Poly(sodium 4-styrene sulfonate) and poly(2-acrylamidoglycolic acid) nanocomposite hydrogels: montmorillonite effect on water absorption,thermal, and rheological properties

A systematic study of water absorbency, thermal, and rheological properties was performed on nanocomposite hydrogels of poly(sodium 4-styrene sulfonate) (PSSNa) and poly(2-acrylamide glycolic acid) (PAAG). Montmorillonite was used as clay filler and was previously modified to hydrogel synthesis by addition of (3-acrylamide propyl)trimethylammonium chloride. Syntheses were carried out by in situ radical polymerization, using N,N-methylen-bis-acrylamide as crosslinker reagent. Nanocomposites showed an exfoliated morphology, confirmed by transmission electron microscopy and X-ray diffraction. The water absorption capacity (WAC) of unloaded PSSNa hydrogel was three times higher than for PAAG; due to clay addition, absorption capacity increased for PSSNa nanocomposites and decreased for PAAG. Finally, rheological properties of nanocomposite hydrogels were studied by both dynamic oscillatory test and shear creep analysis. Results showed improvements on mechanical properties, such as yield point, elastic recovery, and storage modulus as consequence of montmorillonite addition.     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of Some N-Alkyl-N-Phenyl-Dithiocarbamates

The thermal decomposition of Zn(II), Cd(II) and Hg(II) complexes of N-ethyl-N-phenyl and N-butyl-N-phenyl dithiocarbamates have been studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The products of the decomposition, at two different temperatures, were further characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The results show that while the zinc and cadmium complexes undergo decomposition to form metal sulphides, and further undergo oxidation forming metal oxides as final products, the mercury complexes gave unstable volatiles as the final product.     

Synthesis,characterization, and properties of polychelates of poly(styrene sulfonic acid‐co‐maleic acid) with Co(II), Cu(II), Ni(II), and Zn(II)

Polymer metal complexes of poly(styrene sulfonic acid‐co‐maleic acid) and Cu(II), Ni(II), Co(II), and Zn(II) were synthesized. The magnetic, spectral, and thermal properties, as well as the electrical conductivities, of the chelates were investigated, and possible structures were assigned to the polychelates. Semiempirical calculations at the AM1 level were carried out on the geometrical arrangement of the polychelates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2546–2551, 2002     

Removal of Cd(II), Hg(II), and Pb(II) ions from aqueous solution using p(HEMA/chitosan) membranes

An interpenetration network (IPN) was synthesized from 2‐hydroxyethyl methacrylate (HEMA) and chitosan, p(HEMA/chitosan) via UV‐initiated photo‐polymerization. The selectivity to different heavy metal ions viz Cd(II), Pb(II), and Hg(II) to the IPN membrane has been investigated from aqueous solution using bare pHEMA membrane as a control system. Removal efficiency of metal ions from aqueous solution using the IPN membranes increased with increasing chitosan content and initial metal ions concentrations, and the equilibrium time was reached within 60 min. Adsorption of all the tested heavy metal ions on the IPN membranes was found to be pH dependent and maximum adsorption was obtained at pH 5.0. The maximum adsorption capacities of the IPN membrane for Cd(II), Pb(II), and Hg(II) were 0.063, 0.179, and 0.197 mmol/g membrane, respectively. The adsorption of the Cd(II), Hg(II), and Pb(II) metal ions on the bare pHEMA membrane was not significant. When the heavy metal ions were in competition, the amounts of adsorbed metal ions were found to be 0.035 mmol/g for Cd(II), 0.074 mmol/g for Hg(II), and 0.153 mmol/g for Pb(II), the IPN membrane is significantly selective for Pb(II) ions. The stability constants of IPN membrane–metal ions complexes were calculated by the method of Ruzic. The results obtained from the kinetics and isotherm studies showed that the experimental data for the removal of heavy metal ions were well described with the second‐order kinetic equations and the Langmuir isotherm model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and Characterization of Poly(2,2-dimethyl-1,3-propylene oxalate) Polymer and the Study of its Metal Uptake Behavior Toward Pb(II), Cd(II), and Hg(II) Ions

