Nanocomposites of poly(L‐lysine) and single‐walled carbon nanotubes

BACKGROUND: Single‐walled carbon nanotubes have inspired research owing to their promise in a broad range of applications. The dispersion of carbon nanotubes is of key importance for the utilization of this interesting material for various potential applications. RESULTS: A novel and simple method was developed to fabricate polymer composites with single‐walled carbon nanotubes based on a solid‐state reaction, in which the nanotubes were reacted with poly(L ‐lysine) using high‐speed vibration milling. Fourier transform infrared and UV‐visible spectroscopy as well as thermogravimetry were employed to characterize the novel composites. The morphology and the dispersion of the carbon nanotubes were determined using scanning and transmission electron microscopy. CONCLUSION: The resulting composites were dispersable in water and are expected to have great potential for both molecular‐level studies and device applications of nanotubes. Copyright © 2007 Society of Chemical Industry     

Synthesis of azo‐functionalized ion‐imprinted polymeric resin for selective extraction of nickel(II) ions

The work presented involved the fabrication and evaluation of an ion‐imprinted azo‐functionalized phenolic resin for selective extraction of Ni²⁺ ions from aqueous media. The azo‐containing ligand was first synthesized by coupling of a p‐aminophenol diazonium salt with resorcinol. The ligand was coordinated with Ni²⁺ ion template before condensation polymerization with formaldehyde and resorcinol was performed. The Ni²⁺ ions were extracted from the crosslinked resin matrix to finally afford the Ni²⁺ ion‐imprinted Ni‐PARF adsorbent. The synthetic steps were extensively investigated using elemental analysis and Fourier transform infrared, NMR and energy‐dispersive X‐ray spectroscopies. Also, the surface morphologies along with the surface areas of the adsorbent resin were evaluated using scanning electron microscopy and Brunauer–Emmett–Teller techniques, respectively. Batch experiments indicated that the pseudo‐second‐order kinetic equation provided the best fit with the experimentally obtained kinetic data and equilibrium was reached after 40 min. The isotherm studies were also in a good fit with the Langmuir model and the maximum adsorption capacities of Ni²⁺ ions with respect to both Ni‐PARF and control non‐imprinted C‐PARF adsorbents were around 260 and 100 mg g^?1, respectively. In the presence of Co²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ as competing coexisting ions, the relative selectivity coefficients of Ni‐PARF for Ni²⁺ were, respectively, 84.91, 44.97, 30.41 and 32.20. Regeneration experiments indicated that after eight adsorption/desorption cycles, the Ni‐PARF adsorbent still maintained around 97% of its initial efficiency. © 2018 Society of Chemical Industry     

Dynamic mechanical and Raman spectroscopy studies on interaction between single‐walled carbon nanotubes and natural rubber

The effects of the incorporation of single‐walled carbon nanotubes (SWNTs) on the physical and mechanical properties of natural rubber (NR) are described. Characterization of these new materials has been performed by dynamic mechanical analysis, differential scanning calorimetry, and Raman spectroscopy to obtain information about of the possible interactions between both materials as well as the dispersion of SWNTs on elastomer matrix. The results are then compared with those obtained for NR–carbon black composites. Dynamic mechanical analysis indicates a stronger filler–matrix interaction in the case of SWNTs incorporation, showing a noticeable decrease of the height of tan δ peak, as well as a marked shift of T_g towards higher temperatures. In particular, the increase of the storage modulus indicates a beneficial effect of SWNTs incorporation with respect to NR filled with carbon black and the pristine polymer matrix. In addition, calorimetric analysis indicates that both fillers accelerate the NR vulcanization reaction, this effect being more evident when SWNTs are added into the matrix. Raman spectroscopy indicates that SWNTs dispersion into the elastomer matrix creates residual strain on the nanotubes bundle. We demonstrate that the Raman microprobe technique provides a means for load transfer effectiveness of SWNTs. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3394–3400, 2004     

