前寒武纪干酪根微结构的高分辨电镜研究

本文根据高分辨电镜观察结果,描述了若干前寒武纪干酪根的微结构,讨论了干酪根微结构与母岩变质作用的关系。发现,在变生和变质过程中,干酪根微结构的变化趋势是不同的;层间距(d_(002))不是H/C比值的线性函数;干酪根的微结构可以指示母岩的变质程度。     

叶腊石微结构及其晶体结构缺陷的高分辨透射电镜分析

采用场发射扫描电镜（FE-SEM）、高分辨透射电镜（HRTEM）结合选区电子衍射（SAED）、X射线粉晶衍射（XRD）及X射线荧光光谱（XRF）等对浙江青田叶腊石的微结构特征进行较系统的研究。结果表明：①粉晶X射线衍射证实青田叶腊石具有典型的单斜晶系特征,该结论与叶腊石粉体选区电子衍射结果吻合,且其伴生矿为石英。②叶腊石微晶体呈＂复式板片＂构型,且＂复式＂板片中薄片厚度约为8±2 nm。③在高能电子束辐照下,叶腊石矿物颗粒形貌及晶格结构发生明显的改变,且由此产生晶格膨胀,并最终形成非晶态。     

松烟和桐油烟的高分辨电镜观察

利用高分辨透射电镜(HRTEM)对传统工艺生产的制墨用桐油烟和松烟的微结构进行研究发现桐油烟和松烟具有比较典型的同心取向准石墨结构。桐油烟的颗粒比较均匀，颗粒直径多分布在50nm～30nm范围内；而松烟中的颗粒主要分布在直径150nm～100nm和50nm～30nm两个范围内。在研究中首次发现松烟、桐油烟中含有螺旋状、洋葱状等多种形态的类富勒烯微结构，为燃烧成因的富勒烯物质提供了直接证据。     

苏皖交界地区坡缕石的矿物学特征

本文对苏皖交界地区内沉积成因的坡缕石及全椒热液成因的坡缕石进行了物性、形貌、化学成分和晶体化学特征及结构特征的研究。研究表明，研究区内坡缕石的矿物学特征与美国凹凸堡的坡缕石一致，而有别于全椒热液型坡缕石，此外，对坡缕石的吸附性能也进行了讨论。     

海泡石坡缕石的有机吸附研究

本研究采用红外光谱分析、Ｘ射线衍射分析和电泳等方法对坡缕石和海泡石吸附有机气体进行了研究。实验表明,这种吸附是因静电力的作用而产生的。矿物表面的吸附水可减弱静电力的作用。坡缕石、海泡石对有机气体的吸附量与气体温度、蒸气压、气体分子偶极矩、样品纯度、矿物结晶有关。温度升高,气体分子热运动将加剧,吸附数量随之减少;若气体分子偶极矩加大,则吸附量增加;增大蒸气压能提高气体分子与矿物微粒间的接触频率,从而     

凹凸棒石粘土吸附废水中污染物机理探讨

凹凸棒石是链层状硅酸盐,具有0.38nm×0.63nm的孔道。许多研究者据此都把凹凸棒石粘土吸附废水中污染物的机理解释为凹凸棒石具有微孔道和较大的比表面积,并且这一解释被普遍接受。作者根据凹凸棒石矿物晶体结构和吸附选择性以及吸附实验研究认为,由于凹凸棒石孔道直径小于大多数分子及水合离子的直径,除少数简单分子和离子外,多数分子和离子都不能进入凹凸棒石孔道,而且凹凸棒石内孔道选择性优先吸附水分子,因而在 多数水处理中,凹凸棒石对吸附质的吸附不是内表面吸附,而是外表面吸附。并且这种外表 面吸附属于凹凸棒石的胶体和离子交换吸附。除了溶液的pH值等介质条件外,共存胶体蒙脱石和凹凸棒石的相互作用可能对凹凸棒石粘土的吸附性能起重要作用。     

