Natural Montmorillonite Clay Research Articles

The Evaluation of Polyethylene/Clay Composite from Solid State NMR

Polymeric nanocomposites based on polyethylene (PE) and Brazilian natural montmorillonite clay (MN) were obtained by melt processing, using a twin-screw extruder. The main objective of this work is focusing on the characterization of composites materials by solid-state nuclear magnetic resonance (NMR). The solid-state NMR measurements were used to observe both polymer matrix (through carbon-13 and hydrogen nuclei) and the clay (silicon-29 and aluminum-27). The polymer matrix analyses were carried out applying solid state techniques, such as: cross-polarization magic angle spinning (CPMAS), variable contact time (VCT) and by the proton spin-lattice relaxation time in the rotating frame parameter (T1ρH), detected from the resolved carbon-13 decay of the VCT experiment and through the determination of spin-lattice relaxation time, T1H (using low field NMR). The clay was analyzed by 29Si and 27Al, employing MAS NMR technique. From those techniques we can have principally response on clay dispersion in the polyethylene matrix, as well as the interactions between both components in the nanostructured material. The T1H response was an important result which showed, that the materials formed, presented different molecular domains (according to the domain size that varied from 25 to 50 nm, measured by relaxation), considering the clay dispersion mode in terms of intercalation and/or exfoliation in the polymer matrix.

Injection-molded nanocomposites and materials based on wheat gluten

This is, to our knowledge, the first study of the injection molding of materials where wheat gluten (WG) is the main component. In addition to a plasticizer (glycerol), 5 wt.% natural montmorillonite clay was added. X-ray indicated intercalated clay and transmission electron microscopy indicated locally good clay platelet dispersion. Prior to feeding into the injection molder, the material was first compression molded into plates and pelletized. The filling of the circular mold via the central gate was characterized by a divergent flow yielding, in general, a stronger and stiffer material in the circumferential direction. It was observed that 20–30 wt.% glycerol yielded the best combination of processability and mechanical properties. The clay yielded improved processability, plate homogeneity and tensile stiffness. IR spectroscopy and protein solubility indicated that the injection molding process yielded a highly aggregated structure. The overall conclusion was that injection molding is a very promising method for producing WG objects.

Evaluation on Cytotoxicity and Genotoxicity of the Exfoliated Silicate Nanoclay

The concern about toxicity for nanosilicate platelets (NSP) derived from natural montmorillonite clay is addressed. The NSP nanoclay was isolated from polyamine-salt exfoliation of the layered silicate clay into randomized individual plates, possessing multiple ionic charges on the surface of silicate plates with an average geometric dimension of ca. 80 x 80 x 1 nm(3). The material had been previously shown to be effective for antimicrobial and tendency for adhering onto the biomaterial surface based on the direct observation by using scanning electron microscope. The material safety on genotoxic effect was investigated by using three different test systems: the Comet assay test on Chinese Hamster Ovary (CHO) cells in vitro, micronucleus (MN) assay in vivo and the Salmonella gene mutation assay on strain TA98, TA100, TA102, TA1535 and TA1537. The Comet assay showed no DNA damage after 24 h of incubation with NSP of 1000 microg/mL. The MN test indicated no significant micronucleus induction in the CHO cells at the concentrations tested. With all five strains of Salmonella typhimurium, none of mutations was found. Furthermore, cytotoxicity of the same material was assayed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and lactate dehydrogenase (LDH) release, showing a low cytotoxicity on CHO cells below 1000 microg/mL after 12 h incubation period and a dose-dependent effect after 24 h incubation. For feeding to rats, the acute oral toxicity was shown a low lethal dose (LD(50)) or greater than 5700 mg/kg body weight for both male and female Sprague-Dawley rats. Overall, the study has demonstrated the safety of the NSP for potential uses in biomedical areas.