Poly(trimethylene terephthalate‐block‐tetramethylene oxide) elastomer/single‐walled carbon nanotubes nanocomposites: Synthesis,structure, and properties

Nanocomposites based on poly(trimethylene terephthalate)‐block‐poly(tetramethylene oxide) (PTT‐PTMO)‐segmented copolymer and COOH‐functionalized single‐walled carbon nanotubes (SWCNTs) were prepared by in situ polymerization method. The obtained nanocomposites were characterized by thermogravimetric analysis, scanning electron microscopy, differential scanning calorimetry (DSC), DMTA, wide‐angle x‐ray scattering (WAXS), small‐angle X‐ray scattering, and tensile testing. The nanocomposites with low SWCNTs loading (<0.5 wt %) shows uniform dispersion of CNT in polymer matrix. As the SWCNTs loading in the nanocomposites increase, the significant improvement of thermo‐oxidative stability was observed. It was found that the nanocomposites have slightly higher degree of crystallinity (determined by DSC and WAXS) of poly(trimethylene terephthalate) (PTT) hard phase than neat PTT‐PTMO copolymer. The melting point of PTT hard phase and glass transition temperature of poly(tetramethylene oxide)‐rich phase were not affected by the presence of CNTs in polymer matrix. The SWCNTs played a role as nucleating agent in PTT‐PTMO matrix, which led to increase in the crystallization rate. Tensile tests showed that the tensile strength of the nanocomposites with 0.05–0.3 wt % loading of SWCNTs have improved tensile strength in comparison to the neat PTT‐PTMO copolymer without reduction elongation at break. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis, characterization and ion-exchange properties of a fibrous type ‘polymeric-inorganic’ composite cation-exchanger Nylon-6,6 Sn(IV) phosphate: Its application in making Hg(II) selective membrane electrode

A polymeric-inorganic composite cation-exchanger, i.e. Nylon-6,6 Sn(IV) phosphate was synthesized via mixing of polymer Nylon-6,6 into the matrices of inorganic precipitate of Sn(IV) phosphate to form composite cation-exchanger. Ion-exchange capacity (IEC), ion-exchange properties, thermal stability and distribution behavior, etc. were also carried out to understand the cation-exchange behavior of the material. The physico-chemical properties of the material were determined using AAS, CHN elemental analysis, FTIR, TGA-DTA, XRD, and SEM studies. On the basis of distribution studies, the material was found to be highly selective for Hg(II), a highly toxic environmental pollutant. Using this electroactive composite material, a new heterogeneous precipitate based selective membrane electrode was fabricated for the determination of Hg(II) ions in solutions. The membrane electrode is mechanically stable, with a quick response time, and can be operated within a wide pH range. The selectivity coefficients for different cations determined by mixed solution method were found to be less than unity. The electrode was also found to be satisfactory in potentiometric titrations.     

Optical and vibrational studies on single walled carbon nanotubes/short oligo‐para‐methoxy‐toluene composite

In a solution state, an oligophenylene prepared by electrochemical oxidation of para‐methoxy‐toluene exhibited luminescence in the violet‐to‐blue region. However, in a solid state, a clear red shift was observed as a signature of a supramolecular π‐stacking interaction between oligomer chains. In a de‐doped state, by chemical reduction, a fine structure in the form of two peaks was observed and luminescence intensity was strongly improved. When mixed with single walled carbon nanotubes (SWNTs), a quenching in the luminescence intensity accompanied by a slight blue shift of the PL peak of the nanocomposite was observed. This implies the shortening of the oligomer's effective π‐conjugation length caused by the added amount of SWNTs. A charge transfer in the photo‐excited state was also noted. The interaction taking place between the two materials was supported by optical infrared absorption and Raman scattering measurements and then a functionalizing mechanism was proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of pH and temperature on the ion‐exchange isotherm of Cd(II) and Pb(II) on clinoptilolite

