插层还原法制备纳米钯/石墨烯复合材料的研究

以氧化石墨和氯化双乙二胺钯Pd(en)2Cl2为前驱体,将金属钯前驱体与氧化石墨发生插层反应,再将插层了Pd(en)2+2的氧化石墨在溶液中用NaBH4还原,制备出纳米钯/石墨烯复合材料。采用X射线衍射(XRD)、场扫描电子显微镜(FE-SEM)、透射电子显微镜(TEM)、电感耦合等离子体发射光谱(ICP)、低温氮气吸附等手段对复合材料进行表征并对复合材料进行了储氢性能的测试。研究结果表明:复合材料具有规则的中孔结构,直径为2~6 nm钯的纳米粒子弥散地分布在石墨烯的层间,起着支撑作用,阻止石墨烯片层的重新聚集;复合材料具有较高的BET比表面积,在77 K及0.11 MPa条件下其储氢量达到了3.4%(质量分数)。     

ZnO纳米片状晶体的生长及其表征

采用高温碳热还原反应工艺．以氧化锌和碳粉为主要原料，在N2／H2O气氛中制备成功ZnO纳米片状晶体.所制薄片直径在100nm．厚度约50nm.采用场发射扫描电子显做镜（FESEM）、高分辨透射电子显做镜（HETEM）、X射线衍射分析仪（XRD）、拉曼（RAMAN）光谱等测试手段对产物进行表征。结果表明产物为ZnO，呈单一六角晶系纤锌矿结构，在相同的反应时间内，提高反应温度可使纳米片生长为六角塔状晶体，证填ZnO纳米片是六角平板状结构。     

A theoretical study of the electronic properties of intercalated graphite

We present the results of electronic structure calculations for first and second stages of lithium intercalated graphite (LiC₆ and LiC₁₂). The various stages of Li intercalated graphite all have hexagonal symmetry, where different carbon layers are stacked with C-atoms directly on top of each other (AIAI…), as opposed to natural graphite where the C-layers are staggered (ABAB…). All our calculations have been performed within the framework of the extended tight binding method with Gaussian type basis sets. From the orbital and total densities of states, we conclude that Li-2s electrons are transferred into carbon π-bands. This results in shifting the Fermi level into the region of high density of states (compared with pure graphite) and, hence, to observed metallic behavior. The calculated density of states for LiC₆ and LiC₁₂ is 0.25 and 0.12/(eV C-atom), respectively. Recall that for pure graphite the value is nearly zero and for copper it is 0.29. We also found it instructive to obtain the electronic structure of LiC₆ and LiC₁₂ based on a rigid band model.     

Electronic structures of polyacenacene and polyphenanthrophen anthrene. Design of one-dimensional graphite

The electronic structures of polyacenacene (PAA) and its geometrical isomer, polyphenanthrophenanthrene (PPhP) have been studied using the tight-binding SCF-CO (self consistent field-crystal orbital) method with respect to a design of one-dimensional (1D) graphite. The geometry of each polymer is optimized from the energetic point of view. It has been found that from the analysis of the electronic structure of its optimized geometry, PAA favours the structure without the carbon-carbon bond alternations, yielding no band gap. In this sense, PAA is a typical 1D-graphite. On the other hand, it is predicted that the magnitude of the band gap of PPhP in its optimized geometry is almost equal to that of trans-polyacetylene.     

Improvement of water/resin wettability of graphite using carbon black nano particles coating via ink media

Carbon coated graphite with high resin and water wettability characteristics could expand the refractory and carbon–carbon composites application in different fields. Improvement of water and resin wettability of graphite using carbon black coating via ink media is reported. Present method is based on preparing colloidal disperion of carbon black in ink followed by adding proper amount of graphite to the mixture which was dried and heat treated at 250 °C afterwards. The results showed that by controlling the amount of carbon black in ink and optimizing the process, a uniform coating with a thickness of 50 nm could be developed on the graphite surface.The wettability was evaluated by measuring contact angle and the microstructure of samples was characterized by optic microscope (OM) and scanning electron microscope (SEM). Also Raman spectroscopy was employed to support the results. The microstructure of coating was found to be uniform composed of carbon black nanoparticles. It was also demonstrated that the coating that could enhance the phenolic resin wettability was well. We also showed the coating could be applied on other ceramic particles such as MgO.     

