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.     

On the mechanical properties of synthetic kaolinite/quartz fault gouge

The mechanical properties and microstructures of mixed kaolinite/ quartz fault gouge have been studied by means of triaxial tests, wherein a 1 mm thickness of fault gouge was sheared between rigid, sintered alumina sliders. Test conditions ranged up to 200 MPa confining pressure, 175 MPa pore water pressure and temperatures to 600°C. Constant displacement rate tests were carried out at 5×10^-4 mm s^-1, and the stress relaxation technique was used to access a wide range of lower displacement rates down to 10^-10 mm s^-1. The effects of different ratios of clay: quartz were studied, and some experiments were cafried out using crushed Tennessee sandstone gouge and pre-faulted cylinders of Tennessee sandstone. Deformation-induced microstructures were studied by optical, scanning and transmission electron microscopy, and mineral chemistry changes were identified using EDS analysis in the STEM. The most important factor determining the strength of these gouges is effective confining pressure, and the effective stress law was obeyed at all test conditions. Increasing the proportion of quartz in the gouge slightly increases the strength, as does increase of temperature. Under all test conditions the gouges deformed by strain-hardening stable sliding. At 2 mm displacement the friction coefficient is similar to that for rock and rock sliding (μ= 0.85). Over wide ranges of strain-rate and temperature the strength of these gouges is little affected if the effective pressure is high, but strength drops rapidly with decreasing strain-rate if effective pressure is low (or if pore water pressure is high). Reloading of the gouge after stress relaxation at high temperatures demonstrated hardening arising from hydrothermal cementation during stress relaxation, which led to sudden rupture of the cemented gouge. This phenomenon may be responsible for cyclic rupture of natural faults. New mineral phases were produced in these experiments only at 600°C. At 400°C, anticipated production of pyrophyllite from kaolinite plus quartz was not found, but recrystallization of kaolinite is believed to have occurred and evidence of healing of cracks in quartz was seen. Microstructural studies revealed the ubiquitous development of P and R₁ foliations and other features, which are identical to those found in natural clay-bearing fault zones. Microstructural evolution is associated with the strain-hardening, and apparent hardening is strongly associated with the stress path during loading.     

Effect of heavy metal and alkali contamination on the swelling properties of kaolinite

One of the most important factors that determine engineering properties of soils are the type and the amount of clay present in soil. Kaolinite being a very common and non-swelling clay mineral in soil was chosen as the medium, and significance of the change in swelling property of kaolinite due to contaminant-clay interaction was investigated. The amount of change in swelling percentages of the kaolinite due to contamination with 10,000 ppm solutions of Pb(NO₃)₂ and Zn(NO₃)₂ was determined using oedometers. For uncontaminated kaolinite, the amount of swell was determined as 2.2%. For Pb-contaminated and Zn-contaminated kaolinite, these values reached to 5.8 and 5.3%, respectively. Besides heavy metals, kaolinite was also contaminated with 4 N NaOH. The biggest change in the amount of swelling was obtained from NaOH-contaminated kaolinite which is 13.9%. In addition to swelling percentages, swelling pressures were also determined. The swelling pressure of the uncontaminated kaolinite was found as 1.06 N/cm². For Zn and Pb-contaminated kaolinite, this value reached up to 2.0 and 2.6 N/cm². The NaOH-contaminated kaolinite has the greatest swelling pressure which was 230 N/cm².     

Influence of vibration grinding and calcination on the physico-chemical properties of Egyptian kaolinite

Summary The effects of vibratory grinding and calcination on the structure and reactivity of Kalabsha kaolinite were studied by means of XRD, IR, DTA and surface area determination. Leaching experiments on ground and calcined samples were carried out using 20% HCl for aluminum extraction. At the early stages of grinding, partial destruction of stacked kaolinite layers occurred. These changes were associated with an increase in surface area due to formation of fine grains with numerous boundaries. Further grinding, as well as calcination, led to deterioration of the kaolinite structure. A significant increase of surface area was observed, starting from 18 m²/g for the original sample to a maximum of 42 m²/g after 120 minutes of grinding and 30 m²/g after calcination at 300°C. The extraction of aluminum after 30 minutes leaching time was about 97% for kaolinite ground for 240 minutes, and about 93% for kaolinite calcined at 550°C.