The ion‐exchange equilibrium of Pb(II) and Cd(II) on clinoptilolite from different deposits was studied in this work. The Langmuir isotherm fitted the ion‐exchange equilibrium data of both ions better than the Freundlich isotherm. The capacity of the natural zeolite to exchange Cd(II) and Pb(II) increased, augmenting the solution pH. This behaviour was attributed to the interactions between the ions in solution and the surface charge of the zeolite. Moreover, the capacity of the natural zeolite to exchange Cd(II) and Pb(II) was increased when the temperature was raised from 15 to 35 °C. This tendency was explained by assuming that the ion exchange was an endothermic reaction. The selectivity of the zeolite for the metal cations decreased in the following order: Pb(II) > Cd(II). This order was not modified while reducing the solution pH, but the zeolite selectivity was increased. At pH 2 the selectivity of the zeolite for Pb(II) was nearly three times larger than at pH 4. Copyright © 2006 Society of Chemical Industry     

Improving the thermal and mechanical properties of poly(vinyl butyral) through the incorporation of acid‐treated single‐walled carbon nanotubes

In this study, to investigate the effect of functionalized carbon nanotubes on the thermal and mechanical properties of the poly(vinyl butyral) (PVB) resin, PVB/functionalized single‐walled carbon nanotube (f‐SWCNT) composites were fabricated by a solution casting method. The functionalized nanotubes were prepared by acid treatment. The formation of oxygen‐containing functional groups on the surface of the nanotubes was confirmed by Fourier transform infrared spectroscopy, energy‐dispersive X‐ray spectroscopy, and scanning electron microscopy (SEM) measurements. SEM analysis also showed that the nanotubes were dispersed well in the PVB matrix. The thermal stability of the composites were investigated with thermogravimetric analysis, and the results show better stability for PVB in the presence of a very low content of the f‐SWCNTs. The prepared composites exhibited a significant increase in the temperature of degradation at 50 wt % loss and also in the onset temperature and decomposition temperature at the maximum rate of weight loss of butyral degradation. A significant enhancement in the mechanical properties was also achieved for these prepared composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40481.     

Ion-exchange adsorption of copper(II) ions on functionalized single-wall carbon nanotubes immobilized on a glassy carbon electrode

The cation-exchange property of oxidatively treated carbon nanotubes (CNTs) is newly reported. Single-wall carbon nanotubes (SWNTs), which were oxidatively treated, were immobilized on a glassy carbon surface and, on this CNT-modified electrode, Cu(II) ions were spontaneously adsorbed and their redox waves electrochemically measured. It is suggested that the adsorption of the cationic Cu(II) ions occurs by their electrostatic interaction with the negatively charged carboxylic anions on the CNTs after the ion-exchange with protons. The surface coverage of the adsorbed Cu(II) ions depending on the dipping time, the amount of immobilized CNTs, and the Cu(II) concentration was estimated from the electrochemical chronocoulometric measurements. The effect of the ionic strength on the adsorption of the Cu(II) ions was investigated and the adsorption strengths of various alkali metal cations and protons were compared. It is hoped that this new cation-exchange property of CNT-modified electrodes may extend their range of electrochemical applications.     

Synthesis and characterization of highly dispersed multi‐walled carbon nanotubes/polyvinylpyrrolidone composite nanofibers for EMI shielding application

