Electrokinetic potential of kaolinite clay in the presence of polystyrene sulfonate

The determination of the electrokinetic potential of clay is very important in many applications. Therefore, this work was aimed at studying the effect of poly(4‐ sodium styrene sulfonate) on the electrokinetic potential and the sedimentation behavior of kaolinite clays at different pH values and/or in the presence of sodium or calcium chlorides. At pH values lower than the point of zero charge (PZC) of the kaolinite clay, the zeta potential of Na‐ or Ca‐kaolinite in CaCl₂ solutions was higher than that in NaCl solutions at the same concentration. Above the PZC, the zeta potential of Na‐ or Ca‐kaolinite in NaCl solution was higher than that in CaCl₂ at the same electrolyte concentration. These results reflect the ability of calcium cations to compress the double layer of the kaolinite clay better than sodium cations. Also, below the PZC and at low concentrations of poly(4‐sodium styrene sulfonate), the zeta potential of the kaolinite clay suspensions had low value, while the sediment volumes had higher values. On the other hand, above the PZC at increasing polymer concentrations, the zeta potentials increased but the sediment volumes had lower values compared to those produced below the PZC. The data showed the zeta potential of Na‐kaolinite suspensions are higher than Ca‐kaolinite, producing lower sediment volumes of Na‐kaolinite compared to Ca‐kaolinite at the same concentrations of polymer and/or pHs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1705–1711, 2006     

Arsenic adsorption mechanism on clay minerals and its dependence on temperature

In the present study, the As(V) removal efficiency of different clay minerals was investigated as a function of solution pH, time, As(V) concentration, and temperature. Arsenic mobility was also investigated by determining the As(V) released from the loaded samples by leaching with various aqueous solutions. The kinetics of adsorption was observed to be fast and reached equilibrium within 3 h. As(V) adsorption on studied clays was pH dependent and maximum adsorption was achieved at pH 5.0. The maximum adsorption capacity was calculated by fitting the Langmuir equation to the adsorption isotherms and found to be 0.86, 0.64, and 0.52 mg As(V)/g of kaolinite, montmorillonite, and illite, respectively. The negative effect of temperature on As(V) adsorption showed the interactions to be exothermic. Based on the results, it was found that among the studied clay minerals, kaolinite was the best As(V) adsorbent and montmorillonite had strong retention capacity. The electrokinetic behavior of kaolinite and montmorillonite was modified in the presence of As(V), indicating that adsorption involves inner sphere surface complexation and strong specific ion adsorption.     

Effect on 2,2′-bipyridine adsorption of poly(vinyl alcohol) adsorbed on Na-kaolinite

The adsorption (pH 6) of 2,2′-bipyridine (BP) on Na⁺-kaolinite and on samples of the same clay containing 4.35 and 7.45 mg/g, respectively, of previously adsorbed poly(vinyl alcohol) (PVA) was studied. Specific adsorption of BP decreases with increasing clay particle size in the suspension as a result of particle association. Aqueous suspensions with a 1–4% concentration of kaolinite exhibit flocculation in the absence or presence of PVA, forming clusters of 43–64 units of single clay particles. The PVA adsorbed on the surface of sodium kaolinite particles causes partial dispersion of the kaolinite in the aqueous suspension; however, 7.45 mg/g of PVA adsorption or even lower (4.35 mg/g) is not able to fully impede the association of kaolinite particles.     

Adsorption characteristics of polyacrylamide and sulfonate-containing polyacrylamide copolymers on sodium kaolinite

Polyacrylamide and its copolymer containing 6.8 mole % 2-acrylamido-2-methylpropane sulfonic acid were prepared by an irradiation-initiated precipitation polymerization technique. The polymer was characterized by intrinsic viscosity under conditions similar to those used during adsorption measurements. Hydrolytic degradation of the polyacrylamide was found to be negligible under conditions used. The adsorption substrate, sodium kaolinite, was prepared by extensive ion exchange treatment. Equilibrium adsorption of the polymers on the sodium kaolinite was made as a function of polymer concentration, solution pH, ionic strength, and temperature.     

