Curling and closure of graphitic networks under electron-beam irradiation

The discovery of buckminsterfullerene (C60) and its production in macroscopic quantities has stimulated a great deal of research. More recently, attention has turned towards other curved graphitic networks, such as the giant fullerenes (Cn, n > 100) and carbon nanotubes. A general mechanism has been proposed in which the graphitic sheets bend in an attempt to eliminate the highly energetic dangling bonds present at the edge of the growing structure. Here, I report the response of carbon soot particles and tubular graphitic structures to intense electron-beam irradiation in a high-resolution electron microscope; such conditions resemble a high-temperature regime, permitting a degree of structural fluidity. With increased irradiation, there is a gradual reorganization of the initial material into quasi-spherical particles composed of concentric graphitic shells. This lends weight to the nucleation scheme proposed for fullerenes, and moreover, suggests that planar graphite may not be the most stable allotrope of carbon in systems of limited size.     

Different effects of substrates on the morphologies of single-walled carbon nanotubes

In this work, different effects of substrates on the morphologies of single-walled carbon nanotubes （SWNTs） are studied. SWNTs were produced by floating catalytic chemical vapor deposition using CH4 as carbon source gas and Ar as carrier gas. Then the SWNTs were deposited on lithography-patterned different substrates. The as-grown SWNTs at the boundaries between SiO2 and metal were characterized by scanning electron microscopy, atomic force spectroscopy and Raman spectroscopy. It is found that SWNTs deposited on low-conductivity substrates trend to have curved morphologies and some of them form rings, while SWNTs deposited on metal sub- strates remain straight and orientated. The mechanism of these effects was also discussed, which is closely related to the thermal conductivities and the principle of energy dissipation.     

Simple method to rapidly fabricate chain-like carbon nanotube films and its field emission properties

A simple process to fabricate chain-like carbon nanotube (CNT) films by microwave plasma-enhanced chemical vapor deposition (MPCVD) was developed successfully. Prior to deposition, the Ti/Al₂O₃ substrates were ground with Fe-doped SiO₂ powder. The nano-structure of the deposited films was analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy. The field electron emission characteristics of the chain-like carbon nanotube films were measured under the vacuum of 10-5 Pa. The low turn-on field of 0.80 V/μm and the emission current density of 8.5 mA/cm2 at the electric field of 3.0 V/μm are obtained. Based on the above results, chain-like carbon nanotube films probably have important applications in cold cathode materials and electrode materials.     

长宁地区富有机质页岩脆性及与裂缝发育关系

页岩的脆性控制着裂缝的形成和演化,对页岩气层的体积改造和页岩气的增产极为关键。以川南长宁地区龙马溪组页岩为例,通过岩石矿物、地球化学和岩石力学等实验对龙一₁亚段的矿物组分、有机地球化学、孔隙-裂缝结构以及力学性质进行测试,分析不同脆性矿物、有机质以及埋深的页岩脆性特征及其与裂缝发育的关系。结果表明,龙一₁亚段脆性最高者为富有机质硅质页岩岩相,石英、长石和黄铁矿等脆性矿物的总含量大于50%,它们能够调节岩石断块的剪切滑移,所积累的能量大于完成岩石整体剪切破坏过程所需的能量;有机质及其在成熟过程中所产生的有机孔隙与微裂缝可促进裂缝的拓展、贯通以及连接,有机碳含量越高,裂缝系统越发育;随着埋深增加,页岩的脆性下降,岩石破裂模式由复杂的劈裂型向单一的剪切型转变;龙一₁¹、龙一₁²小层脆性矿物和有机碳含量最高,脆性指数分别达到了61.31%和60.70%,为压裂甜点层段。     

Effect of radiation on wettability and floatability of sulfide minerals

The feasibility for modifying the wettability and floatability of sulfide minerals by electron beam irradiation has been studied experimentally. The wettability of crystalline pyrite and floatability of some sulfide as pyrite, arsenopyrite, chalcopyrite and marmatite after irradiation were examined by flotation in a modified Hallimond tube. Experimental results show that the hydrophobicity of crystalline pyrite enhances with the increase of irradiation dose in a low dose range. And the flotation responses of sulfide minerals on irradiation dosevary with the mineral species and particle size. The floatability of minerals can be regulated by altering irradiation dose. An explanationfor the mechanism has been suggested based on the principle of radiation chemistry.     

