Covalent attachment of poly(ethylene glycol) on multi-walled carbon nanotubes

A new 'graft-onto' method to attach poly(ethylene glycol) (PEG) onto multi-walled carbon nanotubes (MWNTs) has been developed. The method is based on the coupling reaction of radicals formed at the chain end of PEG onto the surface of MWNTs. The polymeric radicals are generated by atom (halogen) transfer reaction between chloroacetyl-terminated PEG and transition metal catalysts. The method allows direct covalent attachment of PEG to pristine MWNTs without pretreatment that could alter their original structure. The resulting PEG-grafted MWNTs showed improved dispersion stability in isopropanol and methanol.     

Effect of a Novel Polymeric Coupling Agent on the Water Uptake Property and Warp Stability of Poly(vinyl chloride)/Bamboo Flour Composite

Water uptake property and warp stability of poly(vinyl chloride) (PVC)/bamboo flour composite were investigated employing a novel polymeric coupling agent, poly(styrene-co-maleic anhydride)-block-poly(styrene-co-acrylonitrile) {P[(SMA)-b-(SAN)]}. P[(SMA)-b-(SAN)] was synthesized through controlled/'living' radical polymerization (CRP) technique in an one-pot reaction and incorporated into the composite to improve the interfacial adhesion between PVC and bamboo flour. The structure of P[(SMA)-b-(SAN)] was confirmed by ¹H-NMR, FT-IR and GPC. PVC/bamboo flour composite sheets were then prepared from a single screw extruder and two-roll mill in the presence of P[(SMA)-b-(SAN)] coupling agent. As the content of the coupling agent increased, improved interfacial bonding between PVC and bamboo flour filler was observed. Water uptake property and warp stability were also improved in the presence of the coupling agent. These results suggest that the block copolymer successfully acted as a coupling agent in PVC/bamboo flour composites.     

Functionalization of vertically aligned carbon nanotubes with polystyrene via surface initiated reversible addition fragmentation chain transfer polymerization

Here we demonstrate the covalent attachment of vertically aligned (VA) acid treated single-walled carbon nanotubes (SWCNTs) onto a silicon substrate via dicyclohexylcarbodiimide (DCC) coupling chemistry. Subsequently, the pendant carboxyl moieties on the sidewalls of the VA-SWCNTs were derivatized to acyl chlorides, and then finally to bis(dithioester) moieties using a magnesium chloride dithiobenzoate salt. The bis(dithioester) moieties were then successfully shown to act as a chain transfer agent (CTA) in the reversible addition fragmentation chain transfer (RAFT) polymerization of styrene in a surface initiated “grafting-from” process from the VA-SWCNT surface. Atomic force microscopy (AFM) verified vertical alignment of the SWCNTs and the maintenance thereof throughout the synthesis process. Finally, Raman scattering spectroscopy and AFM confirmed polystyrene functionalization.     

Micromechanical properties of poly(butylene terephthalate) nanocomposites with single- and multi-walled carbon nanotubes

Polymer nanocomposites with carbon nanotubes (CNT) are becoming important structural materials because of their superior mechanical properties and easy processability. The objective of the work is to investigate the influence of small amounts of single walled carbon nanotubes (SWCNT), as well as multi-walled carbon nanotubes (MWCNT), on the microhardness of a thermoplastic polymer such as poly(butylene terephthalate) (PBT). The nanocomposites were obtained by introducing the CNT into the reaction mixture during the synthesis of PBT. The polymers without carbon nanotubes (reference material) and with carbon nanotubes were synthesized using an in-situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of the single walled and from 0.01 to 0.35 wt% of the multi-walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and by ultra high speed stirring. The nanocomposites were extruded followed by injection molding. The samples were characterized by electron microscopy and microindentation hardness techniques. The variations of the micromechanical properties (indentation hardness) of the nanocomposites with nanotube content and with temperature are discussed in the light of the stress transfer between the polymer matrix and nanotubes, the degree of dispersion, the nature of the tubes and other structural parameters.     

