Sorption and Diffusion of Supercritical Carbon Dioxide in a Biodegradable Polymer

A gravimetric method was used to study the sorption and diffusion of supercritical carbon dioxide in a temperature range from 40°C to 80°C and a pressure range from 8.0 to 18.0 MPa in a biodegradable polymer, namely poly(butylene adipate-co-terephthalate) (PBAT). The PBAT presented Fickian behavior and Fick's diffusion model was applied to determine the amount of carbon dioxide present in the samples after a predetermined exposure time as well as the diffusion coefficients. The variations of diffusion coefficients of CO₂ for the sorption under supercritical conditions and desorption at ambient conditions as well as equilibrium sorption amounts of CO₂ with variations of pressure and temperature were determined and compared.     

Electromechanical actuation of CNT/PVDF composite films based on a bridge configuration

Bridged strips consisting of carbon nanotubes and poly(vinylidene fluoride) are developed, which exhibit notable deflection in response to very low driven voltages( 1 V), because of both the excellent conductivity of the unique carbon nanotube film and the powerful thermal expansion capability of the polymer. The actuators demonstrate periodic vibrations motivated by the alternating signals. The amplitude of displacement is dependent not only on the driven voltage but also on the applied frequency. The mechanism of actuation is confirmed to be the thermal power induced by the electrical heating. By accelerating the dissipation of heat, the vibration response at higher frequencies can be significantly enhanced.The useful locomotion shows great promise in potential applications such as miniature smart devices and micro power generators.     

碳纳米管受限空间对共轭高分子聚(9,9-二辛基芴-2,7-二基)链段运动行为的影响

在纳米受限空间中,高分子往往会表现出与本体状态不同的性质,如异常的链段运动特性及晶相间转变行为等,这些性质对于研究和开发新型高分子材料具有重要的意义,因此针对受限环境下高分子的物理化学特性研究也一直是高分子界关注的焦点.本文通过化学气相沉积法制备垂直取向排列的多壁碳纳米管阵列,借助溶剂润湿–收缩法获得规整的高密度阵列结构,其取向排列的碳纳米管间隙形成了准一维的纳米受限空间,尺寸在5—50 nm尺度下可调.进一步将共轭高分子聚(9,9-二辛基芴-2,7-二基)(PFO)填充到碳管间隙的纳米空间中,制备PFO与取向多壁碳纳米管阵列复合膜.结果发现在碳纳米管形成的纳米受限空间中,PFO的链段热运动行为与本征态PFO薄膜相比受到了明显的抑制,不同晶型间转变速度大大减缓,提高了构象的热稳定性,同时取向排列的碳纳米管对PFO分子链取向排列分布具有明显的诱导作用,有利于获得高性能的PFO晶体.这种高密度取向排列的碳纳米管阵列结构未来可以用于制备优良发光性能及高稳定性的PFO光电器件.     

Supercritical carbon dioxide-assisted preparation of palladium nanoparticles on cyclotriphosphazene-containing polymer nanospheres

Poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) nanospheres with average diameter of 410 nm were synthesized rapidly at room temperature and then homogeneously decorated with Pd nanoparticles through an inorganic reaction in supercritical carbon dioxide-ethanol solution using PdCl₂ as a metal precursor. The resultant Pd/PZS nanocomposites were morphologically and structurally characterized by means of scanning electron microscopy, transmission electron microscope equipped with energy-dispersive X-ray spectroscopy, and X-ray diffraction techniques. Characterization results showed that the Pd nanoparticles with good dispersibility could be well anchored onto the surfaces of the PZS nanospheres and the size of Pd nanoparticles could be controlled easily by varying the ethanol-reduction time.     