Hydrophobic Modification of Layered Clays and Compatibility for Epoxy Nanocomposites

Recent studies on the intercalation and exfoliation of layered clays with polymeric intercalating agents involving poly(oxypropylene)-amines and the particular uses for epoxy nanocomposites are reviewed. For intercalation, counter-ionic exchange reactions of clays including cationic layered silicates and anionic Al-Mg layered double hydroxide (LDH) with polymeric organic ions afforded organoclays led to spatial interlayer expansion from 12 to 92 Å (X-ray diffraction) as well as hydrophobic property. The inorganic clays of layered structure could be modified by the poly(oxypropylene)amine-salts as the intercalating agents with molecular weights ranging from 230 to 5,000 g/mol. Furthermore, natural montmorillonite (MMT) clay could be exfoliated into thin layer silicate platelets (ca. 1 nm thickness) in one step by using polymeric types of exfoliating agents. Different lateral dimensions of MMT, synthetic fluorinated Mica and LDH clays had been cured into epoxy nanocomposites. The hydrophobic amine-salt modification resulting in high spacing of layered or exfoliation of individual clay platelets is the most important factor for gaining significant improvements of properties. In particular, these modified clays were reported to gain significant improvements such as reduced coefficient of thermal expansion (CTE), enhanced thermal stability, and hardness. The utilization of these layered clays for initiating the epoxy self-polymerization was also reported to have a unique compatibility between clay and organic resin matrix. However, the matrix domain lacks of covalently bonded crosslink and leads to the isolation of powder material. It is generally concluded that the hydrophobic expansion of the clay inter-gallery spacing is the crucial step for enhancing the compatibility and the ultimate preparation of the advanced epoxy materials.

Structure peculiarities and optical properties of nanocomposite: 5CB liquid crystal–CTAB-modified montmorillonite clay

The effects of the modification of natural layered montmorillonite (MMT) clay by cetyltrimethylammonium bromide (CTAB) cations on the structure and optical properties of the composite material based on this mineral (4.5%mass) and a nematic liquid crystal (LC), 4-pentyl-4'-cyanobiphenyl (5CB), have been investigated. As shown by small-angle X-ray diffraction and infrared (IR) spectroscopy experiments, this modification results in a significant expansion of the interplane spaces in the MMT nanoparticles and a considerable growth of their surface affinity to the 5CB molecules, which allows the LC molecules to penetrate into the MMT galleries and additionally expand these galleries. According to IR studies, this heterosystem possesses van der Waals interactions between its components on the phase separation boundary and, as a result, orientation alignment of the molecules in the near-surface layers occurs. These interactions specify the electro-optical properties of the composite. When an electric field is applied to a system, the light transmittance of the material increases due to the induced orientation of the LC dimers. This LC ordering remains even after the voltage is shut off, i.e. the system shows an electro-optical memory effect.

Note: Influence of rinsing and drying routines on growth of multilayer thin films using automated deposition system

A versatile, high speed robot for layer-by-layer deposition of multifunctional thin films, which integrates concepts from previous dipping systems, has been designed with dramatic improvements in software, positioning, rinsing, drying, and waste removal. This system exploits the electrostatic interaction of oppositely charged species to deposit nanolayers (1-10 nm thick) from water onto the surface of a substrate. Dip times and number of deposited layers are adjustable through a graphical user interface. In between dips the system spray rinses and dries the substrate by positioning it in the two-tiered rinse-dry station. This feature significantly reduces processing time and provides the flexibility to choose from four different procedures for rinsing and drying. Assemblies of natural montmorillonite clay and polyethylenimine are deposited onto 175 microm poly(ethylene terephthalate) film to demonstrate the utility of this automated deposition system. By altering the type of rinse-dry procedure, these clay-based assemblies are shown to exhibit variations in film thickness and oxygen transmission rate. This type of system reproducibly deposits films containing 20 or more layers and may also be useful for other types of coatings that make use of dipping.