Covalent functionalization of graphene oxide with polyglycerol and their use as templates for anchoring magnetic nanoparticles

An efficient strategy for the preparation of water-dispersible hybrid material containing graphene oxide and polyglycerol for the first time is demonstrated. Pristine graphite was firstly oxidized to obtain graphene oxide with hydroxyl functional groups. Then, the covalent grafting of polyglycerol onto the surface of graphene oxide was carried out based on in situ ring-opening polymerization of glycidol. For the construction of novel hybrid nanostructure, Fe-core/Au-shell nanoparticles were prepared and further functionalized using 4-mercaptophenylboronic acid through the well-developed Au–S chemistry. Subsequently, magnetic nanoparticles were anchored on the surface of polyglycerol-grafted graphene nanosheets via boroester bonds. The resulting hybrid materials were characterized using a range of analytical techniques. Fourier transform infrared spectroscopy (FT-IR) was employed to investigate the initial changes in surface functionalities. While X-ray diffraction (XRD) was used to confirm the structure of graphene oxide nanosheets, high resolution transmission electron microscopy (HR-TEM), and field emission scanning electronic microscopy (FE-SEM) equipped with an energy dispersive X-ray (EDX) spectrometer were used to study the morphologies and distribution of magnetic nanoparticles onto the surface of polyglycerol-grafted graphene. Thermogravimetric analysis (TGA) was used to study the weight loss of the samples on heating. Superconducting quantum interference device magnetometer (SQUID) was employed to the magnetic property of magnetic nanoparticles. The digital images provided a vivid observation on the high dispersion stability of the prepared novel hybrid materials in distilled water.     

Regularity control of porous anodic alumina and photodegradation activity of highly ordered titania nanostructures

A two-step anodizing process was used to prepare wide-range highly ordered porous anodic alumina membrane （PAA） in the electrolyte of oxalic acid. The effects of anodic voltage, anodizing time, size of aluminium foil and additives on the regularity of PAA membrane were also studied in the process of two-step anodization. The template method was combined with the sol-electrophoresis deposition and sol-gel method respectively to prepare highly ordered titania nanostructures. The diameter and length of the obtained nanostructures were determined by the pore size and depth of the PAA template. Scanning electron microscopy （SEM） and X-ray diffraction （XRD） were, used to characterize the morphology and phase structure of the PAA template and the titania nanostructures. The results show that the anodizing time and the additive of ethanol have a great effect on the regularity of PAA template. This can be explained from the self-organized process and the current density theory. A theoretical model based on the self-organized process was established to discuss the formation mechanism of PAA template from the chemical perspective. The titania nanostructures prepared with this method has a high specific surface area. Furthermore, the photocatalytic activity of titania nanostructures on methyl orange were studied. Compared with ordinary titania membranes, the titania nanostructures synthesized with this method have higher photodegradation activity.     

In situ synthesis of one eco-friendly polyacrylic acid/zinc colloidal particles doped polyacrylic acid as an efficient corrosion inhibitor for iron

Commonly used organic inhibitors face one common problem: Environmental friendliness and excellent inhibition efficiency cannot be simultaneously realized. Here, we report one facile method that can be used for the in situ synthesis of one stable polyacrylic acid/zinc colloidal particles (PZCPs) doped polyacrylic acid (PAA) through the electrostatic interaction between polyacrylic acid and Zn ²⁺ as a corrosion inhibitor of iron. The results of microstructure characterization indicated that the diameter of the colloidal particles was around 150 nm. The various electrochemical experimental results indicated that PZCPs doped PAA exhibited excellent inhibition efficiency, and the maximum inhibition efficiency was 82.3%. The PZCPs doped PAA exhibited higher inhibition efficiency than PAA because the adsorption ability of PZCPs doped PAA was stronger than that of PAA and the formed PZCPs doped PAA inhibition layer on the iron surface was thicker and denser than the PAA inhibition layer. Given the eco-friendly, facile synthesis, excellent inhibition efficiency, and low price, this strategy to synthesize effective inhibitors will find widespread application in the anti-corrosion industry.     

