两种超微细矿物粉体材料的制备及应用研究

Superfine mineral materials are mainly resulted from the pulverization of natural mineral resources, and are a type of new materials that can replace traditional materials and enjoy the most extensive application and the highest degree of consumption in the present day market. As a result, superfine mineral materials have a very broad and promising prospect in terms of market potential. Superfine pulverization technology is the only way for the in-depth processing of most of the traditional materials, and is also one of the major means for which mineral materials can realize their application. China is rich in natural resources such as heavy calcite, kaolin, wollastonite, etc., which enjoy a very wide market of application in paper making, rubber, plastics, painting, coating, medicine, environment-friendly recycle paper and fine chemical industries, for example. However, because the processing of these resources is generally at the low level, economic benefit and scale for the processing of these resources have not been realized to their full potential even up to now. Big difference in product indices and superfine processing equipment and technologies between China and advanced western countries still exists. Based on resource assessment and market potential analysis, an in-depth study was carried out in this paper about the superfine pulverization technology and superfine pulverized mineral materials from the point of mineralogical features, determination of processing technologies, analytical methods and applications, by utilizing a variety of modern analytical methods in mineralogy, superfine pulverization technology, macromolecular chemistry, material science and physical chemistry together with computer technology and so on. The focus was placed on the innovative study about the in-depth processing technology and the processing apparatus for kaolin and heavy calcite as well as the application of superfine products. The main contents and the major achievements of this study are listed as follows: 1. Superfine pulverization processing of mineral materials shall be integrated with the study of their crystal structures and chemical composition. And special attention shall be put on the post-processing technologies, rather than on the indices for particle size, of these materials, based on their fields of application. Both technical feasibility and economic feasibility shall be taken into account for the study about superfine pulverization technologies, since these two kinds of feasibilities serve as the premise for the industrialized application of superfine pulverized mineral materials. Based on this principle, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in this study, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in this study. Heavy calcite and kaolin are two kinds of superfine mineral materials that enjoy the highest consumption in the industry. Heavy calcite is mainly applied in paper making, coating and plastics industries, the hard kaolin in northern China is mainly used in macromolecular materials and chemical industries, while the soft kaolin in southern China is mainly used for paper making. On the other hand, superfine pulverized heavy calcite and kaolin can both be used as the functional additives to cement, a kind of material that enjoys the biggest consumption in the world. A variety of analytical methods and instruments such as transmission and scanning electron microscopy, X-ray diffraction analysis, infrared analysis, laser particle size analysis and so on were applied for the elucidation of the properties and the mechanisms for the functions of superfine mineral materials as used in plastics and high-performance cement. Detection of superfine mineral materials is closely related to the post-processing and application of these materials. Traditional detection and analytical methods for superfine mineral materials include optical microscopy, infrared spectral analysis and a series of microbeam techniques such as transmission and scanning electron microscopy, X-ray diffraction analysis, and so on. In addition to these traditional methods, super-weak luminescent photon detection technology of high precision, high sensitivity and high signal to noise ratio was also utilized by the author for the first time in the study of superfine mineral materials, in an attempt to explore a completely new method and means for the study of the characterization of superfine materials. The experimental results are really exciting! The innovation of this study is represented in the following aspects: 1. In this study, preposed chemical treatment method, technology of synchronized superfine pulverization and gradation, processing technology and apparatus of integrated modification and depolymerization were utilized in an innovative way, and narrow distribution in terms of particle size, good dispersibility, good application effects, low consumption as well as high effectiveness of superfine products were achieved in the industrialized production process*. Moreover, a new modification technology and related directions for producing the chemicals were invented, and the modification technology was even awarded a patent. 2. The detection technology of super-weak luminescent photon of high precision, high sensitivity and high signal to noise ratio was utilized for the first time in this study to explore the superfine mineral materials, and the experimental results can be compared with those acquired with scanning electron microscopy and has demonstrated its unique advantages. It can be expected that further study may possibly help to result in a completely new method and means for the characterization of superfine materials. 3. During the heating of kaolinite and its decomposition into pianlinite, the diffraction peaks disappear gradually. First comes the disappearance of the reflection of the basal plane (001), and then comes the slow disappearance of the (hkl) diffraction peaks. And this was first discovered during the experiments by the author, and it has never before reported by other scholars. 4. The first discovery of the functions that superfine mineral materials can be used as dispersants in plastics, and the first discovery of the comprehensive functions that superfine mineral materials can also be used as activators, water-reducing agents and aggregates in high-performance cement were made in this study, together with a detailed discussion. This study was jointly supported by two key grants from Guangdong Province for Scientific and Technological Research in the 10th Five-year Plan Period (1,200,000 yuan for Preparation technology, apparatus and post-processing research by using sub-micron superfine pulverization machinery method, and 300,000 yuan for Method and instruments for biological photon technology in the characterization of nanometer materials), and two grants from Guangdong Province for 100 projects for scientific and technological innovation (700,000 yuan for Pilot experimentation of superfine and modified heavy calcite used in paper-making, rubber and plastics industry, and 400,000 yuan for Study of superfine, modified wollastonite of large length-to-diameter ratio).