Natural montmorillonite clay as prebiotic catalyst

It is shown that complex intramolecular and intermolecular transformations of natural pinene terpenoids can proceed in the presence of natural montmorillonite clays with the preservation of optical activity. These facts support our assumption that natural clays could act as prebiotic catalysts and favor preservation of chirality in complex compounds formed from simple optically active molecules at early stages of life. The article is published in the original.

Adsorption characteristics of a cationic porphyrin on nanoclay at various pH

Natural and synthetic porphyrin derivatives offer a range of applications including enzymatic catalysis, photosensitizers for light harvesting and chemical reactions, and molecular electronics. They exhibit unique optical spectra dominated by the presence of Soret and Q-band structures whose position and shape offer a straightforward method to characterize porphyrins in various surroundings. In many applications it is often beneficial to have porphyrins adsorbed onto a solid matrix. Applications of porphyrin–clay complexes extend to numerous biological applications including pharmaceutical drug delivery, cosmetics, and agricultural applications and thus a full understanding of porphyrin–clay surface interactions are essential. Here we investigated the adsorption behavior of meso-tetra(4-N,N,N-trimethylanilinium) porphine (TMAP) onto sodium containing, natural montmorillonite clay (Cloisite Na +) in characteristic biological buffers over a range of pHs (∼2–9). Spectroscopic analyses show a linear absorption response at acidic and basic pHs but a slight deviation at intermediate pHs. Absorption spectra for TMAP on clay showed distinct red shifts of the Soret and Q-bands compared to free TMAP for all buffer conditions indicating core π-electron delocalization into the substituent rings. At intermediate pHs, a gradual transition between protonated/deprotonated states were seen, presumably due to higher H + concentration at the surface than in bulk. Results indicate TMAP adsorption to clay occurs in a monolayer fashion at low/high pH while slightly acidic/neutral pH possibly rearrange on the surface and/or form aggregates. AFM images of clay saturated with TMAP are reported and show single isolated clay sheets without aggregation, similar to clay without TMAP.

Influence of clays on the flame retardancy and high temperature viscoelastic properties of polymeric intumescent formulations

A natural Brazilian montmorillonite clay was submitted to organophilization treatments to evaluate the effect of these treatments on the flame retardancy potential of polymer composites containing an intumescent ammonium polyphosphate and pentaerythritol formulation. An ethylene–butyl acrylate copolymer was used as the polymer matrix. Natural or organophilic clays were added both to the pure polymer and to the polymer containing the intumescent mixture. The influence of these mineral fillers, and of their organophilization treatments, on flame retardancy was investigated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), UL-94 rating standard, heating microscopy, rheological measurements and cone calorimetry. The results show that these inorganic additives have a synergistic effect on composites containing the intumescent formulation.

Segregated Networks of Carbon Black in Poly(vinyl acetate) Latex: Influence of Clay on the Electrical and Mechanical Behavior

AbstractFilms were prepared from mixtures of PVAc latex, CB, and natural sodium montmorillonite clay. In the absence of clay, these composites exhibit a percolation threshold of 1.2 vol.‐% CB, which is nearly an order of magnitude lower than that observed for composites prepared using PVAc solution. SEM images reveal a segregated CB network that is the result of excluded volume created by the much larger polymer particles in the latex. With the addition of 0.2 wt.‐% clay, the percolation threshold is reduced to 0.9 vol.‐% carbon black due to clay‐induced networking. The storage modulus is also enhanced by the presence of clay, although higher clay concentration appears to adversely affect electrical and mechanical behavior of these composites.magnified image

Studies on Selective Adsorption of Biogas Components on Pillared Clays: Approach for Biogas Improvement