少层石墨烯的微波辐照法快速制备及表征(英文)

以可膨胀石墨为原料制备少层石墨烯,通过初次微波辐照3 min、混酸(浓硫酸与浓硝酸的体积比为1:1)浸泡处理24 h及二次微波辐照剥离3 min的工艺流程,得到了少层石墨烯。用扫描电镜(SEM)、X射线衍射(XRD)、拉曼光谱(Raman)、原子力显微镜(AFM)、X射线光电子能谱(XPS)、红外光谱(FTIR)和燃烧法元素分析对实验产物进行表征。结果表明:经过初次微波辐照处理,伴随闪光及爆裂声,可膨胀石墨层片结构被剥离,迅速形成疏松、多孔的蠕虫形貌。通过混酸浸泡、二次微波辐照和超声分散等后续处理,可快速制得厚度约为4.7 nm的约十几层的石墨烯,且石墨烯未被严重氧化,纯度高,结晶度高。     

Characterization of phase transformation and microstructure of nano hard phase Ti（C,N）-based cermet by spark plasma sintering

By means of optical microscope (OM), scanning electron microscope (SEM) and transmission electron microscope (TEM), the process of densification, the characterization of phase transformation and the microstructure for spark plasma sintering (SPS) nano hard phase Ti(C, N)-based cermet were investigated. It is found that the spark plasma sintering (SPS) enables the nano hard phase Ti(C,N)-based cermet to densify rapidly, however, the full densification of the sintered samples can not be obtained. The rate of phase transformation is significantly quick.When being sintered at 1 200℃ for 8 min, Mo2C is completely dissolved, and TiN dissolves into TiC entirely and disappears. Above 1200℃, Ti(C,N) begins to decompose and the atoms of C and N separate from Ti(C,N) resul-ting in the generation of N2 and the graphite. Due to the denitrification and the graphitization, the density and the hardness of sintered samples are rather low. The distribution of grain size of the sample sintered at 1350℃ covers a wide range of 90-500 nm, and most of the grain size are about 200 nm. The hard phase is not of typical core-rim structure. Oxides on the surface of particles can not be fully removed and present in sample as titanium oxide TiO2.Graphite exists in band-like shape.     

Synthesis and characterization of lithium-carbon compounds for hydrogen storage

Three carbon materials were prepared for the synthesis of Li-C compounds, such as Li intercalated graphite. The materials were as-received high purity polycrystalline graphite (G), graphite milled under a hydrogen atmosphere (HG), and graphite milled an argon atmosphere (AG). With respect to the difference for them, HG preserved a better crystalline structure than AG. Each material was milled with Li, where the products are denoted as Li-G, Li-HG, and Li-AG. In XRD patterns of Li-G and Li-HG, the peaks corresponding to LiC₆ and LiC₁₂ were revealed, while no peaks were observed in the case of Li-AG. However, the formation of lithium carbide Li₂C₂ was suggested for Li-AG by a thermal analysis under an inert gas. After the hydrogenation, LiH was formed for all the compounds, and graphite was recovered for Li-G and Li-HG. Each hydrogenated compound desorbed H₂ with different profile by heating up to 500 °C. As a reaction product, Li₂C₂ was formed for the hydrogenated Li-HG and Li-AG. In the case of the hydrogenated Li-G with better crystalline structure, Li intercalated graphite were formed after the dehydrogenation. Therefore, it is concluded that the hydrogen absorption and desorption process of Li intercalated graphite was different from those of Li₂C₂.     

