Advanced Materials Based on Ethylene-Propylene-Diene Terpolymers and Organically Modified Montmorillonite

This paper presents studies on the development and characterization of nanocomposites based on ethylene-propylene terpolymer rubber (EPDM), chlorobutyl rubber (IIR-Cl) and organically modified montmorillonite (OMMT). Mixtures were made containing 0, 3 and 6 phr (parts per 100 parts rubber) OMMT, respectively. They were obtained by melt intercalation in an internal mixer - Plasti-Corder Brabender, in suitable blending parameters, at high temperature for 11 minutes. Curing agents were embedded on a laboratory roller at 70-100 ºC, friction 1:1.1, processing time 5 minutes. Rubber specimens were obtained by compression, using a hydraulic press at 165 ºC and a pressing force of 300 kN. Curing time, determined using the Monsanto rheometer, decreases with the increased amount of OMMT in the mixtures. At the same time, it was noticed that mixtures containing OMMT show improvement in physical-mechanical properties. These types of nanocomposites may be used to obtain rubber seals for the space application or for other areas of application.

Sustainable Hydrogel Nanocomposites Based on Grafted Chitosan and Clay for Effective Adsorption of Cationic Dye

Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (qm) was found to increase from 2173 mg g−1 until 2221 mg g−1 by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.

Influence of Organic Modifier Loading on Particle Dispersion of Biodegradable Polycaprolactone/Montmorillonite Nanocomposites

Natural sodium montmorillonite (NaMMT), Cloisite Na+ and two organophilic montmorillonites (OMMTs), Cloisites 20A and 15A were used. Polycaprolactone (PCL)/MMT composites containing 1, 3, 5, and 10 wt% of Cloisite Na+ and PCL/OMMT nanocomposites containing 5 and 10 wt% of Cloisites 20A and 15A were prepared via solution intercalation technique to study the influence of organic modifier loading on particle dispersion of PCL/ NaMMT composites. Thermal stabilities of the obtained composites were characterized by thermal analysis using the thermogravimetric analyzer (TGA) which showed that in the presence of nitrogen flow the incorporation of 5 and 10 wt% of filler brings some decrease in PCL thermal stability in the sequence: Cloisite Na+>Cloisite 15A > Cloisite 20A, while in the presence of air flow these fillers scarcely influenced the thermoxidative stability of PCL by slightly accelerating the process. The interaction between PCL and silicate layers was studied by Fourier transform infrared (FTIR) spectroscopy which confirmed moderate interactions between nanometric silicate layers and PCL segments. The electrical conductivity (σ) which describes the ionic mobility of the systems was studied as a function of temperature and showed that σ of PCL was enhanced on increasing the modifier loading at filler content of 5 wt%, especially at higher temperatures in the sequence: Cloisite Na+

The Microstructural and Mechanical Characterization of Organo-Clay-Modified Bitumen, Calcareous Aggregate, and Organo-Clay Blends

Bitumen has been widely used as the binder of aggregate in road pavement due to its good viscoelastic properties, as a viscous organic mixture with various chemical compositions. Bitumen is a liquid at high temperature and it becomes brittle at low temperatures, and this temperature-sensitivity can cause the rutting and cracking of the pavement and limit its application. Therefore, the properties of existing asphalt materials need to be enhanced. The pavement with polymer modified bitumen exhibits greater resistance to rutting and thermal cracking, decreased fatigue damage, as well as stripping and temperature susceptibility; however, they are expensive and their applications have disadvantages. Bituminous mixtures are composed of very irregular aggregates bound together with hydrocarbon-based asphalt, with a low volume fraction of voids dispersed within the matrix. Montmorillonite (MMT) is a layered silicate with low cost and abundance, which consists of layers of tetrahedral silicate and octahedral hydroxide sheets. Recently, the layered silicates have been widely used for the modification of polymers, as well as in many different fields. However, there are not too much studies related with the preparation of the modified asphalt with MMT, currently. In this study, organo-clay-modified bitumen, and calcareous aggregate and organo-clay blends were prepared by hot blending method with OMMT, which has been synthesized using a cationic surfactant (Cetyltrymethylammonium bromide, CTAB) and long chain hydrocarbon, and MMT. When the exchangeable cations in the interlayer region of pristine MMT were exchanged with hydrocarbon attached surfactant ions, the MMT becomes organophilic and more compatible with bitumen. The effects of the super hydrophobic OMMT onto the micro structural and mechanic properties (Marshall Stability and volumetric parameters) of the prepared blends were investigated. Stability and volumetric parameters of the blends prepared were measured using Marshall Test. Also, in order to investigate the morphological and micro structural properties of the organo-clay-modified bitumen and calcareous aggregate and organo-clay blends, their SEM and HRTEM images were taken. It was observed that the stability and volumetric parameters of the prepared mixtures improved significantly compared to the conventional hot mixes and even the stone matrix mixture. A micro structural analysis based on SEM images indicates that the organo-clay platelets dispersed in the bitumen have a dominant role in the increase of effectiveness of bitumen - aggregate interactions.