Multi‐walled carbon nanotubes (MWCNTs)/polyvinylpyrrolidone (PVP) composite nanofibers having varying amounts of MWCNTs were fabricated with an aim to investigate the potential of such nanofibers as an effective light weight electromagnetic interference (EMI) shielding material in the frequency range of 8.2–12.4 GHz (X‐band). The state of dispersion of MWCNTs in PVP matrix was studied by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The TEM and SEM analyses confirmed the presence of individual dispersion MWCNTs encapsulated within the electrospun nanofibers and showed MWCNTs/PVP composite nanofiber morphologies with diameters of 150–600 nm. Moreover, the MWCNTs/PVP composite nanofibers were characterized by X‐ray diffraction and Raman spectrophotometer. The thermal stability of composite nanofibers studied from thermogravimetric analysis was increased after addition of MWCNTs to PVP matrix. The EMI shielding efficiency of MWCNTs/PVP composite nanofibers increased up to 42 dB. The MWCNTs/PVP composite nanofibers developed in this study have benefits in being light weight and having effective EMI shielding performance and can be best candidates for a broad range of electronic applications. POLYM. COMPOS., 38:2026–2034, 2017. © 2016 Society of Plastics Engineers     

Investigation of the rheological,dynamic mechanical,and tensile properties of single‐walled carbon nanotubes reinforced poly(vinyl chloride)

Polymer nanocomposites consisting of single‐walled carbon nanotubes (SWCNTs) and poly(vinyl chloride) were prepared by casting technique. The complex viscosity increased with increasing SWCNTs content, and it had a percolation concentration threshold equal to 0.45 wt % of SWCNTs. The storage modulus, G′, increased with increasing either SWCNTs content or frequency. A gradual decrease in the terminal zone slope of G′ for the nanocomposites with increasing SWCNTs content may be explained by the fact that the nanotube–nanotube interactions will be dominant at higher CNTs content, and lead to the formation of the interconnected or network‐like structures of SWCNTs in the polymer nanocomposites. The rheological loss factor indicates two relaxation peaks at frequencies of 0.11 and 12.8 Hz due to the interaction between SWCNTs and polymer chains and glass transition, respectively. Dynamic mechanical properties were measured for the prepared composites. The results indicate that the storage modulus changes steadily, and the tanδ peaks are less intense for high SWCNTs content. Tensile tests were measured and depicted by an increase in the elastic modulus with increasing SWCNTs content, but it decreases for all composites as the testing temperature increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Heavy toxic metal ion exchange kinetics: Validation of ion exchange process on composite cation exchanger nylon 6,6 Zr(IV) phosphate

Nernst–Planck equation was applied to study the heavy metal ion exchange kinetics over the surface of nylon 6,6 Zr(IV) phosphate at various temperatures under particle diffusion controlled phenomena. Various useful ion exchange kinetic parameters such as self-diffusion coefficient (D_o), energy of activation (E_a), and entropy of activation (ΔS*) were evaluated to validate the ion exchange process for practical applicability of this composite cation exchanger in remediation processes of the environment. This study is also supported for the good selectivity of Cu(II) to validate the practical application of this cation exchanger in environmental analysis.     

Cation‐exchange kinetics and electrical conductivity studies of an ‘organic‐inorganic’ composite cation‐exchanger: Polypyrrole Th(IV) phosphate

Polypyrrole Th(IV) phosphate, an electrically conducting ‘organic‐inorganic’ cation‐exchange composite material was prepared by the incorporation of an electrically conducting polymer, i.e., polypyrrole, into the matrix of a fibrous type inorganic cation‐exchanger thorium(IV) phosphate. The composite cation‐exchanger has been of interest because of its good ion‐exchange capacity, higher chemical and thermal stability, and high selectivity for heavy metal ions. The temperature dependence of electrical conductivity of this composite system with increasing temperatures was measured on compressed pellets by using four‐in‐line‐probe dc electrical conductivity measuring instrument. The conductivity values lie in the semiconducting region, i.e., in the order of 10^?6 to 10^?4 S cm^?1 that follow the Arrhenius equation. Nernst–Plank equation has been applied to determine some kinetic parameters such as self‐diffusion coefficient (D₀), energy of activation (E_a), and entropy of activation (ΔS*) for Mg(II), Ca(II), Sr(II), Ba(II), Ni(II), Cu(II), Mn(II), and Zn(II) exchange with H⁺ at different temperatures on this composite material. These results are useful for predicting the ion‐exchange process occurring on the surface of this cation‐exchanger. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Facile way to disperse single‐walled carbon nanotubes using a noncovalent method and their reinforcing effect in poly(methyl methacrylate) composites