Comparative adsorptions of four gases (natural gas and landfill gas components), viz., CO2, CH4, C2H6, and N2, were studied on four different pillared clays (PILCs) to develop a selective material. Such material could be useful forthe separation/purification process of waste gases. These materials (PILCs) were prepared from two different natural montmorillonite clays, by pillaring with Al2O3 and ZrO2, separately and were characterized by means of nitrogen adsorption and XRD. The adsorption isotherms for pure component gases were determined for each PILC, up to 10(3) kPa. The isotherms data were explored to calculate the selectivity of PILCs for either gas in any binary mixture. It was observed that the surface area of the clays pillared with Al2O3 was higher than that of the clays pillared with ZrO2. At the highest studied equilibrium pressure, the order of maximum adsorption was found to be CO2 > C2H6 > CH4 > N2 for each material. With the help of adsorption modeling, the selective adsorption from binary mixtures was predicted at different equilibrium pressures and compositions. Among the four PILCs, a ZrO2 PILC was found to be the most suitable material, in terms of separation possibility. To further assess the efficiency of these materials in commercial processes, the adsorption capacity in terms of working capacity was also calculated at two different regeneration pressures, i.e., at 1.0 atm and 1.0 Torr.

Compatibilized polyimide (R-BAPS)/BAPS-modified clay nanocomposites with improved dispersion and properties

There is a need for clay modifiers that will not thermally degrade at elevated temperatures commonly used in polymer processing operations such as extrusion and injection molding. In this context, natural montmorillonite clay (Na-MMT) was organically modified by varying concentrations of 4,4′-bis(4″-aminophenoxy)diphenylsulfone (BAPS) using different chemical dispersion methods to yield new chemically modified clays that are relatively thermally stable at elevated temperatures compared with current commercial modified clays. This paper shows that the Na-MMT chemical modification (BAPS-MMT) was confirmed by XRD that showed a shift of diffraction peak at 2Θ=7.3° for Na-MMT towards lower 2Θ=5.8°. Thermogravimetric analysis of the samples showed a weight loss of organically modified clay that started at a temperature of 350°C, corresponding to the degradation temperature of the BAPS monomer. Rheological measurements in combination with XRD data showed clearly that the quality of dispersion of BAPS-MMT type particles in R-BAPS type polyimide and oligoimides strongly depends on the clay surface modification, the specific chemical modification method used, and on the polymer molecular weight. Note that the oligoimides were specifically used as model systems to confirm our expectation of improved chemical compatibility between the BAPS-MMT and the polyimide system. This study may stimulate a better understanding of the effects of rational chemical modification methods on the quality of clay dispersion in polyimide matrices, enhancing our ability to prepare useful polyimide/clay nanocomposites with improved properties for targeted high-temperature applications where current polymer nanocomposite systems are not useable.

Synthesis and characterization of montmorillonite clays with modulable porosity induced with acids and superacids

The structural transformation of natural montmorillonite clay with different acids and superacids (hydrochloric, HCl; sulfuric, H2SO4; hydrofluoric, HF; perchloric, HClO4; chlorosulfonic, HSO3Cl; and trifluoromethanesulfonic, HSO3CF3 acids) is evaluated by various techniques, allowing its full characterization. The process involves the modulated digestion of the aluminum and silicon atoms from the original clay without the loss of the original mass in the material from a careful drying methodology. The x-ray diffraction technique suggests that the process is disruptive, causing different magnitudes of modification, depending on the acidic source, taking the material with natural lamellar structure as reference. By 27Al and 29Si magnetic resonance, it is also shown that all the silicon and aluminum atoms were removed from the chemical structure to be physisorbed or dispersed in the interstices of the clay lattice when HF, HSO3Cl, and H2SO4 acid treatments were carried out. However, with treatment of HClO4, the results suggest that only was achieved partial digestion and physisorption of the aluminosilicate core. Treatment with HCl led to a mild digestion that increased the laminar distance of the montmorillonite. Finally, HSO3CF3 acid achieved a total disorder of the lamellar structure of the clay. In addition, by infrared spectrometry, the disappearance of the absorption peaks assigned to Al2OH, AlMgOH, and Al-O-Si are other evidence of the complete digestion of silicon and aluminum atoms caused by the acidic medium. On the other hand, the Brunauer–Emmett–Teller (BET) surface areas of the acidified clays showed a great enlargement in comparison with the unmodified clay. The porosimetry measurements demonstrate the presence of mesopores and hysteresis as observed in the physisorption isotherms, which indeed exhibited a capillary condensation into the porous structures. The present results are the first full characterization research and structural comparison between the acidic and the not-extensively-studied superacidic modified clays of this type.

