Electrochemical preparation and properties of polypyrrole and its blend with poly(vinyl sulfonate) doped with perchlorate anions

In this article, we report polypyrrole (PPy)/poly(vinyl sulfonate) (PVS) and PPy/perchlorate (ClO) composite films generated by the electrochemical oxidation of pyrrole on a glassy carbon electrode (GCE) in an aqueous solution. The response of the produced films to an applied potential at 0.7 V was obtained by a cyclic voltammetry study in acetonitrile media. The films were significantly similar in their electrochemical behavior when ClO ions doped during the redox process. We concluded that with an increasing number of cycles, the anodic current increased because the number of the electroactive participants transported in the copolymer matrix was increased. Theoretical studies based on the Nernst and Butler–Volmer equations indicated that the ClO ion was transported during the oxidation/reduction process of the PPY/PVS and PPY/ClO films. The produced films were characterized further by means of IR spectroscopy, electrochemical impedance spectroscopy, and scanning electron microscopy to verify that the anion of ClO was doped into the copolymer matrix as well. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A new composite sorbent for water and dye uptake: Highly swollen acrylamide/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid/clay hydrogels crosslinked by 1,4‐butanediol dimethacrylate

A novel type of highly swollen hydrogels based on acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) crosslinked by 1,4‐butanediol dimethacrylate (BDMA) was prepared by free radical solution polymerization in aqueous media. Water uptake and dye sorption properties of polyelectrolyte AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were investigated as a function of composition to find materials with swelling and sorption properties. FTIR analyses were made. Swelling experiments were performed in water and dye solution at 25°C, gravimetrically. Highly swollen AAm/AMPS and AAm/AMPS/Bent hydrogels were used in experiments on sorption of water‐soluble monovalent cationic dye such as Lauths violet “LV, (Thionin).” Swelling of AAm/AMPS hydrogels was increased up to 1,920–9,222% in water and 867–4,644% in LV solutions, while AAm hydrogels swelled 905% in water and swelling of AAm/AMPS/Bent hydrogels was increased up to 2,756–10,422% in water and 1,200–3,332% in LV solutions, while AAm/Bent hydrogels swelled 849% in water. Some swelling kinetic and diffusional parameters were found. Water and LV diffusion into hydrogels was found to be non‐Fickian in character. For sorption of cationic dye, LV into AAm/AMPS and AAm/AMPS/Bent hydrogel was studied by batch sorption technique at 25°C. The amount of the dye sorbed per unit mass removal effiency and partition coefficient of the hydrogels was investigated. The influence of AMPS content in the hydrogels to sorption was examined. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Behaviors of polyelectrolyte AAm/AMPS/bentonite composite hydrogels in uptake of uranyl ions from aqueous solutions

Uranyl ion (UO₂²⁺) sorption properties of polyelectrolyte composite hydrogels made by the polymerization of acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) were investigated as a function of composition to find materials with swelling and uranyl ion sorption properties. Highly swollen AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with AMPS as co‐monomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of AMPS content in hydrogels was examined. Uranyl ion adsorption from aqueous solutions was studied by batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of AMPS on the uranyl ion adsorption were examined. Finally, adsorption capacity (the amount of sorbed uranyl ion per gram of dry hydrogel) (q) was calculated to be 0.67 × 10⁻³–2.11 × 10⁻³ mol uranyl ion per gram for the hydrogels. Removal effiency of uranyl ions (RE%) was changed range 9.05–29.92%. The values of partition ratio (K_d) of uranyl ions was calculated to be 0.10–0.43 for AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Synthesis and characterization of soluble polypyrrole with improved electrical conductivity

Polypyrroles doped with two dopants were prepared by chemical polymerization in aqueous solutions of pyrrole monomer. The solutions contained dodecylbenzenesulfonic acid (DBSA) as a dopant, tetraethylammonium tetrafluoroborate (TEABF₄) as a codopant, and ammonium persulfate (APS) as an oxidant. The PPy composites [polypyrrole‐dodecylbenzenesulfonates (PPy‐DBS) codoped with tetrafluoroborate (BF)—PPy‐DBS‐BF] were soluble in m‐cresol, NMP, and conditionally soluble in chloroform. Cyclic voltammetry was measured to know the electrochemical property of PPy‐DBS‐BF. The maximum electrical conductivity of room temperature for PPy‐DBS‐BF is 1.18 s/cm, which is greatly higher than that of polypyrrole doped with DBS^? (0.04 s/cm). The composition and structural characterization of PPy‐DBS‐BF were inferred from elemental analysis, nuclear magnetic resonance, and Fourier transform infrared spectroscopy. Scanning electron microscopy was performed to know the morphology of PPy‐DBS‐BF. The results of UV‐Vis spectra and electron spin resonance measurements showed that polaron and bipolaron existed as charge carrier of soluble PPy‐DBS‐BF. From the temperature dependence of the electrical conductivity, it was suggested that possible conduction mechanism for soluble PPy‐DBS‐BF should be hopping conduction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2583–2590, 2002     