富镁与贫镁坡缕石在热处理下的结构变化研究

研究了安徽明光富镁坡缕石和江苏盱眙贫镁坡缕石热处理后的结构变化,结果表明:富镁坡缕石八面体片对称性好,晶体结构稳定性高,结晶度高,热稳定性好;贫镁坡缕石八面体片中存在连续八面体空位,对称性差,晶体结构稳定性低,结晶度差,热稳定性差。在脱除结晶水和羟基过程中,富镁坡缕石由正交晶系转变为单斜晶系,层间距变小,孔道变形、塌陷但一直保持链层结构,显示晶质特性;而贫镁坡缕石的晶体结构发生折叠,链层结构逐步破坏,700℃煅烧后部分四面体片遭到破坏,虽然显示多晶特性为主,但开始出现非晶化现象。     

Adsorption Kinetics of Methylene Blue from Aqueous Solutions onto Palygorskite

The adsorption kinetics of methylene blue from aqueous solutions on purified palygorskite was investigated. The kinetics data related to the adsorption of methylene blue from aqueous solutions are in good agreement with the pseudo-second order equation in ranges of initial concentration of 120-210 mg/L, oscillation speed of 100-200 r/min and temperature of 298-328K. The experimental results show that methylene blue is only adsorbed onto the external surface of purified palygorskite, and the apparent adsorption activation energy is 13.92 kJ/mol. The relatively low apparent adsorption activation energy suggests that the adsorption of methylene blue involves in not only a chemical, but also a physical adsorption process, and it is controlled by the combination of chemical adsorption and liquid-film diffusion.     

活化处理中坡缕石结构变化与性能关系的研究

以活化坡缕石作为吸附剂的应用已经十分广泛,活化方法一般有酸活化和焙烧活化,本文用X射线衍射和红外光谱分析,研究了纤维状坡缕石和土状坡缕石经HCl活化和焙烧活化后晶体结构的变化,结果表明,HCl活化对纤维状坡缕石结构没有影响,而土状坡缕石则不然,当HCl浓度为1.0mol/L时,呈人面体配位的阳离子部分坡H^-取代或溶出,导致晶胞参数减小,当HCl浓度为1.5mol/L时,出现人面体片坍塌,游离出SiO2,结构出现较大破坏,对进一步提高活性没有贡献,在350℃及以上温度焙烧活化会使坡缕石晶体结构产生明显破坏,分解氧化形成的Fe2O3使其脱色率明显下降。     

凹凸棒粘土中坡缕石的内标法X衍射定量分析研究

用聚丙烯酸钠（PAAs）作分散剂,从凹凸棒粘土中提纯得到坡缕石纯样,再被按照5％的含量间隔将坡缕石和刚玉以及石英配比制成一系列的混和样品,采用NBS方法制成X衍射样片,扣除X射线衍射背景后计算出坡缕石110衍射峰和刚玉113衍射峰的积分强度比,以此为y轴,以坡缕石含量为x轴作图,拟合出线性方程,可用于凹凸棒粘土中坡缕石的定量分析。实例验证了该方法中定量分析线性方程的可行性,证明了粘土中非晶态物质的存在。     

坡缕石粘土对Cu2+的吸附热力学

将坡缕石粘土分离提纯后作为吸附剂,通过对水中Cu2+的静态吸附实验,考察了时间及介质pH值对吸附效果的影响,并对吸附平衡和吸附热力学特征进行了探讨。结果表明:在实验条件下坡缕石粘土对水中的Cu2+离子具有较强的吸附作用,吸附平衡时间约为60 min,pH值对吸附效果有显著的影响,吸附量随pH值的升高而增加,当平衡溶液pH>7时吸附率超过99%;吸附平衡与Langmuir方程的符合程度优于D-R方程和Freundlich方程,由Langmuir方程拟合饱和吸附量为33.0～34.0 mg/g,由D-R方程得平均吸附能Es为13 kJ/mol,吸附过程为离子交换反应;吸附过程吸热,吸附焓为16.97 kJ/mol,吸附Gibbs函数在-27～-24 kJ/mol之间,吸附熵大于零,吸附过程可自发进行。     