Interaction of metal ions with clays: I. A case study with Pb(II)

Pb(II) adsorption was studied under different conditions (pH, time, metal ion concentration, clay amount, temperature) on kaolinite, montmorillonite, and their poly(hydroxo)zirconium (ZrO–kaolinite, ZrO–montmorillonite) and tetrabutylammonium (TBA–kaolinite, TBA–montmorillonite) derivatives. All samples were calcined (ZrO-derivatives at 773 K, TBA-derivatives at 973 K) before using as adsorbents. The data were interpreted assuming first- and second-order kinetics. The rate constants including the pore diffusion rate constant are reported. The adsorption data could be fitted with Freundlich and Langmuir isotherms, and the coefficients indicated favorable adsorption of Pb(II) on the clays. Determination of the thermodynamic parameters, ΔH, ΔS, and ΔG showed the adsorption to be exothermic accompanied by decrease in entropy and Gibbs energy.     

Uptake of Ni(II) Ions from Aqueous Solution by Kaolinite and Montmorillonite: Influence of Acid Activation of the Clays

Abstract

Kaolinite and montmorillonite were treated with 0.25 M H₂SO₄ and the acid activated clays along with the parent clays were tested for their uptake capacity for Ni(II) ions from aqueous solution. The batch adsorption experiments were conducted under a set of variables (concentration of Ni(II) ion, amount of clay, pH, time and temperature of interaction). Increasing pH favored Ni(II) uptake till the ions were precipitated as the insoluble hydroxides at pH > 8.0. The uptake was rapid up to 40 min and equilibrium was obtained within 180 min. The kinetics of the process was evaluated by subjecting the results to a number of models like the pseudo-first order, second order, Elovich equation, liquid film diffusion, and intra-particle diffusion and it was found that the data more closely resembled a second order process. The experimental data conformed to both Langmuir and Freundlich isotherms showing that the interactions were mostly chemical in nature. The clays had reasonable monolayer adsorption capacity of 10.4, 11.9, 28.4, and 29.5 mg g^?1 for kaolinite, acid activated kaolinite, montmorillonite, and acid-activated montmorillonite respectively. Montmorillonite had much better adsorption capacity than kaolinite and the acid activation boosted the adsorption capacity of both kaolinite and montmorillonite. The interactions were exothermic in nature, accompanied by decrease in both entropy and Gibbs energy. The results have established good potentiality for kaolinite, montmorillonite and their acid-activated forms to take up and separate Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Dispersion—flocculation studies on a Goethite-clay system

Dispersion–flocculation studies on a Goethite–clay system using flocculants were carried out as a function of flocculant concentrations, pH of slurry, time of agitation and dispersant dosage. Also, the effects of pH and polymer concentrations on the adsorption behaviour of the system were investigated. Results show that well flocculated goethite was preferentially obtained from 4% goethite/kaolinite clay suspensions, with 50 ppm causticised starch in the slurry at pH values of 3–11·5 and with 50 ppm polyacrylamide at pH values of 3–8. Good flocs were also obtained on flocculation of the goethite suspension with 50 ppm polyacrylamide at pH values of 5–7, while the kaolinite suspension did not respond to the same dosage of causticised starch in the same pH range. Results further reveal that for the goethite/kaolinite suspension, the best results was obtained with 50 ppm polyacrylamide at pH values of 7–10. Based on the data generated in the study, it was concluded that causticised starch is a better flocculant than polyacrylamide for goethite suspensions although polyacrylamide is an excellent flocculant for kaolinite suspensions.     

