methanol permeability. POLYM. COMPOS., 37:2632–2638, 2016. © 2015 Society of Plastics Engineers

The effect of clay modification on the mechanical properties of poly(methyl methacrylate)/organomodified montmorillonite nanocomposites prepared byin sitususpension polymerization

Poly(methylmethacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared byin sitususpension polymerization. MMT was previously organically modified by different modification agents [dioctadecyl dimethyl ammonium chloride (DODAC) and methacrylatoethyltrimethyl ammonium chloride (MTC)] and different modification method (cation‐exchange reaction and grafting reaction), ultimately giving rise to five kinds of organomodified MMT (OMMT). The structure of the OMMT was studied by Wide angle X‐ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). Meanwhile, the structure of the PMMA/MMT nanocomposites microspheres was also investigated by WAXD. The molecular weight of the polymers extracted from PMMA/MMT nanocomposites was measured by gel permeation chromatograph (GPC). Finally, the mechanical properties of these PMMA/MMT nanocomposites were studied in detail. It was found that large interlayer spacing (d001) of OMMT could not entirely ensure an exfoliated structure of resultant PMMA/MMT nanocomposites, while OMMT with relative smalld001could still yield exfoliated structure as long as the compatibility between OMMT and polymer matrix was favorable. In addition, the results of mechanical investigation indicated that the compatibility between OMMT and PMMA matrix turned out to be the dominant factor deciding the final mechanical properties of PMMA/MMT nanocomposites. POLYM. COMPOS., 37:1705–1714, 2016. © 2014 Society of Plastics Engineers

Studying rheological behavior of nanoclay as oil well drilling fluid

Bentonite is commonly used to control the rheology and filtrate loss required for water-based drilling fluids. In this study, the effect of clay modification on fluid viscosity and its dispersion in oil-wet fluids were investigated and the thixotropic behavior of nanoclay and common bentonite samples were evaluated. Moreover, the viscosity of a nanoclay suspension which was produced from bentonite supplied by Kheirabad mine in Kerman (Iran) was studied, and the results were compared to common bentonite, used in oil well drilling fluids. The swelling index, cation exchange capacity, nanoclay dispersion in oil-wet phase, and the rheological properties of the produced mud were improved by purification and organification. This study showed that Kheirabad modified clay shows good behavior for drilling purposes at optimum clay concentrations. Moreover, organo clay was a proper additive with adequate rheological properties as an oil base drilling fluid.

Poly(l-lactic acid)/organically modified vermiculite nanocomposites prepared by melt compounding: Effect of clay modification on microstructure and thermal properties

In this work, vermiculite (VMT) was successfully modified by organic cation intercalation (oleyl bis(2-hydroxyethyl) methyl ammonium), silane grafting (glycidoxypropyl trimethoxy silane), and combining silane grafting and alkylammonium cation intercalation. The organically modified VMTs were melt compounded with poly(l-lactic acid) (PLLA), and the effect of the nanofiller concentration and type of modification of the VMT on the nanostructure and thermal properties of the PLLA/organo-VMT nanocomposites was investigated. The effect of the melt processing conditions used in the preparation of nanocomposites on the molecular weights of the polymer matrix was determined by gel permeation chromatography (GPC). The structure of the intercalated surfactant in the modified clays was characterized by X-ray diffraction (XRD) analysis. The morphology of the nanocomposites was examined by XRD and transmission and scanning electron microscopy (TEM, SEM). The thermal behavior of the clays and nanocomposites was analyzed by differential scanning calorimetry (DSC) and thermogravimetry (TGA), and microscale pyrolysis combustion calorimetry (PCFC) was used to measure the flammability of the nanocomposites. GPC analysis showed that the molecular weights of native and unfilled extruded PLLA were similar, while the incorporation of organo-VMTs resulted in a reduction of the PLLA molecular weights. XRD and TEM investigations showed that exfoliation predominantly occurred in 2wt% nanocomposites, whereas intercalated structures together with exfoliated clays were observed with high contents of organoclays. The double modification of the clay resulted in a higher level of exfoliation, attributed to the enhanced interactions between the end groups of the PLLA and the clay containing the epoxy groups. DSC analysis showed that the glass transition and cold crystallization temperatures of nanocomposites were slightly lower than those of neat PLLA. The crystallization enthalpies increased with the addition of organo-VMTs. However, the crystallinity of the PLLA was unaffected by the addition of clays, only the crystal size and perfection were affected. The nanocomposites prepared with 2wt% of organoclays displayed increased thermal stability. The flammability test revealed that no significant reduction of fire hazards was caused by the presence of organo-VMTs.