Low-voltage soft robots based on carbon nanotube/polymer electrothermal composites

Nowadays, soft robots have become a research hot spot due to high degree of freedom, adaptability to the environment and safer interaction with humans. The carbon nanotube (CNT)/polydimethylsiloxane (PDMS) electrothermal composites have attracted wide attention in the field of flexible actuations due to large deformation at low voltages. Here, the preparation process of CNT/PDMS composites was designed and optimized, and electrothermal actuators (ETAs) were fabricated by cutting the CNT/PDMS composite films into a "U" shape and coating conductive adhesive. The deformation performance of the ETAs with different thicknesses at different voltages was studied. At a low voltage of about 7 V, the ETA has a deformation rate of up to 93%. Finally, two kinds of electrothermal soft robots (ETSRs) with four-legged and three-legged structures were fabricated, and their inchworm-like motion characteristics were studied. The ETSR2 has the best motion performance due to the moderate thickness and three-legged electrode structure.     

High performance pentacene organic field-effect transistors consisting of biocompatible PMMA/silk fibroin bilayer dielectric

Pentacene organic field-effect transistors （OFETs） based on single- or double-layer biocompatible dielectrics of poly（methyl methacrylate） （PMMA） and/or silk fibroin （SF） are fabricated. Compared with those devices based on sin- gle PMMA or SF dielectric or SF/PMMA bilayer dielectric, the OFETs with biocompatible PMMA/SF bilayer dielectric exhibit optimal performance with a high field-effect mobility of 0.21 cm2/Vs and a current on/off ratio of 1.5 × 104. By investigating the surface morphology of the pentacene active layer through atom force microscopy and analyzing the elec- trical properties, the performance enhancement is mainly attributed to the crystallization improvement of the pentacene and the smaller interface trap density at the dielectric/organic interface. Meanwhile, a low contact resistance also indicates that a good electrode/organic contact is formed, thereby assisting the performance improvement of the OFET.     

Effect of Morphology and Composition of Organic Montmorillonite on the Structure and Properties of Poly(Butylene Terephthalate) Nanocomposites

The morphology and composition of organic montmorillonites are critical for their dispersion in polymer matrixes. In the current study, the pristine montmorillonite (MMT) was first surface modified with silane and then intercalated using two kinds of intercalating agents in supercritical carbon dioxide (scCO₂). The obtained OMMTs with tunable morphology and composition, together with pristine MMT and commercial MMT, were introduced into poly(butylene terephthalate) (PBT) to investigate the MMTs dispersion in the PBT matrix and the final properties of the PBT/MMT nanocomposites. The structure of the different MMTs and their dispersion in the PBT matrix were characterized by SEM and TEM, respectively. The crystallization behavior, storage moduli and loss factors of the PBT/MMT nanocomposites were also investigated.     

Enhanced β Crystalline Phase in Poly(vinylidene fluoride) via the Incorporation of Graphene Oxide Sheets assisted by Supercritical CO2 Treatment

Graphene oxide (GO) sheets were pre-modified with a typical piezoelectric polymer, poly(vinylidene fluoride) (PVDF), using a simple supercritical carbon dioxide (SC CO₂) method, and then the PVDF-decorated GO was added into a PVDF matrix by solution blending. Transmission electron microscopy (TEM) revealed that the decorating degree of PVDF on the surface of the GO increased significantly with increasing of SC CO₂ pressure and PVDF concentration. The mechanism of the polymer adsorption on the GO sheets through favorable interaction between the GO and PVDF chains was identified via Fourier transform infrared spectroscopy (FTIR). Further, the crystallization behavior of PVDF/GO composites was investigated by differential scanning calorimetry (DSC), FTIR and polarized optical microscopy (POM). Interestingly, the composite with PVDF-decorated GO as the filler showed higher β-phase content compared to the composite with pristine GO as the filler. The study showed that the supercritical fluid-induced epitaxial crystallization process has significant potential for fabricating functional GO-based nanocomposties containing piezoelectric or conducting materials.     