Abstract

Poly(2,2-dimethyl-1,3-propylene oxalate) was synthesized from oxalyl chloride and 2,2-dimethyl-1,3-propane diol. The polymer was characterized by inherent viscosity, FT-IR, XRD, SEM, ¹H-NMR, ¹³C-NMR, DSC, and TGA. The polymer uptake behavior towards Pb(II), Cd(II), and Hg(II) ions was studied by the batch equilibrium technique as a function of pH and contact time. The adsorption isotherms of metal ions were also investigated. Column experiments were used to determine the loading capacity and study desorption of metal ions. The polymer showed high metal-ion uptake capacity towards Pb(II), but moderate capacity towards Cd(II) and Hg(II) ions. Interestingly, the polymer was found to be highly selective for Pb(II) ions at pH 5 and 25°C. The metal ion uptake properties of the polymer show fittings for both Langmuir's and Freundlich equations. The metal-bound polymer was regenerated by treatment with 1 M HNO₃. Therefore, it may be employed for the removal of heavy metal pollutants in environmental and industrial applications.     

Mechanism of Hg(II), Cd(II) and Pb(II) ions sorption from aqueous solutions by Aspergillus niger spores

ABSTRACT

Recent work has focused on the removal of Pb²⁺, Hg²⁺, and Cd²⁺ by using an organ of Aspergillus niger – spores, which were spherical particles with small diameter (2 µm) characterized by negative charge. Results shown that the biosorption of Pb²⁺, Hg²⁺, and Cd²⁺ from aqueous solutions using spores was analyzed at varying biosorbent dosages, pH levels, contact times and initial heavy metal concentrations. The maximum biosorption capacities of Pb²⁺, Hg²⁺, and Cd²⁺ were 23.9, 27.2, and 21.5 mg/g at a natural pH with the initial concentration were 30 mg/L, respectively. The sequence of biosorption capacity for cationic heavy metals was Pb²⁺>Cd²⁺>Hg²⁺. Spores exhibited a short biosorption equilibrium time of 60 min at a pH range of 4.0–6.0, and the main biosorption mechanism was electronic attraction, ion exchanges and complexation(involved in C = C, C-H, C-O, N-H), the data fit well in the pseudo-second-order kinetic equation and the Freundlich isotherm. In addition, Spores can grow on many kinds of moist agriculture waste without any added nutrition. The results showed that spores could be considered as a potential biosorbent for the removal of cationic heavy metals from aqueous solutions.     

Synthesis, characterization, and properties of polychelates of poly(maleic acid-co-olefin) with Cu(II), Co(II), Ni(II), and Zn(II)

SUMMARY Polychelates of poly(maleic acid-co-olefin) with Cu(II), Co(II), Ni(II), and Zn(II) metal ions are synthesized. These compounds are characterized by FT IR, UV-vis spectroscopy, and thermal analysis. The electrical conductivity measurements are carried out. These demonstrate that at temperature close to 130°C the electrical conductivity increased to values near to the semiconductor range. The PM3 calculations are also carried to study the geometry of the polychelates. Received: 1 November 2000/Revised version: 20 March 2001/Accepted: 21 March 2001     

Removal Characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) by Natural Mongolian Zeolite through Batch and Column Experiments

The removal characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) from model aqueous solutions by 5 natural Mongolian zeolites were investigated. The adsorption of metals on zeolites reached a plateau value within 6 h. The adsorption kinetic data were fitted with adsorption kinetic models. The equilibrium adsorption capacity of the zeolites was measured and fitted using Langmuir and Freundlich isotherm models. The order of adsorption capacity of zeolite was Pb(II) > Zn(II) > Cu(II) > Cd(II). The maximum adsorption capacity of natural zeolite depends on its cation exchange capacity and pH. The leaching properties of metals were simulated using four leaching solutions. The results show that natural zeolite can be used as an adsorbent for metal ions from aqueous solutions or as a stabilizer for metal-contaminated soils.     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Thin-Layer Chromatography of Metal Ions on Stannic Arsenate: Quantitative Separation of Hg(II) from Cd(II), Zn(II), and Cu(II)

Abstract

Stannic arsenate thin layers (0.25 mm) have been applied for the chromatographic studies of 42 metal ions without using any binder. As a result, some important binary separations, such as Cd-Sb, V-Nb, V-Ta, Ni-Fe, Pd-Nb, Hg-Pb, and Pb-Mo, have been performed. Quantitative separation of Hg from Cd, Zn, and Cu has also been made by this technique. The study has been found to give reproducible results on refluxed and nonrefluxed samples of stannic arsenate used simultaneously.     

