Heavy metal ions removal through poly(acrylamide-co-methacrylic acid) resin

The resin poly(acrylamide-co-methacrylic acid) P(AAm-co-MA) by radical polymerization was synthesized and its metal ion binding was studied using the batch and column equilibrium procedures for: Cd(II), Zn(II), Pb(II), Hg(II), Al(III), and Cr(III). Experiments were carried out at different pH, metal ion concentration, temperature, and contact time. The resin’s retention behavior was influenced by the pH. The highest retention 91% (0.248 mmol/g, 6.7 mg/g) was achieved at pH 5 for Al(III), and 87% (0.265 mmol/g, 54.9 mg/g) for Pb(II). For Hg(II), the yield was 85% (0.318 mmol/g, 63.7 mg/g) at pH 2. The metal-ion retention properties were dependent on the polymer/metal ion ratio. Under competitive conditions of Pb(II), Hg(II), and Al(III), the resin showed a higher retention of Hg(II), allowing the selective separation of this metal.     

Amphiphilic diblock copolymers poly(2‐hydroxyethylmethacrylate)‐b‐(N‐phenylmaleimide) and poly(2‐hydroxyethylmethacrylate)‐b‐(styrene) using the macroinitiator poly(HEMA)‐Cl by ATRP: Preparation,characterization, and thermal properties

In recent years, much attention has been given to the development of specialty polymers from useful materials. In this context, amphiphilic block copolymers were prepared by atom transfer radical polymerization (ATRP) of N‐phenylmaleimide (N‐PhMI) or styrene using a poly(2‐hydroxyethylmethacrylate)‐Cl macroinitiator/CuBr/bipyridine initiating system. The macroinitiator P(HEMA)‐Cl was directly prepared in toluene by reverse ATRP using BPO/FeCl₃ 6 H₂O/PPh₃ as initiating system. The microstructure of the block copolymers were characterized using FTIR, ¹H‐NMR, ¹³C‐NMR spectroscopic techniques and scanning electron microscopy (SEM). The thermal behavior was studied by differential scanning calorimetry (DSC), and thermogravimetry (TG). The theoretical number average molecular weight (M_n,th) was calculated from the feed capacity. The microphotographs of the film's surfaces show that the film's top surfaces were generally smooth. The TDT of the block copolymer P(HEMA)₈₀‐b‐P(N‐PhMI)₂₀ and P(HEMA)₉₀‐b‐P(St)₁₀ of about 290°C was also lower than that found for the macroi′nitiator poly(HEMA)‐Cl. The block copolymers exhibited only one T_g before thermal decomposition, which could be attributed to the low molar content of the N‐PhMI or St blocks respectively. This result also indicates that the phase behavior of the copolymers is predominately determined by the HEMA block. The curves reveal that the polymers show phase transition behavior of amorphous polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and metal ion uptake properties of water-insoluble functional copolymers: removal of metal ions with environmental impact

New adsorbents, poly(N-(3-dimethylamino)propylmethacrylamide-co-acrylic acid), P(NDAPA-AA), poly(N-(3-dimethylamino)propylmethacrylamide-co-4-acryloylmorpholine), P(NDAPA-AMo), and poly(N-(3-dimethylamino)propylmethacrylamide-co-2-acrylamidoglycolic acid), P(NDAPA-AAg) were obtained by radical polymerization and characterized by Fourier transform infrared spectroscopy and thermogravimetry. The uptake metal ion properties of cadmium(II), zinc(II), lead(II), mercury(II), and chromium(III) were examined by batch-equilibrium technique with respect to the initial pH, temperature, and initial metal ion concentration under competitive and noncompetitive conditions. Maximum adsorption capacity was determined. Acid and basic regeneration was tested in order to restore the adsorbent to initial conditions. Resins P(NDAPA-AA) and P(NDAPA-AMo) showed a great ability to retain Cr(III), whereas P(NDAPA-co-AAg) to retain Hg(II).     

A weak-to-strong inversion mismatch model for analog circuit design

This paper reports on a new CMOS transistor mismatch model that is continuous from weak to strong inversion. The model is completely described by analytical equations which are based on either the ACM or EKV transistor models. Large signal ACM and EKV transistor equations including the relevant parameters for mismatch are used for fitting the measured data. Five parameters are found to be relevant for predicting mismatch from weak to strong inversion: specific current I _s , threshold voltage V _T0, gamma γ, θ _o (dependent on mobility degradation and source-drain series resistances), and θ _e (dependent on velocity saturation and drain series resistance). Arrays of NMOS and PMOS transistors of 30 different sizes were fabricated in a 0.35 μm CMOS process. For each transistor size 12 different curves were measured. Different mismatch parameter extraction methods were used and compared. Average current mismatch prediction error was found to be in the range between 4 and 10% in the whole bias range from weak to strong inversion. Worst case mismatch prediction errors were in the range 23–61%. Since mismatch was predicted for a large number of sizes, the model could be implemented in a conventional circuit simulator to predict transistor mismatch not only as a function of transistor area but as function of transistor width and length independently. It was found that minimum mismatch is not always achieved by square transistors, and that mismatch is less sensitive to reducing width than to reducing length.     