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Der Einfluß von Aufmahlen und Kalzinierung auf die physiko-chemischen Eigenschaften von ägyptischem Kaolinit

Zusammenfassung Die Effekte von Vibrations-Mahlung und Kalzinierung auf die Struktur und die Reaktivität von Kalolinit aus Kalabsha wurden mit XRD, IR, DTA und Methoden zur Bestimmung der Oberfläche untersucht. Auslaugungsexperimente zur Extraktion des Aluminiums erfolgten an gemahlenen und kalzinierten Proben unter Verwendung 20% er Salzsäure. In den Frühstadien des Mahlprozesses tritt eine teilweise Zerstörung der Kaolinitschichtstruktur auf. Diese Änderungen gehen mit einer Zunahme der Oberfläche, infolge der Neubildung von Körnern mit zahlreichen Korngrenzen, einher. Weiteres Aufmahlen und Kalzinieren führt zu zusätzlicher Zerstörung der Kaolinitstruktur. Eine signifikante Zunahme der Oberfläche von 18 m²/g für das Ausgangsmaterial auf 42m²/g nach 120 min Aufmahlen, bzw. auf 30 m²/ g nach Kalzinierung bei 300°C ist zu beobachten. Die Extraktion von Aluminium nach 30 minütiger Auslaugung liegt bei 97% für gemahlenen Kaolinit (240 min) und bei 93% für bei 550°C kalzinierten Kaolinit.

     

高岭石表面酸碱反应的电位滴定实验研究

采用表面酸碱电位滴定法探讨高岭石表面酸碱性质,基于多位模式(即假定高岭石表面存在3种基团Al2 OH 、AlOH 和SiOH ) ,根据实验所得数据对高岭石表面的质子化和去质子化过程的相关参数进行拟合,讨论各个位点所发生的反应,并探讨了支持电解质浓度、高岭石溶解过程对表面酸碱电位滴定结果的影响。高岭石的表面零净质子电荷点(pHPZNPC,5 .2 )不等同于零电荷点,当pH <5 .2时,高岭石表面荷正电荷,主要由于表面富硅贫铝层的形成和Al位的质子化所致;当pH >5 .2时,高岭石表面荷负电荷,以Si位和Al的去质子化反应为主。     

淮北闸河矿区高岭岩特征及其利用途径

用差热、X射线衍射及红外光谱等方法,对淮北闸河矿区下石盒子组底部5^#、6^#煤层间一层高岭岩矿层进行了研究。结果表明:矿层平均厚3.8m,矿石几乎全部是由高岭石组成的单矿物岩,有益组分Al₂O₃含量一般在36%~39%;主要有害组分Fe₂O₃含量变化在0.78%~1.71%之间;TiO₂含量多在0.4 9%~0.97%。为矿物组成纯净,有益组分含量高但有害组分亦较高的高岭岩。这种岩石是生产化工产品,以及煅烧高岭土的良好原料。     

机械研磨对平鲁煤系高岭石热行为的影响

对煤系高岭石进行0-2h的研磨之后，再在900℃、1000℃、1400℃的温度条件下分别对其加热1h，然后利用X射线衍射（XRD）、差热分析（DTA）、红外光谱（IR）等手段，研究机械研磨对于煤系高岭石晶体结构的破坏作用以及对其热行为的影响。结果显示，煤系高岭石被研磨1h之后，高岭石的晶体结构几乎全部跨塌。把研磨1h的煤系高岭石加热到1000℃（加热1h），便能形成结晶良好的莫来石。     