Adsorption behavior of aqueous europium on kaolinite under various disposal conditions

This work investigated the adsorption behavior of europium on kaolinite under various disposal conditions. Batch-wise adsorption and precipitation experiments and equilibrium model calculations were performed over a pH range of 4–10 and CO₂ concentration range of 0%, 0.03%, and 10%. Experimental precipitation behaviors are in agreement with the results of equilibrium model calculations using the geochemical code MINTEQA2. Aqueous species of Eu³⁺ exists mainly at pH 5 or below and solid phases of Eu(OH)₃(s), Eu(OH)CO₃(s), and Eu₂(CO₃)₃·3H₂O(s) are formed at higher pH ranges. Adsorption behavior of Eu on kaolinite in the low pH range can be explained by interlayer ion-exchange reaction. The significant increase in adsorbed amount at pH 5–6 is due to the surface complexation at the edge site of kaolinite. In the high pH range, precipitation of Eu contributes mainly to the adsorption quantity. The rapid decrease in adsorbed amount above pH 7 under 10% CO₂ condition occurs by the formation of anionic europium species of Eu(CO₃) ₂ ^- .The adsorption of Eu on kaolinite could be well interpreted by the Freundlich adsorption isotherm. The data except for the highest equilibrium concentration ranges were also explained by Langmuir isotherm and the maximum adsorbed quantity of Eu on kaolinite,b, is 1.2 mg/g.     

Effect of Temperature on the Charge on KaoIinite Particles in Water

An electrophoretic technique was used to determine the variation of charge on a kaolinite particle as a function of temperature. A monodies-persed fraction of kaolinite was treated with various amounts of sodium hydroxide. The pH, conductivity, and electrophoretic mobility of the clay were determined as functions of temperature. From this information the charge on the particles and an energy related to the energy of adsorption     

Adsorption of Co(II) from Aqueous Medium on Natural and Acid Activated Kaolinite and Montmorillonite

Abstract

Hazardous metal cations enter water through the natural geochemical route or from the industrial wastes. Their separation and removal can be achieved by adsorptive accumulation of the cations on a suitable adsorbent. In the present work, toxic Co(II) ions are removed from water by accumulating them on the surface of clay minerals. Clay adsorbents are obtained from kaolinite, montmorillonite, and their acid activated forms, and are characterized with the measurement of XRD patterns, specific surface area, and cation exchange capacity. The adsorption experiments are carried out in a batch process in environments of different pH, initial Co(II) concentration, amount of clay, interaction time, and temperature. Adsorption of Co(II) on the clays increases continuously from pH 1.0 to 8.0 after which adsorption could not be carried out due to the decreasing solubility of Co(II). Under appropriate conditions, the adsorption of Co(II) is very fast at low coverage approaching equilibrium within 240 min and the interactions are best described by second order kinetics. Langmuir monolayer capacity has been computed in the range of 11.2 to 29.7 mg/g and Co(II) accumulation has the order of acid‐activated montmorillonite>montmorillonite>acid activated kaolinite>kaolinite. Adsorption of Co(II) on kaolinite and acid‐activated kaolinite is endothermic driven by entropy increase but the same process follows exothermically on montmorillonite and acid‐activated montmorillonite supported by entropy decrease. In both cases, spontaneous adsorptive accumulation is ensured by favorable Gibbs energy decrease. It is found that acid activation enhances the adsorption capacity of kaolinite and montmorillonite.     

Methylene Blue Adsorption on Natural and Modified Clays

Toxic methylene blue dye is removed from water by accumulating it on the surface of clay minerals. Clay adsorbents are obtained from kaolinite, montmorillonite, and their acid activated forms. The adsorption experiments are carried out in a batch process in environments of different pH, initial dye concentration, amount of clay, interaction time, and temperature. Adsorption of dye is best described by second order kinetics. In the temperature range of 303 to 333 K, the Langmuir monolayer capacity for three kaolinite species increased from 45.5 to 56.5 mg g^?1, 45.9 to 57.8 mg g^?1, 46.3 to 58.8 mg g^?1, and for three montmorillonites species from 163.9 to 181.8 mg g^?1, 166.7 to 188.8 mg g^?1, and 172.4 to 192.3 mg g^?1. The interaction is an endothermic process driven by entropy increase and spontaneous adsorptive accumulation is ensured by favorable Gibbs energy decrease. It is found that acid activation enhances the adsorption capacity of kaolinite and montmorillonite.     

