Aqueous suspension of carbon nanotubes via non-covalent functionalization with oligothiophene-terminated poly(ethylene glycol)

A new polymeric amphiphilic molecule for dispersing carbon nanotubes (CNTs) in water, oligothiophene-terminated poly(ethylene glycol) (TN-PEG), was synthesized and its ability to stabilize aqueous CNT dispersions was examined by UV-Vis spectroscopy and transmission electron microscopy. It was observed that the TN-PEGs were strongly adsorbed onto the nanotube surface via a strong π-π interaction, and thus only gentle sonication causes exfoliation of CNT ropes and bundles into well-separated individual objects and small bundles comprising 2-10 tubes. The dispersion ability of the TN-PEGs and the long-term stability of their resulting dispersions were much better than commercial surfactants.     

Towards optimization of functionalized single-walled carbon nanotubes adhering with poly(3-hexylthiophene) for highly efficient polymer solar cells

In this paper, we present the optimization of single-walled carbon nanotubes (SWCNTs) by acid-treatment, solution ultrasonication time and dispersion in photoactive layer for efficient organic solar cells. After non-covalently adhering with poly(3-hexylthiophene) (P3HT), pre-functionalized SWCNTs were blended into the composites of P3HT and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as photoactive layer, and a maximum power conversion efficiency (PCE) of 3.02% with a short-circuit current density of 11.46 mA/cm² was obtained from photovoltaic cell indium-tin oxide (ITO)/poly(ethylene-dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM:SWCNTs/Al with an optimum 0.3 wt% SWCNTs in P3HT:PCBM:SWCNTs nanocomposite, the PCE can be enhanced by more than 10% as compared to the control device ITO/PEDOT:PSS/P3HT:PCBM/Al. The performance improvement by incorporating with functionalized SWCNTs is mainly attributed to the extension of excitons dissociation area and fastening charge carriers transfer across the active layer.     

Preparation and properties of single-walled carbon nanotubes/poly(butylene terephthalate) nanocomposites

A neat poly(butylene terephthalate) (PBT) polymer and functionalized single-walled carbon nanotubes (F-SWNTs)/PBT nanocomposite films were prepared by solution casting technique. The SWNTs were functionalized by acid treatment, which introduced carboxylic groups onto the SWNTs. The morphological studies showed that the F-SWNTs were embedded and dispersed well within the PBT polymer matrix. The POM study illustrated that a neat PBT showed Maltese-type spherulites. It was also observed that the size of neat PBT spherulites was larger than F-SWNTs/PBT nanocomposite spherulites, which might be due to the nucleation effect of F-SWNTs in the case of nanocomposites. The thermal stabilities and mechanical properties such as stress yield and moduli of F-SWNTs/PBT nanocomposites were enhanced as compared to neat PBT. The DSC study showed that the melting temperature (T _m) of PBT was slightly increased by addition of F-SWNTs. This increase in T _m might be due to the formation of compact structure, which was formed through different types of molecular interactions with addition of F-SWNTs. It was also found that initially the solvent (distilled water, kerosene, 2 M HNO₃ solution) uptake by neat PBT polymer and its nanocomposites increased gradually, which became steady after specific intervals for each sample. The results also exhibited that the solvent uptake of F-SWNTs/PBT nanocomposites was less than neat PBT.     

One-pot purification and functionalization of single-walled carbon nanotubes in less-corrosive poly(phosphoric acid)

As-received commercial single-walled carbon nanotubes (SWCNTs) were treated in mild, inorganic polyacid, viz. polyphosphoric acid (PPA) with or without additional phosphorous pentoxide (P₂O₅) at 130, 160, and 190 °C. Unlike the treatment in strong acids such as nitric acid/sulfuric acid mixtures, nitric acid and hydrochloric acid, PPA with or without additional P₂O₅ could selectively remove the tenacious carbonaceous and metallic impurities with little or no damage to the basic frameworks of SWCNTs and crystalline carbon materials. Since the medium PPA/P₂O₅ is known for an efficient “direct” Friedel-Crafts acylation using a carboxylic acid instead of a carboxylic acid chloride, it provides the advantage of combining both purification and functionalization steps into a one-pot process in manufacturing of functionalized SWCNTs.     