Synthesis of graphene oxide-poly(2-hydroxyethyl methacrylate) composite by dispersion polymerization in supercritical CO2: adsorption behavior for the removal of organic dye

The use of a biocompatible and thermoresponsive polymer, poly(2-hydroxyethyl methacrylate) (PHEMA) grafted onto the surface of graphene oxide (GO) as an adsorbent for the removal of a cationic dye (methylene blue [MB]) from an aqueous solution is examined in this work. GO–PHEMA forms a hydrogel in water thus overcoming the problem faced by carbon-based adsorbent materials during post-treatment (i.e., separation of adsorbent from the aqueous phase). The GO–PHEMA composite was synthesized using a green approach through dispersion polymerization in supercritical CO₂. The successful preparation of this composite was confirmed by a series of characterization techniques. The adsorption behavior of the composite toward MB such as the effect of the adsorbent dosage, pH, contact time, dye concentration, and recyclability were observed. In addition, the adsorption isotherm, kinetics and thermodynamics were investigated. According to the experimental data, the adsorption parameters were found to fit well into the Freundlich adsorption isotherm with a correlation coefficient of 0.975 and a maximum predicted adsorption capacity of 39.41 mg g^?1 at 25 °C. The adsorption kinetics studies showed that the adsorption behavior followed a pseudo-second-order reaction. On the other hand, the thermodynamics studies showed that the adsorption of MB on GO–PHEMA composite followed spontaneous and endothermic adsorption process with an efficient adsorption temperature at 45 °C. The experimental results also showed that the GO–PHEMA composite could remove 99.8% of the dye in 45 min. Therefore, GO–PHEMA composite is a favorable green adsorbent for environmental applications.     

碳纳米管的生长机理、可控生长及应用探索

碳纳米管的可控制生长,及其宏观尺度结构的制备,对于碳纳米管的应用具有重要的意义,为了实现准确的生长控制,对碳纳米管生长机理的深入了解是不可缺少的前提条件.文章介绍了我们近年来在碳纳米管生长机理、可控生长及其应用方面的一些进展.通过引入^13C标记法,我们证实了化学气相沉积法中碳纳米管以析出模式生长;实时改变生长的气相成份和流量,可以在碳纳米管阵列上留下标记序列,并据此测量出其生长速率及活化能.将超顺排碳纳米管阵列的合成扩展到4英寸规模,并发展了用挥发性有机溶剂处理碳纳米管线的方法,大大提高了其强度和可操作性.处理后的碳纳米管线可以方便地用于热电子源、高电流密度冷阴极以及荧光灯等.热界面材料在IT产业中具有重要的应用背景,我们用碳纳米管阵列制备的复合材料具有极高的热导率和极低的界面热阻,同时发展了化学修饰、端部剪裁、金属集热层等新技术以制备高性能的碳纳米管热界面材料.     

Thermal Stability and Degradation Kinetics of Poly(Methyl Methacrylate)/Sepiolite Nanocomposites by Direct Melt Compounding

Poly(methyl methacrylate) (PMMA) nanocomposites based on sepiolite modified with trimethyl hydrogenated tallow amine by an adsorption process were prepared by melt compounding using a corotating twin screw extruder. The morphology and dispersion of sepiolite in the PMMA were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Thermal stability and the activation energies were investigated by thermogravimetric analysis/differential thermogravimetric (TGA/DTG). The XRD and TEM results show that the sepiolite was dispersed homogeneously in the PMMA matrix at a nanometer scale. The TGA analysis revealed that the addition of sepiolite improved the thermal stability of PMMA. The apparent activation energies were calculated by the method of Flynn–Wall–Ozawa in nitrogen at four different heating rates, showing that sepiolite increased the apparent activation energies by about 20 kJ/mol within the degree of conversion (α) of 0.35–0.9, as compared with the reference PMMA sample.     

碳纳米管的生长机理、可控生长及应用探索

碳纳米管的可控制生长,及其宏观尺度结构的制备,对于碳纳米管的应用具有重要的意义,为了实现准确的生长控制,对碳纳米管生长机理的深入了解是不可缺少的前提条件.文章介绍了我们近年来在碳纳米管生长机理、可控生长及其应用方面的一些进展.通过引入13C标记法,我们证实了化学气相沉积法中碳纳米管以析出模式生长;实时改变生长的气相成份和流量,可以在碳纳米管阵列上留下标记序列,并据此测量出其生长速率及活化能.将超顺排碳纳米管阵列的合成扩展到4英寸规模,并发展了用挥发性有机溶剂处理碳纳米管线的方法,大大提高了其强度和可操作性.处理后的碳纳米管线可以方便地用于热电子源、高电流密度冷阴极以及荧光灯等.热界面材料在IT产业中具有重要的应用背景,我们用碳纳米管阵列制备的复合材料具有极高的热导率和极低的界面热阻,同时发展了化学修饰、端部剪裁、金属集热层等新技术以制备高性能的碳纳米管热界面材料.     