Hydrogeological Factors of the Ore Genesis in the Sedimentary Basins

The present work was made for the purpose of evaluating the interstitial water’s role in the mobilization of metal elements of clay deposits and occurrences in sedimentary formation in the hydro-geological basins. The experiments were performed by using a special facility, which allows adjusting the pressure, temperature, and the frequency of the acoustic vibrations. The dates for study were samples of the oil shales (Baltic career, O2kk) and clay rocks, mainly montmorillonite composition (Borehole SG-12000, the depth of selection 1000–3600 m, the Azov-Kuban trough, N1). After interstitial water squeezing from the rock samples, decrease in the original content of the rock forming components including trace metals V, Cr, Co, Ni, Cu, Zn, Zr, Mo, Pb, W, Ti, and others was recorded. The experiments made it possible to evaluate the ore elements output and organic matters with the interstitial waters. Calculations have shown that, in standard conditions, from each ton of the oil shales, 5-6 kg of ore elements and 9-10 kg of organic matter can be escaped. A quantity of matter, migrating from clays in the process of solidification, is changed depending on the lithogenesis stage: more recent unrealized deposits lose more ore and organic materials than the clay rocks, selected from depth over 3000 m. Each ton of clays in the depth interval 1000-1500 m is able to generate 3-5 kg of the ore elements and 6-8 kg of the organic matters. The interstitial waters are a freight forwarder over transferring these matters in the reservoir beds. It was concluded that the interstitial waters which escaped from the study samples are solutions with abnormal high concentrations of the metals and organic matters. In the discharge zones of the sediment basins, such fluids can create paragenetic associations of the sedimentary-catagenetic ore and hydrocarbon mineral resources accumulations.

Clay Mineralogy of Mukdadiya Formation in Shewasoor Area: Northeastern Kirkuk City, Iraq

14 mudstone samples were collected within the sedimentary succession of Mukdadiya Formation (Late Miocene – Early Pliocene) from Shewasoor area at Northeastern Iraq. The samples were subjected to laboratory studies including mineralogical analysis (using X-ray Diffraction technique) in order to identify the clay mineralogy of Mukdadiya Formation of both clay and non-clay minerals. The results of non-clay minerals are: quartz, feldspar and carbonate (calcite and dolomite) minerals. The clay minerals are: montmorillonite, kaolinite, palygorskite, chlorite, and illite by the major basal reflections of each mineral. The origins of these minerals are deduced also.

Studying the Effect of Nanoclays on the Mechanical Properties of Polypropylene/Polyamide Nanocomposites

Nanocomposites based on polypropylene/polyamide 66 (PP/PA66) nanoblends containing organophilic montmorillonite (OMMT) and maleic anhydride grafted polypropylene (PP-g-MAH) were prepared by melt compounding method followed by injection molding. Two different types of nanoclays were used in this work. DELLITE LVF is the untreated nanoclay and DELLITE 67G is the treated one. The morphology of the nanocomposites was studied using the XR diffraction (XRD). The results indicate that the incorporation of treated nanoclay has a significant effect on the impact strength of PP/PA66 nanocomposites. Furthermore, it was found that XRD results revealed the intercalation, exfoliation of nanaclays of nanocomposites.

Synthesis of Gold Nanoparticles Stabilized in Na-Montmorillonite for Nitrophenol Reduction

Synthesis of gold nanoparticles has attracted much attention since the pioneering discovery of the high catalytic activity of supported gold nanoparticles in the reaction of CO oxidation at low temperature. In this research field, we used Na-montmorillonite for gold nanoparticles stabilization; various gold loading percentage 1, 2 and 5% were used for gold nanoparticles preparation. The gold nanoparticles were obtained using chemical reduction method using NaBH4 as reductant agent. The obtained gold nanoparticles stabilized in Na-montmorillonite were used as catalysts for the reduction of 4- nitrophenol to aminophenol with sodium borohydride at room temperature. The UV-Vis results confirmed directly the gold nanoparticles formation. The XRD and N2 adsorption results showed the formation of gold nanoparticles in the pores of montmorillonite with an average size of 5 nm obtained on samples with 2% gold loading percentage. The gold particles size increased with the increase of gold loading percentage. The reduction reaction of 4- nitrophenol into 4-aminophenol with NaBH4 catalyzed by Au-Namontmorillonite catalyst exhibits remarkably a high activity; the reaction was completed within 9 min for 1%Au-Na-montmorillonite and within 3 min for 2%Au-Na-montmorillonite.