In this work, a noncovalent method was used to functionalize and thereby disperse single‐walled carbon nanotubes (SWCNTs) in dimethylformamide with poly[methyl methacrylate‐co‐(fluorescein O‐acrylate)] as a surfactant, and then the resultant poly(methyl methacrylate) (PMMA)‐based nanocomposites were fabricated via solution casting. The dispersion level of carbon nanotubes in the solvent was investigated by means of scanning electron microscopy and atomic force microscopy. The results showed that carbon nanotubes were well wrapped by the surfactant, and small carbon nanotube bundles several nanometers or less in diameter and several micrometers in length were obtained. Both scanning electron microscopy and transmission electron microscopy confirmed the uniform dispersion of SWCNTs in the PMMA matrix. The mechanical properties of the composites were determined with a universal tension tester. The PMMA composite containing 2 wt % SWCNTs showed improved tensile properties versus neat PMMA, showing 56 and 30% enhancements of the tensile modulus and tensile stress, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrochemical characterization and transport properties of polyvinyl chloride based carboxymethyl cellulose Ce(IV) molybdophosphate composite cation exchange membrane

The polyvinyl chloride (PVC) based carboxymethyl cellulose Ce(IV) molybdophosphate composite membrane are prepared and characterized by the Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Fourier transformed infrared (FTIR), and thermogravimetric analysis (TGA) studies. The inorganic–organic composite membrane was found to be crystalline in nature with consistent arrangement of particles and indicating no sign of visible cracks. The FTIR spectra verify the binding of organic polymer with inorganic component. The membrane was found to be cation-selective. The order of surface charge density for uni-univalent electrolytes solution was found to be KCl > NaCl > LiCl.     

Adsorption and electroanalytical studies of a poly‐o‐toluidine Zr(IV) phosphate nanocomposite for zinc(II) dimethyldithiocarbamate

The adsorption behavior of zinc(II) dimethyldithiocarbamate (Ziram) was studied on the surface of a poly‐o‐toluidine Zr(IV) phosphate nanocomposite cation exchanger. A spectrophotometric method based on the conversion of Ziram into a copper dimethyldithiocarbamate complex was applied for the study of Ziram at the maximum absorption wavelength of 437 nm. A Ziram‐ sensitive membrane electrode was fabricated with poly‐o‐toluidine Zr(IV) phosphate (an electroactive composite material). The sensitivity of Ziram for the composite cation‐exchange material was monitored with potentiometric methods. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis, characterization and the electrocatalytic behaviour of nickel (II) tetraamino-phthalocyanine chemically linked to single walled carbon nanotubes

In this work we report on the synthesis, characterization and the electrochemical behavior of amide linked nickel (II) tetraamino-phthalocyanine (NiTAPc)-single walled carbon nanotube (SWCNT) nanomaterials (NiTAPc-SWCNT (linked)). UV-vis, XRD, IR and Raman spectroscopies were used in characterization whilst cyclic voltammetry was used to study the electrochemical behavior of NiTAPc-SWCNT (linked)-GCE. Relative to the bare glassy carbon electrode (bare-GCE), SWCNT-GCE, NiTAPc-GCE, and NiTAPc/SWCNT (mixed)-GCE, the NiTAPc-SWCNT (linked)-GCE gave the best current responses for the oxidation of 2-mercaptoethanol (2-ME). The catalytic rate constant is of the magnitude of 10³ M⁻¹ s⁻¹ while the detection limit (LOD) is 0.15 μM using the 3δ notation, with a sensitivity of 2.53 μA μM⁻¹ cm⁻².     