Microencapsulation of TiO2 Nanoparticles with Polymer by Rapid Expansion of Supercritical Solution

A novel preparation method is reported for the microencapsulation of TiO₂ nanoparticles by rapid expansion of supercritical solution with a nonsolvent. A suspension of TiO₂ nanoparticles in carbon dioxide containing a cosolvent and dissolved polymer is sprayed through a nozzle to atmospheric pressure. After rapid expansion, polymer microspheres were obtained. The microspheres do not tend to agglomerate, since the pure cosolvent is a nonsolvent for the polymer. The structure and morphology of microspheres were investigated by SEM, TEM and XRD. The obtained polymer microspheres are microcapsules of TiO₂ nanoparticles. The mean particle diameter and particle size distribution of microcapsules, could be controlled by changing the polymer concentration, pre-expansion pressure, temperature and injection distance. The polymer feed compositions are more effective than other factors on the control of particle size.     

Electrical,optical and fluorescence percolations in P(VAc-co-BuA)/MWCNT composite films

Effects of multiwall carbon nanotube (MWCNT) addition on the electrical conductivities, optical transparencies and fluorescence emissions of poly(vinyl acetate-co-butyl acrylate) (P(VAc-co-BuA))/MWCNT composite films were studied. Optical transmission, fluorescence emission and two point probe resistivity techniques were used to determine the variations of the optical, fluorescence and electrical properties of the composites, respectively. Transmitted photon intensity (I _tr), fluorescence emission intensity (I _fl) and surface resistivity (ρ _s) of the composite films were monitored as a function of MWCNT mass fraction (M) at room temperature. All these measured quantities of the composites were decreased by increasing the content of MWCNT in the composite. The conductivity and the optical results were attributed to the classical and site percolation theories, respectively. The fluorescence results, however, possessed both the site and classical percolation theories at low and high MWCNT content regions, respectively.     

碳纳米管电缆式复合材料的热导率

通过非平衡分子动力学方法, 对单壁碳管填充金纳米线的碳纳米管电缆式复合材料开展热导率的模拟分析. 采用Tersoff势函数描述碳-碳原子间的相互作用, Lennard-Jones长程作用势描述碳-金原子间的相互作用, 嵌入原子势函数描述金-金原子间相互作用. 研究结果表明: 相同尺寸下, 金纳米线的电子热导率相较于空碳管以及电缆式复合材料的声子热导率小很多, 对复合材料总热导率的贡献可以忽略; 由于管内金纳米线的存在, 其与碳管的相互作用使得碳管碳原子倾向于沿着轴向振动, 声子间U散射随之减少, 声子平均自由程增加, 导致复合材料热导率明显大于空碳管, 在100–500 K温度范围内高出约20%–45%, 但增大幅度随温升呈降低趋势; 复合材料热导率随着管长增加而增大, 变化趋势和空碳管相似, 但其增长幅度更大; 复合材料和空碳管的热导率随管径增大而减小, 且变化幅度基本一致. 关键词： 碳纳米管 纳米线 电缆式复合材料 导热     

Monte Carlo simulation of carbon monoxide,carbon dioxide and methane adsorption on activated carbon

In this study, the adsorption capacity of pure and activated carbon with regard to carbon monoxide (CO), carbon dioxide (CO₂) and methane (CH₄) gases at 298?K and pressure from 0.01 up to 2.0?MPa has been investigated computationally. Computational work refers to Monte Carlo (MC) simulation of each adsorbed gas on a graphite model with varying density of activation sites. The Grand Canonical Monte Carlo (GCMC) simulation technique was employed to obtain the uptake of each adsorbed gas by considering a graphite model of parallel sheets activated by carboxyl and hydroxyl groups, as observed experimentally. The simulation adsorption data for these gases within the examined carbon pore material are presented and discussed in terms of the adsorbate fluid molecular characteristics and corresponding interactions between adsorbate species and adsorbent material. We found that the simulated adsorption uptake of the examined graphite model under these conditions with regard to the aforementioned fluids increases in the order CO?<?CH₄?<?CO₂.     