Synthesis and electrochemistry of grafted copolymers of cellulose with 4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone,and 9-vinylcarbazole

Some new cellulosic materials, suitable for the adsorption of noble metal ions, were syn-thesized by chemical and electrochemical modification of cellulose. The polymerizable groups were introduced in cellulose with ∼ 80% yield of substitution by esterification with acryloyl chloride. The vinyl monomers (4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone, and 9-vinylcarbazole) were readily grafted into cellulose acrylate via radical polymerization in acetonitrile. The grafted copolymers of cellulose with 4-vinylpyridine and 4-vinylimidazole were reacted with methyl iodide and the corresponding 1-methylpyridinium iodide ( 6 ) and 3-methylimidazolium iodide ( 7 ) copolymers of cellulose were obtained. Copolymers 6 and 7 were transformed into new polymeric regents, differing in anions (ClO, CF₃COO⁻, NO, p-TsO⁻, BF, PF) by using a supporting electrolyte carrying the desired anions through the ion-exchange-electrochemical oxidation of the released iodide at a controlled anodic potential. © 1996 John Wiley & Sons, Inc.     

Surface-free energy analysis of hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate (E-VA) copolymers containing 12, 28, and 40 wt% of vinyl acetate, ethylene-vinyl acetate-vinyl alcohol terpolymers obtained by partial hydrolysis of (E-VA) copolymers and ethylene-vinyl alcohol (E-VOH) copolymers obtained by complete hydrolysis of (E-VA) copolymers were investigated by one-liquid contact-angle method. The polar force component of surface-free energy (γ) of copolymers drastically increased by the substitution of the acetate groups with hydroxyl groups. The dispersion force component (γ) of copolymers increased only slightly with the hydrolysis degree and deviated largely from the additivity law in regards of the surface area functions. The surface-free energy analysis of the cross-linked ethylene-vinyl alcohol and surface-hydrolyzed ethylene-vinyl acetate copolymers was also carried out.     

Polymeric absorbent for water sorption based on chemically crosslinked poly (acrylamide/2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt) hydrogels

Summary Swelling equilibrium of polyelectrolyte copolymer gels containing of acrylamide (AAm) and 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (AMPS) have been studied as a function of copolymer composition. AAm/AMPS hydrogels were prepared by free radical solution polymerization in aqueous solution of AAm with AMPS as anionic comonomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTA). Swelling experiments were performed in water at 25 °C, gravimetrically. The influence of AMPS content in hydrogels was examined. Swelling of AAm/AMPS hydrogels was increased up to 1018% (for containing 2% AMPS and crosslinked by EGDMA) 15246% (for containing 8% AMPS and crosslinked by TMPTA), while AAm hydrogels swelled up to 804% (crosslinked by TMPTA)–770% (crosslinked by EGDMA). The values of equilibrium water content of the hydrogels are 0.8851–0.9935. Diffusion behavior was investigated. Water diffusion into hydrogels was found to be non-Fickian in character.     

Two‐dimensional electrolyte nature of exfoliated montmorillonite nanoplatelets fabricated by soap‐free emulsion polymerization and their affinity for cations

Montmorillonite (MMT) nanoplatelets, fabricated by the exfoliation of MMT during participating in the soap‐free emulsion polymerization of methyl methacrylate, were well‐dispersed in water and performed like a two‐dimensional electrolyte. Their ionic conductivity roughly follows the Manning's limiting law for the conduction of a polyelectrolyte. The dissociated MMT nanoplatelets that carry negative charges in water were able to rapidly adsorb cations, such as tris(2,2′‐bipyridyl)ruthenium(II) (Ru(bpy)) and methylene blue (MB⁺), and recover into a smectic configuration floating as a separating phase. By using the Langmuir equation, we were able to estimate the occupied surface areas of MMT nanoplatelets by each Ru(bpy) and MB⁺ cations as 4.708 and 1.806 nm²/ion, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of pH,ionic strength,and temperature on uranyl ion adsorption by poly(N‐vinyl 2‐pyrrolidone‐g‐tartaric acid) hydrogels