Formation of nanoporous oxide at aluminum anodizing

The effect of electrochemical anodic oxidation on the formation of porous anodic oxide films (PAOF) on a high-grade aluminum (99.99%) in a sulfuric acid solution is studied. Anodizing modes are chosen such as to obtain PAOF with ordered nanostructure. It is shown that under an atomic force microscope, the anodic film reveals a cellular structure. The parameters of the latter are as follows: diameters of a pore (30–35 nm) and a circle circumscribed around a hexahedral cell (90 nm). A possible mechanism of the formation of regular nanoporous structures of anodic aluminum oxide is proposed.     

Characterization of reactively sputtered permeation barrier materials on polymer substrates

Transparent permeation barrier layers are not only used for food packaging but are also needed to encapsulate flexible electronic devices. Magnetron sputtering allows the deposition of high quality oxide barrier layers with a low water vapor and oxygen permeation. This paper compares different metal oxide layers which are deposited onto a polyethylene terephthalate (PET) film using a reactive dual magnetron sputtering process. The oxides of aluminum, silicon, titanium, zinc and a zinc-tin alloy are compared regarding their permeation barrier, structural and surface properties to determine the relationship between the layer structure and the gas permeation. Thereby, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology and surface structure of the layers and X-ray diffraction analysis (XRD) was used to determine the solid state phase.Cross-section images taken with SEM show a very compact structure for both aluminum oxide and zinc-tin oxide layers. These materials also have the lowest water vapor permeation compared to all other materials. Zinc oxide and titanium oxide layers both exhibit a columnar structure. Zinc oxide is polycrystalline and has a surprising low water vapor and oxygen permeation. In contrast to that the amorphous titanium oxide layers show a high water vapor and oxygen permeation which is not decreasing with an increasing layer thickness above 40 nm.     

球磨法制备纳米TiC及其生成机理

采用高能球磨法制备纳米TiC颗粒,通过对不同球磨时间试样进行X射线衍射分析、扫描电镜及透射电镜进行形貌观察,得出球磨过程中TiC的生成机理。结果表明,球磨过程中,首先石墨和钛粉细化,石墨形成片状而钛粉形成细小颗粒;随着球磨时间的延长,片状石墨包裹钛粉;当磨球碰撞时达到Ti和C反应温度,Ti和C发生反应产生TiC,反应放出的热量维持反应的进行。制备的TiC粒度为10～100nm。     

Electrical and mechanical properties of copper chloride-intercalated pitch-based carbon fibers

Using chlorine vapor transport we have intercalated pitch-based fibers, highly oriented pyrolytic graphite (HOPG), and natural single crystals of graphite with CuCl₂. In this paper we report mainly on the electrical properties of pitch-based fibers heat treated to 2500, 2750 and 3000 °C and then intercalated. The electrical resistivity both above and below room temperature, the tensile strength, and Young's modulus are reported. In very high magnetic fields at 4 K the fibers exhibit Shubnikov-de Haas oscillations, which means this powerful technique is now available as a diagnostic tool for intercalated fibers.     

聚苯胺纳米线复合材料的制备与储能性分析

针对软、硬模板法制备纳米线的缺陷,提出一种步骤简单、快速且低成本的方法来获得直径均匀的PANI纳米线复合材料,并对所制备出的PANI纳米线复合材料进行表征和电化学性能研究。首先,采用阳极氧化剥离法,分别在硝酸体系、磷酸还原体系及硫酸体系中对表面光滑的石墨板进行电化学剥离处理。随后,在经过电化学剥离后的粗糙石墨表面上进行电聚合,从而得到PANI纳米线复合材料。表征分析发现,经电化学剥离处理的石墨纸表面分别生成具有大量活性点的石墨烯和氧化石墨烯,与PANI结合显著提高了PANI的导电性。其中硝酸体系制备的聚苯胺复合材料(PANI/GO)微观为纳米线组成的三维网状结构;磷酸还原体系制备的聚苯胺复合材料(PANI/GR1)微观是纳米线和纳米片层混合结构;硫酸体系制备的聚苯胺复合材料(PANI/GR2)的微观结构介于二者之间。以镁合金和上述三种PANI复合材料为电极,制备出简易的海水电池。使其在电流密度为3.75 m A·cm^-2下放电至0.9 V时止。三种电池的比能量分别为540、228和363 m Wh·g^-1,结果表明PANI/GO的储能性最优。...     