煤系高岭石的原始晶粒尺寸及结晶度对插层作用的影响

采用SEM、XRF、XRD和IR研究了大同、平朔和淮北煤系高岭石的结构、粒度及其特性,探讨了粒度大小对高岭石插层作用的影响及其机理。研究发现:粒度中等且结晶有序的平朔煤系高岭石插层率最高,其次为晶体粗大但结晶有序的大同高岭石,粒度最小且结晶无序的淮北高岭石插层率最低。研究认为高岭石原始晶粒粒度对高岭石插层作用有重要影响,中等粒度最有利于高岭石插层作用的进行,粒度过大或过小均不利于高岭石插层作用的进行,其原因是由于不同粒度的高岭石插层作用过程中导致的差异弹性变形引起的。结晶有序度对高岭石插层作用也有重要影响,结构无序不利于插层作用的进行。     

Temperature dependence of the relationship of thermal diffusivity versus thermal conductivity for crystalline rocks

Thermal diffusivity governs the transient heat transport equation. Thus, a realistic characterisation of this parameter and its temperature dependence is crucial for geothermal modelling. Due to sparse information from boreholes, lack of samples, and elaborate measurement procedures, there is often insufficient data on thermal diffusivity at elevated temperatures. We make use of existing data on crystalline (metamorphic and magmatic) rock samples from the Kola Peninsula and the Eastern Alps and develop a general relationship for the temperature dependence of thermal diffusivity up to 300°C. The temperature dependence of thermal conductivity is parameterised itself, using an empirical relationship which is set up for both data sets as well. Hence, only thermal conductivity at ambient temperatures is required for determining the temperature dependence of thermal diffusivity. We obtain different coefficients for both data sets which can be explained by different geological settings, and therefore different mineral compositions and internal structures. Comparisons with other expressions for these rock physical parameters show a good agreement at ambient conditions. General relations for thermal diffusivity at elevated temperatures are rare. A comparison of our results with data from two crystalline samples from the KTB and data from the Southern Indian Granulite Province highlights the need for further data, which will help to quantify uncertainties.     

Structure of sediments of kaolinite

In an assembly of clay particles placed in a fluid, each particle is typically subjected to: (1) double-layer repulsive forces; (2) van der Waals attractive forces; and (3) contact mechanical forces. The study presented here concerns an approximate, quantitative analysis of clay suspensions, with considerations to the first two - the physico-chemical forces. Using recent theories to calculate the physico-chemical forces between two clay particles in an approximate model of an assembly, the equilibrium void ratio of a clay suspension is computed. The mechanical forces are ignored in the analysis. The results serve to verify the validity of physico-chemical theories employed and help interpret experimental data more fundamentally in terms of the system variables.     

Sorption of lanthanides on smectite and kaolinite

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3-9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO₃ or NaClO₄) under atmospheric conditions or N₂ flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO₂, but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient (K_D) above pH 5.5. At 0.025 M, the measured K_D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K_D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K_D. This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.     

Intercalation of kaolinite with acetamide

Upon intercalation of both ordered (low defect) and disordered (high defect) kaolinites with acetamide, two types of interaction are observed. Firstly, hydrogen bonding between the NH₂ groups of the acetamide with the siloxane oxygens is formed, as evidenced by the formation of two new bands at 3400 and 3509 cm^–1. Secondly, the appearance of additional bands at ∼3600 cm^–1 in both the infrared and Raman spectra of the acetamide intercalates is attributed to a second type of hydrogen bonding by the interaction of the C=O group and the inner surface hydroxyls. Changes in the intensity of the hydroxyl deformation modes in the 895 to 940 cm^–1 region are attributed to the changes in the hydrogen bonding of the kaolinite surfaces. It is proposed that the hydrogen bonding between the adjacent kaolinite layers is replaced with hydrogen bonding between both kaolinite surfaces and the acetamide molecule. Changes in the molecular structure of acetamide are observed upon intercalation. The amide 1 band is lost and replaced with a well-defined NH₂ deformation vibration. The loss of the amide 1 band is attributed the hydrogen bond formation between the amide hydrogens and the siloxane surface. The bands of the C=O group at 1680 and 1740 cm^–1 become a single band at 1680 cm^–1. The amide 2 band remains unchanged. The lack of intensity of the 1740 cm^–1 band is attributed to the formation of hydrogen bonding between the inner surface hydroxyl groups and the carbonyl group. Received: 4 February 1998/ Revised, accepted: 30 June 1998     