水悬浮体系中凹凸棒石与Cu2+作用机理

研究矿物吸附重金属性能和机理,对正确认识矿物吸附性质、环境矿物材料应用研究以及重金属环境化学行为具有重要理论和实际意义。凹凸棒石是重要粘土矿物之一,也是重要的环境矿物材料,其吸附净化功能潜在应用受到广泛关注。在制备凹凸棒石纯样基础上,进行了凹凸棒石吸附Cu^2 单因素实验,吸附前后溶液pH值变化观测和吸附Cu^2 后凹凸棒石表面结构高分辨透射电镜调查。结果表明,从表面来看,凹凸棒石对Cu^2 的吸附性能主要受振荡速度、吸附时间、初始溶液pH值、吸附剂用量等因素影响,但实际上,凹凸棒石对Cu^2 的吸附作用主要是凹凸棒石诱导的Cu^2 水解沉淀作用以及凹凸棒石(带负电荷)与氢氧化铜(带正电荷)正负电荷胶体颗粒的互相作用,这有别于严格意义的矿物界面吸附作用。产生这种作用的机制在于凹凸棒石属于天然纳米矿物材料,具有较高的表面化学活性,凹凸棒石一水悬浮体系中凹凸棒石表面水解呈现出碱性,结果导致吸附平衡水溶液pH值较初始水溶液有较大程度的升高,达到Cu^2 水解基本完全的pH条件.     

临夏盆地晚渐新世沉积物中坡缕石的发现及其环境气候意义

为揭示临夏盆地晚渐新世沉积物的矿物组成对环境气候的指示意义, 利用X射线衍射和扫描电子显微分析方法, 对临夏盆地晚渐新世的沉积物的矿物组成以及坡缕石的矿物学特征进行了深入的研究.结果表明, 沉积物中的坡缕石主要为自生成因, 极少量具有碎屑成因.自生成因的坡缕石呈细长丝状的形态特征, 往往沿片状的伊/蒙混层粘土矿物颗粒的边缘交代、生长;碎屑成因的坡缕石呈平直细纤维状的, 以单颗粒形式产出, 与细小的粘土矿物颗粒混杂, 或叠合在片状粘土矿物颗粒的表面.在临夏盆地晚渐新世沉积物中, 下段岩层中的粘土矿物组合为伊利石、伊/蒙混层粘土和高岭石;中段岩层的为伊利石、伊/蒙混层粘土;而上段岩层则为伊利石、伊/蒙混层粘土和绿泥石, 反映在盆地形成之后, 气候演化经历从湿润→冷干的变化过程.而沉积物中坡缕石的含量自下而上逐渐增多, 其分布特征与粘土矿物组合所反映的气候环境变化趋势相吻合.伊利石和伊/蒙混层粘土普遍存在于临夏盆地晚渐新世沉积物中, 伊利石、伊/蒙混层粘土和高岭石的共存表明这些粘土矿物具有不同的来源.坡缕石是干旱、半干旱地区泥灰岩风化以及风成沙漠尘土沉积物的特征矿物, 临夏盆地晚渐新世的沉积物中碎屑成因坡缕石的发现, 表明自~9Ma以来便出现风成黄土的沉积.      

Distribution of Palygorskite in the Lingtai Profile of Chinese Loess Plateau： Its Paleoclimatic Implications

Palygorskite is a typical indicator mineral of the arid and strong evaporation environment. Distribution of palygorskite in loess-red clay sequences may act as an important indicator for reconstruction of the paleoenvironment and paleoclimate.In this paper,field emission scanning electron microscope and high-resolution transmission electron microscope observations on the red clay-loess-paleosol of the Renjiapo profile at Lingtai,Gansu Province indicate that palygorskite occurs widely in red clay sequences formed before 3.6 Ma,but no occurrence has been found in eolian sediments since 3.2 Ma.Micromorphological features and microstructure of palygorskite show that it is an autogenic mineral formed during pedogenesis,and transformed from illite-montmorillonite under the pore water action.In the Lingtai profile,the disappearance horizon of palygorskite is consistent with those of increasing magnetic susceptibility,dust flux and depositional rate.The distribution of palygorskite in the profile indicates that the interval of around 3.6 Ma was an important transformation period of the East Asian paleomonsoon,when changes took place in the East Asia paleoclimate pattern,i.e.a high-frequency strong fluctuation alternative evolution of the environment. Therefore,palygorskite is a key indicator mineral of the East Asian paleomonsoon evolution of that time.     

