Transparent Thin Films of Multiwalled Carbon Nanotubes Self‐Assembled on Polyamide 11 Nanofibers

Electrospun polyamide 11 (PA11) nanofiber films are used as a guide for the deposition of two‐dimensional networks of multi‐walled carbon nanotubes (MWNTs). This method allows for the manufacturing of transparent and electrically conductive thin films. It is demonstrated that the sheet resistance (Rs) and transmittance (T) decrease, as the films become thicker due to longer electrospinning times or larger fibers. The transmittance could be improved by fusing (melting) the fibers at moderate temperatures or impregnating the film with a resin, showing that light scattering rather than absorption by the MWNTs or the polymer was responsible for a low transmittance. As the number of MWNT deposition cycles increases, the Rs decreases with a constant transmittance. A fused 100 nm film obtained after 10 min of electrospinning of the 2 wt % PA11 solution shows Rs = 154 kΩ sq^?1 and T = 83% after ten MWNT deposition cycles. A 95% transmittance was achieved after removing the polymer fibers by heating the glass plate in air (Rs = 440 kΩ sq^?1 after five MWNT deposition cycles).     

Functionalizing Carbon Nanotubes by Grafting on Intumescent Flame Retardant: Nanocomposite Synthesis,Morphology, Rheology,and Flammability

An intumescent flame retardant, poly(diaminodiphenyl methane spirocyclic pentaerythritol bisphosphonate) (PDSPB) has been covalently grafted onto the surfaces of multiwalled carbon nanotubes (MWNTs) to obtain MWNT‐PDSPB and according nanocomposites were prepared via melt blending. After high density PDSPB (65 wt %) were attached to the MWNTs, core‐shell nanostructures with MWNTs as the hard core and PDSPB as the soft shell were formed. The resultant MWNT‐PDSPB was soluble and stable in polar solvents, such as DMF. The optical microscopy and TEM results showed that the functionalized MWNTs can achieve better dispersion in ABS matrix. The linear viscoelastic behavior indicated that MWNT‐PDSPB can form network structure at very low nanotube loading than un‐functionalized MWNTs. The results of flammability showed that better flame retardancy was obtained for ABS/MWNT‐PDSPB nanocomposites due to the better dispersion of MWNT‐PDSPB in ABS matrix. The flammability of the composites is strongly dependent on the network structure of nanotubes which reduces the diffusion of volatile combustible fragments generated by polymer degradation which diffuse towards the surface of the burning polymer to evaporate to feed the flame. The grafting of intumescent flame retardant of PDSPB can improve both the dispersion of nanotubes in polymer matrix and flame retardancy of the nanocomposites.     

Influence of carbon on the formation and the microstructure of B(P)SCCO-110-K-phase in Ag-sheathed tapes

To investigate the influence of carbon on the formation and microstructure of B(P)SCCO-110-K-phase in Ag-sheathed tapes, powder in tube tape samples were prepared with calcined oxide-carbonate mixtures containing different amounts of carbon. The thermochemical behaviour of the samples was studied by quenching experiments in the early stage of the heat treatment. Appearance of 2201 phase in the as-quenched tapes indicates the existence of melt during the heat treatment. Melting of the ceramic core is considerably influenced by carbon. The onset of partial melting is reduced from 820 to 825°C in carbon poor samples to 810°C in carbon rich samples. At these temperatures alkaline-earth cuprate, 2212, and melt, present as 2201 in quenched tapes, seem to coexist. Formation of 2223 phase appears to be a three step process. After a rapid solid state transformation from 2201 to 2212 and the partial formation of liquid, the 2223 reaction takes place in the presence of melt.     

