蒙脱石热处理产物的微结构变化研究

本文对广东和平蒙脱石及其热处理产物进行了化学分析、差热和热重分析、X射线粉末衍射分析、红外吸收光谱分析、扫描电镜、原子力显微镜及魔角旋转核磁共振等研究。结果表明,蒙脱石在热处理温度为126℃-148℃时,主要脱出吸附水和层间水,这一脱水过程是可逆的。当热处理温度达到659℃时,蒙脱石八面体片中的羟基开始脱失,但层状结构仍然保持,这种羟基的脱失过程对应着八面体片中Al^Ⅵ向Al^Ⅳ的转变。当温度达到900℃时,蒙脱石的层状结构完全被破坏,并有新的矿物相μ-堇青石产生。当温度为1200℃时,则出现方英石及莫来石相。当热处理温度达到1350℃时,方英石及莫来石的含量略有减少,并出现较多的含铁堇青石相。     

固体核磁光谱法研究镁铝复合氧化物的水热转化机制

复合金属氧化物广泛分布于自然界,其中镁铝复合氧化物(简称MMO)则大量分布于基性-超基性岩浆岩、蒸发河湖相和海相沉积岩等之中。本研究以镁铝水滑石(HT)煅烧产物MMO为研究对象,采用水热合成方法,通过改变反应时长,考察并揭示MMO在富硅、碱性和160℃水热条件下的结构复原特性及其转化机制。X射线衍射结果显示,该条件下MMO首先复水形成水滑石相,进而水滑石相逐渐向皂石转化,并伴有钠霞石等杂相的形成与溶解。29Si和27Al魔角旋转核磁共振谱(MAS NMR)的结果证明,在皂石结晶过程中,Al3+优先占据四面体片层的四配位位置。该研究对揭示水滑石稳定性、水滑石与硅酸盐矿物异相成核与生长、热液类型的天然皂石矿床的形成过程等具有重要指示意义。     

蒙脱石酸处理产物的表面结构变化

本文对广东和平蒙脱石及其酸处理产物进行了化学分析、Ｘ射线粉末衍射分析、红外吸收光谱分析、原子力显微镜及魔角旋转核磁共振等研究。结果表明,酸处理浓度对蒙脱石的表面结构有很大的影响。当酸处理浓度达到２０％时,蒙脱石硅氧四面体中的Ｑ＾３Ｓｉ环境发生结构重组,有部分转变为畸变的Ｑ＾３Ｓｉ环境和Ｑ４Ｓｉ环境,而Ａ１的结构状态则没有发生任何变化,这与原子力显微阄的观察结果相一致。     

天然烧变高岭石中水铝英石的发现

作者用DTA、TG、XRD、29Si和27AlMASNMR等手段对我国北方的一些天然烧变高岭石及其热处理产物进行了研究．首次在天然烧变高岭石的29Si魔角旋转核磁共振谱中（MASNMR）记录到了-79．0×10－6位置附近的水铝英石的特征29Si信号，说明在一定的自然条件下，经过水的化学作用，变高岭石可以转变成水铝英石。但是，水铝英石是一种非晶质相物质，它不稳定，易脱失结构水而转变成其它物相，这些发现对完善高岭石的相变理论具有重要的科学意义     

反复插层对高岭石结构和性能的影响

利用二甲基亚砜(DMSO)和去离子水对高岭石进行重复的插层与水洗,并采用X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、旋转魔角核磁共振(MAS NMR)、扫描电镜(SEM)对产物进行表征。研究发现,经10次重复插层与水洗,高岭石结晶度降低,结构遭到一定程度破坏但未发生崩塌。MAS NMR数据显示,Si谱未发生较大变化,Al谱化学位移变化了3.5×10-6,但Si原子和Al原子聚合度保持不变,高岭石主体结构仍呈层状结构。此外,随着水洗次数的增加,高岭石叠置片层减少,晶形遭到一定破坏。     

硅藻土的~(29)Si魔角旋转核磁共振谱

硅藻土的２９Ｓｉ魔角旋转核磁共振谱冯璜张惠芬郭九皋王辅亚王德强（中国科学院广州地球化学研究所广州５１０６４０）胡澄（南京大学固体微结构物理实验室，南京２１００９３）关键词硅藻土核磁共振微结构硅藻土轻质、吸附性强和对热、电、声极差的传导性，使其能广泛应...     