Rheological Properties of Polysulfone-Sepiolite Nanocomposites

Polysulfone (PSU) is a specialty engineering polymer having various industrial applications. PSU is especially used in waste water treatment membranes due to its good mechanical properties, structural and chemical stability. But it is a hydrophobic material and therefore its surface aim to pollute easily. In order to resolve this problem and extend the properties of membrane, PSU surface is rendered hydrophilic by addition of the sepiolite nanofibers. Sepiolite is one of the natural clays, which is a hydrate magnesium silicate fiber, also one of the well known layered clays of the montmorillonites where has several unique channels and pores within. It has also moisture durability, strength and low price. Sepiolite channels give great capacity of absorption and good surface properties. In this study, nanocomposites of commercial PSU and Sepiolite were prepared by solvent mixing method. Different organic solvents and their mixtures were used. Rheological characteristics of PSU-Sepiolite solvent mixtures were analyzed, the solubility of nanocomposite content in those mixtures were studied.

Use of Nanoclay in Various Modified Polyolefins

Polyethylene (PE), Polypropylene (PP), Polyethylene (vinyl acetate) (EVA) and PE-ionomer nanocomposite samples were prepared by mixing of the polymer with organofilized montmorillonite fillers Cloisite 93A and Dellite 67G. The amount of each modified montmorillonite (MMT) was fixed to 5% (w/w). The twin-screw kneader was used for the compounding of polymer matrix and chosen nanofillers. The level of MMT exfoliation was studied by the transmission electron microscopy (TEM) observations. The mechanical properties of prepared materials were evaluated by dynamical mechanical analysis at 30°C and by the measurement of tensile properties (stress and strain at break).

Catalytic Activity of Aluminum Impregnated Catalysts for the Degradation of Waste Polystyrene

The aluminum impregnated catalysts of Al-alumina (Al-Al2O3), Al-montmorillonite (Al-Mmn) and Al-activated charcoal (Al-AC) of various percent loadings were prepared by wet impregnation method and characterized by SEM, XRD and N2 adsorption/desorption (BET). The catalytic properties were investigated in the degradation of waste polystyrene (WPS). The results of catalytic degradation of Al metal, 20% Al-Al2O3, 5% Al-Mmn and 20% Al-AC were compared with each other for optimum conditions. Among the catalyst used 20% Al-Al2O3 was found the most effective catalyst. The BET surface area of 20% Al-Al2O3 determined was 70.2 m2/g. The SEM data revealed the catalyst with porous structure throughout the frame work with small nanosized crystallites. The yield of liquid products with 20% Al-Al2O3 (91.53 ± 2.27 wt%) was the same as compared to Al metal (91.20 ± 0.35 wt%) but the selectivity of hydrocarbons and yield of styrene monomer (56.32 wt%) was higher with 20% Al-Al2O3 catalyst.  

Synthesis of Iron-Modified Montmorillonite as Filler for Electrospun Nanocomposite Fibers

Montmorillonite (MMT) is a very abundant clay mineral and is versatile such that it can be chemically or physically altered by changing the ions between the sheets of its layered structure. This clay mineral can be prepared into functional nanoparticles that can be used as fillers in other nanomaterials such as nanofibers to achieve special properties. In this study, two types of iron-modified MMT, Iron-MMT (FeMMT) and Zero Valent Iron-MMT (ZVIMMT) were synthesized via ion exchange technique. The modified clay was incorporated in polymer nanofibers which were produced using a process called electrospinning. ICP analysis confirmed that clay modification was successful where there is an observed decrease in the concentration of Na and an increase in the concentration of Fe after ion exchange. XRD analysis also confirmed that modification took place because of the changes in the d-spacing of Na-MMT from 11.5 Å to 13.6 Å and 12.6 Å after synthesis of FeMMT and ZVIMMT, respectively. SEM images of the electrospun nanofibers revealed that the ZVIMMT-filled fibers have a smaller average diameter than the FeMMT-filled fibers because of the lower resistance of the suspensions of the former to the elongation force from the applied electric field. The resistance to the electric field was measured by getting the bulk voltage of the suspensions.