海底天然气水合物绞吸式开采方法研究

 根据海底天然气水合物藏特点,结合绞吸式挖泥船工作原理和大洋多金属结核开采技术,提出了一种全新的绞吸式海底天然气水合物开采方法,克服了海底天然气水合物开采依赖构筑封闭开采环境的技术瓶颈;然后根据管道输送原理和两相流理论,对绞吸式开采方法的提升系统进行了水力参数分析。由分析结果可知,将体积浓度为15%~25%天然气水合物流体从1 000 m海底提升到海面所需泵的扬程为30~50 m;将体积浓度为10%~20%天然气水合物流体从4 000 m海底提升到海面所需扬程为90~150 m,现有的矿浆泵就能满足要求;由于天然气水合物和海底沉积物硬度较低,并且其混合流体的密度与海水密度相差不大,采用矿浆泵进行直接输送其对泵的磨损不会严重,能保证系统长期稳定的工作,证明了该开采方法在理论上是可行的。     

在超临界流体中将PtRu纳米粒子沉积在石墨烯片层及其电催化性能研究

在超临界二氧化碳的辅助下,使用乙酰丙酮铂和乙酰丙酮钌作为前驱体,甲醇作为共溶剂,H2作为还原剂,在200℃将PtRu纳米颗粒还原负载在石墨烯（EG）上.制备产物的形貌和微结构用X射线衍射（XRD）、X射线光电子能谱（XPS）和透射电子显微镜（TEM）进行了分析.同时,用相同的方法制备了PtRu/C（炭黑Vulcan XC-72）复合材料,将其与PtRu/EG对于甲醇氧化的电催化活性和稳定性也通过循环伏安和计时电流法进行了比较.研究证实,用超临界流体方法沉积在石墨烯上的PtRu纳米颗粒具有较小的平均粒径和尺寸分布.与PtRu/C相比,PtRu/EG复合材料对于甲醇电氧化展示出更高的电催化活性和稳定性.     

喷射器内含湿含硫天然气形成水合物预测

针对高含硫气田天然气含湿含硫且井口压力不断降低的特点,利用高压气井的富余压力通过喷射器增压输送低压天然气。采用Fluent软件对喷射器内单相和气液两相含湿含硫天然气的沿程温度、压力进行了数值模拟,应用天然气水合物生成预测模型ZahediⅠ对天然气喷射器内部天然气水合物生成区域进行了预测分析,预测了工作流体入口温度、含硫量、含湿量对天然气水合物生成的影响。工作流体入口温度增加,喷射器内天然气水合物生成区域范围减小,硫化氢含量越高,天然气水合物生成区域范围越大,工作流体含水滴,喷射器内天然气水合物生成区域小于单相工质下的天然气水合物生成区域,进而提出了消除含湿含硫天然气喷射器内形成水合物的措施。     

First discovery and characterizations of late Cretaceous seep carbonates from Xigaze in Tibet, China

Hydrocarbon seeps,widely occurring in continental margins,have become increasingly focused owing to their close relationships with gas hydrates,strong greenhouse gas methane,and biological resources in extreme environments.Ancient hydrocarbon seeps have already been recognized from Devonian to Quaternary strata worldwide based on seep carbonates or seep-related fossil chemosynthetic assemblages.However,seep-related deposits are rarely found from ancient strata in the mainland China.Here,we report the first discovery of an ancient seep deposit,specifically late Cretaceous seep carbonates from Xigaze in Tibet,China.Xigaze seep carbonates,occurring as nodules,are enclosed in upper Cretaceous turbidite strata in Xigaze forearc basin.These carbonates are composed of authigenic carbonate(56.2% on average),clastic quartz and feldspar(27.3% on average),and clay minerals(chlorite,illite and smectite,16.5% on average).Clotted micrites,peloids and framboid pyrites are frequently observed,all of which are common in modern seep carbonates.The carbonates have negative δ13 C values varying from 27.7‰ to 4.0‰(V-PDB),suggesting that thermogenic methane is the primary carbon source.Ce/Ce* values revised by eliminating La effects show no real Ce anomaly,indicating the carbonates were primarily precipitated in a weak reducing environment.Overall,these features provide unequivocal evidences that the seafloor of Xigaze forearc basin developed hydrocarbon seeps in late Cretaceous.     

山东焦家金矿深部载金矿物的研究

焦家金矿床为著名的构造破碎蚀变岩型大型金矿床,随着矿石不断开采,许多矿石工艺矿物学性质发生改变.为了提高金的回收率和确定选矿流程,开展了焦家金矿深部的载金矿物研究.采用光学显微镜、电镜、能谱分析等手段,对矿石的载金矿物种类、金赋存状态、金矿物粒度等矿石性质开展了深入研究.研究表明焦家金矿载金矿物主要有:黄铁矿、黄铜矿,其次是石英、闪锌矿、方铅矿.其中硫化物载金占8650%,硅酸盐矿物载金占1350%.赋存在黄铁矿、黄铜矿晶体中的金粒度比在硅酸盐矿物中大得多.在黄铁矿、黄铜矿和石英中的金颗粒分别为0074~0037mm,0043~0037以及>0037mm范围之内.焦家金矿金的赋存状态有:裂隙金、包裹金和晶隙金,其中裂隙金占6551%,包裹金占1819%,晶隙金占1666%.     