氧化铬-铝混杂柱支撑蒙脱石的制备和性能

以浙江和新疆的膨润为原料合成了氧化铬－铝混杂柱支撑蒙脱石。分别用铝盐及铬盐溶液,经碱水解生成的聚羟基铬－铝混杂阳离子的成柱溶液,聚羟基铬－铝混杂阳离子通过阳离子交换引入蒙脱石,所得产物的性质用Ｘ射线衍射、热分析、红外光谱和ＢＥＴ比表面及孔径分布测量等方法研究并与氧化铬柱支撑脱石（简称铬蒙脱石）的性能进行比较,所得氧化铬－铝混杂柱支撑蒙脱石（简称铬－名蒙脱石）,其基面间距较高（２．１ｎｍ＾２／ｇ,这     

Cr~(3+)在蒙脱石中吸附位置研究——基于蒙脱石、CTAB-和NH_4~+-交换层间域的蒙脱石吸附铬研究

蒙脱石具良好的阳离子可交换吸附特性。在提纯蒙脱石的基础上,用氯化铵(NH_4Cl)和十六烷基三甲基溴化铵(CTAB)分别交换蒙脱石层间阳离子制备了改性蒙脱石,并用提纯蒙脱石、改性后的蒙脱石吸附碱式硫酸铬溶液中的铬离子,获得含铬蒙脱石样品。针对上述的含铬蒙脱石进行包括粉末X射线衍射术(XRD)、电子顺磁共振谱术(EPR)和傅里叶变换红外吸收光谱术(FTIR)以及电感耦合与等离子体原子发射光谱(ICP-AES)等测试和分析。吸附残余液的化学分析结果和含铬蒙脱石样品的XRD结果显示CTAB对蒙脱石的层间的封闭是较完全的,层间几乎未发生交换吸附;而NH_4~+—蒙脱石和蒙脱石层间则发生交换吸附。吸附前后样品的红外吸收谱发生了较大变化,表明三个含铬样品的红外吸收谱上出现的硅醇和铝醇向低波数延展的现象是由铬离子吸附在蒙脱石结构片的六方孔中所致。EPR的结果指示甚至在蒙脱石的少量四面体和/(或)八面体位中也有Cr~(3+)占位。     

甘肃金昌红泉镁基膨润土属型分类

膨润土是一种以蒙脱石为主要成分的粘土类矿物。确定膨润土的属型,实质上是依据蒙脱石晶层间吸附阳离子的种类及其丰度。 (一) 蒙脱石吸附阳离子的主要原因 1.蒙脱石是属于一种2:1层状结构,即由二个硅氧四面体片夹一个铝氧八面体片构成的层状体。蒙脱石因四面体中Al~(3+)置换Si~(4+)和八面体中Mg~(2+)置换Al~(3+),使蒙脱石晶层间产生永久性负电荷,为了保持晶格电荷平衡,因而晶层间具有吸附阳离子和交换性阳离子的性能。     

蒙脱石中铁的赋存状态的研究

通过对徐闻、三水、高州等地五个样品的Ｘ射线衍射分析，化学全分析，分析它们为含铁量不同的蒙脱石，层间可交换阳离子主要为Ｃａ＾２＋。几个样品穆斯堡尔谱表明铁主要以Ｆｅ＾３＋的形式存在，含铁量较高的样品ＸＧＡ、ＸＳＡ、ＳＳ的谱可以拟合出Ｆｅ＾３＋的二对四级双峰，表明铁在蒙脱石中占据两种不等同的八面体位置。     