1-Amino-4-aryl-2(1H)-pyrimidinthione: Acidität und Komplexbildung mit Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Pb(II) und Ag(I)

1-Amino-4-aryl-2(1H)-pyrimidinethiones: Acidity and Complex Formation with Nonferrous Metal Ions and Ag(I) Acid dissociation constants of new 2, 3 and already known 1 substituted 1-amino-4-aryl-2(1H)-pyrimidinethiones and stability constants of their nonferrous metal ion and silver complexes have been measured pH-potentiometrically in a 75% (v/v) mixture of dioxane/water. The influence of the substituents on pK_a- and lgβ_n-values is discussed. The X-ray structure analysis of bis[1-(4-toluenesulfonamido)-4-(4-tolyl)-2(1H)-pyrimidinethionatol]-nickel(II) 5 proves that pyrimidinethiones coordinate via their thione sulphur and aminonitrogen. However, the bond lengths are not levelled in the chelating ring.     

Polymer-metal complexes: Synthesis, characterization, and properties of poly(maleic acid) metal complexes with Cu(II), Co(II), Ni(II), and Zn(II)

SUMMARY Polymer metal complexes of poly(maleic acid) and Cu(II), Co(II), Ni(II), and Zn(II) were synthesized. Elemental analysis, as well as magnetic, spectral and thermal properties, in addition to electrical conductivities of the chelates were investigated, and possible structures have been assigned to the polychelates. Semi-empirical calculations at the PM3 level were carried out on the geometrical arrangement of the polychelates. Received: 19 November 1999/Revised version: 22 March 2000/Accepted: 31 March 2000     

Synthesis, Crystal Structure, Fluorescence and Thermostability of Ni(II), Zn(II), Cd(II) Complexes with Schiff Base 2-Acetylpyridine-d-tryptophan

Three novel transition metal coordination polymers, [Ni(C₁₈H₁₆N₃O₂)₂·2CH₃OH] _n (1), [Zn(C₁₈H₁₆N₃O₂)₂·4CH₃OH] _n (2) and [Cd(C₁₈H₁₆N₃O₂)₂·2CH₃OH] _n (3) (C₁₈H₁₆N₃O₂=2-acetylpyridine-d-tryptophan) were synthesized and characterized by elemental analysis, IR, UV, ¹H NMR and X-ray diffraction single crystal analysis. The analyses of the structures indicate that all three materials crystallize in the tetragonal crystal system, space group P4₁2₁2. They have similar structures; i.e., the Schiff base coordinates in its deprotonated form and behaves as a hexadentate (4N+2O) coordinated ligand to form a distorted octahedron geometry. On the other hand, as a result of the alternate arrangement of chains through N–H···O intermolecular hydrogen bonds interactions, 2-D layers are formed for the three complexes. Furthermore, the luminescent properties and thermal stabilities of the three complexes were investigated.     

A new method for the simultaneous determination of Fe(III), Cu(II), Pb(II), Zn(II), Cd(II), and Ni(II) in wine using differential pulse polarography

A new and simple differential pulse polarographic method for the analysis of wine has been established. With this method, it was possible to determine simultaneously six trace elements in wine. There was no need for time consuming extraction and separation procedures with danger of contamination. The polarogram of wet digested wine was taken initially in pH 2 acetate buffer and Pb, Cd, and Zn were determined by standard additions. Ethylene diamine tetraacetic acid (EDTA) was added and pH was increased to six by addition of NaOH. Fe and Cu were determined subsequently. The ammonia buffer, pH 9.5, was identified as the best medium for separation and determination of Ni and Zn. The quantities of trace elements were found as Cu 290 ± 20 μg L⁻¹, Fe 8960 ± 50 μg L⁻¹, Pb 148 ± 17 μg L⁻¹, Cd 16 ± 8 μg L⁻¹, Zn 460 ± 25 μg L⁻¹, and Ni 78 ± 17 μg L⁻¹.     