Enhanced mechanical and electrical properties of carbon fiber/poly(ether ether ketone) laminates via inserting carbon nanotubes interleaves

The carbon fiber/(carbon nanotubes/polyetherimide)/poly ether ether ketone (CF/(CNTs/PEI)/PEEK) laminates are prepared by inserting carbon nanotubes/polyetherimide (CNTs/PEI) interleaves into interlaminar region. The mechanical properties and electrical conductivities of the developed laminates are evaluated. The results indicate that the interlaminar shear strength and flexural strength of CF/(CNTs/PEI)/PEEK laminates are increased by 42.9% and 24.7%, after inserting CNTs2.91/PEI interleaves, respectively. The cross-sectional images of laminates after mechanical tests verify strong fiber-resin adhesion by scanning electron microscope observation. The pertinent mechanism responsible for the improvement of mechanical properties is mechanical interlocking effect of CNTs. After incorporating CNTs/PEI interleaves, the electrical conductivity of laminates is markedly improved due to the formation of conductive pathway. This work suggests that this method is compatible with the preparation process of thermoplastic composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48658.     

Preparation and characterization of poly(styrene-co-butyl acrylate)-encapsulated single-walled carbon nanotubes under ultrasonic irradiation

Polymeric composite materials filled with single-walled carbon nanotubes (SWNTs) have attracted much attention, but successful applications of such composites require uniform dispersion of SWNTs in the polymeric matrix and the strong SWNTs-polymer interface interaction. In this paper, chemical modification combined with ultrasonically initiated in situ polymerization was successfully employed to prepare poly(styrene-co-butyl acrylate)/single-walled carbon nanotubes composites [P(St-BA)/SWNTs]. The whole procedure contained two steps: in the first step, 3-(trimethoxy)-propylmethacrylate-silane (silane-coupling agent, KH570), a kind of polymerizable vinyl monomer, was grafted onto the surface of SWNTs, forming KH570-g-SWNTs by reacting KH570 with hydroxyl groups on the surface of SWNTs, which was proved by combination of FTIR and XPS results. Due to the presence of polymerizable KH570 on the surface of SWNTs, this provides a basis for the next stage of polymerization to prepare polymer-encapsulated SWNTs composites. In the second step, an ultrasonically initiated in situ emulsion polymerization of monomer styrene (St) and n-butyl acrylate (BA) proceeded in the presence of KH570-g-SWNTs. Consequently, P(St-BA)/SWNTs composite emulsion was obtained. TEM confirmed that SWNTs were coated with the obtained polymer. FTIR and XPS further showed that even after 72 h of soxhlet extraction with boiling toluene, there were still unextracted polymers in P(St-BA)/SWNTs composite, indicating strong interaction between the polymer and carbon nanotubes. Finally, a mechanism for formation of polymer-encapsulated SWNTs through ultrasonically initiated in situ emulsion polymerization was proposed. This study could provide a new way to resolve the problems of the dispersion, stabilization, and compositing of SWNTs with polymer matrix and prepare polymer/SWNTs composites.     

Grafting of poly(acrylic acid) onto polyethylene filament and its distribution

Radiation-induced simultaneous grafting of acrylic acid onto high density polyethylene filament is carried out with aqueous solution of acrylic acid in the absence and presence of ethylene dichloride. Distribution of grafted poly(acrylic acid) is studied by two methods. One is optical microscopic investigation of cross sections of dyed filament, and the other is electron probe microscopy of acrylic acid graft filament after conversion to calcium acrylate. Qualitative study with WAXS is also carried out. Grafting begins from the surface or periphery and proceeds, with sharp boundary, to the core. The reaction takes place only in the amorphous part of polyethylene. The percent graft in the grafted part is homogeneous and rather high from the beginning of the reaction; it is true that additional grafting to the already grafted part takes place, but it is not so noticeable.     