Enhanced Thermal, Mechanical and Morphological Properties of CNT/HDPE Nanocomposite Using MMT as Secondary Filler

This study explains the influence of secondary filler on the dispersion of carbon nanotube (CNT) reinforced high density polyethylene (HDPE) nanocomposites (CNT/HDPE). In order to understand the mixed-fillers system, Montmorillonite (MMT) was added to CNT/HDPE nanocomposites. It was followed by investigating their effect on the thermal, mechanical and morphological properties of the aforesaid nanocomposite. Incorporation of 3 wt% each of MMT into CNT/HDPE nanocomposite resulted to the increased values for the tensile and flexural strength, as compared to the pure HDPE matrix. The thermal analysis result showed improved thermal stability of the formulated nanocomposites. Transmission electron microscopy (TEM) images revealed that larger aggregates of CNTs were disappeared upon addition of these two components leading to the enhancement of thermo-mechanical properties for such composites.

Preparation and Physical Characterization of Nanocomposites of PLA / Layered Silicates

This work was focused in to study the compatibility, dispersion and exfoliation of modified nanoclays in biodegradable polymers and evaluate its effect on the physical, mechanical and thermal properties on the biodegradable matrix used. The formulations have been developed with polylactic acid (PLA) and organically modified montmorillonite-type commercial nanoclays (Cloisite 15, Cloisite 20, and Cloisite 30B) in the presence of a plasticizer agent, specifically Polyethylene Glycol of low molecular weight. Different compositions were evaluated, in order to identify the influence of each nanoclayin the polymeric matrix. The mixtures were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (DRX), transmission electron microscopy (TEM) and Tensile Test. These tests have allowed understanding the behavior of each of the mixtures developed.

On the Fatigue Behavior of a Triphasic Composite

This paper presents the results of an experimental characterization of a glass fibre-epoxy composite. The behavior of the traditional two-phase composite has been compared with the one of a new three-phase composite where the epoxy matrix was modified by addition of a 3% weight fraction of montmorillonite nano-particles. Two different types of nano-clays, Cloisite® 30B and RXG7000, produced by Southern Clay Products Inc., have been considered. Three-point bending tests, both monotonic and cyclic, were carried out. A strong reduction of the ultimate flexural strength upon nano-modification has been observed in quasi-static tests. Fatigue tests yielded a smaller strength loss. In both quasi-static and fatigue tests a more pronounced tendency to delamination has been noticed in three-phase composites, especially in the case of 30B nano-clay, with respect to the standard two-phase glass fiber composite.

Paleoclimate Reconstruction during Pabdeh, Gurpi, Kazhdumi and Gadvan Formations (Cretaceous-Tertiary) Based on Clay Mineral Distribution

Paleoclimate was reconstructed by the clay mineral assemblages of shale units of Pabdeh (Paleocene- Oligocene), Gurpi (Upper Cretaceous), Kazhdumi (Albian-Cenomanian) and Gadvan (Aptian-Neocomian) formations in the Bangestan anticline. To compare with clay minerals assemblages in these formations, selected samples also taken from available formations in drilled wells in Ahvaz, Marun, Karanj, and Parsi oil fields. Collected samples prepared using standard clay mineral methodology. They were treated as normal, glycolated and heated oriented glass slides. Their identification was made on X-Ray diffractographs. Illite % varies from 8 to 36. Illite quantity increased from Pabdeh to Gurpi Formation. This may be due to dominant dry climate. Kaolinite is in range of 12-49%. Its variation style in different formations could be a marker of climate changes from wet to dry which is supported by the lithological changes. Chlorite (4-28%) can also be detected in those samples without any kaolinite. Mixed layer minerals as the mixture of illite-chlorite and illite-vermiculite-montmorillonite are varied from 6 to 36%, decreased during Kazhdumi deposition from the base to the top. This result may be according to decreasing of illite leaching process. Vermiculite was also determined in very less quantity and found in those units without kaolinite. Montmorillonite varies from 8 to 43%, and its presence is due to terrestrial depositional condition. Stratigraphical documents is also supported this idea that clay mineral distribution is a function of the climate changes. It seems, thus, the present results can be indicated a possible procedure for ancient climate changes evaluation.