Poly‐electrolyte N‐vinyl 2‐pyrrolidone‐g‐tartaric acid (PVP‐g‐TA) hydrogels with varying compositions were prepared in the form of rods from ternary mixtures of N‐vinyl 2‐pyrrolidone/tartaric acid/water. The effect of external stimuli, such as the solution pH, ionic strength, and temperature, on uranyl adsorption by these hydrogels was investigated. Uranyl adsorption capacities of the hydrogels were determined to be 53.2–72.2 (mg UO/g dry gel) at pH 1.8, and 35.3–60.7 (mg UO/g dry gel) at pH 3.8, depending on the amount of TA in the hydrogel. The adsorption studies have shown that the temperature and the ionic strength of the swelling solution also influence uranyl ion adsorption by PVP‐g‐TA hydrogels. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2219–2226, 2000     

Electrochemical Nanogravimetric Studies of Ruthenium(III) Trichloride Microcrystals

Ruthenium (III) trichlorid solid crystals have been mechanically attached to gold and paraffin-impregnated graphite surfaces and studied in the presence of aqueous solutions of M⁺Cl⁻ electrolytes, where M⁺ = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and K₂SO₄ by cyclic voltammetry and electrochemical nanogravimetry at a quartz crystal microbalance (EQCM). The electrochemical reduction of the layered α-RuCl₃ microcrystals causes drastic changes in the composition and the structure of crystals. The comparison of the current—potential and surface mass change—potential functions belonging to the first reduction-reoxidation cycle with the subsequent ones reveals that the simple intercalation scheme described in the literature cannot be entirely valid. During the first reduction step at ca. 0.2 V vs. SCE the charge consumption is substantially higher than in the course of the further potential cycling, and the simultaneous rapid and intense mass decrease indicates that considerable chemical and structural transformations occurs. Although a loss of the surface mass cannot be entirely excluded, the frequency increase most likely is not related to the dissolution of the microcrystals, however, large amounts of water molecules and—to a much smaller extent—chloride ions leave the crystal phase, and in fact a new material, which remains strongly attached to the gold or graphite surface, is formed. The extremely high frequency change at the first reduction process during the first cycle is most likely related to the stress effect originating in the phase transition of the surface layer and/or the removal of the water rigidly coupled to the surface into voids of the immobilized microcrystals. Depending on the amount of microcrystals on the electrode surface and the experimental conditions (the nature and concentration of the contacting electrolyte, scan rate, and potential range) used, after the “break-in” cycle stable electrochemical and nanogravimetric responses develop. The several reduction and reoxidation pairs of waves in the cyclic voltammograms and the simultaneous mass changes are in connection with the wide variety of intercalation reactions and complex formation during the electrochemical transformations. The mass change was reversible, in general, during reduction mass increase, while during oxidation mass decrease occurred at medium electrolyte concentrations in three or more steps. The mass excursions are rather complicated, involving different mass increase/decrease regions as a function of potential and the composition of the contacting solution. Taking into account the layered structure of RuCl₃, the electrochemical reduction can be explained as an intercalation reaction in that mixed valence intercalation phases with a general formula K Ru [Ru Cl_3z-y (H₂O)_y] • dH₂O are formed from z (RuCl₃ · H₂O). The reduction/reoxidation waves are related to the redox transformations of Ru(III) to Ru(II) sites and the insertion/deinsertion of cations and water molecules, while the composition of the polynuclear complexes and the structure of microcrystals change.     

Swelling behavior and diffusion studies of high‐water‐retaining acrylamide/potassium methacrylate hydrogels

Poly(acrylamide‐co‐potassium methacrylate) hydrogels were prepared by free‐radical simultaneous polymerization with aqueous solutions of acrylamide (AAm) and potassium methacrylate (KMA) with a redox initiator. The copolymerization was performed with eight different compositions of KMA at a fixed concentration of oil‐soluble crosslinkers, including 1,4‐butanediol diacrylate and ethylene glycol dimethacrylate (EGDMA). For every composition of AAm/KMA copolymer, the percentage swelling, swelling equilibrium, and diffusion characteristics were investigated. The copolymers were further studied for deswelling properties. The power law relationships of the hydrogels were evaluated for variation in terms of saline concentration. The AAm/KMA copolymers were confirmed by IR spectroscopy. Thermal studies of hydrogels were performed with differential scanning calorimetry and thermogravimetric analysis. EGDMA was found to be a better crosslinker for obtaining higher swelling and deswelling properties for the AAm/KMA hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1153–1164, 2005     