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

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

Synthesis,characterization and evaluation of a quadripolymer with low molecular weight as a water based drilling fluid viscosity reducer at high temperature (245 °C)

To construct an ultra‐high temperature stable drilling mud with a relatively low viscosity, a new viscosity‐reducing additive was synthesized and evaluated. This additive is a quadripolymer of acrylic acid (AA), 2‐acryl‐amido‐2‐methyl‐1‐propane sulfonic acid (AMPS), methyl acrylate (MA) and dimethyl diallyl ammonium chloride (DDAC) with low molecular weight synthesized by free radical polymerization, and its general molecular composition was confirmed by Fourier transform infrared spectroscopy. Thermal gravimetric analysis showed that the polymer has a very high temperature tolerance, i.e. it is stable up to 340 °C. Turbidity measurements with a UV?visible spectrophotometer showed that the polymer has a high salt tolerance in solution. It remained in solution at NaCl concentrations of up to 266 958 mg L^?1 and at CaCl₂ concentrations of up to 5000 mg L^?1. The quadripolymer was found to inhibit hydration of the exchangeable ions in the clay particles and this was affirmed by a reduction in interlayer spacing. It also displayed high adsorption on calcium montmorillonite at different pH and even in the presence of NaCl, and caused the breakup of the particle network structure. This additive, when added to drilling mud prepared in both fresh and salt water, was found to reduce the mud viscosity and yield stress before and after aging for 16 h at 245 °C compared to base mud especially below 220 °C and 4.5 MPa. Importantly, this additive in mud was found to perform effectively at a relatively high pH and in a broad pH range of 7–11. © 2015 Society of Chemical Industry     

Hydrogen Consumption and Silica Release During Initial Stages of Phosphate Adsorption on Kaolinite at a Constant pH

The release of silica from kaolinite is enhanced immediately after application of phosphate. The rate of the silica release was inferred from the rate of hydrogen additions needed to keep the system at a constant pH. Potassium increases silica hydrolysis from kaolinite surfaces in 1N solution more than calcium or sodium.     

The effect of the hydration of the exchangeable cation on the flocculation behaviour of China clay—polyacrylamide suspensions

The flocculation of the sodium, potassium and lithium forms of a kaolinite material have been investigated and discussed in relation to the thickness of the adsorbed layer of water molecules on the clay surfaces. Two methods of assessing flocculation in concentrated suspensions were used, namely the rates of fall of the flocculated suspensions and the rates of filtration through the settled flocs. The flocculating agent was neutral polyacrylamide. Nitrogen and water vapour adsorption isotherms are reported on the various samples, together with heats of immersion in water.The extent of flocculation decreased in the order of Li clay > K clay > Na clay; the amount of adsorbed water decreased in the order Na clay > K clay > Li clay; and the heat of wetting in the order Na clay > Li clay ? K clay. The anomalous behaviour of the Li clay is associated with the strong hydration of the Li ion on the clay surface.     

Durability of glass‐fiber‐reinforced polymer nanocomposites in an alkaline environment