Processing, Morphological, Thermal and Absorption Behavior of PLA/Thermoplastic Starch/Montmorillonite Nanocomposites

Thermoplastic starch, polylactic acid glycerol and maleic anhydride (MA) were compounded with natural montmorillonite (MMT) through a twin screw extruder to investigate the effects of different loading of MMT on structure, thermal and absorption behavior of the nanocomposites. X-ray diffraction analysis (XRD) showed that sample with MMT loading 4phr exhibited exfoliated structure while sample that contained MMT 8 phr exhibited intercalated structure. FESEM images showed big lump when MMT loading was at 8 phr. The thermal properties were characterized by using differential scanning calorimeter (DSC). The results showed that MMT increased melting temperature and crystallization temperature of matrix but reduction in glass transition temperature was observed Meanwhile the addition of MMT has improved the water barrier property. The nanosize MMT particle is also able to block a tortuous pathway for water to enter the starch chain, thus reducing the water uptake and improved the physical barrier of nanocomposite.

Thermal Stability and Crystallization Behaviour of Modified ABS/PP Nanocomposites

In this research work, poly (acrylonitrile-butadienestyrene)/ polypropylene (ABS/PP) blends were processed by melt compounding in a twin-screw extruder. Upgrading of the thermal characteristics of the obtained materials was attempted by the incorporation of organically modified montmorillonite (OMMT), as well as, by the addition of two types of compatibilizers; polypropylene grafted with maleic anhydride (PP-g-MAH) and ABS grafted with maleic anhydride (ABS-g-MAH). The effect of the above treatments was investigated separately and in combination. Increasing the PP content in ABS matrix seems to increase the thermal stability of their blend and the glass transition temperature (Tg) of SAN phase of ABS. From the other part, the addition of ABS to PP promotes the formation of its β-phase, which is maximum at 30 wt% ABS concentration, and increases the crystallization temperature (Tc) of PP. In addition, it increases the crystallization rate of PP.The β-phase of PP in ABS/PP blends is reduced by the addition of compatibilizers or/and organoclay reinforcement. The incorporation of compatibilizers increases the thermal stability of PP and reduces its melting (ΔΗm) and crystallization (ΔΗc) enthalpies. Furthermore it decreases slightly the Tgs of PP and SAN phases of ABS/PP blends. Regarding the storage modulus of the ABS/PP blends, it presents a change in their behavior at about 10°C and return to their initial behavior at ~110°C. The incorporation of OMMT to no compatibilized and compatibilized ABS/PP blends enhances their storage modulus.

Synthesis and Properties of Biobased Polyurethane/Montmorillonite Nanocomposites

Polyurethanes (PURs) are very versatile polymeric materials with a wide range of physical and chemical properties. PURs have desirable properties such as high abrasion resistance, tear strength, shock absorption, flexibility and elasticity. Although they have relatively poor thermal stability, this can be improved by using treated clay. Polyurethane/clay nanocomposites have been synthesized from renewable sources. A polyol for the production of polyurethane by reaction with an isocyanate was obtained by the synthesis of palm oil-based oleic acid with glycerol. Dodecylbenzene sulfonic acid (DBSA) was used as catalyst and emulsifier. The unmodified clay (kunipia-F) was treated with cetyltrimethyl ammonium bromide (CTAB-mont) and octadodecylamine (ODAmont). The d-spacing in CTAB-mont and ODA-mont were 1.571 nm and 1.798 nm respectively and larger than that of the pure-mont (1.142 nm). The organoclay was completely intercalated in the polyurethane, as confirmed by a wide angle x-ray diffraction (WAXD) pattern. The results showed that adding clay demonstrated better thermal stability in comparison with the virgin polyurethane. Onset degradation of pure PU is at 200oC, and is lower than that of the CTAB-mont PU and ODA-mont PU which takes place at about 318oC and 330oC, respectively. The mechanical properties (including the dynamic mechanical properties) of pure polyurethane (PU) and PU/clay nanocomposites, were measured. The modified organoclay had a remarkably beneficial effect on the strength and elongation at break of the nanocomposites, which both increased with increasing clay content with the increase of the tensile strength of more than 214% and 267% by the addition of only 5 wt% of the montmorillonite CTAB-mont PU and ODA-mont PU, respectively.

[Ca(2,2'-bipyridine)3]2+ -Montmorillonite: A Potentiometric Sensor for Sulfide ion

Sulfide ion (S2-) is one of the most important ions to be monitored due to its high toxicity, especially for aquatic organisms. In this work, [Ca(2,2'-bipyridine)3]2+-intercalated montmorillonite was prepared and used as a sensor to construct a potentiometric electrode to measure sulfide ion in solution. The formation of [Ca(2,2'- bipyridine)3]2+ in montmorillonite was confirmed by Fourier Transform Infrared spectra. The electrode worked well at pH 4-12 and 4-10 in sulfide solution 10-2 M and 10-3 M, respectively, in terms of Nernstian slope. The sensor gave good precision and low cost.