Efficient Load Transfer to Polymer‐Grafted Multiwalled Carbon Nanotubes in Polymer Composites

Multiwalled carbon nanotubes (MWNTs) grafted with poly(methyl methacrylate) (PMMA) were synthesized by emulsion reactions and used as a reinforcement for commercial PMMA. Both scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the applied tensile load on the composites was transferred to the PMMA‐grafted MWNTs, leading to a strain failure of the MWNTs rather than an adhesive failure between the MWNTs and the matrix. Dynamic mechanical analysis (DMA) data showed that the storage modulus at 20 °C of the PMMA composite containing 20 wt.‐% of the PMMA‐grafted MWNTs was significantly enhanced by ～ 29 GPa (or by ～ 1100 %) as compared with commercial PMMA.     

Transparent Poly(methyl methacrylate)/Single‐Walled Carbon Nanotube (PMMA/SWNT) Composite Films with Increased Dielectric Constants

Poly(methyl methacrylate)/single‐walled carbon nanotube (PMMA/SWNT) composites were prepared via in situ polymerization induced either by heat, ultraviolet (UV) light, or ionizing (gamma) radiation. The composites dissolved in methylene chloride and then cast into films exhibited enhanced transparency as compared with the melt‐blended composite material. UV/visible spectroscopy was used to quantitatively analyze the transparency of the composites. The dielectric constant (ε′) was measured via dielectric analysis (DEA) and correlated to the refractive‐index values using Maxwell's relationship. The dielectric constant increased in the composite samples as compared with the neat PMMA samples prepared by the same methods. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) provided images of the polymer–nanotube composites and single‐walled CNTs, respectively.     

Synthesis of Poly(4‐vinylpyridine) Thin Films by Initiated Chemical Vapor Deposition (iCVD) for Selective Nanotrench‐Based Sensing of Nitroaromatics

A new nanoscale sensing concept for the detection of nitroaromatic explosives is described. The design consists of nitroaromatic‐selective polymeric layers deposited inside microfabricated trenches. As the layers are exposed to nitroaromatic vapors, they swell and contact each other to close an electrical circuit. The nitroaromatic selective polymer, poly(4‐vinylpyridine) (P4VP), is deposited in the trenches using initiated chemical vapor deposition (iCVD). P4VP is characterized for the first time as a selective layer for the absorption of nitroaromatic vapors. The Flory–Huggins equation is used to model the swelling response to nitroaromatic vapors. The Flory–Huggins interaction parameter for the P4VP–nitrobenzene system at 40 °C is 0.71 and 0.25 for P4VP–4‐nitrotoluene at 60 °C. Sensing of nitrobenzene vapors is demonstrated in a prototype device, while techniques to improve the performance of the design in terms of response time and sensitivities are described. Modeling shows that concentration and mass limits of detection of 0.95 ppb and 3 fg, respectively, can be achieved.     

Poly(ϵ‐caprolactone)‐Functionalized Carbon Nanotubes and Their Biodegradation Properties

Biodegradable poly(?‐caprolactone) (PCL) has been covalently grafted onto the surfaces of multiwalled carbon nanotubes (MWNTs) by the “grafting from” approach based on in‐situ ring‐opening polymerization of ?‐caprolactone. The grafted PCL content can be controlled easily by adjusting the feed ratio of monomer to MWNT‐supported macroinitiators (MWNT‐OH). The resulting products have been characterized with Fourier‐transform IR (FTIR), NMR, and Raman spectroscopies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM). After PCL was coated onto MWNT surfaces, core/shell structures with nanotubes as the “hard” core and the hairy polymer layer as the “soft” shell are formed, especially for MWNTs coated with a high density of polymer chains. Such a polymer shell promises good solubility/dispersibility of the MWNT–PCL nanohybrids in low‐boiling‐point organic solvents such as chloroform and tetrahydrofuran. Biodegradation experiments have shown that the PCL grafted onto MWNTs can be completely enzymatically degraded within 4 days in a phosphate buffer solution in the presence of pseudomonas (PS) lipase, and the carbon nanotubes retain their tubelike morphologies, as observed by SEM and TEM. The results present possible applications for these biocompatible PCL‐functionalized CNTs in bionanomaterials, biomedicine, and artificial bones.     