Mechanical Reinforcement of Polyethylene Using Polyethylene‐Grafted Multiwalled Carbon Nanotubes

The incorporation of carbon nanotubes to a polymer generally improves the stiffness and strength of the polymer, but the ductility and toughness of the polymer are compromised in most cases. Here we report the mechanical reinforcement of polyethylene (PE) using polyethylene‐grafted multiwalled carbon nanotubes (PE‐g‐MWNTs). The stiffness, strength, ductility and toughness of PE are all improved by the addition of PE‐g‐MWNTs. The grafting of PE onto MWNTs enables the well‐dispersion of nanotubes in the PE matrix and improves MWNT/PE interfacial adhesion. The grafting was achieved by a reactive blending process through melt blending of PE containing 0.85 wt % of maleic anhydride and amine‐functionalized MWNTs. The reaction between maleic anhydride and amine groups, as evidenced by X‐ray photoelectron spectroscopy and Raman spectroscopy, leads to the grafting of PE onto the nanotubes.     

Glass Fibers with Carbon Nanotube Networks as Multifunctional Sensors

A simple approach to deposit multiwalled carbon nanotube (MWNT) networks onto glass fiber surfaces achieving semiconductive MWNT–glass fibers is reported, along with application of fiber/polymer interphases as in‐situ multifunctional sensors. This approach demonstrates for the first time that the techniques of conducting electrical resistance measurements could be applicable to glass fibers for in situ sensing of strain and damage; the techniques were previously limited to conductive and semiconductive materials. The electrical properties of the single MWNT–glass fiber and the “unidirectional” fiber/epoxy composite show linear or nonlinear stress/strain, temperature, and relative humidity dependencies, which are capable of detecting piezoresistive effects as well as the local glass transition temperature. The unidirectional composites containing MWNT–glass fibers exhibit ultrahigh anisotropic electrical properties and an ultralow electrical percolation threshold. Based on this approach, the glass fiber—the most widely used reinforcement in composites globally—along with the surface electrical conductivity of MWNTs will stimulate and realize a broad range of multifunctional applications.     

Single‐Walled Carbon Nanotube Dispersions in Poly(ethylene oxide)

Dispersions of single‐walled carbon nanotubes (SWNTs) in poly(ethylene oxide) (PEO) assisted by a lithium‐based anionic surfactant demonstrate an electrical percolation of 0.03 wt.‐% and a geometrical percolation, inferred from melt rheometry, of 0.09 wt.‐%. Both the melting temperature and the extent of crystallinity of the PEO crystals decrease with increasing SWNT loading. Raman spectroscopy of the nanocomposites indicates a down‐shift of the SWNT G‐modes and suggests that the nanotubes are subjected to tensile stress transfer from the polymer at room temperature.     

Highly Conductive Carbon Nanotube‐Graphene Hybrid Yarn

An efficient procedure for the fabrication of highly conductive carbon nanotube/graphene hybrid yarns has been developed. To start, arrays of vertically aligned multi‐walled carbon nanotubes (MWNT) are converted into indefinitely long MWNT sheets by drawing. Graphene flakes are then deposited onto the MWNT sheets by electrospinning to form a composite structure that is transformed into yarn filaments by twisting. The process is scalable for yarn fabrication on an industrial scale. Prepared materials are characterized by electron microscopy, electrical, mechanical, and electrochemical measurements. It is found that the electrical conductivity of the composite MWNT‐graphene yarns is over 900 S/cm. This value is 400% and 1250% higher than electrical conductivity of pristine MWNT yarns or graphene paper, respectively. The increase in conductivity is asssociated with the increase of the density of states near the Fermi level by a factor of 100 and a decrease in the hopping distance by an order of magnitude induced by grapene flakes. It is found also that the MWNT‐graphene yarn has a strong electrochemical response with specific capacitance in excess of 111 Fg^?1. This value is 425% higher than the capacitance of pristine MWNT yarn. Such substantial improvements of key properties of the hybrid material can be associated with the synergy of MWNT and graphene layers in the yarn structure. Prepared hybrid yarns can benefit such applications as high‐performance supercapacitors, batteries, high current capable cables, and artificial muscles.     