29Si and 27Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite

Thermal transformations of kaolinite of different degree of crystallinity have been monitored by ²⁷Al and ²⁹Si high-resolution NMR with magic-angle spinning (MAS NMR), X-ray diffraction, Fourier transform infrared, atomic absorption spectrophotometry and thermogravimetric analysis. NMR shows differences in the dehydroxylation process of kaolinites with different degree of crystallinity and reveals the presence of short-range order in metakaolinite. ²⁹Si NMR spectra acquired with a 30 s recycle delay of poorly and highly crystalline samples heated at 480 and 500° C, respectively, contain three distinct signals; we discuss their assignment in the light of experiments involving leaching of the samples with aqueous KOH. Ca. 40% of Si sites retain their original Q ³ symmetry just above the onset of dehydroxylation and the Q ⁴ environment is present showing that a small amount of amorphous silica has already segregated. The spectrum of samples treated at 1000° C contains a signal at -110ppm (from Q ⁴ silicons) and a faint resonance, from mullite, at ca. -87 ppm. ²⁹Si NMR also shows that cristobalite germs are already present at 950–1000° C. The ²⁷Al MAS NMR spectra of metakaolinite reveal the presence of 4-, 5-and 6-coordinated Al. Changes in the three Al populations as a function of temperature have been monitored quantitatively. Below 800° C, 4-and 5-coordinated Al appears at the expense of 6-coordinated Al, but above 800° C the amount of 6-coordinated Al increases again. We suggest a dehydroxylation scheme which accounts for the presence of 4-and 5 coordinated Al. Above 900–950° C the latter signal is no longer present in the ²⁷Al NMR spectra and new 4-and 6-coordinated Al species (mullite and γ-alumina) appear. We propose new ideas for the structure of metakaolinite.     

Influence of glass composition and alteration solution on leached silicate glass structure: A solid-state NMR investigation

A multinuclear solid-state NMR investigation of the structure of the amorphous alteration products (so called gels) that form during the aqueous alteration of silicate glasses is reported. The studied glass compositions are of increasing complexity, with addition of aluminum, calcium, and zirconium to a sodium borosilicate glass. Two series of gels were obtained, in acidic and in basic solutions, and were analyzed using ¹H, ²⁹Si, and ²⁷Al MAS NMR spectroscopy. Advanced NMR techniques have been employed such as ¹H-²⁹Si and ¹H-²⁷Al cross-polarization (CP) MAS NMR, ¹H double quantum (DQ) MAS NMR and ²⁷Al multiple quantum (MQ) MAS NMR. Under acidic conditions, ²⁹Si CP MAS NMR data show that the repolymerized silicate networks have similar configuration. Zirconium as a second nearest neighbor increases the ²⁹Si isotropic chemical shift. The gel porosity is influenced by the pristine glass composition, modifying the silicon-proton interactions. From ¹H DQ and ¹H-²⁹Si CP MAS NMR experiments, it was possible to discriminate between silanol groups (isolated or not) and physisorbed molecular water near Si (Q²), Si (Q³), and Si (Q⁴) sites, as well as to gain insight into the hydrogen-bonding interaction and the mobility of the proton species. These experiments were also carried out on heated samples (180 °C) to evidence hydrogen bonds between hydroxyl groups on molecular water. Alteration in basic media resulted in a gel structure that is more dependent on the initial glass composition. ²⁷Al MQMAS NMR data revealed an exchange of charge compensating cations of the [AlO₄]⁻ groups during glass alteration. ¹H-²⁷Al CP MAS NMR data provide information about the proximities of these two nuclei and two aluminum environments have been distinguished. The availability of these new structural data should provide a better understanding of the impact of glass composition on the gel structure depending on the nature of the alteration solution.     