This study was conducted to determine the effect of clay content in GFRP (glass‐fiber‐reinforced polymer) composite samples as they were aged in an alkaline solution. Two kinds of GFRP composite samples were prepared. One was E‐glass‐fiber‐reinforced vinyl ester polymer, and the other was nano‐GFRP composites prepared with the addition of 1 and 2 wt% of montmorillonite clay to the polymer matrix. These samples were aged in alkaline solution of pH 13.2 with and without sustained load. The load was 1335 N or 18.7% of the tensile strength of the composite samples. The aging was evaluated by measuring the reduction in tensile strength after 6 months. Also, absorption of alkaline solution into the plain and nano‐GFRP samples was investigated so as to elucidate the diffusion behaviors. It was found that for a short exposure time (e.g. 1 month) and without sustained load, dispersing 2 wt% of the nanoclay in the polymer matrix of the GFRP samples reduces the diffusivity by 39%. However, with the application of sustained load, the glass fiber composite samples deteriorate more with increasing clay content. The reduction in tensile strength was 7.1%, 12.1%, and 18.1% for the samples containing 0, 1, and 2 wt% of clay, respectively. J. VINYL. ADDIT. TECHNOL., 12:25–32, 2006. © 2006 Society of Plastics Engineers     

Adsorption of lactic acid onto three ionic liquid‐modified porous polymers

Three ionic liquid (IL)‐modified porous polymers were synthesized and used for the adsorption of lactic acid. The experimental adsorption kinetics and equilibrium data from the IL‐modified polymers were obtained. The kinetic study revealed a low temperature to be advantageous to the adsorption process. The dependence of the level of lactic acid adsorption on the amount of polymer, initial lactic acid concentration, and pH was examined at equilibrium. The maximum efficiency was obtained using the maximum adsorbent dose. A comparison of lactic acid adsorption at different pH revealed anion exchange to be the main interaction between the lactic acid and polymers, not molecular adsorption. The amounts adsorbed were fitted to the Langmuir, Freundlich, and Temkin equations. The equilibrium data for modified polymers (imidazole modified polymer, methylimidazole modified polymer, and ethylimidazole modified polymer) were best represented by the Langmuir and Freundlich isotherm with R² values of 0.99. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Surface charge heterogeneity of kaolinite in aqueous suspension in comparison with montmorillonite

An analogous study to 2:1 type montmorillonite [Tombácz, E., Szekeres, M., 2004. Colloidal behavior of aqueous montmorillonite suspensions: the specific role of pH in the presence of indifferent electrolytes. Appl. Clay Sci. 27, 75–94.] was performed on 1:1 type kaolinite obtained from Zettlitz kaolin. Clay minerals are built up from silica tetrahedral (T) and alumina octahedral (O) layers. These lamellar particles have patch-wise surface heterogeneity, since different sites are localized on definite parts of particle surface. pH-dependent charges develop on the surface hydroxyls mainly at edges besides the permanent negative charges on silica basal plane due to isomorphic substitutions. Electric double layers (edl) with either constant charge density on T faces (silica basal planes) or constant potential at constant pH on edges and O faces (hydroxyl-terminated planes) form on patches. The local electrostatic field is determined by the crystal structure of clay particles, and influenced by the pH and dissolved electrolytes. The acid–base titration of Na-kaolinite suspensions showed analogous feature to montmorillonite. The initial pH of suspensions and the net proton surface excess vs. pH functions shifted to the lower pH with increasing ionic strength indicating the presence of permanent charges in both cases, but these shifts were smaller for kaolinite in accordance with its much lower layer charge density. The pH-dependent charge formation was similar, positive charges in the protonation reaction of (Si–O)Al–OH sites formed only at pHs below ∼ 6–6.5, considered as point of zero net proton charge (PZNPC) of kaolinite particles. So, oppositely charged surface parts on both clay particles are only below this pH, therefore patch-wise charge heterogeneity exists under acidic conditions. Electrophoretic mobility measurements, however, showed negative values for both clays over the whole range of pH showing the dominance of permanent charges, and only certain decrease in absolute values, much larger for kaolinite was observed with decreasing pH below pH ∼ 6. The charge heterogeneity was supported by the pH-dependent properties of dilute and dense clay suspensions with different NaCl concentrations. Huge aggregates were able to form only below pH ∼ 7 in kaolinite suspensions. Coagulation kinetics measurements at different pHs provided undisputable proofs for heterocoagulation of kaolinite particles. Similarly to montmorillonite, heterocoagulation at pH ∼ 4 occurs only above a threshold electrolyte concentration, which was much smaller, only ∼ 1 mmol l^− 1 NaCl for kaolinite, than that for montmorillonite due to the substantial difference in particle geometry. The electrolyte tolerance of both clay suspensions increased with increasing pH, pH ∼ 6–6.5 range was sensitive, and even a sudden change occurred above pH ∼ 6 in kaolinite. There was practically no difference in the critical coagulation concentration of kaolinite and montmorillonite (c.c.c.∼ 100 mmol l^− 1 NaCl) measured in alkaline region, where homocoagulation of negatively charged lamellae takes place. Rheological measurements showed shear thinning flow character and small thixotropy of suspensions at and above pH ∼ 6.7 proving the existence of repulsive interaction between uniformly charged particles in 0.01 M NaCl for both clays. The appearance of antithixotropy, the sudden increase in yield values, and also the formation of viscoelastic systems only at and below pH ∼ 6 verify the network formation due to attraction between oppositely charged parts of kaolinite particles. Under similar conditions the montmorillonite gels were thixotropic with significant elastic response.     