The effect of chemical treatment on the crystallinity of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were chemically treated using nitric acid solution for different time. Quantitative analysis of the crystallinity of the MWCNTs was performed by wide-angle X-ray diffraction (WAXD). The WAXD patterns were deconvoluted into the crystalline diffraction peaks and the amorphous scattering peaks. The introduction of a correction factor for the integrated peak intensity can enhance the computational accuracy of the crystallinity. With increasing the chemical treatment time, the crystallinity of MWCNTs first increases, and then decreases. When the chemical treatment time is equal to 2 h, the crystallinity of MWCNTs reaches the maximum of 85.9%. Moreover, the degree of order in the structures of chemically treated MWCNTs was further studied by thermogravimetric analysis (TGA) and high-resolution transmission electron microscopy (HRTEM). It was found that the external walls of chemically treated MWCNTs with high crystallinity consist of a series of perfectly continuous and straight graphite layers.     

拓扑缺陷对Armchair型小管径多壁碳纳米管输运性质的影响

采用密度泛函理论和非平衡格林函数方法研究了纯净的及带有不同数目的Stone-Wale拓扑缺陷下的扶手椅型单壁, 双壁和三壁小管径碳纳米管的能带结构和电子输运性质, 通过计算并分析不同偏压下的微分电导和非弹性电子隧穿谱(IETS), 计算结果表明单壁, 双壁和三壁碳纳米管的特征偏压区间分别为[-1.0V, 1.0V], [-0.5V, 0.5V] 和[-0.25V, 0.25V], 特征偏压区间内SW拓扑缺陷所产生的电导波动平缓, 而特征偏压区间外因缺陷的数目变化所带来的电导波动显著, 通过IETS谱线的分析得到单壁, 双壁和三壁碳纳米管的特征峰偏压分别为 1.25V, 0.625V和 0.125V. 碳纳米管的特征偏压区间和IETS特征峰偏压可为较小管径碳纳米管单壁, 双壁和多壁类型的区分提供一种新的途径, 同时也为小管径多壁碳纳米管的输运性质在出现拓扑缺陷时的响应提供参考依据.     

Preparation of nanocomposite superabsorbents based on hydrotalcite and poly(acrylic-co-acrylamide) by inverse suspension polymerization

Firstly, hydrotalcite (HT) was synthesized by the urea method. Then, sodium methyl allyl sulfonate (SMAS) was used as intercalation agent to prepare intercalated HT (SMAS–HT). Finally, a novel poly(acrylic-co-acrylamide)/HT nanocomposite superabsorbent was prepared by inverse suspension polymerization, using N,N′-methylenebisacrylamide (NMBA) as a cross-linking agent and potassium persulfate (KPS) as an initiator. The morphology of the superabsorbents was characterized by FT-IR, XRD, SEM and TEM. The influences of the amount of SMAS–HT on the water (salt) absorbency were investigated. Results showed that the intercalation was successful and the intercalated SMAS–HT incorporated into the superabsorbent was completely exfoliated. The superabsorbent particles approach a spherical shape and the average size is 200–300 nm. The particle sizes of the superabsorbents decrease with increasing the content of SMAS–HT. In addition, the superabsorbent acquired its highest water (salt) absorbency when the content of SMAS–HT is 3 wt%. The highest absorbencies of the superabsorbent for deionized water and 0.9% NaCl_(aq) were 900 g/g and 140 g/g, respectively.     

Effect of multi-walled carbon nanotubes on dielectric and electro-optic properties of a high tilt antiferroelectric liquid crystal

By dispersing a small amount of multi-walled carbon nanotubes in a high tilt antiferroelectric liquid crystal, a nano composite is prepared. Though the phase sequence remains the same, the transition temperatures of the composite get changed, the stability of SmA* and SmC* phases increases whereas that of SmC_A* phase decreases. Pitch of the helicoidal structure shows a discontinuous change at SmC*–SmC_A* transition. Absorption strength and critical frequency of the anti-phase antiferroelectric mode are reduced in the composite. The dielectric increment of the Goldstone mode (GM) decreases and the critical frequency increases due to increased elasticity of the composite. A two-fold increase in the critical field for suppression of the GM is observed which signifies more stable helical structure in the composite. The switching time is reduced by 56% in the nano composite as a result of decrease in rotational viscosity but the high tilt remains intact. An observed lower value of conductivity indicates ion trapping in the composite.     