湛江湖光岩玛珥湖55ka以来植硅体化石记录及古环境变迁

The study of biogenic proxy of tropical and subtropical regions provides important evidence about the process and history of vegetation and environmental changes, and is of globally importance for understanding the dynamic mechanism of paleoclimatic and paleoenvironmental changes. The sediments from the Huguangyan Maar lake in Guangdong Province offer a continuous high-resolution record of the past 55 ka about environmental and vegetational changes. The studies of chronology, and physical, chemical environmental proxies have provided much important information about the paleoenvironmental and paleoclimatic histories. The phytolith, a new biogenicl proxy, has been used to determine the nature and types of plants in this area since the last 55 ka. This study presents a preliminary result about the characteristics of phytolith shapes, the variations of the fossils assemblages, and their significance for environmental changes. Moreover, the author probes the process of special specie evolution and their relationship to climatic parameters. The history of fire has been reconstructed based on the variations in charcoals. The main results and conclusions include: 28 types of phytoliths from 233 samples have been identified. Their environmental meanings are investigated in detail. Based on the variations in phytolith associations, the history and process of climatic and environmental changes in the last 55 kaBP have been established for this region. Climatic changes experienced eight intervals during this period, showing the variations of hot-humid to cool-try climate in the ten thousands years scale, and a shorter dry-hot climate condition in millennial scale. The history of palm plant has been established in this region. Two peaks appeared from 55-39 ka and since the Holocene. Plants in Bambusoideae have been growing in this area all the period, representing the impact of the East Asian summer monsoon. Bamboo plants have similar tendency in their abundance to palm plants, but with a lag of 1-2 ka BP. Panicoideae plants, the representative of C4 plants, have 6 flourishing periods occurred at 54.5, 44, 41.5, 32.5, 14, and 10 kaBP, respectively, reflecting 6 times short-term arid events. Charcoal record from the Huguang Marr lake reveals the history of nature fire, that mostly happened in dry period of last glacial from 55-10 kaBP, centered at 50-45, 40-35, 30-25, and 20-15kaBP, showing about a cycle of 10,000 years.

岩石圈伸展对粤北下庄矿田铀成矿的制约机制研究

地球动力学与成矿关系的研究是地球科学研究的前沿领域，而陆内岩石圈伸展与成矿的关系的研究则是该领域相对比较薄弱的环节。 华南地区于白垩—古近纪发生了岩石圈强烈的伸展减薄事件，且岩石圈伸展减薄与该区同时期形成的众多金属和非金属矿床有密切的成因联系，尤其是华南地区的花岗岩型热液铀矿床，显示了与该区岩石圈伸展作用可能有多方面的成因联系。粤北下庄铀矿田位于位于南岭铀-多金属成矿带的南部，是华南地区典型的花岗岩型热液铀矿区，本次研究在深入细致的野外地质工作的基础上，运用流体包裹体地球化学、元素地球化学、同位素地球化学等方法手段，开展了对下庄铀矿田成矿流体性质、成矿过程中元素的活动规律、成矿流体来源及演化等方面的系统研究，初步探讨了岩石圈伸展对该区铀成矿的制约机制，并建立了可能的矿床成因模式。通过研究，本次工作获得了以下几点主要认识： （1）通过对下庄铀矿田部分铀矿床流体包裹体显微测温、激光拉曼光谱及液相成分分析研究，查明了下庄矿田铀矿床矿前期热液属中高温（200℃~350℃）、低盐度（0.72%~5.95%NaCl）、密度中等（0.703~0.830g/cm3）、活动深度较深（2.29km~5.74km）、富∑CO2、相对还原性质的流体；成矿期热液属中低温（主要为154℃ ~250℃）、低盐度（0~1.83%NaCl）、密度中等（0.628~0.867g/cm3）、活动深度较浅（0.19km~1.62km）、富F-、相对氧化性质的流体。 （2）矿石矿矿物电子探针测试分析及岩、矿石的微量元素地球化学分析研研究表明，本区铀矿床主要的原生铀矿物为沥青铀矿、铀石、钛铀矿，铀矿物的形成与Si、Ca、W等元素有密切的关系，而其它金属元素未显示明显地富集。矿石、脉石矿物部分继承了原岩的稀土元素组成，且在原岩基础上又有高度的演化。 （3）进行了矿区内碳酸盐的C、O同位素和黄铁矿的He、Ar稀有气体同位素的分析研究。研究表明，矿化剂∑CO2主要为幔源，大量的He、Ar等稀有气体也来自于地幔。矿区发育的深大断裂构造可能控制了幔源挥发份的加入。 （4）脉石矿物碳酸盐和萤石的Sr、Nd同位素地球化学研究显示，成矿流体中的这些元素主要源于地壳，南区矿床（338、339）的Sr、Nd组成则为富含壳源Sr、Nd的流体与幔源基性脉岩不同程度的水—岩反应所致。另外，碳酸盐铅同位素研究显示，下庄矿区成矿物质铀可能来自帽峰式后期流体交代的花岗岩体。 （5）岩石圈伸展与下庄矿田铀成矿有关系密切：下庄矿田铀矿床明显受伸展构造控制，伸展构造既为导矿构造，又为储矿构造；岩石圈伸展导致的地温梯度升高，大地热流平均值加大，驱动热液流体的流动，为铀成矿提供了主要的热驱动力；岩石圈伸展产生的深大断裂导通了壳幔间的联系，使幔源脱气成因挥发份（主要为∑CO2）沿断裂上升，加入壳源热水循环系统，从而参与了铀成矿。 （6）初步建立了下庄矿田“岩石圈伸展体系下大陆热水系统铀矿床成因模式”。模式认为，华南地区白垩—古近纪岩石圈伸展作用引发区内热水流体的大规模循环，且伸展引起的幔源脱气作用产生的挥发份（主要为ΣCO2）加入了贫铀、贫矿化剂的循环的地下热水中，形成了富矿化剂热水。富矿化剂热水从富铀花岗岩中浸出铀（氧化作用），变为富矿化剂、富铀热液流体，这种热液流体在伸展引起的热驱动下沿构造上升，热液流体上升到浅部时，由于地球化学障、流体压力释放等因素的影响，U被还原沉淀，并在有利部位富集成矿。