Water solubility mechanism in hydrous aluminosilicate glasses: information from Al MAS and MQMAS NMR

New ²⁷Al NMR data are presented in order to clarify the discrepancies in the interpretation of the previous ²⁷Al Magic Angle Spinning (MAS) spectra from hydrous aluminosilicate glasses. The ²⁷Al MAS data have been collected at much higher magnetic field (14.1 and 17.6 T) than hitherto, and in addition, multiple quantum (MQ) MAS NMR data are presented for dry and hydrous nepheline glasses and NaAlSi_7.7O_17.4 glass that, according to the model of Zeng et al. (Zeng Q., Nekvasil H., and Grey C. P. 2000. In support of a depolymerisation model for water in sodium aluminosilicate glasses: Information from NMR spectroscopy. Geochim. Cosmochim. Acta64, 883-896), should produce a high fraction (up to 30%) of Al in Al Q³-OH on hydration. Although small differences in the MAS spectra of anhydrous and hydrous nepheline glasses are observed, there is no evidence for the existence of significant (>∼2%) amounts of Q³ Al-OH in these glasses in either the MAS or MQMAS data.     

Structural study of synthetic mica–montmorillonite by means of 2D MAS NMR experiments

Syn-1, is a synthetic mica–montmorillonite interstratified mineral that forms one of the standard clay samples in the Clay Minerals Society Source Clays Project. However, there are still controversies regarding some structural aspects such as the interlayer composition or the location of the extra-aluminium determined by chemical analysis. The main objective of this paper is to shed light on those structural aspects that affect the reactivity of the interstratified minerals. For this purpose, we have used ¹ H–²⁹ Si and ¹ H–²⁷Al HETCOR MAS NMR to show that it is likely that the interlayer space of the beidellite part is composed of ammonium ions whereas ammonium and aluminium ions are responsible for the charge balance in the mica type layer.     

A Study on the Formation of Smectite in Silica Scales Precipitated from Geothermal Water: The Effect of Magnesium

Abstract. Silica scales containing large amounts of smectite were recently found in the pipelines for geothermal water at a geothermal power plant. To elucidate the mechanism of smectite formation, seven silica scale samples were characterized by powder X-ray diffraction, chemical analysis and ²⁷A1 MAS NMR. Smectite was present in samples with MgO levels above 10 wt% and Al₂O₃ levels below 10 wt%. In ²⁷A1 MAS NMR spectra, peaks assigned to both tetrahedrally and octahedrally coordinated aluminum (Al(4) and Al(6)) were observed for Mg-rich samples, whereas a peak due to Al(4) alone appeared in Mg-poor samples. From these observation and comparison between ²⁷A1 MAS NMR spectra for synthesized precipitates of Al₂O₃-SiO₂ containing MgO and not containing MgO, it is concluded that magnesium plays an important role in the stabilization of Al(6), and results in the formation of smectite     

Evaluation of aluminum speciation in surface waters in China and its environmental risk assessment

As the ongoing global research on acid precipitation is developing in depth, more and more attention has been paid to the ecological effects of aluminum (Al) due to its toxicity to plants and animals, which is caused by acid precipitation. As a very serious problem of terrestrial and aquatic environmental acidification occurs in China, especially in southwestern China, a systematic investigation of Al speciation in these regions is very important. In this paper, the Al speciation results of surface waters in China are reported and its ecological impacts is evaluated. More than 100 water samples were collected from about twenty provinces of China. Driscoll's Al speciation scheme combined with the modified MINQEL computer model is used for speciation of Al. This study shows that the ecological impacts of acidification are quite different between China and Western countries, because of different geographical environments and geological settings. In Western countries, acidification is mainly caused by NO₂^-. Due to low concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺, the buffer capacities of soil and water are weak. Therefore, natural waters can be acidified to pH<5 very easily, resulting in a considerable mobilization of Al and worsening of the ecological environment. In China, acid precipitation is mainly in the form of sulfuric acid. In northwestern China, concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺ are high in soil and surface waters. This leads to much higher capacity and a high resistance ability to acidification. The pH values of waters in this region are high (around 7) and no serious Al toxicity is found at present. However, in northeastern and southeastern China, the soil is rich in Al (unsaturated aluminosilicates in northeastern China, saturated aluminosilicates in north and central China, aluminum-rich soil in southeastern and southwestern China). The concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺ in soil and waters are lower than those of northwestern China. Therefore the buffer capacity is limited. Numerous surface waters have already been acidified and pH values declined to 5. The impacts of Al toxicity on ecological systems in these regions are very serious, especially in Jiangxi, Hubei Provinces and Chongqing Municipality.     