Synthesis and characterization of carbon-coated cobalt ferrite nanoparticles

Cobalt ferrite nanoparticles (CFNPs) were prepared via a reverse micelle method. The CFNPs were subsequently coated with carbon shells by means of thermal chemical vapor deposition (TCVD). In this process, acetylene gas (C₂H₂) was used as a carbon source and the coating was carried out for 1, 2, or 3 h at 750°C. The Ar/C₂H₂ ratio was 10:1. Heating during the TCVD process resulted in a NP core size that approached 30 nm; the thickness of the shell was less than 10 nm. The composition, structure, and morphology of the fabricated composites were characterized using X-ray diffraction, simultaneous thermal analysis, transmission electron microscopy, high-resolution transmission electron microscopy, and selected-area diffraction. A vibrating sample magnetometer was used to survey the samples’ magnetic properties. The deposited carbon shell substantially affected the growth and magnetic properties of the CFNPs. Micro-Raman spectroscopy was used to study the carbon coating and revealed that the deposited carbon comprised graphite, multiwalled carbon nanotubes, and diamond- like carbon. With an increase in coating time, the intensity ratio between the amorphous and ordered peaks in the Raman spectra decreased, which indicated an increase in crystallite size.     

反应等离子体制备碳锥及其表征

利用等离子体增强热丝化学气相沉积系统,用CH4、H2和NH3为反应气体,分别在沉积有钛膜和碳膜的Si片衬底上制备了锥形碳结构,采用场发射扫描电子显微镜(FESEM)、X射线能谱仪(EDX)和显微Raman光谱仪对其形貌和结构进行了表征.SEM结果表明在沉积有碳膜的Si片衬底上易形成碳锥,EDX谱和Raman谱进一步表明形成的碳锥为碳氮结构,由sp3 C-N、sp2 C和sp2 C=N键形成.根据溅射机制和扩散机制,分析了碳锥的形成.同时,还对碳锥Raman谱的荧光背景进行了分析,结果表明由于氮的掺杂,使得碳锥由非极性的碳材料变成为极性碳材料.     

中国陆域天然气水合物资源勘探开发技术研究进展

天然气将是21世纪的主要能源品种,它的储量巨大,据估计其全球储量是现有天然气、石油储量的两倍,是人类理想的潜在的替代能源。作为非常规天然气资源的天然气水合物被誉为21世纪的新能源,近年来它的研究受到世界上许多国家的高度重视。本文对世界天然气水合物资源基本特征和分布情况进行介绍,主要对国内陆域天然气水合物勘探开发技术以及环境效应进行了阐述。     

三聚氰胺热解产物的特性分析

以有机物三聚氰胺为初始原料, 在真空条件下使其热解（1 000 K）. 采用X射线衍射（XRD）、 透射电子显微镜（TEM）、 X射线光电子能谱(XPS)、 化学元素分析（EA）和傅里叶红外光谱(FT-IR) 分析样品的形貌、 成分和结构. 结果表明, 在真空条件下, 三聚氰胺全部分解, 分解产物为片层石墨相C₃N₄.      

苏里格气田东部致密砂岩储层的沉积-成岩约束

鄂尔多斯盆地苏里格气田是我国陆上产能最大的气田,而储层低孔低渗的特点是制约该气田开发的关键因素。为了探讨砂岩储层低孔低渗的成因机理和主控因素,在岩心观察、薄片鉴定、流体包裹体分析、X-射线衍射、阴极发光分析、扫描电镜分析等基础上,进行了系统的沉积微相和成岩作用研究。研究表明,主要产气层山1、盒8段砂体形成于辫状河心滩、辫状河道及曲流河边滩等水动力条件强的沉积微相;成岩作用无疑是砂岩储层物性变差的主要原因;但沉积微相奠定了岩石结构和沉积期后作用的物质基础,对成岩作用和储集性能产生重要影响。     