Effect of clay modification on the dynamic mechanical and dielectric properties of PMMA nanocomposites via melt blending

AbstractThe dynamic mechanical and dielectric properties of poly(methyl methacrylate)/ clay nanocomposites (PCNs) prepared with melt blending was studied in terms of clay modification and nanoscale dispersion. The pristine clay was modified via various routes, including PMMA concentrates from in situ polymerization and POP-diamine intercalation. Partially exfoliated clay layers were uniformly dispersed in the nanocomposites as evidenced from x-ray diffraction study. The subglass β relaxation, the segmental α relaxation, and the α β-merging process above Tg were observed in the nanocomposites from the dielectric analysis. Compared to neat PMMA, with only 5 wt% clay loading, the modified PCN materials exhibit higher glass-transition temperatures and higher dynamic storage moduli, which was attributed to the polymer chain tethering and confinement effect. Significant increase in dielectric permittivity’s and losses due to interfacial polarization and ionic conduction were observed for the PCNs. The intensity of the interfacial polarization process increases with the dispersion degree of clay layers and hence the relaxation process can be assigned to the space charge polarization of the ionic species in the clay intergalleries.

Effect of Clay Modification on the Mechanism of Local Deformations in PA6 Nanocomposites

AbstractPA nanocomposites are prepared from clays organophilized with a phosphonium and an ammonium salt, and sodium montmorillonite is used as reference. The analysis of mechanical and micromechanical properties of the composites reveal that several micromechanical deformation processes occur in the PA/MMT composites. The matrix cavitates at relatively small stress. Processes related to non‐exfoliated clay structural units are initiated at larger stresses. Sound is emitted mainly by the fracture of particles, but debonding may also occur. The plastic deformation of the matrix dominates at larger stresses and deformations. The various local deformations are independent of each other and composite properties are not determined by silicate related processes but by the deformation of the matrix.magnified image

Effect of clay modification on the morphology and the mechanical/physical properties of ABS/PMMA blends

AbstractThe effect of three types of organoclays on the morphology and mechanical properties of lower critical solution temperature‐type poly(acrylonitrile‐butadiene‐styrene)/poly(methyl methacrylate) (ABS/PMMA) blends was investigated. Polymers were melt‐compounded with 2 and 4 wt % of clays using a twin‐screw extruder. X‐ray scattering and transmission electron microscopy revealed that the intercalation of the nanoclay in the hybrid nanocomposite was more affected by the polarity of the organoclay. Although the morphology of the blends varied by PMMA content, scanning electron microscopy showed smaller PMMA domains for the hybrid systems containing clay particles. Although good dispersion of the nanoclay through the ABS matrix and at the blend interface led to enhancement of tensile strength, the increment of the stiffness was more noticeable for nanocomposites including less polar organoclay. Well‐dispersed clay platelets increased the glass transition temperature. In addition, nanoscratching analysis illustrated an improvement in scratch resistance of ABS because of the presence of PMMA and organoclay. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effect of clay modification on the structure and mechanical properties of polyamide-6 nanocomposites

Polyamide-6 nanocomposites were prepared from a new phosphonium organoclay obtained at pilot scale in supercritical carbon dioxide (scCO 2) and a commercially available ammonium modified-silicate. The composites were homogenised by twin-screw extrusion, then specimens for testing were prepared by injection moulding. The clay content of the composites was varied from 0 to 7 vol.% in 7 steps. The clays were characterised in detail; they differed in their surface coverage and gallery structure, while their particle size was similar and their surface energy differed only slightly. X-ray diffraction, electronic microscopy and rheology were used for the characterisation of composite structure. Different gallery structure of the clays led to dissimilar extent of exfoliation. The phosphonium organoclay exfoliated better in PA than the silicate treated with the ammonium salt in spite of its smaller surface coverage. The nanocomposites showed the usual complex structure: besides individual platelets and intercalated stacks, large particles were also present and the development of a silicate network could be shown at large clay contents. Quantitative determination of the extent of reinforcement revealed two determining factors: contact surface and strength of interaction. The first increases with exfoliation, but the latter decreases as an effect of organophilisation. The extent of exfoliation was also estimated quantitatively, and the calculation confirmed the results of qualitative evaluation showing larger extent of exfoliation for the scCO 2-prepared phosphonium clay.