First Isolation of Individual Silicate Platelets from Clay Exfoliation and Their Unique Self-Assembly into Fibrous Arrays

Thin silicate platelets in a dimension of approximately 80 x 80 x 1 nm(3) are isolated for the first time by a newly developed process involving one-step exfoliation of natural montmorillonite clay and toluene/aqueous NaOH extraction. The platelets are observed to be polygon shape by transmission electron microscopy (TEM) and round bent-leaf shape by dynamic force microscopy (DFM). Individual platelets possessing high-aspect-ratio dimension and ionic character are able to self-assemble into microscale fiber bundles after water evaporation. The self-stacking mechanism indicated strong face-to-face ionic charge stacking propensity in triggering a vertical growth. Regularity of fibrous bundles in an average 5 microm length has been observed.

Synthesis of Optically Active, Cyclic α‐Hydroxy Ketones and 1,2‐Diketones from Verbenone Epoxide

AbstractThe reactivity of verbenone epoxide (5), a terpenoid from the pinane series, towards different aliphatic and aromatic aldehydes in the presence of natural montmorillonite (askanite–bentonite) clay has been studied. A series of mechanistically different transformations afforded a number of new, optically active, polyfunctional compounds (7, 8, 10–14, 16). These products are potentially interesting synthons in asymmetric synthesis.

Thermoplastic elastomeric nanocomposites from poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer and clay: Preparation and characterization

AbstractThermoplastic elastomer (TPE)–clay nanocomposites based on poly[styrene–(ethylene‐co‐butylene)–styrene] triblock copolymer (SEBS) were prepared. Natural sodium montmorillonite (MMT) clay was organically modified by octadecyl amine to produce an amine‐modified hydrophobic nanoclay (OC). Commercially available Cloisite 20A (CL20) and Cloisite 10A, tallow ammine modified nanoclays, were also used. The intergallery spacing of MMT increased on amine modification as suggested by the shifting of the X‐ray diffraction (XRD) peak from 7.6 to 4.5 and 3.8° in the cases of OC and CL20, respectively. The latter demonstrated no XRD peak when it was used at 2 and 4 parts phr in the SEBS system. Transmission electron microscopy studies showed the intercalation–exfoliation morphology in SEBS containing 4 parts of CL204–SEBS, agglomeration in SEBS having 4 parts of MMT, and mixed morphology in SEBS with 4 parts of OC systems. Locations of the clay particles were indicated by the atomic force micrographs. Mechanical and dynamic mechanical thermal analysis studies confirmed the best properties with the CL204–SEBS nanocomposites. Significant improvements in mechanical properties such as tensile strength, modulus, work to break, and elongation at break were achieved with the CL204–SEBS in polymer‐layered silicate nanocomposites. Dynamic mechanical studies further showed the affinity of the organoclays toward both segments of the TPE and a compatibilization effect with CL20 at a 4‐phr loading. Atomic force microscopy showed distinctly different morphologies in nanocomposites prepared through solution and melt processing. Comparisons of the mechanical, dynamic mechanical, and morphological properties of the nanocomposites prepared by melt and solution intercalation processes were done. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2040–2052, 2006

Montmorillonite−Poly(ethylene oxide) Nanocomposites: Interlayer Alkali Metal Behavior