Arsenite retention properties of water‐soluble metal–polymers

The properties of water‐soluble metal–polymers to retain As(III) from aqueous solution are investigated. Poly(acrylic acid)s with different tin contents are prepared. Amounts of 3, 5, 10, and 20 wt % of tin are added to the polymer. The metal compositions are evaluated by thermogravimetry (TG‐DSC) and atomic absorption spectroscopy. Structural properties are analyzed by infrared and ¹H nuclear magnetic resonance spectroscopy, and X‐ray diffraction. Additionally, specific surface area was measured using CO₂ as adsorbate. Arsenic retention properties are studied using the liquid‐phase polymer‐based retention (LPR) technique. The polymers can bind arsenic species from an aqueous solution in the pH range 4–8. The studies show that the retention capacity is a function of tin content and polymer concentration. At pH 8, the following mol ratios poly(AA)‐Sn : As(III) are analyzed: 600 : 1, 400 : 1, 200 : 1, 100 : 1, and 20 : 1. The highest retention, 80%, is obtained with poly(AA)‐Sn at 10 and 20 wt % of tin at mole ratios 400 : 1, and at nearly to 20 : 1 or 40 : 1 Sn‐As(III). The highest retention is observed at pH 8 and 4. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Removal of As(V) using liquid-phase polymer-based retention (LPR) technique with regenerated cellulose membrane as a filter

In this study, regenerated cellulose membrane was used as a filter in liquid-phase polymer-based retention technique. The poly(4-vinyl-1-methylpyridinium bromide), P(BrVMP), was used as extracting reagent of As(V). The role of pH, polymer:As(V) molar ratio, and influence of regenerated cellulose membrane were investigated by washing method. It was observed that the efficient retention was obtained at pH 9 with 20:1 polymer:As molar ratio and it was about 100 % at Z = 10 for P(BrVMP). Experimental data showed that the regenerated cellulose membrane, compared to poly(ethersulfone) membrane, has a capacity to interact with As(V). The maximum retention capacity of P(BrVMP) was determined by enrichment method, and then, using alternately washing and enrichment methods, the charge–discharge process and recovery of P(BrVMP) were performed.     

Optimization of processing parameters for the synthesis of low‐density polyethylene/organically modified montmorillonite nanocomposites using X‐ray diffraction with experimental design

The influence of the processing parameters on the synthesis of low‐density polyethylene (LDPE)/organically modified montmorillonite (OMM) nanocomposite films was studied using experimental design. Intercalation in the nanocomposites was analysed using X‐ray diffraction and verified using atomic force microscopy. Four direct melt processing parameters were studied to obtain surface maps of intercalation in the nanocomposites: concentration of OMM (clay‐%), concentration of Polybond^® 3149 (compatibilizer‐%), mixing temperature (T_mix) and mixing time. An ANOVA validated the polynomial function, and intercalation maps from response surface methodology (RSM) were obtained. The clay‐% parameter had the most significant effect, and T_mix showed no significant effect on intercalation (p < 0.05). A strong synergic interaction between clay‐% and compatibilizer‐% was observed, which is not possible to detect using univariate experiments. RSM provides a powerful tool for choosing the best processing conditions that lead to formulations with the highest intercalations by considering the main factors and their interactions. © 2013 Society of Chemical Industry     

Off-line coupled electrocatalytic oxidation and liquid phase polymer based retention (EO-LPR) techniques to remove arsenic from aqueous solutions

Electrochemistry and membrane ultrafiltration methods (electro-oxidation and liquid phase polymer based retention technique, LPR, respectively) were off-line coupled to remove As(III) inorganic species from aqueous solutions. Our main objective was to achieve an efficient extraction of arsenic species by associating a polymer-assisted liquid phase retention procedure, based on the As(V) adsorption properties of cationic water-soluble polymers, with an electrocatalytic oxidation process of As(III) into its more easily removable analogue As(V). The electrocatalytic oxidation of As(III) to As(V) was performed in the presence of different water-soluble poly(quaternary ammonium) salts acting also as supporting electrolyte, i.e. poly(vinylbenzyl)trimethyl ammonium chloride, P(ClVBTA), poly[3-(methacryloylamine)propyl]trimethyl ammonium chloride, P(ClMPTA), and poly(4-vinyl-1-methylpyridinium bromide), P(BrVMP). After complete electrocatalytic conversion of As(III) into As(V), the mixtures were introduced into an LPR cell to remove the As(V)-polymer adducts. Using P(ClMPTA), P(ClVBTA), or P(BrVMP) ammonium salts in a 20:1 polymer:As(III) mol ratio at pH 8, complete (100%) retention of the arsenic was achieved. Moreover, the As(V) retention efficiency turned out to be directly related to the net charge consumed during the electrochemical conversion of As(III) to As(V).     

Vascular supply as a discriminating factor for pig preantral follicle selection

This research analyses how somatic and vascular compartments change during preantral follicle growth. To address this aim, theca-granulosa (somatic) proliferation indexes (PIs), proportion of proliferating endothelial cells (PE), vascular area (VA) and vascular endothelial growth factor A (VEGFA) expression were simultaneously recorded on single healthy preantral follicles, classified into six different stages on the basis of the diameter and the granulosa layers. An autonomous blood vessel network starts to appear only in class 3. Vascular remodelling requires VEGFA expression, and VEGFA mRNA and VA significantly increase between class 3 and classes 4 and 5 and, further, in class 6. In addition, a positive correlation exists between these parameters in classes 3-5. Despite variation in angiogenesis results from classes 3 to 5, the statistical analysis reveals that the vascular parameters are positively and strictly correlated with somatic PIs. Conversely, class 6, also characterized by higher values of somatic PIs, displays a stable proportion of PEs ( congruent with 40%) without showing any correlation among the different parameters analysed. To identify follicular subpopulations within different classes, a multivariate hierarchical cluster analysis was performed. This analysis reveals that the majority of classes 3 and 4 are quiescent follicles or structures that grow very slowly. Class 5 represents a transitory category, where half of the follicles maintain a low activity and the remaining express significantly higher levels of granulosa PI and VA. The follicles with this high activity are probably able to reach class 6 becoming dominant structures where somatic and vascular parameters are constantly on high levels and the VA remains the unique differentiating element.