Synthetic method of polyethylene-poly(methylmethacrylate) (PE-PMMA) polymer hybrid via reversible addition-fragmentation chain transfer (RAFT) polymerization with functionalized polyethylene

Summary Polyethylene-poly(methylmethacrylate) (PE-PMMA) polymer hybrid was synthesized via RAFT polymerization of MMA with PE chain transfer agent (PE-CTA) for the first time. The structure of PE-CTA produced by sequential functionalization of terminally hydroxylated PE was confirmed by ¹H NMR and FT-IR analyses. The results of GPC after MMA polymerization revealed that the molecular weight (M_w) of the resulting polymers increased compared with the one of the PE-CTA. ¹H NMR analysis of resulting polymers confirmed that the amounts of PMMA segments were in a range of 7.8 and 23 wt %. TEM images indicated the nanometer level microphase-separation morphology between the PE segment and PMMA segment.     

Electrically conductive carbon black (CB) filled in situ microfibrillar poly(ethylene terephthalate) (PET)/polyethylene (PE) composite with a selective CB distribution

In the present study, it was attempted to fabricate a new conductive carbon black (CB) filled poly(ethylene terephthalate) (PET)/polyethylene (PE) in situ microfibrillar composite with a lower percolation threshold through selectively localizing CB particles in the surfaces of the PET microfibrils. The CB particles were first mixed with PE matrix, and then PET was added into CB/PE compound. Subsequently, the CB/PET/PE composite was subjected to a slit die extrusion, hot stretch and quenching process to generate in situ PET microfibrils, in which CB particles moved to the surfaces of the PET microfibrils simultaneously. The morphological observation showed that the PET phases formed well-defined microfibrils, and CB particles did overwhelmingly localize in the surfaces of the PET microfibrils, which led to a very low percolation threshold, i.e., 3.8 vol%, and a good conductivity. The conductive network was built by the contact and overlapping of the CB particles coated PET microfibrils. In addition, the CB particles remaining in the PE matrix also contributed to the conductive paths, especially for the high CB loading filled microfibrillar composites. Because of the complexity of the distribution of CB particles, a high critical resistance exponent t (t = 6.4) exists in this conductive composite. To reveal the possibility of the migration of CB particles from PE to PET, the morphology of the CB/PET/PE composite mixed for different times was examined. It was found that, depending on the mixing time, the CB particles gradually migrated from the PE matrix to the surfaces at first, and then to the center of the PET phases. The preferable distribution of CB particles was originated from several factors including interfacial tension, viscosity, molecule polarity, and mixing process. Furthermore, during the mixing process of the CB/PET/PE composite, the migration of CB particles to PET phase from PE matrix led to the increase of both the viscosity ratio of the dispersed phase to the matrix and the volume of the dispersed phases, thus resulting in larger dispersed CB/PET composite phase particles.     

Synthesis of hybrid TiO2 nanoparticles with well-defined poly(methyl methacrylate) and poly(tert-butyldimethylsilyl methacrylate) via the RAFT process

Surface of titania nanoparticles (TiO₂) was modified by a coupling agent as 3-(trimethoxysilyl)propyl methacrylate (MPS) to form TiO₂-MPS polymerizable particles. Methyl methacrylate (MMA) and tert-butyldimethylsilyl methacrylate (MASi) were radically polymerized through the immobilized vinyl bond on the surface in the presence of the reversible addition-fragmentation chain transfer (RAFT) agent 2-cyanoprop-2-yl dithiobenzoate using 2,2′-azobisisobutylnitrile (AIBN) as an initiator. FTIR spectroscopy confirmed the presence of the coupling molecule and the methacrylate groups on the surface. Thermogravimetric analysis and elemental analysis revealed a surface coverage of the coupling molecule of 2.0 wt%. TGA measurements showed that grafted PMMA and PMASi were accounted for 10% and 4.8% of the particle mass, respectively. ¹H NMR and SEC were used to verify the livingness of the polymerization. Transmission electron microscopy (TEM) was used to study the morphology of the particles before and after the surface grafting.     