Spray‐Layer‐by‐Layer Carbon Nanotube/Electrospun Fiber Electrodes for Flexible Chemiresistive Sensor Applications

Development of a versatile method for incorporating conductive materials into textiles could enable advances in wearable electronics and smart textiles. One area of critical importance is the detection of chemicals in the environment for security and industrial process monitoring. Here, the fabrication of a flexible, sensor material based on functionalized multi‐walled carbon nanotube (MWNT) films on a porous electrospun fiber mat for real‐time detection of a nerve agent simulant is reported. The material is constructed by layer‐by‐layer (LbL) assembly of MWNTs with opposite charges, creating multilayer films of MWNTs without binder. The vacuum‐assisted spray‐LbL process enables conformal coatings of nanostructured MWNT films on individual electrospun fibers throughout the bulk of the mat with controlled loading and electrical conductivity. A thiourea‐based receptor is covalently attached to the primary amine groups on the MWNT films to enhance the sensing response to dimethyl methylphosphonate (DMMP), a simulant for sarin nerve agent. Chemiresistive sensors based on the engineered textiles display reversible responses and detection limits for DMMP as low as 10 ppb in the aqueous phase and 5 ppm in the vapor phase. This fabrication technique provides a versatile and easily scalable strategy for incorporating conformal MWNT films into three‐dimensional substrates for numerous applications.     

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.     

Strong Carbon‐Nanotube–Polymer Bonding by Microwave Irradiation

The vigorous response of multiwalled carbon nanotubes (MWNTs) to microwave irradiation, leading to the release of a large amount of heat, is used to locally melt a plastic matrix adjacent to the nanotubes within a period of seconds. This results in the intercalation of the MWNTs into the polymer matrix at room temperature without any physical damage to the polymer. The so‐called “microwave welding” approach creates a new paradigm for the formation of very strong MWNT–polymer bonds without the use of any adhesive, and represents a significant step forward for the fabrication of functional nanotube composites. Here, we demonstrate the implications of the anisotropic alignment of MWNTs in polymers, patterned conductors/resistors for soft electronics, and high‐strength composites, where the MWNTs are ‘soldered' to flexible polymer substrates.     

Fabrication of a Highly Transparent Conductive Thin Film from Polypyrrole/Poly(methyl methacrylate) Core/Shell Nanospheres

Polypyrrole (PPy)/poly(methyl methacrylate) (PMMA) core/shell nanospheres with diameters of several tens of nanometers have been synthesized by two‐step microemulsion polymerization, and highly transparent conductive thin films have been fabricated using the nanospheres as a filler in a PMMA matrix. The PPy/PMMA core/shell nanoparticles and their composite films have been extensively characterized using transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier‐transform infrared (FT‐IR) and UV‐vis spectroscopies, and electrical‐conductivity measurements. The fabricated polymer films containing the PPy/PMMA core/shell nanofillers show a much better transparent conductive performance than that of uncoated PPy nanoparticles with similar dimensions or bulk PPy particles with diameters of several hundreds of nanometers. The PMMA shell promotes compatibility of the conductive fillers with the PMMA matrix and enhances dispersion of the PPy/PMMA core/shell nanofillers. In addition, the nanometer‐thick PMMA shell has a lower glass‐transition temperature (T_g), and can be effectively annealed to form a conductive‐filler network with a high electrical conductivity at a relatively low filler content.     

A study of ageing effect at elevated temperature of flexible silicon diodes integrated using conductive adhesives

A simple fabrication scheme of using silver-filled conductive tape to form flexible single crystalline Si–Pd Schottky diodes on a polymer substrate has been studied and reported previously. In this investigation, we studied the long term thermal stability of these flexible diodes on polymer annealed at 80 °C in open air for 1 year. The I–V characteristics of the diodes were measured periodically. We found that the barrier height of the Si–Pd diodes remained relatively unchanged at 0.795 eV ± 0.003 with an n-factor of 1.03 ± 0.03, and a series resistance of ∼110 Ω for diodes with a 950 μm diameter, which are almost identical to the values before annealing. The integrated structure stayed flexible to a similar curvature after 1 year. The stability of silver-filled conductive tape was investigated separately over the same period of time and under the same conditions. The resistance of two conductive tapes was found to quickly decrease from high initial values to significantly lower values, and remained constant over the course of the investigation. Based on these results, we conclude that this simple bonding technique of using conductive tape to fabricate flexible devices can be of useful value in practical applications.     