Studies of the relationship between coal petrology and grinding properties

The maceral and microlithotype composition of selected coals has been investigated with respect to the grinding properties, specifically Hardgrove grindability index (HGI), of the coals. The study expands upon previous investigations of HGI and coal petrology by adding the dimension of the amount and composition of the microlithotypes. Coal samples, both lithotypes and whole channels, were selected from restricted rank ranges based on vitrinite maximum reflectance: 0.75–0.80% R_max, 0.85–0.90% R_max and 0.95–1.00% R_max. In this manner, the influence of petrographic composition can be isolated from the influence of rank. Previous investigations of high volatile bituminous coals demonstrated that, while rank is an important factor in coal grindability, the amount of liptinite and liptinite-rich microlithotypes is a more influential factor. In this study, we provide further quantitative evidence for the influence of microlithotypes on HGI and, ultimately, on pulverizer performance.     

Linear relationship between thermo-dehydroxylation and induced-strain by mechanical processing in vacuum: The case of industrial kaolinite, talc and montmorillonite

The thermal behaviour and the structural properties of three important industrial phyllosilicates, such as kaolinite, talc and Ca-rich montmorillonite, have been examined after mechanical treatment in a specifically built planetary ball mill working in vacuum (P = 0.13 Pa) at room temperature (25 °C). It is found that, on increasing the grinding time, the temperature of the dehydroxylation reaction decreases linearly as a result of a decrease of the crystallite size and structural order. To be noted that the mechanical treatment in our milling conditions did not induce significant amorphization. The temperature at which there is the maximum of dehydroxylation and the weight losses of the intralayer OH are linearly related to the increase of the FWHM of the 001 basal plane. These results are useful for predicting the thermal behaviour of layer silicates to be subjected to mechanical processing in industrial application.     

Characterization of dehydration-induced luminescence of kaolinite

Dehydration-induced luminescence (DIL), the emission of light from a clay paste upon dehydration, was characterized experimentally for a colloidal kaolinite. The relationship between total photon count of the emitted light and film thickness is linear up to a thickness of 30 micrometers. The photon emission was obtained over a critical range of water contents (25-60%) of the oven-dry clay, and the kinetics of photon emission was presumed to be closely associated with the kinetics of film dehydration. Whether drying proceeded throughout the bulk or via a moving front was undetermined, but in either mode it was preceded by the formation of a thin dry film at the interface with the atmosphere. Grinding of the kaolinite for several minutes by mortar and pestle before paste preparations resulted in an overall increase of photon emission compared to unground kaolinite and in the formation of more than one emission peak, as well as a prolongation of the light emission. This effect on the kinetics of light emittance was observed for about two months after the application of the mechanical stress and suggests a means of detecting the mechanical stress history of a clay. An estimate was made of the spectral characteristics of the emitted light using optical filters and by incorporating tryptophan and salicylic acid into the kaolinite paste where they acted as fluorescent probes. The latter technique shifted the frequency of the light emitted by the kaolinite from the ultraviolet to the visible range where it was less effectively reabsorbed. The first method showed that the wavelengths of 97% of the emitted light was <460 nm and that 75% of the light had wavelengths < 410 nm. The second method showed that the total intensity of DIL increased in the presence of fluorescence molecules, suggesting that the emittance was in the ultraviolet range.     