Mechanical Properties of Functionalized Single‐Walled Carbon‐Nanotube/Poly(vinyl alcohol) Nanocomposites

Nanocomposites based on semi‐crystalline poly(vinyl alcohol) (PVA) and well‐dispersed chemically functionalized single‐walled carbon nanotubes are combined through simple mixing. The interaction between the nanotubes and the polymer matrix is studied using optical and thermal methods. Significant enhancement of the mechanical properties is obtained for the functionalized‐nanotube‐based composites. These results imply that promoting nanotube dispersion and strong interfacial bonding through adequate functionalization of nanotubes improves the load transfer from the matrix to the reinforcing phase.     

In Situ Growth of Mesoporous SnO2 on Multiwalled Carbon Nanotubes: A Novel Composite with Porous‐Tube Structure as Anode for Lithium Batteries

A novel mesoporous‐nanotube hybrid composite, namely mesoporous tin dioxide (SnO₂) overlaying on the surface of multiwalled carbon nanotubes (MWCNTs), was prepared by a simple method that included in situ growth of mesoporous SnO₂ on the surface of MWCNTs through hydrothermal method utilizing Cetyltrimethylammonium bromide (CTAB) as structure‐directing agents. Nitrogen adsorption–desorption, X‐ray diffraction and transmission electron microscopy analysis techniques were used to characterize the samples. It was observed that a thin layer tetragonal SnO₂ with a disordered porous was embedded on the surface of MWCNTs, which resulted in the formation of a novel mesoporous‐nanotube hybrid composite. On the base of TEM analysis of products from controlled experiment, a possible mechanism was proposed to explain the formation of the mesoporous‐nanotube structure. The electrochemical properties of the samples as anode materials for lithium batteries were studied by cyclic voltammograms and Galvanostatic method. Results showed that the mesoporous‐tube hybrid composites displayed higher capacity and better cycle performance in comparison with the mesoporous tin dioxide. It was concluded that such a large improvement of electrochemical performance within the hybrid composites may in general be related to mesoporous‐tube structure that possess properties such as one‐dimensional hollow structure, high‐strength with flexibility, excellent electric conductivity and large surface area.     

Synthesis and Properties of a Water‐Soluble Single‐Walled Carbon Nanotube–Poly(m‐aminobenzene sulfonic acid) Graft Copolymer

Poly(m‐aminobenzene sulfonic acid) (PABS), was covalently bonded to single‐walled carbon nanotubes (SWNTs) to form a water‐soluble nanotube–polymer compound (SWNT–PABS). The conductivity of the SWNT–PABS graft copolymer was about 5.6 × 10^–3 S cm^–1, which is much higher than that of neat PABS (5.4 × 10^–7 S cm^–1). The mid‐IR spectrum confirmed the formation of an amide bond between the SWNTs and PABS. The ¹H NMR spectrum of SWNT–PABS showed the absence of free PABS, while the UV/VIS/NIR spectrum of SWNT–PABS showed the presence of the interband transitions of the semiconducting SWNTs and an absorption at 17 750 cm^–1 due to the PABS addend.     

Nanostructured Crystalline Comb Polymer of Perylenebisimide by Directed Self‐Assembly: Poly(4‐vinylpyridine)‐pentadecylphenol Perylenebisimide

Well defined nanostructured polymeric supramolecular assemblies are formed when an asymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3‐pentadecylphenol at the other termini ( PDP‐UPBI ) is complexed with poly(4‐vinylpyridine) (P4VP) via a non‐covalent specific interaction such as hydrogen‐bonding. The resulting P4VP(PDP‐UPBI) _n complexes are fully solution processable. The bulk structure and morphologies of the supramolecular film studied using small angle and wide angle X‐ray scattering reveals highly crystalline nature of the complex. Thin film morphology of the 1:1 complex analyzed using transmission electron microscopy shows uniform lamellar structures in the domain range of 5–10 nm. A clear trend of improved electrical parameters in P4VP(PDP‐UPBI) system compared to pristine ( PDP‐UPBI ) is observed from space charge limited current measurements. In short, a simple and facile method to obtain spatially defined organization of n‐type semiconductor perylenebisimide molecules using hydrogen bonding interactions with P4VP as the structural motif is showcased herein.     