Carbon‐13 nuclear magnetic resonance investigation of styrene–α‐methylstyrene copolymers

A copolymer based on α‐methylstyrene (AMS) was investigated by nuclear magnetic resonance (NMR). The styrene‐co‐α‐methylstyrene (SAMS) was analyzed by solution and solid‐state NMR techniques. Three copolymers of SAMS with different compositions presented a particular behavior. The solution results showed the copolymer microstructure and the AMS content. The carbon‐13 spectra of SAMS C indicated that the AMS CH₃ signal was detected at three distinct chemical shifts, because of the different comonomer‐sequences distribution. The proton spin–lattice relaxation time in the rotating frame (Tρ) parameter was chosen because it permits the evaluation of changes in the molecular mobility. The values of Tρ found for the copolymers confirmed the random distribution in the samples. The copolymer with a low quantity of AMS (1.7%), when analyzed by this relaxation parameter, showed lower values that were interpreted as an antiplasticization effect. The SAMS copolymer with a higher AMS quantity showed a plasticization effect. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 261–266, 2001     

Spherulitic crystallization behavior of linear low‐density polyethylene

In this study the crystallization behavior of linear low‐density polyethylenes (LLDPEs) (ethylene‐α‐olefin copolymers) was studied by polarized light microscopy. A modified Hoffman‐Lauritzen (MHL) expression is proposed whereby the equilibrium melting temperature, T (T), is replaced with the melting temperature of the crystal stem is replaced with the maximum possible stem length, T. It successfully describes the crystalline spherulitic growth kinetics for both homogeneous and heterogeneous LLDPEs. In addition to regimes III and II, another regime (IM) was found in the high crystallization temperature range. Linear growth behavior of crystalline spherulites was observed in regime III, and nonlinear growth behavior was found in regimes II and IM. The basal surface free energy can be estimated from the short chain branching polydispersity (SCBP) for LLDPEs with excluded comonomers. Polym. Eng. Sci. 45:74–83, 2005. © 2004 Society of Plastics Engineers.     

Synthesis and electrochemical properties of phloroglucin‐based ferrocenyl compounds and their application in anion recognition

Phloroglucin‐based ferrocenyl compounds, including hyperbranched phloroglucin‐based ferrocenyl polymer and phloroglucin‐based ferrocenyl dendrimer (Generation0), were prepared by a convenient approach. Cyclic voltammograms were used to investigate their electrochemical properties, and we found that the scanning rate and solvent had remarkable effects on electrochemical behavior of the compounds. These compounds showed electrochemical responses to the anions, and a selective recognition for H₂PO over other anions was observed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of polypyrrole‐au coated SiO2@poly(4‐vinylpyridine) composites

Microspheres with silica as core and poly(4‐vinylpyridine) (P4VP) as shell were synthesized. AuCl ions were bound by P4VP chains to form the complex, which acted both as an oxidant of pyrrole monomers and as a source of Au atoms. By vapor phase polymerization, the PPy and Au nanoparticles were simultaneously formed on the surfaces of SiO₂@P4VP microspheres. The core‐shell structure was confirmed by transmission electron microscopy. The surface morphologies of the composites were observed by scanning electron microscopy. The molecular structures of composites were characterized in detail by Raman spectra, X‐ray diffraction, and X‐ray photoelectron spectroscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of magnetite and silver poly(2‐acrylamido‐2‐methyl propane sulfonic acid‐co‐acrylamide) nanocomposites for adsorption and catalytic degradation of methylene blue water pollutant

The aim of the present work was to prepare microgel nanocomposites based on silver and magnetite to apply as adsorbents and heterogeneous catalysts for removal of methylene blue (MB) cationic dye from aqueous solution. For this, 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) and acrylamide (AAm) monomers were used to prepare AMPS/AAm microgel based on the emulsion technique. Ag and Fe₃O₄ nanoparticles were embedded into the AMPS/AAm microgel using the in situ technique. Their particle sizes, surface charges, crystalline lattice structure, morphology, magnetic properties and thermal stability were investigated. The AMPS/AAm hydrogel nanocomposites were used as an adsorbent to remove MB dye. The AMPS/AAm microgel nanocomposites were tested as catalysts to reduce MB and degrade its chemical structure with heterogeneous Fenton oxidation using Ag and Fe₃O₄ nanocomposites, respectively. This study presents promising data as the prepared materials used as adsorbents and catalysts show competitive features compared with the data presented in the literature. © 2019 Society of Chemical Industry     