Room Temperature Fluorescent Conjugated Polymer Gums

High molecular weight poly(diphenylacetylene) [PDPA] derivatives are introduced as fluorescent, soft conjugated polymers that exist in the gum state at room temperature. The gum‐like behavior of the polymers is easily modified according to the side alkyl chain length and substitution position. Long alkyl chain‐coupled PDPA derivatives provide soft and sticky gums at room temperature. Manual kneading of gum polymers produce soft films with very smooth surfaces. The gum polymers show an endothermic transition due to the melting of long alkyl chains. The X‐ray diffraction of gum polymers reveals a new signal due to the molten aliphatic chains. The gum polymers show significant viscoelastic relaxation at the melting temperature of the alkyl side chains. The dynamic thermo‐mechanical analysis (DTMA) of gum polymers at room temperature suggest that the meta‐substituted polymer is softer and stickier than para‐polymer. Rheological analysis suggests that the meta‐polymer has less entanglement than para‐polymer. The fluorescence emission of gum polymer is quite intense in the film and solution. The gum polymer film is readily stretched to produce a uniaxually oriented film. Stretching and subsequent relaxation of elastomer‐supported gum polymer film generate buckles perpendicular to the axis of strain. The gum polymer film accommodates the large strain without cracking and delamination.     

用导电聚合物电极的超电容器研究概况

导电聚合物制备电极的超电容器（Ｓｕｐｅｒｃａｐａｃｉｔｏｒｓ） 有两种类型： 导电聚合物直接制备电极和导电聚合物高温热解为硬碳（Ｈａｒｄ ｃａｒｂｏｎ）制备电极的电容器。导电聚合物超电容器基于法拉第准电容（Ｆａｒａｄａｉｃｐｓｅｕ－ｄｏｃａｐａｃｉｔａｎｃｅ） 原理， 进出正极的是阴离子， 进出负极的是阳离子。该电容器结构中一个电极是ｎ 型掺杂， 另一个是ｐ 型掺杂。聚合物超电容器的能量密度比活性碳作电极的双电层电容器大２～３倍， 作为电容性储能装置应用前景诱人     

High Mechanical Performance Composite Conductor: Multi‐Walled Carbon Nanotube Sheet/Bismaleimide Nanocomposites

Multi‐walled carbon nanotube (MWNT)‐sheet‐reinforced bismaleimide (BMI) resin nanocomposites with high concentrations (～60 wt%) of aligned MWNTs are successfully fabricated. Applying simple mechanical stretching and prepregging (pre‐resin impregnation) processes on initially randomly dispersed, commercially available sheets of millimeter‐long MWNTs leads to substantial alignment enhancement, good dispersion, and high packing density of nanotubes in the resultant nanocomposites. The tensile strength and Young's modulus of the nanocomposites reaches 2 088 MPa and 169 GPa, respectively, which are very high experimental results and comparable to the state‐of‐the‐art unidirectional IM7 carbon‐fiber‐reinforced composites for high‐performance structural applications. The nanocomposites demonstrate unprecedentedly high electrical conductivity of 5 500 S cm^?1 along the alignment direction. Such unique integration of high mechanical properties and electrical conductance opens the door for developing polymeric composite conductors and eventually structural composites with multifunctionalities. New fracture morphology and failure modes due to self‐assembly and spreading of MWNT bundles are also observed.     