Distribution of Palygorskite in the Lingtai Profile of Chinese Loess Plateau: Its Paleoclimatic Implications

Palygorskite is a typical indicator mineral of the arid and strong evaporation environment. Distribution of palygorskite in loess-red clay sequences may act as an important indicator for reconstruction of the paleoenvironment and paleoclimate. In this paper, field emission scanning electron microscope and high-resolution transmission electron microscope observations on the red clay-loess-paleosol of the Renjiapo profile at Lingtai, Gansu Province indicate that palygorskite occurs widely in red clay sequences formed before 3.6 Ma, but no occurrence has been found in eolian sediments since 3.2 Ma. Micromorphological features and microstructure of palygorskite show that it is an autogenic mineral formed during pedogenesis, and transformed from iilite-montmorilionite under the pore water action. In the Lingtai profile, the disappearance horizon of palygorskite is consistent with those of increasing magnetic susceptibility, dust flux and depositional rate. The distribution of palygorskite in the profile indicates that the interval of around 3.6 Ma was an important transformation period of the East Asian paleomonsoon, when changes took place in the East Asia paleoclimate pattern, i.e. a high-frequency strong fluctuation alternative evolution of the environment. Therefore, palygorskite is a key indicator mineral of the East Asian paleomonsoon evolution of that time.     

TEM and HRTEM Study of Microstructures in Omphacite from UHP Eclogites at Shima, Dabie Mountains, China

Transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) analyses have been performed on omphacite from ultra-high pressure (UHP) eclogites at the locality of Shima, Dabie Mountains, China. TEM reveals that the microstructures consist dominantly of dislocation substructures, including free dislocations, loops, tiltwalls, dislocation tangles and subboundaries. They were produced by high-temperature ductile deformation, of which the main mechanism was dislocation creep. Antiphase domain (APD) boundaries are common planar defects; an age of 470±6 Ma for UHP eclogite formation has been obtained from the equiaxial size of APDs in ordered omphacites from Shima, coincident with ages given by single-zircon U-Pb dating (471±2 Ma). HRTEM reveals C2/c and P2ln space groups in different parts of one single omphacite crystal, and no exsolution is observed in the studied samples, which is attributed to rapid cooling. It is suggested that the UHP eclogites underwent a long     

湖南湘潭锰矿锰钾矿-天然氧化物八面体分子筛(OMS-2)在HRTEM下的微结构特征研究

在对湖南湘潭锰矿次生氧化带中天然锰钾矿鉴定的基础上．采用HRTEM对该地区结晶程度差、呈隐晶质集合体的天然锰钾矿微结构进行研究．结果表明：Mn,K,O为样品的主要元素．还含少量Cu,Si．Al,Mg,Fe等杂质元素;锰钾矿表现出一维针状的纳米晶,大多数纳米晶的宽度〈100nm;对选区电子衍射（SAED）计算d值并指标化．确定是锰钾矿,而电子衍射所表现出的弥散环、衍射斑点圆弧化和拉长,均表明该地区样品结晶度差、具有超结构和一定择优取向的特征,这与锰钾矿呈一维针状纳米晶的特征相一致。在锰钾矿的晶格像中,普遍存在晶格畸变、位错缺陷和超结构现象。因此,结晶度较差、颗粒细小至纳米级、结构的有序度较低等是该地区锰钾矿的主要特点。     

Molecular Structure of Kerogen in the Longmaxi Shale: Insights from Solid State NMR,FT‐IR,XRD and HRTEM

