Anionic Clays as Potential Slow-Release Fertilizers: Nitrate Ion Exchange

Several nitrate containing anionic clays were synthesized at different temperatures and the kinetics of NO₃ ^– release were determined to test their suitability as slow-release N fertilizers. A sample (Mg:Al = 2:1) synthesized at 60°C with smaller particle size released 75, 86 and 100% of its NO₃ ^– in 1, 3 and 7 days, respectively when equilibrated with a simulated soil solution. On the other hand, the 175°C/2 hrs sample with larger particle size released 65, 77 and 84% of its nitrate in 1, 3 and 7 days, respectively. Another anionic clay (synthesized at 175°C/24 hrs) of higher charge density (Mg:Al = 2:1) containing NO₃ ^– was equilibrated with a 0.012 N NaCl or Na₂CO₃ to test the role of different anions in releasing the NO₃ ^– anion from the interlayers. The results showed that Cl^– released more NO₃ ^– than did CO₃ ^2– from this anionic clay after all the treatment times probably as a result of the CO₃ ^2– anion blocking the release of NO₃ ^– from the interior of the crystals. When a lower charge density (Mg:Al = 3:1) sample (synthesized at 175°C/48 hrs) was equilibrated with 0.02N solution of anions the release of nitrate was as follows: Cl^– < F^– < SO₄ ⁼ CO₃ ^2–. These results suggest that the divalent SO₄ ⁼ and CO₃ ^2– anions are more effective in the release of NO₃ ^– from this lower charge density anionic clay. Time-resolved structural analysis of NO₃ ^– exchange with CO₃ ^2– in the above anionic clay using synchrotron x-ray diffraction showed that ion exchange is rapid because of small crystal size and lower charge density. Thus the release of NO₃ ^– from anionic clays is an interplay among the type of anions present in soil solution, their concentration, pH of soil solution, the charge density and crystal size of anionic clay etc.     

Effect of montmorillonite on the swelling behavior and drug‐release behavior of nanocomposite hydrogels

A series of nanocomposite hydrogels were prepared from various ratios of N‐isopropylacrylamide (NIPAAm) and organic montmorillonite (MMT). The influence of the extent of MMT in the NIPAAm/MMT nanocomposite hydrogels on the physical properties and drug‐release behavior was the main purpose of this study. The microstructure and morphology were identified by X‐ray diffraction (XRD) and scanning electronic microscopy (SEM). The results showed that the swelling ratios for these nanocomposite hydrogels decreased with increase in the content of MMT. The gel strength and Young's modulus of the gels also increased with increase in the content of MMT. XRD results indicated that the exfoliation of MMT was achieved in the swollen state. Finally, the drug‐release behavior for the gels was also assessed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3652–3660, 2003     

Mechanical properties and structures of dicyanate–clay nanocomposites

Dicyanate–clay nanocomposites comprising a dicyanate resin and a type of organically modified clay were prepared and characterized, and their thermomechanical properties were investigated. The organically modified clay had silicate layers of nanometer size intercalated with an organic modifier, which improved the compatibility between the clay and organic materials, such as dicyanate resins. Dynamic mechanical analysis was performed to investigate the thermomechanical properties of the dicyanate–clay nanocomposites containing various amounts of the clay. The storage modulus of the nanocomposites below their glass‐transition temperatures slightly increased with increasing clay content. The glass‐transition temperature of the dicyanate–clay nanocomposites increased with increasing clay content. The nanostructures of the dicyanate–clay nanocomposites were characterized by transmission electron microscopy and X‐ray diffraction analysis. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2629–2633, 2003     

Rubber–clay nanocomposite by solution blending

Ethylene vinyl acetate rubber (45% vinyl acetate content, EVA‐45) and organomodified clay (12Me‐MMT) composites were prepared by solution blending of the rubber and the clay. A combination of X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy studies showed that the composites obtained are on the nanometer scale. The measurements of the dynamic mechanical properties for different compositions over a temperature range (?100 to +100°C) showed that the storage moduli of these rubber–clay nanocomposites are higher above the glass to rubber transition temperature compared to the neat rubber. The tensile strength of the nanocomposites is about 1.6 times higher than that of the EVA‐45. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2216–2220, 2003     

Bonding phase formation in eco-friendly periclase−spinel−Al bricks used in RH degassing process

Mere unburnt periclase–spinel–Al bricks have been accepted by steel mills in the chromium-free campaign of the lining materials for Ruhrstahl ?Heraeus (RH) degassers, in terms of comparable/optimistic performance to traditional material, low carbon emission due to unburnt manufacturing process and chromium-free material for eco-friendly steel-making process. Investigations are made on the used periclase–spinel–Al bricks for the thermal evolution of their components and the formation of novel phase and bonding structure. Under the working atmosphere of RH degasser, metallic Al particles got molten above its melting point, leaving Al rim around their circumference, and AlN formed in the gaseous state dispersing into overall matrix of periclase–spinel–Al bricks with rising temperature. AlN formed and Mg reduced in their gaseous state germinated MgAlON whisker initially in the original space of metallic Al particles, and MgAlON whisker grew further all over the matrix. A whisker-interwoven network has been full of the matrix behind the hot face and toward the cold face of the used bricks, which is a completely novel type of bond and distinguished from traditional ceramic one. The whisker-interwoven network is somewhat like the stripe graphite containing microstructure of magnesia–carbon brick, which results in low wettability and high flexibility. The superior performance of periclase–spinel–Al bricks is attributed to such a bonding structure of whisker-interwoven network, which could reduce slag penetration and facilitate thermomechanical stress resistance.     