Perovskite-type B-site Bi-doped ceramic membranes for oxygen separation

Novel mixed conducting oxides, B-site Bi-doped perovskites were exploited and synthesized. Cubic perovskite structures were formed for BaBi0.2COyFe0.8-yO3-delta (y less than or equal to 0.4) and BaBixCo0.2Fe0.8-xP3-delta (x=0.1-0.5) The materials exhibited considerable high oxygen permeability at high temperature. The oxygen permeation flux of BaBi0.2Co0.35Fe0.45O3-delta membrane reached about 0.77 x 10(-6) mol/cm(2) s under an air/helium oxygen partial pressure gradient at 900 degrees C, which was much higher than that of other bismuth-contained mixed conducting membranes. The permeation fluxes of the materials increased with the increase of cobalt content, but no apparent simple relationship was found with the bismuth content. The materials also demonstrated excellent reversibility of oxygen adsorption and desorption. Stable time-related oxygen permeation fluxes were found for BaBi0.2CO0.35Fe0.45O3-delta and BaBi0.3Co0.2Fe0.5O3-delta a membranes at 875 degrees C.

A novel method to synthesize amorphous silica-alumina materials with mesoporous distribution without using templates and pore-regulating agents

In this study, a novel sol-gel method is used to synthesize amorphous silica-alumina materials with a narrow mesoporous distribution and various Si/Al molar ratios without using any templates and pore-regulating agents. During the preparation procedure, only inexpensive inorganic salts were used as raw materials, instead of expensive and harmful alkoxides. The precursor sol was dried at room temperature in a vacuum box kept at 60 mmHg until it began to form the gel. The results of a nitrogen sorption experiment indicate that the synthesized materials with different Si/Al molar ratios have similar mesoporous distributions (within 2-12 nm). Moreover, it was found that the material's pore size distribution remains at a similar value during the heat treatment from room temperature to 550 degreesC. On the basis of the nitrogen sorption, TEM, and AFM characterization results, a formation mechanism of mesopores which accounts for the experimental data is also suggested. This suggested mechanism involves rearrangement of the primary particles during the drying process to form the precursors of the similarly sized mesopores. The synthesized materials were characterized by XRD, thermal analysis (TG/DTA), Al-27 and Si-29 MAS NMR spectroscopy, SEM, TEM, and AFM. The results of Al-27 and 29Si MAS NMR indicate that the distribution of silicon and aluminum in the synthesized materials is more uniform and homogeneous than that in the mixed oxides prepared via the traditional sol-gel method even at high alumina contents. The type and density of the acid sites were studied using pyridine adsorption-desorption FTIR spectroscopy. It was shown that the acidity of the synthesized materials is higher than that of the silica-alumina materials prepared by conventional methods.