Kerogen plays an important role in shale gas adsorption, desorption and diffusion. Therefore, it is necessary to characterize the molecular structure of kerogen. In this study, four kerogen samples were isolated from the organic-rich shale of the Longmaxi Formation. Raman spectroscopy was used to determine the maturity of these kerogen samples. High-resolution transmission electron microscopy (HRTEM), 13C nuclear magnetic resonance (13C NMR) , X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy were conducted to characterize the molecular structure of the shale samples. The results demonstrate that VReqv of these kerogen samples vary from 2.3% to 2.8%, suggesting that all the kerogen samples are in the dry gas window. The macromolecular carbon skeleton of the Longmaxi Formation kerogen is mainly aromatic (fa’=0.56). In addition, the aromatic structural units are mainly composed of naphthalene (23%), anthracene (23%) and phenanthrene (29%). However, the aliphatic structure of the kerogen macromolecules is relatively low (fal*+falH=0.08), which is presumed to be distributed in the form of methyl and short aliphatic chains at the edge of the aromatic units. The oxygen-containing functional groups in the macromolecules are mainly present in the form of carbonyl groups (fac=0.23) and hydroxyl groups or ether groups (falO=0.13). The crystallite structural parameters of kerogen, including the stacking height (Lc=22.84 ?), average lateral size (La=29.29 ?) and interlayer spacing (d002=3.43 ?), are close to the aromatic structural parameters of anthracite or overmature kerogen. High-resolution transmission electron microscopy reveals that the aromatic structure is well oriented, and more than 65% of the diffractive aromatic layers are concentrated in the main direction. Due to the continuous deep burial, the longer aliphatic chains and oxygen-containing functional groups in the kerogen are substantially depleted. However, the ductility and stacking degree of the aromatic structure increases during thermal evolution. This study provides quantitative information on the molecular structure of kerogen samples based on multiple research methods, which may contribute to an improved understanding of the organic pores in black shale.     

煤基石墨微结构的高分辨电镜研究

煤体经热变质作用形成的石墨叫煤基石墨。湖南省鲁塘地区煤基石墨,经与之共生的红柱石的相图分析,它属于低压相系矿物,在200—800℃和5.5×10~5Pa以下条件下形成。它的高分辨电子显微象显示,煤基石墨按其石墨化程度有四种类型微结构。因而。将煤基石墨划分为相继的四个石墨化阶段。同时有四种石墨产物,它们是:前石墨化阶段——芳层石墨;初石墨化阶段——微柱石墨;中石墨化阶段——柔绉石墨;高石墨化阶段——平直石墨     

凹凸棒石与酸反应纳米尺度研究——反应机理和表面积变化

利用高分辨透射电子显微镜(HRTEM)和BET-比表面积分析(BET-SSA)技术调查了沉积型凹凸棒石与酸作用过程中形态和比表面积变化,并探讨了凹凸棒石与酸反应机理。对不同条件下凹凸棒石与酸反应产物纳米尺度观察表明,凹凸棒石的酸溶反应既表现出棒状晶体端部四面体和八面体一致溶解,也表现出柱面位置四面体和八面体不一致溶解。纳米尺度观察揭示出凹凸棒石与酸反应机制是质子从外表面扩散渗透,而不是质子从晶体孔道的渗透,反应速率主要受穿过酸溶产物硅酸层扩散速率控制。凹凸棒石的酸溶反应过程中,酸处理凹凸棒石的纳米孔结构现象与柱面位置四面体硅局部溶蚀有关。酸处理凹凸棒石比表面积增加归因于凹凸棒石中八面体不均匀、不连续溶解和局部四面体硅的溶蚀导致凹凸棒石孔道开放和直径扩大,从而使N2分子更多的进入凹凸棒石的孔道。部分八面体残留对四面体片起支撑作用,当凹凸棒石中八面体阳离子近于完全溶解时,四面体片失去支撑,结构塌陷,内孔孔道消失,比表面积再度下降。