苏皖凹凸棒石粘土纳米尺度矿物学及地球化学
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摘要
本论文研究目的是深入揭示凹凸棒石形成机制、成矿过程、与玄武岩之间的演化关系；认识凹凸棒石物理化学性能以及加工处理改变凹凸棒石性能的本质，为凹凸棒石粘土深加工和应用奠定理论基础；探讨和研究凹凸棒石在纳米材料和环境材料科学领域的应用前景和加工技术；揭示自然环境中纳米颗粒，表生条件下矿物结晶作用和机制，纳米矿物形成过程，纳米孔地球化学现象，以及纳米孔界面地球化学问题。
本论文以高分辨透射电镜为主要研究手段，着重从纳米尺度揭示凹凸棒石粘土中矿物以及加工处理凹凸棒石形貌、晶体结构、化学成分特征、演化规律，调查超微观结构，研究矿物变化、转化轨迹，从纳米尺度建立矿物之间成因关系。以纳米尺度观察研究为基础，配合传统的光学显微镜、X射线衍射、扫描电镜、ICP-MS、XRF等现代分析技术，对苏皖凹凸棒石粘上进行了较为系统的凹凸棒石矿物学、凹凸棒石粘土成因矿物学和凹凸棒石粘土应用矿物学以及地球化学研究。
凹凸棒石粘土、风化玄武矿物组成和纳米尺度矿物学研究，发现凹凸棒石平行于蒙脱石(001)面连生属于蒙脱石向凹凸棒石的转化并导致蒙脱石结构破坏。发现苏皖凹凸棒石粘土矿层中存在富opal-A和富opal-CT的交互层，单层厚度仅几个厘米厚，并探讨了形成机制及其古气候意义。发现苏皖凹凸棒石粘土中白云石属于纳米颗粒，研究了白云石超微观结构特征，提出纳米孔界面化学和地球化学对白云石化的可能影响，初步模拟实验验证白云石化与纳米孔界面化学、纳米孔地球化学的关联，白云石交代过程中成分转化和结构转化的多步骤过程。
微量元素地球化学以及同位素地球化学示踪，得出凹凸棒石粘土与玄武岩的成因关系、成矿过程，提出苏皖沉积型凹凸棒石形成的两种机制，并得到两种凹凸棒石形态、成分、结构标形特征。对凹凸棒石粘土矿床矿物碳、氢、氧稳定同位素组成提出新的解释，认识同位素组成变化与古环境的关系。
提出凹凸棒石属于天然一维纳米材料，单根纤维具有弹性，凹凸棒石对有机分子包括非极性的N_2分子吸附皆为外表面吸附，凹凸棒石的吸附性质、胶体性质等主要与凹凸棒石的纳米颗粒效应和较大的外比表面积有关。测定纯凹凸棒石BET-N_2比表面积205m~2/g，热液型为108m~2/g，阳离子交换容量11meq/g，近饱和湿度吸附水量为30％。分析研究了胶体体系中凹凸棒石与蒙脱石的面-面互相作用，探讨其材料科学意义。
从纳米尺度调查研究热液型和沉积型凹凸棒石与酸作用过程中产物、形态、结构、成分、物理化学性质的变化。热处理凹凸棒石形貌结构变化，讨论了差热分析图谱中800℃左右宽泛的吸热谷的归属。研究了凹凸棒石-Au、凹凸棒石-Ag、凹凸棒石-TiO_2等纳米复合催化剂和抗菌剂功能材料制备方法，并初步测试了催化和抗菌效果。研究了制备纳米棒状活性二氧化硅最佳工艺参数。利用凹凸棒石酸活化废液等制备阴离子粘土(LDH)产品。
The objectives of the thesis are that open out the formation mechanism and process of palygorskite as well as relation with basalts, understand physical and chemical properties of palygorskite and changes of physical and chemical properties because of processing, discuss and study potential utilization as nanometer materials and environmental materials and processing technology, investigate nanometer particles in environment, mineral crystallization in earth surface condition, forming process nanometer minerals, phenomena of mesoporous materials, geochemistry and interface chemistry of mesoporous materials.