Effect of clay modification on the morphological, mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

AbstractPolyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 Society of Plastics Engineers

Effect of Clay Modification on Photooxidation of Polyethylene/Clay Nanocomposites

In this paper, effect of clay modification and the resultant clay dispersion and orientation structure on the photooxidation of polyethylene has been investigated upon ultraviolet exposure using the technique of infrared spectroscopy. Polyethylene/clay nanocomposites have been prepared using different clay modification. Both the pristine MMT clay and CTAB ammonium intercalated clay were modified via grafting reaction of silane with hydroxyl groups on the clay edge. The grafting modification leads to decreased photooxidation rate compared with that of neat PE, while the pristine MMT and ammoniums accelerate the photooxidation rate of the corresponding composites. Effect of the dispersion and orientation structure of clay in polymer matrix has also been discussed. In addition, the influence of photooxidation behavior on crystallization and morphology of the composites was studied by means of DSC and SEM.

Enhanced Clay Dispersion in Polypropylene by the Modification of Clay with Poly(Oxypropylene) Diamine

Polypropylene (PP) is a highly non-polar polymer. Where as the clay is a polar material. Hence generally we get poor dispersion out of it. In this work, effort has been taken to improve the dispersion of clay in to polypropylene matrix. Clay was modified with Poly (oxypropylene) ammonium chloride. Composites were prepared by melt blending method in a twin screw extruder. Three different ratios namely 1.5, 3.0, and 4.5 weight % loadings of clay were adopted to prepare these composites by this technique. Their structures were characterized by FTIR, x-ray diffraction (XRD). Notable change in the crystallization and melting temperatures were observed by differential scanning calorimetry (DSC). The distribution of clay in the matrix was also studied through optical microscope (OM) and scanning electron microscope (SEM). The effect of clay modification on the performance of the composites was studied.

Mechanical, Thermal and Viscoelastic Behavior of Nylon 6/Clay Nanocomposites with Cotreated Montmorillonites

Nylon 6 nanocomposites were prepared using melt intercalation technique. Sodium montmorillonite (Na-MMT) was modified with octadecyl ammonium salt to evaluate the effect of clay modification on the performance of the nanocomposites. A comparative account with the nanocomposites prepared, using commercial clay cloisite 30B has been presented. X-ray diffraction (XRD) studies indicated an increase in the basal spacing of organically modified clays. Further, X-ray diffractograms of the nanocomposites displayed the absence of basal reflections suggesting the formation of an exfoliated structure. Transmission electron microscopy (TEM) investigations also confirmed exfoliation of clay galleries in the nanocomposites. Differential scanning calorimetry (DSC) measurements revealed both γ and α transitions in the matrix polymer as well as the nanocomposites. The crystallization temperature (Tc) exhibited a marginal increase in the C30B/Nylon 6 nanocomposites. Thermal stability of virgin Nylon 6 and the nanocomposites has been investigated using thermogravimetric analysis. Mechanical test revealed an increase in the tensile and flexural properties of Nylon 6 with the incorporation of nanoclays. Storage and loss modulus of virgin matrix increased with the incorporation of nanoclays. C30B/Nylon 6 nanocomposites exhibited optimum performance at 5% clay loading. Further, water absorption studies also confirmed comparatively lesser tendency of water uptake in these nanocomposites.