Templateless synthesis of catalysts with narrow mesoporous distribution

In this study, amorphous silica-alumina nanomaterials with narrow mesoporous distribution can be obtained by two novel sol-gel processes, without the use of any templates. The results of our experiments show that the preparation method has a great influence on the precursor sol structure as well as the specific surface area and mesopore volume of the final product, but has no effect on the pore size distribution.

Ultrasonic synthesis of silica-alumina nanomaterials with controlled mesopore distribution without using surfactants

A novel sol-gel process has been developed for the synthesis of amorphous silica-aluminas with controlled mesopore distribution without the use of organic templating agents, e.g., surfactant molecules. Ultrasonic treatment during the synthesis enables production of precursor sols with narrow particle size distribution. Atomic force microscopy analysis shows that these sol particles are spherical in shape with a narrow size distribution (i.e., 13-25 nm) and their aggregation during the gelation creates clusters containing similar sized interparticle mesopores. A nitrogen physiadsorption study indicates that the mesoporous materials containing different Si/Al ratios prepared by the new synthesis method has a large specific surface area (i.e., 587-692 m(2)/g) and similar pore sizes of 2-11 nm. Solid-state Al-27 magic angle spinning (MAS) NMR shows that most of the aluminum is located in the tetrahedral position. A transmission electron microscopy (TEM) image shows that the mesoporous silica-alumina consists of 12-25 nm spheres. Additionally, high-resolution TEM and electron diffraction indicate that some nanoparticles are characteristic of a crystal, although X-ray diffraction and Si-29 MAS NMR analysis show an amorphous material.

Mesoporous spinel MgAl2O4 prepared by in situ modification of boehmite sol particle surface: I Synthesis and characterization of the unsupported membranes

Mesoporous spinel membranes as ultrafiltration membranes were prepared through a novel sol-gel technique. By in situ modification of the sol particle surface during the sol-gel process, control of the material structure on a nanometer scale from the earliest stages of processing was realized. Nano-particles with a chocolate-nut-like morphology, i.e. spinel MgAl2O4 as a shell and gamma -Al2O3 as a core, were first revealed by HRTEM results. The formation of the spinel phase was confirmed by X-ray diffraction (XRD). N-2 adsorption-desorption results showed that the mesoporous membranes had a narrow pore size distribution. (C) 2001 Elsevier Science B.V. All rights reserved.

Mechanistic studies of methane partial oxidation to syngas over LiNiLaOx/Al2O3 catalyst

Temperature-programmed reduction (TPR) characterization of the LiNiLaOx/Al2O3 catalyst before or after partial oxidation of methane (POM) reaction and a series of O-2, CH4 and CH4/O-2 pulse reaction experiments over the catalyst under different pretreatments were performed. It was found that CH4 dissociatively adsorbs on active center nickel producing H-2 and surface carbon, C(a). The surface carbon reacts with surface lattice oxygen or surface adsorbed oxygen to produce CO. Because the activation barrier for the reaction C(a)+ O(a) =CO(a) is the highest among all the elementary reactions, the rate-determining step of the POM may be the reaction C(a) + O(a) =CO(a).

Alkanes-assisted low temperature formation of highly ordered SBA-15 with large cylindrical mesopores

Highly ordered SBA-15 silicas with large cylindrical mesopores (similar to 15 nm) are successfully obtained with the help of NH4F by controlling the initial reaction temperatures in the presence of excess amounts of alkanes.

Separation of compounds interacting with liposome membrane in combined prescription of traditional Chinese medicines with immobilized liposome chromatography

Immobilized liposome chromatography (ILC), the stationary phase of which has been regarded as a mimic biomembranes system was used to separate and analyze compounds interacting with liposome membrane in Danggui Buxue decoction, a combined prescription of traditional Chinese medicines (CPTCMs), and its compositions Radix Astragli and Radix Angelica Sinensis. More than 10 main peaks in the extract of Danggui Buxue decoction were resolved on the ILC column, suggesting that more than 10 components in the prescription have significant retention on ILC column. Ligustilide, astragaloside, TV and formononetin, three main bioactive ingredients in Danggui Buxue decoction, were found to have relatively significant, while ferulic acid, another bioactive ingredient in the prescription, relatively weak retention on ILC column. Effects of the eluent pH and amount of immobilized phosphatidylcholine (PC) on separation of interactional compounds in the extract of Danggui Buxue decoction were also investigated. It was found that these two factors strongly affected the retention of some interactional compounds. In addition, the fractions partitioned with different solvents from water extract of this combined prescription were evaluated with this ILC column system. (c) 2005 Elsevier B.V. All rights reserved.