Characteristics and change disciplinarian of morphology, crystal structure, chemical composition of palygorskite and heat or acid treatment palygorskite from nanometer scale, ultra-micro structure of the minerals in the palygorskite clays are investigated using high resolution transmission electron microscopy as main method. Using TEM combining with Optic microscopy, XRD, SEM, ICP-MS and XRF, palygorskite mineralogy, palygorskite clay genesis mineralogy, applied mineralogy as well as geochemistry have been investigated in the thesis.
From the nanometer investigation it has been found that palygorskite paralleling (001) of montmorillonite is transformed from montmorillonite and caused the destruction of montomrillonite crystal; oscillation of rich opal-A and rich opal-CT layer in several centimeters is concerned with period change of paleoclimate; dolomite in playgorskite clays is nanometer. Ultra-micro structure of dolomite is investigated, we put forward that interface chemistry and geochemistry in nanometer hole should affect on the dolomization.
From the trace element and isotope geochemistry, the relationship between the palygorskite and basalt as well as process of formation of palygorskite has been understood. Two mechanisms of formation of palygorskite aer put forward and mark characteristics of morphology and composition, structure is provided. The stable isotope of hydrogen, oxygen and carbon are reinterpreted. The relationship between isotope constituent and paleoenvironment is understood.
From the results of nanometer investigation, It is proposed that palygorskite is natural one dimension nanometer material and is found that palygorksite crystal behave elasticity. Adsorption to organic molecules, including N2 belongs to outer surface adsorption. Excellent properties of adsorption and colloid of palygorskite are determined by its nanometer scale effect and large specific surface area, rather than its channel surface. Pure palygorskite has been separated, BET-N2 specific surface area are 205m2/g and 108 m2/g for sedimentary and hydrothermal respectively. Cation exchange capability is llmeq/g and sum of adsorption water is 30% near saturation humidity for sedimentary pure palygorskite. It is studied about interaction between palygorskite and montmorillonite in aqueous suspension, discussed the signification of the interaction for materials science. We investigated products and changes of morphology, structure, composition, physical and chemical properties during acid and heat treatment of the s
edimentary and hydrothermal palygorskite. Nanometer composite catalysis and anti-bacteria materials of palygorskite-Au, palygorskite-Ag, palygorskite-TiO2 and palygorskite-NiO have been prepared and characterized. Nanometer rod active SiO2 has been prepared, best technological parameter has been obtained. Layer double hydroxide has been synthesis from wastewater of acid treatment of palygorskite clay.
本论文以高分辨透射电镜为主要研究手段，着重从纳米尺度揭示凹凸棒石粘土中矿物以及加工处理凹凸棒石形貌、晶体结构、化学成分特征、演化规律，调查超微观结构，研究矿物变化、转化轨迹，从纳米尺度建立矿物之间成因关系。以纳米尺度观察研究为基础，配合传统的光学显微镜、X射线衍射、扫描电镜、ICP-MS、XRF等现代分析技术，对苏皖凹凸棒石粘上进行了较为系统的凹凸棒石矿物学、凹凸棒石粘土成因矿物学和凹凸棒石粘土应用矿物学以及地球化学研究。
凹凸棒石粘土、风化玄武矿物组成和纳米尺度矿物学研究，发现凹凸棒石平行于蒙脱石(001)面连生属于蒙脱石向凹凸棒石的转化并导致蒙脱石结构破坏。发现苏皖凹凸棒石粘土矿层中存在富opal-A和富opal-CT的交互层，单层厚度仅几个厘米厚，并探讨了形成机制及其古气候意义。发现苏皖凹凸棒石粘土中白云石属于纳米颗粒，研究了白云石超微观结构特征，提出纳米孔界面化学和地球化学对白云石化的可能影响，初步模拟实验验证白云石化与纳米孔界面化学、纳米孔地球化学的关联，白云石交代过程中成分转化和结构转化的多步骤过程。
微量元素地球化学以及同位素地球化学示踪，得出凹凸棒石粘土与玄武岩的成因关系、成矿过程，提出苏皖沉积型凹凸棒石形成的两种机制，并得到两种凹凸棒石形态、成分、结构标形特征。对凹凸棒石粘土矿床矿物碳、氢、氧稳定同位素组成提出新的解释，认识同位素组成变化与古环境的关系。
提出凹凸棒石属于天然一维纳米材料，单根纤维具有弹性，凹凸棒石对有机分子包括非极性的N_2分子吸附皆为外表面吸附，凹凸棒石的吸附性质、胶体性质等主要与凹凸棒石的纳米颗粒效应和较大的外比表面积有关。测定纯凹凸棒石BET-N_2比表面积205m~2/g，热液型为108m~2/g，阳离子交换容量11meq/g，近饱和湿度吸附水量为30％。分析研究了胶体体系中凹凸棒石与蒙脱石的面-面互相作用，探讨其材料科学意义。