^29Si,^27Al Magic—Angle—Spinning Nuclear Magnetic Resonance（MAS NMR） Studies of Kaolinite and Its Thermal Transformation Products

²⁷Al,²⁹Si MAS NMR studies of kaolinite and its thermal transformation products show that in the kaolinite-mullite reaction series there is an extensive segregation of Al₂O₃ and SiO₂ and the reaction of Al₂O₃ with SiO₂ to form mullite is the main path of mullite formation. At about 850° C, the peak intensity of A1(V) reaches its maximum and with the further rise of temperature the A1(V) signal completely disappears. At about 950°C, γ-Al₂O₃ accounts for about 71% of the material phases containing Al atoms. In the series there is no obvious presence of Al-Si spinel. The²⁷Al and²⁹Si MAS NMR spectra show that there is an obvious difference between the temperature points for Al-O₂(OH)₄ octahedral sheet collapsing and Si-O₄ tetrahedral sheet breaking down.     

Interactions of uranium with bacteria and kaolinite clay

We assessed the accumulation of uranium (VI) by a bacterium, Bacillus subtilis, suspended in a slurry of kaolinite clay, to elucidate the role of microbes on the mobility of U(VI). Various mixtures of bacteria and the koalinite were exposed to solutions of 8 × 10^− 6 M- and 4 × 10^− 4 M-U(VI) in 0.01 M NaCl at pH 4.7. After 48 h, the mixtures were separated from the solutions by centrifugation, and treated with a 1 M CH₃COOK for 24 h to determine the associations of U within the mixture. The mixture exposed to 4 × 10^− 4 M U was analyzed by transmission electron microscope (TEM) equipped with EDS. The accumulation of U by the mixture increased with an increase in the amount of B. subtilis cells present at both U concentrations. Treatment of kaolinite with CH₃COOK, removed approximately 80% of the associated uranium. However, in the presence of B. subtilis the amount of U removed was much less. TEM–EDS analysis confirmed that most of the U removed from solution was associated with B. subtilis. XANES analysis of the oxidation state of uranium associated with B. subtilis, kaolinite, and with the mixture containing both revealed that it was present as U(VI). These results suggest that the bacteria have a higher affinity for U than the kaolinite clay mineral under the experimental conditions tested, and that they can immobilize significant amount of uranium.     

Effects of gasoline and diesel additives on kaolinite

Centrifuge tests were carried out to confirm and determine the effect of different pure alcohols, methyl t-butyl ether (MTBE) and mixtures of alcohols with gasoline and diesel on a thin disc of consolidated clay. The evolution of changes in the clay hydraulic conductivity with time was investigated and other structural changes due to chemical attack were monitored. The findings presented here demonstrate that the hydraulic conductivity of the clay appear to be generally related to the polarity of the chemicals and the dielectric constant. The cracking effect of butanol and MTBE on consolidated clay at low flow rate and low stress level was observed. The addition of ethanol or MTBE to diesel increased the clay permeability and the migration of organic chemical. The addition of ethanol to gasoline also caused an increase in the clay hydraulic conductivity. The effect of the association of alcohols with gasoline or diesel on the clay hydraulic conductivity is discussed, with a view to improving current pollution remediation techniques.     

铅在高岭石表面的吸附模式

采用表面络合模式,研究了高岭石表面的酸碱性质以及高岭石表面对铅的吸附行为。结果表明,高岭石表面在不同ｐＨ条件下对质子和铅离子的吸附反应可以用单一表面基团、无静电表面络合模式来描述。高岭石表面酸度常数拟合值分别为ｐＫａ１＝２．７５和ｐＫａ２＝５．５２,电荷零点ｐＨｚｐｃ＝４．１铅在高岭石表面的吸附量随ｐＨ值的升高而增加,吸附铅的两种表面化合态〉ＳＯＰｂ＾＋和〉ＳＯＰｂＯＨ的浓度也随ｐＨ值的变化而变化