Strongly localized states in a single carbon nanotube with polymer molecules

A single-walled carbon nanotube (SWCNT) with conjugated polymer molecules is analyzed via optical spectroscopy. The presence of strongly localized excitonic states in the SWCNT is confirmed using time-integrated photoluminescence (PL). The PL spectrum exhibits extremely narrow width (~0.8 meV) which is attributed to the strong confinement of the states by polymer molecules. In addition, I observed that the excited states are gradually filled as a function of the excitation power, which supports the localized excitonic behavior. Only the ground excitonic state is observed at low excitation powers, but three additional PL peaks appear as the excitation power is increased. Especially, the power-dependent PL spectrum shows a blueshift and increased width, which can be elucidated in terms of quantum confined stark effect and the screening of induced electric fields. Overall, I demonstrate that the presence of polymer molecules induces several localized states in a single SWCNT.     

Field emission properties of carbon nanotube cathodes produced using composite plating

Field emission properties of carbon nanotube field emission cathodes (CNT-FECs) produced using composite plating are studied. The experiment uses a CNT suspension and electroless Ni plating bath to carry out composite plating. The CNTs were first purified by an acid solution, dispersed in a Ni electrobath, and finally co-deposited with Ni on glass substrates to synthesize electrically conductive films. Field emission scanning electron microscopy and Raman spectroscopy results show that the field emission characteristics and graphitic properties of CNT-FECs depend on the pH value of the electrobath. Experiments show that the optimum electrobath pH value is 5.4, achieving a field emission current density of 1.0 mA/cm² at an applied electric field of 1.5 V/μm. The proposed CNT-FECs possess good field emission characteristics and have potential for backlight unit application in liquid crystal displays.     

Preparation of Aromatic Polycarbonate Nanoparticles using Supercritical Carbon Dioxide

A novel synthetic process for producing aromatic polycarbonate (PC) nanoparticles using supercritical CO₂ was developed. The objective of the present research work was to synthesize high molecular weight PC nanoparticles using transesterification between bisphenol-A (BPA) and diphenyl carbonate (DPC) in supercritical CO₂ which is an excellent plasticizing agent and a good solvent for phenol, a by-product of the reaction. Poly(propylene oxide)–poly(ethylene oxide)–poly(propylene oxide) tri-block copolymer with CO₂-phobic anchor and CO₂-philic tail group was used as a stabilizer for the preparation of stable dispersions of BPA–DPC mixture in a CO₂ continuous phase. As the reaction was proceeding, phenol formed from the reaction was dissolved and diffused into supercritical CO₂ phase. The PC nanoparticles were isolated by simple venting of the supercritical CO₂ from the reactor. Spherical morphology of PC particles was confirmed by scanning electron microscopy. Particle size and morphology of PC particles were modified upon variation of the process conditions. The resulting PC particles with a nano-size of 30–140nm have a high molecular weight (M _w) of 3.1×10⁵ (g/mol).     

Preparation and Properties of Antimicrobial Poly(butylene adipate-co-terephthalate)/TiO2 Nanocomposites Films

Abstract

Poly(butylene adipate-co-terephthalate) (PBAT) nanocomposite films with various contents of nano-titanium dioxide (TiO₂) and titanium dioxide doped silver (Ag-TiO₂) were prepared by a solvent casting method. The TiO₂ and Ag-TiO₂ nanoparticles were surface-modified with silane coupling agents to improve their compatibility and dispersibility in the PBAT matrix. They were denoted as mTiO₂ and mAg-TiO₂, and were characrterized by Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). The morphology of the PBAT nanocomposite films was studied by field emission scanning electron microscopy (FE-SEM). The crystallinity of the PBAT film increased upon the introduction of the nano-TiO₂/Ag-TiO₂. Its mechanical properties and gas barrier properties were also significantly improved. In addition, the PBAT/mTiO₂ and PBAT/mAg-TiO₂ nanocomposite films showed a strong antibacterial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) food-borne pathogenic bacteria.