Preparation and shear properties of carbon nanotubes/poly(butyl methacrylate) hybrid material

Composites containing carbon nanotubes (CNTs) in a poly(butyl methacrylate) (PBMA) have been prepared by in situ polymerization. Scanning electron microscopy and high‐resolution transmission electron microscope showed that CNTs were well dispersed into PBMA matrix and wrapped with PBMA. The infrared spectrum illustrated that CNTs were covalently linked with PBMA through a C C bond. Owing to this covalent linkage, the composites had a better solubility in organic solvents and had higher thermal stability over pure PBMA. The direct shear testing showed strong mechanical behavior with up to 200% increase in Young's modulus. The possible strengthening mechanism was discussed. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Enhanced Zn(II) uptake using zinc imprinted form of novel nanobiosorbent and its application as an antimicrobial agent

We investigated the use of zinc imprinted of novel nanobiosorbent prepared from Candida rugosa to remove Zn(II) from aqueous solution. The nanobiosorbent was characterized by SEM, FTIR and XRD. Effects of various parameters including pH of the solution, adsorbent dosage, initial Zn(II) ion concentration and contact time on Zn(II) removal by the nanobiosorbents were investigated through batch process. Equilibrium data for Zn(II) removal was fitted to Langmuir isotherm model with an enhanced adsorption capacity of 275.48mg/g for zinc imprinted C. rugosa nanobiosorbent, compared to nonimprinted nanobiosorbent of 172.41 mg/g. Pseudo-second-order kinetic model was best fitted to predict the sorption kinetics for both the nanobiosorbents. AFM study revealed monolayer adsorption with thin film diffusion for Zn(II) removal. The antimicrobial activity of zinc imprinted nanobiosorbent was investigated against pathogenic yeasts viz. Candida albicans and Cryptococcus neoformans using agar well diffusion method.     

Analysis of energy transfer and ternary non-covalent filler/matrix/UV stabilizer interactions in carbon nanofiber and oxidized carbon nanofiber filled poly(methyl methacrylate) composites

Ternary non-covalent interactions between carbon nanofibers (CNFs), oxidized carbon nanofibers (ox-CNFs), poly(methyl methacrylate) (PMMA) chains, and benzotriazole-containing UV stabilizers were analyzed using Fourier-transform infra red spectroscopy (FTIR), time-resolved fluorescence emission spectroscopy, and fluorescence lifetime imaging microscopy. The results indicated that PMMA chains form hydrogen bonds both with ox-CNF fibers and the UV stabilizer molecules. It was also determined that UV stabilizers strongly interact with CNF particles via π-π interactions. The extent of π-π and hydrogen bonding interactions was determined to be lower between ox-CNF particles and UV stabilizers due to less perfect graphitic structure of the former. The morphology of the composites indicated that the hydrogen bonds between PMMA chains and ox-CNF particles resulted in highly improved state of filler dispersion in ox-CNF/PMMA composites.     

Noncovalent hybrid of CoMn2O4 spinel nanocrystals and poly (diallyldimethylammonium chloride) functionalized carbon nanotubes as efficient electrocatalysts for oxygen reduction reaction