Clay-PEO nanocomposites can have large electrical conductivities that make them potential electrolyte materials for rechargeable lithium batteries, but the origin of these large conductivities, especially for Li-containing materials, is poorly understood. This paper presents X-ray diffraction (XRD), TGA-DTA, and (7)Li and (23)Na NMR data for PEO nanocomposites made with natural (SWy-1) and synthetic (MNTS) montmorillonite clays that provide new insight into interlayer structure. An increase in basal d(001)-spacings demonstrates successful intercalation of PEO in all samples, and X-ray line narrowing shows that this intercalation improves the layer stacking order. The basal spacings of 17.9-19.4 A are consistent with a helical or bilayer structure of PEO in the interlayer. TGA-DTA provides quantitative results for the hydration state of the nanocomposites, demonstrates PEO intercalation, and shows that the composites prepared from the synthetic montmorillonite are less stable than those made with SWy-1. (7)Li NMR shows that the nearest neighbor hydration state of Li(+) is unaffected by PEO intercalation and suggests weak interaction of Li(+) with PEO. (23)Na NMR shows that PEO intercalation results in the conversion of the multiple Na(+) hydration states observed for the pristine clay into inner sphere sites most likely formed through coordination with the basal oxygens of the clay. These differences between lithium and sodium suggested that tighter binding of the Na to the clay may be the origin of the conductivity of Li-montmorillonite-PEO nanocomposites being as much as 2 orders of magnitude larger than those of Na-montmorillonite-PEO nanocomposites. The results confirm the idea that polymer oxygen atoms do not participate in sequestering the exchangeable cations and agree with the jump process for cation migration advanced by Kuppa and Manias (Kuppa, V.; Manias, E. Chem. Mater. 2002, 14, 2171).

Study of individual Na-montmorillonite particles size, morphology, and apparent charge

Size, morphology, and apparent charge of individual Na-montmorillonite particles of natural MX-80 sodium montmorillonite were investigated in the present study by the use of three coupling methods. In the first part of this work, natural and synthetic montmorillonite clays were studied with atomic force microscopy (AFM) and photo-correlation spectroscopy (PCS). Both techniques exhibit the presence of two clay populations with a high dispersion of the length distribution. Microscopic analysis of the system revealed that clay particles could be reasonably approximated at low concentrations to ellipsoidal tactoids about 1.2 nm high. Average dimensions of the first population were typically 320–400 nm long/250 nm wide and 200–250 nm long/120 nm wide for natural and synthetic clays, respectively. The second population exhibits smaller sizes: 65 and 50 nm long and 35 and 25 nm wide for natural and synthetic clays, respectively. The statistics obtained for natural clay were then verified by PCS experiments on sodium montmorillonite suspensions. Both techniques reveal an important length dispersion. However, the relative proportions of the two kinds of particles could not be established properly because of both lack of statistics and limitations of the employed techniques. In the following part, conductivity measurements were performed on dilute montmorillonite clay suspensions. Raw data were then interpreted with the sizes and morphological information gained in the first part of the present work. The apparent charge of the clay sheets was found to be 8% of the structural charge.

Adsorption of petroleum organic compounds on natural Wyoming montmorillonite

Adsorption of petroleum organic compounds on natural Wyoming montmorillonite clay is an irreversible process, as most of organic species still remain adsorbed on mineral after aging. The process is conditioned by the petroleum paraffinic content and by molecules containing alkane chains, as only these type of compounds easy intercalate within the clay interlayer. Such adsorption also involves an irreversible displacement of part of the clay interlayer water. The partial dissolution of the clay matrix is indicated by XRD as an irreversible modification of the clay structure. On the contrary, adsorption of n-heptane or toluene molecules on the same clay are reversible processes, since the clay mineral recover its original crystalline structure after aging and evaporation of the organic species.

Peculiarities of Adsorption of Some Polar Substances from Vapor Phase on a Microporous Clay Adsorbent

The adsorption of polar organic substances (methanol, pyridine, and acetonitrile) and water was studied from the vapor phase on microporous adsorbent prepared by the substitution of polyhydroxyaluminum ions for the sodium ions of natural montmorillonite clay. The differential isosteric heats of adsorption of these substances were calculated and analyzed in a wide range of fillings.