Highly Stretchable Conductors Integrated with a Conductive Carbon Nanotube/Graphene Network and 3D Porous Poly(dimethylsiloxane)

Here, a novel and facile method is reported for manufacturing a new stretchable conductive material that integrates a hybrid three dimensional (3D) carbon nanotube (CNT)/reduced graphene oxide (rGO) network with a porous poly(dimethylsiloxane) (p‐PDMS) elastomer (pPCG). This reciprocal architecture not only alleviates the aggregation of carbon nanofillers but also significantly improves the conductivity of pPCG under large strains. Consequently, the pPCG exhibits high electrical conductivity with a low nanofiller loading (27 S m^?1 with 2 wt% CNTs/graphene) and a notable retention capability after bending and stretching. The simulation of the mechanical properties of the p‐PDMS model demonstrates that an extremely large applied strain (ε_appl) can be accommodated through local rotations and bending of cell walls. Thus, after a slight decrease, the conductivity of pPCG can continue to remain constant even as the strain increases to 50%. In general, this architecture of pPCG with a combination of a porous polymer substrate and 3D carbon nanofiller network possesses considerable potential for numerous applications in next‐generation stretchable electronics.     

Epitaxial Growth of Highly Oriented Fibers of Semiconducting Polymers with a Shish‐Kebab‐Like Superstructure

Highly oriented fibers of regioregular poly(3‐alkylthiophene)s (P3ATs) showing a “shish‐kebab” morphology are prepared by oriented epitaxial crystallization in a mixture of 1,3,5‐trichlorobenzene (TCB) and pyridine. The superstructure of the P3AT fibers consists of an oriented thread‐like core several hundreds of micrometers long, the “shish”, onto which lateral crystalline fibrils made of folded polymer chains, the “kebabs”, are connected in a periodic way with a periodicity in the range 18–30 nm. The P3AT‐chain axis is oriented parallel to the fiber axis whereas the π‐stacking direction is oriented perpendicular to it. The oriented character of the shish‐kebab fibers results in polarized optical absorption and photoluminescence. The formation of oriented precursors by epitaxial orientation of polymer chains onto long needles of a molecular crystal—TCB in the present case—appears to be an original alternative to the crystallization usually performed under external flow conditions.     

导电纤维高分子复合材料研究现状与发展趋势

介绍了国内外专家在以不锈钢纤维、铜纤维、碳纤维为填充物的导电高分子复合材料方面的研究成果,比较了这几种复合材料的性能。阐述了限制导电高分子复合材料进一步发展的因素及改进措施。     

掺Eu3+聚合物光纤的团簇现象

用热聚合法制备了掺Eu(DBM)3Phen螯合物的聚合物光纤,建立了团簇化铕离子相互作用模型,以此为基础研究该掺杂聚合物光纤的团簇现象。利用速率方程理论,结合光纤的抽运光透射率实验,得到所研究光纤中团簇化铕离子浓度。掺铕质量分数为0.1%,0.2%,0.3%,0.4%,0.5%,1%的聚合物光纤中团簇化铕离子的浓度分别为0.045,0.07,0.07,0.07,0.07,0.08。因此,该掺杂聚合物光纤的团簇化铕离子浓度较低且基本不随掺杂浓度的增加而增加,铕离子之间的团簇化现象不明显。     

Electrical Interconnection with a Smart ACA Composed of Fluxing Polymer and Solder Powder

The interconnection mechanisms of a smart anisotropic conductive adhesive (ACA) during processing have been characterized. For an understanding of chemorheological mechanisms between the fluxing polymer and solder powder, a thermal analysis as well as solder wetting and coalescence experiments were conducted. The compatibility between the viscosity of the fluxing polymer and melting temperature of solder was characterized to optimize the processing cycle. A fluxing agent was also used to remove the oxide layer performed on the surface of the solder. Based on these chemorheological phenomena of the fluxing polymer and solder, an optimum polymer system and its processing cycle were designed for high performance and reliability in an electrical interconnection system. In the present research, a bonding mechanism of the smart ACA with a polymer spacer ball to control the gap between both substrates is newly proposed and investigated. The solder powder was used as a conductive material instead of polymer‐based spherical conductive particles in a conventional anisotropic conductive film.