Homogeneous and heterogeneous catalytic reactions in a cobalt oxide/graphite air electrode. Part IV. Mechanistic studies on a ring-disk carbon electrode in alkaline solution

The redox properties of HCoO on a glassy carbon electrode in the absence and presence of hydrogen peroxide have been investigated by using cyclic voltammetry and UV-Vis spectroscopy in alkaline solution. Corresponding rotating ring-disk experiments showed that the disk current increased by about 60% in the presence of HCoO, confirming the important role played by HCoO in the homogeneous decomposition of hydrogen peroxide.     

Surface activity and micellar behavior of dimethylamino‐ and trimethylammonium‐ tipped oxyethylene–oxybutylene diblock copolymers in aqueous media

Surface activity and micellar behavior in aqueous media in the temperature range 20–50°C of the two block copolymers, Me₂N(CH₂)₂OE₃₉B₁₈, (DE₄₀B₁₈) and I^?Me₃N⁺(CH₂)₂OE₃₉B₁₈, (TE₄₀B₁₈) in the premicellar and postmicellar regions have been studied by surface tensiometry, viscometry, and densitometry. Where E represents an oxyethylene unit while B an oxybutylene unit. Various fundamental parameters such as, surface excess concentrations (Γ_m), area per molecule (a) at air/water interface and standard Gibbs free energy for adsorption, ΔG have been investigated for the premicellar region at several temperatures. The thermodynamic parameters of micellization such as, critical micelle concentrations, CMC, enthalpy of micellization, ΔH, standard free energy of micellization ΔG, and entropy of micellization ΔS have also been calculated from surface tension measurements. Dilute solution viscosities have been used to estimate the intrinsic viscosities, solute‐solvent interaction parameter and hydration of micelle. Partial specific volume and density of the micelle were obtained from the density measurements at various temperatures. The effect of modifying the end group of the hydrophilic block was investigated by comparing the behavior of trimethylammonium‐ and dimethylamino‐tipped copolymers, designated TE₄₀B₁₈, and DE₄₀B₁₈, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on the surface properties of grafted polyethylene particles by inverse gas chromatography

Inverse gas chromatography (IGC) studies on the surface of polyethylene (PE) particles grafted with acrylic acid and acryl amide have been reported. Surface properties of the virgin and grafting‐modified PE were compared by IGC. The dispersive contributions of the surface free energy γ and the K_A and K_B parameters expressing the ability of the stationary phase to act as Lewis acid or Lewis base were calculated. The results showed that the γ value increased significantly after grafting. The PE samples grafted with acrylic acid and acrylamide showed a predominantly basic character while the virgin PE was acidic. All of these suggested that the surface of PE has been modified through the grafting reaction, and thus is expected to improve its adhesions with other polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrochemical synthesis and properties of poly(3‐methylthiophene): Novel synthesis of poly(3‐methylthiophene) with pentachlorostannate and hexachloroantimonate

Poly(3‐methylthiophene) (P3‐MeT) doped with different anions were prepared electrochemically in the presence of tetraalkylammonium salts. The new poly(3‐methylthiophene) SnCl and SbCl (P3‐MeT SnCl₅ and P3‐MeT SbCl₆) were prepared electrochemically using tetra‐n‐butylammonium pentachlorostannate and tetra‐n‐butylammonium hexachloroantimonate as the supporting electrolytes. The effect of current density, salt concentration, reaction temperature, and the nature of solvents on the polymer yield and polymer conductivities have been investigated. Cyclic voltammetry of poly(3‐methylthiophene) has been examined at platinum electrode in 1,2‐dichloroethane medium containing n‐Bu₄NSnCl₅, Bu₄NSbCl₆, and Bu₄NClO₄ as the supporting electrolytes in the range of −1.0 to 1.7 V versus SCE in the presence and absence of 3‐methylthiophene. Electrical conductivity, magnetic susceptibility measurements, and structural determination by elemental analysis and infrared studies were also made. Scanning electron microscopy revealed a globular, branched, fibrous and a spongy, fibrous morphology of poly(3‐methylthiophene) SnCl, ClO, and SbCl, respectively. The thermal analysis of the polymers was also investigated. Possible causes for the observed lower conductivity of these polymers have also been discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 91–102, 1999