Melt Blended Polystyrene/Layered Silicate Nanocomposites: Effect of Clay Modification on the Mechanical, Thermal, Morphological and Viscoelastic Behavior

Polystyrene (PS)/layered silicate nanocomposites are prepared by the melt blending technique. Na-MMT is modified with stearyltrimethyl ammonium chloride to evaluate the effect of clay modification on the performance of the nanocomposites. A comparative account with the nanocomposites prepared using commercial clay cloisite 20A (C20A) has been presented. The effect of addition of untreated and treated clays on the morphological, thermal, mechanical, and dynamic mechanical properties of PS matrix has been studied. The dispersion characteristics of the clays and the formation of tactoids within the matrix polymer is investigated through transmission electron microscopy (TEM) analysis. X-ray diffraction (XRD) studies confirm an increase in the clay gallery spacing in the treated clay nanocomposites. Thermal measurements employing differential scanning calorimetry (DSC) and thermogravimetric analyzer (TGA) are carried out to evaluate the effect of addition of nanoclays on the Tg and thermal stability of PS matrix. C20A-PS nanocomposites exhibit optimum performance at 3% clay loading. Mechanical tests reveal an increase of tensile, flexural, and impact strengths to the tune of 83, 55, and 74%, respectively. Further, dynamic mechanical analysis (DMA) shows a substantial increase in the storage modulus of PS in the treated nanocomposites.

Poly(ethylene oxide)/Laponite nanocomposites via melt-compounding: effect of clay modification and matrix molar mass

The present study focuses on the preparation of poly(ethylene oxide) (PEO) nanocomposites based on the synthetic Laponite clay. The clay was added both in its pure form as well as organically modified with low molar mass poly(ethylene glycol) (PEG) components in order to enhance the compatibility between Laponite and PEO. Several PEG's with different end groups were used. Almost all of them were found to intercalate in the clay intergallery spacing. An order of intercalation efficiency could be established. The modified clays displayed a good thermal stability at the nanocomposite processing temperature.The nanocomposites based on the pure Laponite clay as well as the modified clays display an intercalated structure with a modest intergallery spacing. The ion-dipole modification with the PEG's was ineffective in improving the compatibility between PEO and the Laponite silicate layers. Their respective mechanical properties were found to be increased a little, which can be attributed to the low effective aspect ratio of the silicate platelets present in the nanocomposites. This is caused by the low initial aspect ratio of Laponite (w/t=25) and the limited basal spacing increase. The addition of clay does not result in nucleation of the PEO crystallisation. In contrast, the crystallisation was inhibited, resulting in decreased heat of fusions, especially for the pure Laponite nanocomposites. The nanocomposites based on the modified Laponites display a good thermal stability.

Effect of modified layered silicates and compatibilizer on properties of PMP/clay nanocomposites

AbstractThe preparation and properties of poly(4‐methyl‐1‐pentene) (PMP)/clay nano‐composites are described for the first time. The effect of clay modification and compatibilizer on the formation and properties of the nanocomposites is studied. Layered silicates modified with two types of quaternary ammonium salts are used. The X‐ray diffraction results indicate intercalation of the polymer into the intergallery spacing of the clay. Thermogravimetric analysis shows a delay in the degradation process. Dynamic mechanical analysis shows an increase in the storage modulus for the nanocomposites. The use of compatibilizer containing maleic anhydride and acrylic ester groups is explored. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3233–3238, 2003

Preparation and characteristics of nitrile rubber (NBR) nanocomposites based on organophilic layered clay

AbstractThe effect of clay modification on organo‐montmorillonite/NBR nanocomposites has been studied. Organo‐montmorillonite/NBR nanocomposites were prepared through a melt intercalation process. NBR nanocomposites were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), dynamic mechanical thermal analysis (DMTA) and a universal testing machine (UTM). XRD showed that the basal spacing in the clay increased, which means that the NBR matrix was intercalated in the clay layer galleries. On TEM images, organo‐montmorillonite (MMT) particles were clearly observed, having been exfoliated into nanoscale layers of about 10–20 nm thickness from their original 40 µm particle size. These layers were uniformly dispersed in the NBR matrix. The DMTA test showed that for these nanocomposites the plateau modulus and glass transition temperature (Tg) increased with respect to the corresponding values of pure NBR (without clay). UTM test showed that the nanocomposites had superior mechanical properties, ie strength and modulus. These improved properties are due to the nanoscale effects and strong interactions between the NBR matrix and the clay interface. Copyright © 2003 Society of Chemical Industry