Reduction mechanisms of pyrite cinder-carbon composite pellets

The non-isothermal reduction mechanisms of pyrite cinder-carbon composite pellets were studied at laboratory scale under argon (Ar) atmosphere. The composite pellets as well as the specimens of separate layers containing pyrite cinder and coal were tested. The degree of reduction was measured by mass loss. The microstructures of the reduced composite pellets were characterized by scanning electron microscopy (SEM). It is found that the reduction processes of the composite pellets may be divided into four stages:reduction via CO and H₂ from volatiles in coal at 673-973 K, reduction via H₂ and C produced by cracking of hydrocarbon at 973-1123 K, direct reduction by carbon via gaseous intermediates at 1123-1323 K, and direct reduction by carbon at above 1323 K. Corresponding to the four stages, the apparent activation energies (E) for the reduction of the composite pellets are 86.26, 78.54, 72.01, and 203.65 kJ·mol-1, respectively.     

Iron speciation in cherts from the Laobao Formation, South China: Implications for anoxic and ferruginous deep-water conditions

Cherts in the Laobao Formation in the Silikou section, South China were deposited in terminal Ediacaran deep-water. The speciations of iron in cherts, such as pyrite Fe (Fe_P), HCl-extractable Fe (Fe_H), and total Fe (Fe_T), and their interrelationships, are proxies for distinguishing oxic, anoxic but ferruginous, and sulfidic conditions, which is an effective method for studying the terminal Ediacaran ocean environment. For chert samples from the Laobao Formation, pyrite concentrations are generally low (<0.56%), degree of pyritization (DOP) ranges from <0.01 to 0.78 and most are <0.45; (Fe_P+Fe_H)/Fe_T ratios are between 0.27 and 0.84 and most exceed 0.38, and most of FeT/Al ratios range from 0.55 to 5.87 (averaging 1.1). Relatively high content of highly reactive Fe and low content of pyrite indicate a scarcity of H₂S and Fe-enriched deep-water. These features suggested that the deposition setting of Laobao cherts was anoxic and ferruginous. Terminal Ediacaran deep-water in the South China Basin was most likely anoxic and ferruginous, which played a key role in the emergence and evolution of early multicellular life.     

枞阳井边金矿金的赋存状态研究

井边金矿位于下扬子台坳、长江褶皱断裂隆起带中段。金矿体赋存于三叠系中统铜头尖组中 ,矿体形态呈不规则脉状。矿石类型主要有以含金褐铁矿为主的氧化矿石和以含金黄铁矿为主的原生矿石两大类。通过矿相鉴定 ,单矿物含金分析、物相分析、多点分析及电子探针分析等 ,查明了载金矿物系列特征的金的赋存状态。金矿物以自然金为主 ,其次为银金矿。金的粒度较细 ,主要为中细粒显微金。金的嵌布类型有包体金、晶隙金及裂隙金 ,金的成色较高 ,平均为 91 0 .4。金主要呈矿物态存在。     

离子轰击碳膜诱导碳纳米尖端的形成和生长

用CH4、NH3和H2为反应气体,利用等离子体增强热丝化学气相沉积系统在沉积有碳膜的Si上制备了碳纳米尖端.用扫描电子显微镜、原子力显微镜和Raman光谱表征了碳膜的结构,以及用扫描电子显微镜和X射线光电子谱表征了碳纳米尖端的结构,结果表明碳膜是凸凹不平的非晶碳膜,碳纳米尖端是由sp2结构的碳组成.根据有关离子的溅射和沉积机制,分析了离子轰击碳膜诱导碳纳米尖端的形成和生长.     

渝东南武隆地区龙马溪组页岩孔裂隙特征研究

为明确渝东南武隆地区龙马溪组页岩孔裂隙发育特征,利用岩芯观察、氩离子抛光扫描电镜分析、低温氮气吸附脱附实验等方法,结合图像分析技术和分形几何理论,对LY-1井龙马溪组页岩孔隙结构及分形特征进行了研究。结果表明,武隆地区龙马溪组页岩宏观裂隙以层间页理缝和成岩收缩缝为主,扫描电镜下可见粒内孔、粒间孔及有机质孔,有机质孔最为发育,孔径几纳米到几十纳米;低温N₂吸附实验结果显示龙马溪组页岩存在3类优势孔径,I类优势孔径分布在1.0~1.5 nm,表明微孔是该区主要的孔隙之一,Ⅱ、Ⅲ类优势孔径分别分布在2.5~3.5 nm、5.0~18.0 nm,孔径>4.0 nm时曲线分维值与TOC、脆性矿物含量及含气量呈负相关性,与黏土矿物呈正相关性。研究认为,有机质孔为页岩气富集提供了最主要的空间,黏土矿物发育复杂结构的孔隙对气体赋存具有一定贡献。