Dried waste activated sludge as biosorbents for metal removal: adsorptive characterization and prevention of organic leaching

Dried waste activated sludge was used for copper removal from simulated waste water in this study. Unconditioned activated sludge (UAS) bound up to 35 mg Cu g^?1, although there was significant leaching of organic material. Organic and copper leaching from the UAS increased significantly as the pH was reduced. Immobilization of UAS by sodium and calcium alginate was utilized in order to overcome the leaching problems, but reduced the adsorption capacity. Based on metal removal and organic leaching, calcium alginate‐conditioned UAS (CACAS) was found to be the most suitable sorbent for copper removal. Kinetic experiments showed that copper removal by both sodium alginate‐conditioned UAS (SACAS) and CACAS was faster than that by activated carbons, but slower than most of the other biosorbents described in the literature. FTIR spectroscopy identified a number of atomic groupings and structures in UAS relevant to copper adsorption. It suggested that hydrogen ions are replaced with copper ions. The Freundlich equation fitted the experimental isotherms better than the Langmuir equation. A computational model based on adsorption isotherm, external mass transfer and diffusion processes successfully described the kinetics of copper ion removal and suggested that the biosorption kinetics was controlled by mass transfer. © 2002 Society of Chemical Industry     

Sorption of tannic acid on zirconium pillared clay

Zirconium pillared clay (PILC) was prepared using montmorillonite as the base clay. Adsorption of tannic acid (tannin) was studied by a batch equilibrium technique, as a function of adsorbate concentration, temperature, pH, agitation speed, particle size of the adsorbent and ionic strength. The process of uptake is governed by diffusion controlled first‐order reversible rate kinetics. The higher uptake for the pH range 4.0–6.0 was attributed to external hydrogen bonding between phenolic‐OH groups of tannin molecules and the hydrogen bonding sites on the clay. The removal of tannin by adsorption was found to be >99.0% depending on the initial concentration in the pH range of 4.0–6.0. The process involves both film and pore diffusion to different extents. The effects of solute concentration, temperature, agitation speed and particle size on the diffusion rate were investigated. Tannin uptake was found to increase with ionic strength due to the compression of diffuse double layers. The applicability of Langmuir and Freundlich isotherm models has been tested. The maximum adsorption capacity of PILC was found to be 45.8 µmol g^?1 of clay and the affinity constant is 2.9 × 10^?2 dm³ µmol^?1 at 30 °C. Thermodynamic parameters such as ΔG °,ΔH ° and ΔS ° were calculated to predict the nature of adsorption. The isosteric enthalpies of adsorption were also determined and found to decrease with increasing surface coverage. Regeneration with hot water (60 °C) has been investigated for several cycles with a view to recovering the adsorbed tannin and also restoring the sorbent to its original state. Copyright © 2001 Society of Chemical Industry