Extent of diagenetic transformations in severely altered biogenic silica deposits from Tunisia: new insights from mineralogy and geochemistry

Sedimentary biogenic silica from Redeyef in Gafsa basin (southern Tunisia) was analysed for its ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra and complemented by X-ray diffraction and SEM observations. The ²⁹Si MAS NMR spectrum is characterized by the abundance of hydroxylated silicon, displayed in resonance intensities and reflects a clear tendency towards dissolution of diatomaceous amorphous silica and the occurrence of the hydrated silica, which is the main component that ensures the diagenetic transition via the mechanism of dissolution–precipitation to other more crystalline silica phases, after the lost of its hydroxyls groups (water) by heating (burial). ²⁷Al MAS NMR reveals two coordinations of Al; the octahedrally coordinated Al suggests the presence of clay relics trapped during crystal growth or a microcrystalline zeolite (clinoptilolite detected by SEM observations), while the tetrahedrally coordinated Al suggests the presence of minor quantities of minerals with tetrahedral Al, such as an Al-rich fluid and/or minerals such as feldspars.     

Analysis of cation distribution in the octahedral sheet of dioctahedral 2:1 phyllosilicates by using inverse Monte Carlo methods

An inverse Monte Carlo (MC) method was developed to determine the distribution of octahedral cations (Al³⁺, Fe³⁺, and Mg²⁺) in bentonite illite–smectite (I–S) samples (dioctahedral 2:1 phyllosilicates) using FT–IR and ²⁷Al MAS NMR spectroscopies. FT–IR allows determination of the nature and proportion of different cation pairs bound to OH groups measuring the intensities of OH-bending bands. ²⁷Al MAS NMR data provide information about cation configuration because ²⁷Al MAS NMR intensity depends on Fe distribution. MC calculations based on FT–IR data alone show Fe segregation by short-range ordering (Fe clusters within 9 to 15?Å from a given Fe atom). Fe segregation increases with illite proportion. MC calculations based on IR and ²⁷Al NMR simultaneously yield similar configurations in which Fe clusters are smaller. The latter calculations fail to build appropriate cation distributions for those samples with higher number of illite layers and significant Fe content, which is indicative of long-range Fe ordering that cannot be detected by FT–IR and ²⁷Al MAS NMR. The proportion of Mg–Mg pairs is negligible in all samples, and calculations, in which the number of Mg atoms, as second neighbours, is minimised, create appropriate configurations.     

High temperature dehydroxylation of muscovite-2M1: a kinetic study by in situ XRPD

Muscovite-2M₁ shows a major phase transition at about 800°C, which is generally attributed in the literature to the structural dehydroxylation process, although a number of structural models have been proposed for the dehydroxylated phase, and different transformation mechanisms have also been put forward. The observed first order transformation involves an increase in the cell volume, and it is not clear to date how the cell expansion is related to the loss of hydroxyl groups. The phase change has been re-investigated here by in situ high temperature powder diffraction, both in non-isothermal and isothermal modes, to combine for the first time the structural and the kinetic interpretation of the transformation. The results unequivocally confirm that the reaction taking place in the temperature range 700–1000°C is truly a dehydroxylation process, involving the nucleation and growth of the high temperature dehydroxylated phase, having Al in 5-fold coordination. Structural simulations of the basal peaks of the powder diffraction patterns indicate that the model originally proposed by Udagawa et al. (1974) for the dehydroxylated phase correctly describes the high temperature phase. The kinetic analysis of the isothermal data using an Avrami-type model yields values for the reaction order compatible with a reaction mechanism limited by a monodimensional diffusion step. Apparent activation energy of the process in vacuum is about 251 kJ/mol. Experiments carried out at temperatures much higher than the onset temperature of the reaction show that the dehydroxylation reaction overlaps with the reaction of formation of mullite, the final product in the reaction pathway. Received: 24 April 1998 / Revised, accepted: 12 October 1998