Cover Picture: Vapor Sorption and Electrical Response of Au‐Nanoparticle– Dendrimer Composites (Adv. Funct. Mater. 6/2007)

The cover shows chemiresistors and mass‐sensitive vapor sensors coated with Au‐nanoparticle/dendrimer composites. The Au nanoparticles provide the film with electrical conductivity and the dendrimers control the chemical selectivity, as reported by Nadjedja Krasteva and co‐workers on p. 881. Analyte sorption follows a combined Henry–Langmuir model, and measurements reveal that sorption‐induced increase in film resistance scales linearly with the concentration of analyte sorbed in the film. The background shows a silicon wafer with lithographically defined microelectrode structures for chemiresistor fabrication. Films comprising Au nanoparticles and polyphenylene dendrimers (first and second generation) are deposited onto transducer substrates via layer‐by‐layer self‐assembly and characterized by atomic force microscopy and X‐ray photoelectron spectroscopy. Their sorption behavior is studied by measuring the uptake of solvents from the vapor phase with quartz crystal microbalances (QCMs). The resistance of the films is simultaneously monitored. Both sensor types, QCMs and chemiresistors, give qualitatively very similar response isotherms that are consistent with a combination of Henry‐ and Langmuir‐type sorption processes. The sorption‐induced increase in relative differential resistance scales linearly with the amount of analyte accumulated in the films. This result is in general agreement with an activated tunneling process for charge transport, if little swelling and only small changes in the permittivity of the film occur during analyte sorption (a first‐order approximation). The relative sensitivity of the films to different solvents decreases in the order toluene ≈ tetrachloroethylene > 1‐propanol ? water. Films containing the larger second‐generation dendrimers show higher sensitivity than films containing first‐generation dendrimers.     

Ultrahigh Electrical Resistance of Poly(cyclohexyl methacrylate)/Carbon Nanotube Composites Prepared Using Surface‐Initiated Polymerization

Multiwalled carbon nanotubes on which poly(cyclohexyl methacrylate)s are densely grafted (PCHMA‐CNTs), are synthesized using a modified surface‐initiated atom transfer radical polymerization technique. The electrical resistance of PCHMA‐CNT is systematically characterized under direct current (DC) and alternating current and compared to that of conventional nanocomposites prepared by blending PCHMA with the CNT (PCHMA/CNT). At a comparable volume fraction of CNT, DC volume resistivity of PCHMA‐CNT is 14 orders of magnitude higher than that of PCHMA/CNT. This is because the grafted polymer with a combination of the high molecular weight and the high grafting density isolates individual CNTs at a long distance in the PCHMA‐CNT system. In addition, impedance analysis reveals that the highly insulated PCHMA‐CNT has the same electrical nature as neat PCHMA, i.e., it is a dielectric. Furthermore, dynamic mechanical analysis shows PCHMA‐CNT has a good mechanical properties as well as ultrahigh electrical resistance.     

Amphiphilic Poly(p‐phenylene)s for Self‐Organized Porous Blue‐Light‐Emitting Thin Films

Micro‐ and nanostructuring of conjugated polymers are of critical importance in the fabrication of molecular electronic devices as well as photonic and bandgap materials. The present report delineates the single‐step self‐organization of highly ordered structures of functionalized poly(p‐phenylene)s without the aid of either a controlled environment or expensive fabrication methodologies. Microporous films of these polymers, with a honeycomb pattern, were prepared by direct spreading of the dilute polymer solution on various substrates, such as glass, quartz, silicon wafer, indium tin oxide, gold‐coated mica, and water, under ambient conditions. The polymeric film obtained from C₁₂PPPOH comprises highly periodic, defect‐free structures with blue‐light‐emitting properties. It is expected that such microstructured, conjugated polymeric films will have interesting applications in photonic and optoelectronic devices. The ability of the polymer to template the facile micropatterning of nanomaterials gives rise to hybrid films with very good spatial dispersion of the carbon nanotubes.     

Multiluminescent Hybrid Organic/Inorganic Nanotubular Structures: One‐Pot Fabrication of Tricolor (Blue–Red–Purple) Luminescent Parallepipedic Organic Superstructure Grafted with Europium Complexes

This article focuses on an innovative one‐pot fabrication of organic/inorganic hybrid parallepipedic tubes with rectangular cavities displaying multicolor luminescence. Firstly, using a novel back‐to‐back coupled 2,6‐di‐pyrazol‐1‐ylpyridine ligand, blue‐emitting several‐micrometer‐long (ca. 50 μm) parallepipedic organic nanotubes with rectangular cavities were fabricated in THF/water via supramolecular (H‐bonding and π–π stacking) and solvent‐assisted self‐assembly. Secondly, in the same pot, the ligand molecules available on the surface of the ligand nanotubes were reacted with Eu(tta)₃ molecules at the solid/liquid interface to form a layer of red‐emitting Eu(III) complex coating on the inner and outer surface of the tubes. The resultant organic/inorganic hybrid parallepipedic nanotubes fabricated using this novel bottom‐up one‐pot technique display tricolor (blue–red–purple) luminescence, i.e., blue and red dual emission from the organic ligand and the Eu(III) complex, respectively, and a purple color due to the mixing of the two colors. This simple technique signifies an innovative and important method in the development of bottom‐up nanotechnology of multiluminescent organic/inorganic hybrid nanotubes.     