Investigation into performance enhancements of Li–S batteries via oxygen-containing functional groups on activated multi-walled carbon nanotubes using Fourier transform infrared spectroscopy

It was demonstrated that the electrochemical performance enhancements in KOH-activated carbon materials should be mainly due to the created polar oxygen-containing functional groups (OFGs, such as such as C–O, CO, –OH, and O–CO), while the role of each OFGs on the electrochemical enhancements is still unclear. In this work, KOH activation treatments were systematically conducted on carbon nanotubes (CNTs) to explore the role of each OFG on the performance enhancements of Li–S batteries (LSBs). Results showed that the capacity of activated-CNT-sulfur (a-CNT-S) cathodes is 33% higher than that of the pristine CNT-S cathodes, and their rate capability and cycling stability are also enhanced. And the electrochemical analysis combining with Fourier transform infrared spectroscopy indicated that the formed C–O bonds are the real factor for the enhanced electrochemical performances of a-CNT-S cathodes. Furthermore, the optimal activation conditions on CNT-based cathodes for LSBs were optimized to be 10 min at 700 °C.     

First-principles study of palladium atom adsorption on the boron- or nitrogen-doped carbon nanotubes

We have performed first-principles calculation to investigate the adsorption of a single palladium atom on the surface of the pristine and boron- or nitrogen-doped carbon nanotubes (CNTs). The results show that for the adsorption of a single palladium atom on the pristine CNT surface, the most stable site is Bridge1 site above the axial carbon–carbon bond. Either boron- or nitrogen-doped CNTs can assist palladium surface adsorption, but the detailed mechanisms are different. The enhanced palladium adsorption on boron-doped CNT is attributed to the palladium d orbital strongly hybridized with both boron p orbital and carbon p orbital. The enhancement in palladium adsorption on nitrogen-doped CNT results from activating the nitrogen-neighboring carbon atoms due to the large electron affinity of nitrogen. Furthermore, the axial bond is preferred over the zigzag bond for a palladium atom adsorbed on the surface of all three types of CNTs. The most energetically favorable site for a palladium atom adsorbed on three types of CNTs is above the axial boron–carbon bond in boron-doped CNT. The enhancement in palladium adsorption is more significant for the boron-doped CNT than it is for nitrogen-doped CNT with a similar configuration. So we conclude that accordingly, the preferred adsorption site is determined by the competition between the electron affinity of doped and adsorbed atoms and preferred degree of the axial bond over the zigzag bond.     

B（N）掺杂单壁碳纳米管的Al原子吸附性能的第一性原理研究

采用基于密度泛函理论的平面波赝势方法和广义梯度近似,对未掺杂、掺B、掺N的碳纳米管(CNT)不同位置上Al原子的吸附进行了几何优化,计算了吸附Al、掺杂前后CNT的能带结构、态密度、差分电荷密度、电荷布居数和吸附能.计算结果表明,掺B使CNT形成缺电子状态,利于具有自由电子的Al原子的吸附结合,可显著提高Al在金属性的(5,5)CNT和半导性的(8,0)CNT外壁的吸附能;掺杂N形成多电子状态,在费米能级附近半满的施主能级也利于填充Al的价电子,改善Al在(5,5)CNT和(8,0)CNT外壁的吸附结合性 关键词： 密度泛函理论 单壁碳纳米管 B(N)掺杂 Al原子吸附     

Effects of oxygen-containing defect complex on the electronic structures and transport properties of single-walled carbon nanotubes

The electronic structures and transport properties of (10,0)$(10,0)$ single-walled carbon nanotube ((10,0)$(10,0)$ (SWNT)) with oxygen-containing defect complex are investigated using density functional theory in combination with nonequilibrium Green?s function method. The complex delocalizes the local states of (10,0)$(10,0)$ SWNT induced by mono- and di-vacancy but strengthens the localization of the states induced by the Stone–Wales defect. As a result, the complex partially restores the transport properties of (10,0)$(10,0)$ SWNT with vacancies, but reduces the transmission of (10,0)$(10,0)$ SWNT with Stone–Wales defect. However, the oxygen-containing defect complex only slightly influences the transmission gap and threshold voltage of the system.