Synthesis and application of ion‐imprinted resin based on modified melamine–thiourea for selective removal of Hg(II)

A novel Hg(II) ion‐imprinted resin based on thiourea‐modified melamine was manufactured for selective elimination of Hg²⁺ from aqueous solutions. The polymerizable thiourea–melamine ligand together with its Hg(II) complex were extensively investigated using elemental analysis, Fourier transform infrared (FTIR) and ¹H NMR spectroscopies. The Hg(II) complex was used in a condensation polymerization in the presence of formaldehyde crosslinker and then the Hg(II) ions were leached out from the crosslinked polymeric network to finally leave the ion‐imprinted Hg‐PMTF resin. Both ion‐imprinted Hg‐PMTF and non‐imprinted resins were examined utilizing scanning electron microscopy and FTIR spectroscopy. The potential of the prepared resin for selective separation of Hg(II) ions from aqueous solutions was then evaluated by performing a series of batch experiments. Hg‐PMTF displayed an obvious rapid removal of Hg(II) ions with a pseudo‐second‐order kinetic pattern. In addition, the Langmuir adsorption isotherm model exhibited the best fit with the experimental data with comparatively high maximum adsorption capacity (360.5 mg g^?1). © 2015 Society of Chemical Industry     

Electrical conductivity and tensile properties of block‐copolymer‐wrapped single‐walled carbon nanotube/poly(methyl methacrylate) composites

Poly(methyl methacrylate) (PMMA) composites containing raw or purified single‐walled carbon nanotubes (SWCNTs) are prepared by in situ polymerization and solution processing. The SWCNTs are purified by centrifugation in a Pluronic surfactant, which consists of polyethyleneoxide and polypropyleneoxide blocks. Both the effects of SWCNT purity and non‐covalent functionalization with Pluronic are evaluated. Electrical conductivity of PMMA increases by 7 orders of magnitude upon the integration of raw or purified SWCNTs. The best electrical properties are measured for composites made of purified SWCNTs and prepared by in situ polymerization. Strains at fracture of the SWCNT/PMMA composites are nearly identical to those of the neat matrix. A certain decrease in the work to fracture is measured, particularly for composites containing purified SWCNTs (?31.6%). Fractography and Raman maps indicate that SWCNT dispersion in the PMMA matrix improves upon the direct addition of Pluronic, while dispersion becomes more difficult in the case of purified SWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41547.     

Sol–gel synthesis,physicochemical characterization,and analytical applications of copper selective composite cation exchanger: Polyvinyl alcohol Ce(IV) phosphate

An organic–inorganic composite cation exchanger polyvinyl alcohol Ce(IV) phosphate was prepared by the sol–gel method. The composite cation exchanger was characterized by some physicochemical properties like FTIR, TGA/DTA/DTG, XRD, SEM, TEM, EDX, and ion exchange properties to validate the structure and the ion exchange behavior. Ion exchange parameters indicated that the composite material is suitable for column operation. The ion exchange capacity of the composite ion exchanger is higher than that of the inorganic counterpart which showed that the incorporation of organic polymer polyvinyl alcohol (PVA) is responsible for prevention of the leaching of inorganic ion exchanger thereby proving mechanical stability and enhanced ion exchange properties. The distribution studies showed the selectivity toward Cu(II) ions, a heavy toxic metal ion. It was also observed that the selectivity depended upon the nature and composition of contacting solvents. The binary separation of a mixture of heavy metal ions Cu(II)–Zn(II), Cu(II)–Cd(II), and Cu(II)–Ni(II) also achieved thus composite cation exchanger proved excellent material could be effectively utilized in the treatment of discharge from copper plating, copper alloy, copper batteries, and smelting industries, whereas outstanding thermal stability of this composite ion exchanger could be utilized for the treatment of wastewater having Cu(II) ions with high temperature such as power generation and desalination plants. This composite ion exchanger with outstanding properties have potential to deal with aquatic toxicology caused by Cu(II) ions in future. POLYM. COMPOS., 38:332–340, 2017. © 2015 Society of Plastics Engineers