Inside Front Cover: One‐Pot Synthesis and Hierarchical Assembly of Hollow Cu2O Microspheres with Nanocrystals‐Composed Porous Multishell and Their Gas‐Sensing Properties (Adv. Funct. Mater. 15/2007)

On p. 2766, Qinshan Zhu and co‐workers report on multishell hollow Cu₂O microspheres that are synthesized by a facile and one‐pot solvothermal route. A two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ are formed first followed by reduction to Cu₂O by glutamic acid, leads to the special multishell and hollow microstructures. Interestingly, a Cu₂O gas sensor fabricated with the multishell microspheres shows a much higher sensitivity to ethanol than solid Cu₂O microspheres. Hierarchical assembly of hollow microstructures is of great scientific and practical value and remains a great challenge. This paper presents a facile and one‐pot synthesis of Cu₂O microspheres with multilayered and porous shells, which were organized by nanocrystals. The time‐dependent experiments revealed a two‐step organization process, in which hollow microspheres of Cu₂(OH)₃NO₃ were formed first due to the Ostwald ripening and then reduced by glutamic acid, the resultant Cu₂O nanocrystals were deposited on the hollow intermediate microspheres and organized into finally multishell structures. The special microstructures actually recorded the evolution process of materials morphologies and microstructures in space and time scales, implying an intermediate‐templating route, which is important for understanding and fabricating complex architectures. The Cu₂O microspheres obtained were used to fabricate a gas sensor, which showed much higher sensitivity than solid Cu₂O microspheres.     

Hydroxyapatite Modified with Carbon‐Nanotube‐Reinforced Poly(methyl methacrylate): A Nanocomposite Material for Biomedical Applications

The paper reports on a freeze‐granulation technique to prepare a novel nanocomposite of poly(methyl methacrylate) (PMMA)‐modified hydroxyapatite (HA) with multiwalled carbon nanotubes (MWCNTs) as reinforcement for a new generation biomedical bone cement and implant coatings. By using this technique it is possible to increase material homogeneity and also enhance the dispersion of MWCNTs in the composite matrix. The phase composition and the surface morphology of the nanocomposite material were studied using X‐ray diffraction, field‐emission scanning electron microscopy, and micro‐Raman spectroscopy. Additionally, nanomechanical properties of different concentrations of MWCNT‐reinforced nanocomposite were performed by a nanoindentation technique, which indicates that a concentration of 0.1 wt % MWCNTs in the PMMA/HA nanocomposite material gives the best mechanical properties.     

Self‐Crosslink Method for a Straightforward Synthesis of Poly(Vinyl Alcohol)‐Based Aerogel Assisted by Carbon Nanotube

As a new concept, a self‐crosslink mechanism for hydrothermal synthesis of poly(vinyl alcohol) (PVA) aerogel, assisted by multiwall carbon nanotubes, is reported. PVA, working as a low‐cost and commercially available raw material, exempts the complicated synthesis process and reserves its nontoxic nature since no organic crosslinkers are used in the synthesis process. The crosslink density and many other properties of the products can be easily tuned by simply altering the concentration of PVA precursors, which is considered to be another feature of our method. Dehydration between hydroxyl groups occurs in the hydrothermal process, leading to a reverse wettability of the products from hydrophilic to hydrophobic, thus their absorbing capacity for several organic solvents, such as bean oil and crude oil, is investigated. The absorbate has 10–52 times the original weight of the aerogel. As exhibited by the cytotoxic tests, the product has neglectable toxicity, suitable for application in environmental bioengineering. Furthermore, the product can be used as a facile substrate for transformation into conductive aerogel by in situ hybridizing with polypyrrole, showing a conductivity of 0.16 S m^?1. As it is rich in hydroxyl groups, the aerogels are believed to be further functionalized by the reactions related to the hydroxyl group.