We have grown CoMn₂O₄ spinel nanocrystals on poly (diallyldimethylammonium chloride) functionalized carbon nanotubes (PDDA-CNTs) by noncovalent functionalization and solvothermal techniques. PDDA plays an important role in homogeneously increasing the surface density of available functional groups, which can provide active sites for decoration of CoMn₂O₄ on CNTs. In addition, PDDA preserves the intrinsic properties of CNTs, increases the active sites of catalysts, and enhances the durability of the catalysts. Here, CoMn₂O₄ nanocrystals were uniformly deposited on PDDA-CNTs with loading amounts from 36% to 83%. The as-prepared CoMn₂O₄/PDDA-CNT catalyst showed high current densities for the oxygen reduction reaction (ORR) in alkaline and neutral conditions, which outperformed the Co₃O₄/PDDA-CNT and Pt/C catalysts at medium overpotential, mainly through a 4e reduction pathway. The obtained CoMn₂O₄/PDDA-CNT hybrid exhibited excellent activity and durability when subjected to an oxygen evolution reaction. These results indicate that the CoMn₂O₄/PDDA-CNT hybrid represents a promising alternative to Pt for ORR electrocatalysis, and this non-precious bifunctional electrocatalyst provides a corrosion resistant and protective cathode layer to fuel cells. The excellent activity and stability of the hybrid materials demonstrate the potential of noncovalent coupling inorganic/carbon composites as novel catalytic systems for lithium–air batteries and chlor-alkali production.     

Hybrid gas sensor based on platinum nanoparticles/poly(methyl methacrylate)-coated single-walled carbon nanotubes for dichloromethane detection with a high response magnitude

A dichloromethane (DCM) sensor with a high response magnitude was successfully fabricated using the integration of single-walled carbon nanotubes (SWNTs), poly(methyl methacrylate) (PMMA) and platinum nanoparticles (Pt NPs). A pristine SWNT network was first formed by drop-casting onto printed circuit board (PCB) substrates. Next, PMMA was coated onto the pre-dropped SWNT network by spin coating using a PMMA-toluene solution, followed by the deposition of Pt NPs by electron-beam evaporation (hereafter referred to as Pt/PMMA/SWNT). The Pt/PMMA/SWNT enabled an approximately 69-fold improvement in DCM detection compared to pristine SWNT. The high response magnitude of the Pt/PMMA/SWNT was successfully achieved because of the incorporation of PMMA and Pt functions. Swelling of the PMMA matrix as a result of DCM adsorption leads to PMMA volume expansion, thereby increasing the SWNT-SWNT distance, which results in an increase in the resistance. Pt NPs promote the dissociation of DCM to CO, and consequently the CO oxidation on the Pt NPs catalyst and electron donation from Pt NPs to SWNTs, resulting in an increase in the resistance. Moreover, a linear relationship was obtained between the sensor response of the Pt/PMMA/SWNT and the concentration of DCM. These results suggest that the integration of SWNTs with PMMA and Pt NPs is a promising approach for improving DCM detection at room temperature.     

Shape memory effect of poly(methylene‐1,3‐cyclopentane) and its copolymer with polyethylene

Poly(methylene‐1,3‐cyclopentane) (PMCP) cyclopolymerized from 1,5‐hexadiene by metallocene catalyst, rac‐(ethylenebis(1‐indenyl))Zr(N(CH₃)₂)₂ is partially crystalline and has a value of elongation at break of more than 400% in the temperature range 25–85 °C. The shape memory effect of PMCP with moderate molecular weight is enhanced by sequentially polymerized polyethylene segments, the crystalline phase of which seems to strengthen the fixed structure which memorizes the original shape. The glass transition temperature or melting temperature of PMCP can be selectively used as shape recovery temperature when an appropriate deformation temperature is chosen. © 2002 Society of Chemical Industry     

Shape memory effects of poly(L-lactide) and its copolymer with poly(ε-caprolactone)

Summary The thermal properties, crystalline structure and shape memory effects of poly(L-lactide) (PLLA) and its copolymer with poly(ε-caprolactone) (PCL) are systematically investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tensile tests. The influences of composition and intrinsic viscosity on structure and shape memory effects are also revealed. It is found that the PLLA homopolymer and poly(L-lactide-co-ε-caprolactone) (PCLA) copolymers exhibit good shape memory effects. The existence of PLLA crystal and amorphous phase play very important roles for shape memory effects. The intrinsic viscosity obviously affects the crystallinity of polymers and further affects the shape memory effects. The shape recovery rate decreases with increasing deformation strain, which is relate to the deformation of PLLA crystal. The recovery stress increase with the increase of the ε-CL content and maximum recovery stress is 3.54MPa obtained in the PCLA804 (20wt% ε-CL content, M_w=304,400). With the increase of cyclic testing number, the shape recovery rates decrease and the shape retention rates increase at the beginning and then approach to a steady value.     