Removal of Cd(II), Pb(II), Cu(II) and Ni(II) from water using modified pine bark

This paper describes the removal of Cd(II), Pb(II), Cu(II), and Ni(II) ions from aqueous solutions using chemically modified pine barks (Pinus nigra). In this article, effects of chemical modification methods on the adsorption capacity have been investigated. Changes of the surface properties were examined by the FTIR, SEM and zeta potential analyses. HCl, NaOH, Fenton reactive, polymerization, acetone, ethanol, chloroform, tetra ethylene glycol, diethyl ether and glycol were used for modification processes. Maximum adsorption capacities were obtained by modification with NaOH (13-20 mg/g), Fenton (12-17 mg/g) and polymerization (12-16.5 mg/g). These modification processes also decreased Chemical Oxygen Demand of water from 1820 mg/L for raw pine barks to 35 mg/L for NaOH modified barks. Adsorption capacities of adsorbents increased from 2 mg/g to 20 mg/g as a result of modification that accordingly increase adsorbent surface activity.     

Adsorption of Cd(II), Hg(II) and Zn(II) from aqueous solution using mesoporous activated carbon produced from Bambusa vulgaris striata

Mesoporous activated carbon (surface area of 608 m²/g) has achieved high efficiency in removal of cadmium, mercury and zinc ions from water solution. The proposed low-cost adsorbent was physically activated with water steam from the bamboo species Bambusa vulgaris striata. The batch studies suggested an activated carbon dose of 0.6 g/L, solution pH of 9 and an equilibrium time of 16 h in static conditions. The pseudo-second order equations represented the adsorption kinetics with high correlation. Fitting of the experimental results to the Langmuir, Freundlich, Redlich–Peterson and Toth isotherm models showed an almost homogeneous surface coverage and presence of physical adsorption. The highest adsorption capacities, calculated from the Langmuir model, are 239.45, 248.05 and 254.39 mg/g of cadmium, mercury and zinc, respectively.     

Poly(acrylic acid–sodium styrene sulfonate) organogels: Preparation,characterization, and alcohol superabsorbency

Polymeric organogels based on acrylic acid and sodium styrene sulfonate (SSS) were synthesized and characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, dynamic mechanical thermal analysis (DMTA), and rheometrical analyses. The organogels exhibited medium alcohol absorbency because of counterion binding that formed in solvents with low dielectric constants. After acid treatment, the possibility of counterion binding was decreased, and the organogels achieved superabsorbency in alcohols, for example, about 80 and 50 g/g in methanol and ethanol, respectively. The superabsorbency was also measured in higher alcohols (i.e., n‐propanol and isopropyl alcohol) and polyols (i.e., ethylene glycol, propylene glycol, 1,3‐propanediol, and glycerol). The dielectric constant, viscosity, and structural features of the alcohols were investigated as important parameters determining the alcohol superabsorbency. DMTA of dried samples showed two glass‐transition temperatures (T_g's), that is, the matrix T_g and the complex T_g, which increased with increasing SSS content. The tan δ peak intensity increased after the acid treatment. With increasing SSS, the storage modulus of the dried gel increased; whereas that of the rheometrically measured hydrated gel decreased. Tan δ decreased with increasing SSS because of enhanced counterion binding. These alcohol‐specific superabsorbing organogels are suggested as excellent candidates for the manufacture of products with high alcohol contents, such as hand sanitizers and fuel gels. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-Methyl-N-Phenyldithiocarbamate: The Single Crystal Structure of [(C(6)H(5))(CH(3))NCS(2)](4)Hg(2)

Zn(II), Cd(II) and Hg(II) complexes of N-methyl-N-phenyl dithiocarbamate have been synthesized and characterized by elemental analysis and spectral studies (IR, (1)H and (13)C-NMR). The single crystal X-ray structure of the mercury complex revealed that the complex contains a Hg centre with a distorted tetrahedral coordination sphere in which the dinuclear Hg complex resides on a crystallographic inversion centre and each Hg atom is coordinated to four S atoms from the dithiocarbamate moiety. One dithiocarbamate ligand acts as chelating ligand while the other acts as chelating bridging ligand between two Hg atoms, resulting in a dinuclear eight-member ring. The course of the thermal degradation of the complexes has been investigated using thermogravimetric and differential thermal analyses techniques. Thermogravimetric analysis of the complexes show a single weight loss to give MS (M = Zn, Cd, Hg) indicating that they might be useful as single source precursors for the synthesis of MS nanoparticles and thin films.