Application of nanotechnology in a silver／graphite contact material and optimization of its physical and mechanical properties

By applying nanotechnology, a new type of silver/graphite (AgC) electrical contact was fabricated and charac-terized. The AgC coating powders were obtained through high-energy ball milling and reducer liquid spraying-coating method. The as-prepared powders were examined by transmission electron microscope (TEM), scanning electron micro-scope (SEM), and X-my diffraction (XRD). The results show that the thickness of graphite flakes milled for 10 h is about 50-60 nm and the AgC coating powders exhibit flocculent structure with quite free and homogeneous intemal micropores.XRD implies that the average crystalline size of silver in coating powders is about 50 rim. The mechanical and physical properties of this newly developed AgC contact made from the above-mentioned nanocrystalline powders by traditional powder metallurgy technique were measured. Compared with its counterparts made from other techniques, the properties of this new AgC contact have been optimized. High surface energy and high-energy interfaces of the nanocrystalline AgC coating powders provide powerful driving force for sintering densification. Moreover, the flocculent structure of the pow-ders is also an important factor to acquire fine density ratio.     

Intercalation of polypyrrole into graphite oxide

In this paper we report on the insertion of polypyrrole into layered graphite oxide. This was achieved by using the exfoliating and re-stacking properties of the host. The resulting intercalated product was characterized by powder X-ray diffraction, FT-IR spectroscopy, thermogravimetric analysis and scanning electron microscopy.     

石墨含量对镍基高温合金在900 ℃氧化行为的影响

采用粉末冶金方法制各不同石墨含量(0%、3%、6%)的镍基高温合金,研究合金材料在900℃和100 h下的恒温氧化行为,用扫描电镜和X射线衍射对其氧化表面形貌和成分进行观察和分析.结果表明:石墨含量较低(0%,3%)时,镍基合金氧化动力学符合抛物线规律,表面氧化膜无剥落;石墨含量为0%的合金氧化膜由Cr2O3和NiCr2O4组成,石墨含量为3%的合金氧化膜由Cr2O3组成,当石墨含量增加到6%时,大量石墨的氧化分解导致合金初始氧化严重,石墨分解后的孔洞加速氧化反应过程.根据氧化膜的组成分析了合金的氧化机制.     

Influence of Bismuth on Graphite Nodule Count in Thin-section Spheroidal-graphite Cast Iron

Abstract

Cast irons containing 3.8% C and 2.2% Si were melted in a graphite crucible using a high-frequency induction furnace. Nodularisation treatment was carried out at 1530°C by the addition of 1.6% Fe-Si-Mg alloy and various amounts of bismuth as metallic bismuth, bismuth oxide and bismuth sulphide. When the magnesium reaction subsided, the melts were post-inoculated with Fe-Si and then poured into CO₂ Process sand moulds. The occurrence of chilled structure and graphite-nodule counts were determined using an optical microscope and an image analyser. X-ray microanalysis and emission spectrochemical analysis were carried out to detect Bi in the graphite nodules and also in nodules extracted with dilute hydrochloric acid. The nodule count was enhanced by the addition of extremely small amounts of metallic bismuth, bismuth oxide and/or bismuth sulphide. Some heterogeneous phases containing Bi, Mg, Ti, Fe and Si, with diameters of 1 μm or less were observed at the centres of graphite spheroids using back-scattered electron imaging and an energy dispersion X-ray microanalyser. Graphite crystallises on these phases during eutectic solidification. It is suggested that large numbers of fine liquid bismuth particles contribute to the formation of graphite spheroids by acting on the substrate.