Time-dependent viscosity of structured clay suspensions

Time-dependent viscosity of structured clay suspensions under a fixed shear was revealed in the prepared slurry samples of clay lenses from the Athabasca oil sands deposit, differing from thixotropic or rheopectic suspensions. At a lower salt (Na or Ca) concentration, the viscosity oscillated with time, which was slowly damped with increasing salt concentrations. The viscosity increased without reaching a maximum plateau, even after a run of a few hours. At 1000 ppm Na concentration, a maximum viscosity was reached, followed by viscosity fluctuation within a narrow range to approach an equilibrium value with time. Both sample ageing and shear history affected the slurry viscosity. It was speculated that the Brownian motion of colloidal clay particles and the applied shear induced rearrangement and continued formation of clay microstructures with time, due to the rotation of anisotropic colloidal clay particles under simple shear flow. Its implications to oil sands research and operation were briefly discussed.     

In-situ growth of layered double hydroxide on montmorillonite nanosheets to improve the flame retardant performance of ABS resin

Layered double hydroxide (LDH) is a widely used flame retardant in polymer materials; however, the poor dispersion due to its high hydrophilic nature results in disappointing thermal stability and fire safety. In this work, LDH was in-situ grown on the disordered montmorillonite (MMT) nanosheets to obtain the hybrid of LDH and MMT nanosheets (LDH@MMT, simplified as LM). Various techniques, including X-ray diffraction, Fourier-transform infrared spectroscopy, field emission scanning electron microscopy, and transmission electron microscope were used to characterize the microstructure of LM. In addition, the acrylonitrile-butadiene-styrene (ABS) composite containing LM and intumescent flame retardant (IFR) was prepared, and its mechanical and flame-retardant properties were also measured. The characterization results demonstrate that the LM exhibits a periodically alternating layered structure. The Limiting Oxygen Index (LOI) of the ABS composite reaches 27.2% with a V-0 rating in the UL-94 vertical burning test, while its flexural strength and tensile strength decrease by only 17.82% and 13.45%, respectively. Furthermore, the heat release rate, total heat release, smoke production rate, and carbon monoxide production rate of the ABS composite present a significant decline in cone calorimeter tests compared with those of pure ABS. The results further indicate that the hybridization could effectively improve the flame-retardant performance of ABS composites and perform lesser impacts on their mechanical properties.     

Performance of clay masonry prisms with light weight plaster exposed to standard fire exposure

Clay bricks are one of the most widely used materials in building construction due to their advantages, including local availability, ease of fabrication and cost-effectiveness. Fire is one of the dangerous hazards that can cause damage the life and property. Lightweight plasters play a vital role in insulating the masonry construction during fire accident. There is only limited data and information available on the fire performance of Clay Brick Masonry (CBM) insulated with lightweight plaster. An extensive investigation was undertaken to evaluate the residual strength properties and physical characteristics of CBM prisms exposed to elevated temperatures. CBM prisms plastered with M-sand mortar, vermiculite mortar, and perlite mortar were used for the investigation. Protected prisms were exposed to elevated temperatures following the ISO 834 standard fire curve for durations of 30 min (821°C), 60 min (925°C), 90 min (986°C), and 120 min (1029°C). Mechanical properties such as axial load carrying capacity, stress–strain behaviour, elastic modulus, and crack pattern were examined. The mechanical properties of CBM prisms were found to be highly influenced by the type of plastering, intensity, and the duration of heating. The microstructure and image analysis confirmed the effects of temperature exposure on protective plasters. Equations are proposed to determine the residual axial compressive strength and the elastic modulus of CBM. It was found that the specimens plastered with perlite mortar had better fire resistance.     

Characterization and anticorrosive properties of poly(2,3‐dimethylaniline)/Na+‐montmorillonite composite prepared by emulsion polymerization

Composites of Poly(2,3‐dimethylaniline) and inorganic Na⁺‐montmorillonite clay were synthesized by emulsion polymerization. The as‐synthesized composites (PDMA) were characterized by Fourier Transform Infrared Spectroscopy, X‐ray diffraction, and scanning electron microscopy. The protective performance against corrosion of the samples was evaluated by Tafel and electrochemical impedance spectroscopy measurements. The results showed that the composite containing 5 wt. % of clay loading (PDMA‐5%) displayed a better anticorrosive performance than other samples. The Epoxy(E) blend with PDMA‐5% (EPM5) coating was founded to have a higher corrosion potential and a lower current density than that of Epoxy blend P(2,3‐DMA) (EP) coating. The impedance value of EPM5 coating was about 6.68×10⁶Ω·cm² in 5 wt. % NaCl solution even after 288 h, compared to EP (4.26×10⁵Ω·cm²) coating, which went to show that the corrosion inhibition of P(2,3‐DMA) could be effectively enhanced by incorporating MMT into the P(2,3‐DMA) matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4528–4533, 2013