Enhanced solubility of novel poly(benzoxazole)s with a soft linkage and a rigid pendant group

Aromatic poly(benzoxazole)s are a class of rigid‐rod conjugated polymers. However, their poor solubility in organic solvents limits potential applications. Thus, a good method that can address this dilemma is needed, given that existing methods involve models with either poor solubility but good thermal stability or good solubility but poor thermal stability. In this paper we report a novel aromatic poly(benzoxazole) with a soft linkage and a rigid pendant group. Structural characterizations of the polymers via Fourier transform infrared and proton nuclear magnetic resonance spectroscopy reveal the formation of a benzoxazole ring and an imide ring. The introduction of rigid pendant groups improved the solubility and enhanced the thermal stability of the polymer, which was impaired by the incorporation of the soft linkage. Most of these polymers are soluble at room temperature or when heated in dimethyl sulfoxide, N,N‐dimethylformamide or N,N‐dimethylacetamide. Some polymers can even be dissolved in m‐cresol and tetrahydrofuran. A 10% weight loss in these polymers was observed at temperatures over 410 °C. Moreover, the incorporation of the imide pendant group increased the conjugation length of the polymer structural unit and accelerated electron delocalization. Copyright © 2012 Society of Chemical Industry     

Morphology and electrical properties of short carbon fiber-filled polymer blends: High-density polyethylene/poly(methyl methacrylate)

Morphology and electrical properties of short carbon fiber-filled high-density polyethylene (HDPE)/poly(methyl methacrylate)(PMMA) polymer blends have been studied. The percolation threshold of HDPE50/PMMA50 blends filled with vapor-grown carbon fiber (VGCF), 1.25 phr VGCF content, is much lower than those of the individual polymers. The SEM micrographs verified that the enhancement of conductivity could be attributed to the selective location of VGCF in the HDPE phase. A double percolation is the basic requirement for the conductivity of the composites, i.e., the percolation of carbon fibers in the HDPE phase and the continuity of this phase in the blends, which hereby are defined as the first percolation and the second percolation, respectively. The SEM micrographs also showed that the short carbon fibers could affect the morphology of the blends. With the increase of VGCF content, the HDPE domains are elongated from spherical into strip shape, finally develop to a continuous structure. As a result, the second percolation threshold of the blends filled with 2.5 phr VGCF, 20 wt % HDPE, is lower than that of the blends filled with 1.5 phr VGCF, 30 wt % HDPE. The influence of molding temperature and time on the second percolation threshold has also been investigated. For the composites molded at a lower temperature, the second percolation threshold is shifted to a higher VGCF content, but there is little influence of molding time on the second percolation threshold. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1813–1819, 1998     

Reusable magnetic nanocluster coated with poly(acrylic acid) and its adsorption with an antibody and an antigen

The synthesis of negatively charged magnetite nanoclusters grafted with poly(acrylic acid) (PAA) and their application as reusable nanosupports for adsorption with antibodies and antigens are presented in this article. They were facilely prepared via the free‐radical polymerization of PAA in the presence of functionalized magnetite nanoparticles to obtain highly negative charged nanoclusters with a high magnetic responsiveness and good dispersibility and stability in water. According to transmission electron microscopy, the sizes of the nanoclusters ranged between 200 and 500 nm, without large aggregation visually observed in water. The hydrodynamic size of the nanocluster consistently increased with increasing pH of the dispersion; this indicated its pH‐responsive properties, which was due to the repulsion of the anionic carboxylate groups in the structure. This nanocluster was successfully used as an efficient and reusable support for adsorption with anti–horseradish peroxidase antibody. It preserved higher than a 97% adsorption ability of the antibody after eight reuse cycles; this signified the potential of this novel nanocluster as a reusable support in the magnetic separation applications of other bioentities. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46160.