从纳米尺度调查研究热液型和沉积型凹凸棒石与酸作用过程中产物、形态、结构、成分、物理化学性质的变化。热处理凹凸棒石形貌结构变化，讨论了差热分析图谱中800℃左右宽泛的吸热谷的归属。研究了凹凸棒石-Au、凹凸棒石-Ag、凹凸棒石-TiO_2等纳米复合催化剂和抗菌剂功能材料制备方法，并初步测试了催化和抗菌效果。研究了制备纳米棒状活性二氧化硅最佳工艺参数。利用凹凸棒石酸活化废液等制备阴离子粘土(LDH)产品。
The objectives of the thesis are that open out the formation mechanism and process of palygorskite as well as relation with basalts, understand physical and chemical properties of palygorskite and changes of physical and chemical properties because of processing, discuss and study potential utilization as nanometer materials and environmental materials and processing technology, investigate nanometer particles in environment, mineral crystallization in earth surface condition, forming process nanometer minerals, phenomena of mesoporous materials, geochemistry and interface chemistry of mesoporous materials.
Characteristics and change disciplinarian of morphology, crystal structure, chemical composition of palygorskite and heat or acid treatment palygorskite from nanometer scale, ultra-micro structure of the minerals in the palygorskite clays are investigated using high resolution transmission electron microscopy as main method. Using TEM combining with Optic microscopy, XRD, SEM, ICP-MS and XRF, palygorskite mineralogy, palygorskite clay genesis mineralogy, applied mineralogy as well as geochemistry have been investigated in the thesis.
From the nanometer investigation it has been found that palygorskite paralleling (001) of montmorillonite is transformed from montmorillonite and caused the destruction of montomrillonite crystal; oscillation of rich opal-A and rich opal-CT layer in several centimeters is concerned with period change of paleoclimate; dolomite in playgorskite clays is nanometer. Ultra-micro structure of dolomite is investigated, we put forward that interface chemistry and geochemistry in nanometer hole should affect on the dolomization.
From the trace element and isotope geochemistry, the relationship between the palygorskite and basalt as well as process of formation of palygorskite has been understood. Two mechanisms of formation of palygorskite aer put forward and mark characteristics of morphology and composition, structure is provided. The stable isotope of hydrogen, oxygen and carbon are reinterpreted. The relationship between isotope constituent and paleoenvironment is understood.
From the results of nanometer investigation, It is proposed that palygorskite is natural one dimension nanometer material and is found that palygorksite crystal behave elasticity. Adsorption to organic molecules, including N2 belongs to outer surface adsorption. Excellent properties of adsorption and colloid of palygorskite are determined by its nanometer scale effect and large specific surface area, rather than its channel surface. Pure palygorskite has been separated, BET-N2 specific surface area are 205m2/g and 108 m2/g for sedimentary and hydrothermal respectively. Cation exchange capability is llmeq/g and sum of adsorption water is 30% near saturation humidity for sedimentary pure palygorskite. It is studied about interaction between palygorskite and montmorillonite in aqueous suspension, discussed the signification of the interaction for materials science. We investigated products and changes of morphology, structure, composition, physical and chemical properties during acid and heat treatment of the s
edimentary and hydrothermal palygorskite. Nanometer composite catalysis and anti-bacteria materials of palygorskite-Au, palygorskite-Ag, palygorskite-TiO2 and palygorskite-NiO have been prepared and characterized. Nanometer rod active SiO2 has been prepared, best technological parameter has been obtained. Layer double hydroxide has been synthesis from wastewater of acid treatment of palygorskite clay.
引文
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