地下水对压实高庙子膨润土冲蚀作用研究

采用膨胀渗透仪和浊度仪,通过检测冲蚀循环溶液浊度和膨润土试样膨胀力的变化,获得了冲蚀液对高庙子（GMZ）膨润土的冲蚀规律,对比分析了膨润土干密度、冲蚀液pH值、冲蚀液渗流方向、围岩裂隙条数、溶液类型和浓度等因素对膨润土冲蚀的影响规律。研究表明：膨润土的膨胀力在冲蚀开始的几天内迅速增长,随后达到稳定,膨润土干密度越大,地下水对膨润土的冲蚀作用越弱;冲蚀液pH值对膨润土的冲蚀作用影响很大,碱性较强的地下水对膨润土的冲蚀作用较弱,而碱性较弱地下水的冲蚀作用则明显;地下水径向渗流时对膨润土的冲蚀作用大于纵向渗流情况,围岩裂隙增多后,地下水对膨润土的冲蚀作用加强;随着冲蚀液中NaCl浓度的增加,冲蚀液对膨润土的冲蚀作用先增强后减弱,冲蚀液中CaCl2的浓度对膨润土的冲蚀影响规律与NaCl浓度对膨润土的冲蚀影响规律相似,但CaCl2浓度的变化对膨润土的冲蚀影响不明显。     

A natural analogue of nuclear waste glass in compacted bentonite

A marine based argillaceous rock containing volcanic glass shards has been investigated to infer the long-term durability of vitrified nuclear waste in compacted bentonite, which is a candidate for buffer material constituting the engineered barrier system for nuclear waste disposal. Fission track ages indicate that the volcanic glass shards, andesitic scoria, have been buried in the argillaceous rock for about 1 Ma. Neither glass matrix dissolution nor precipitation on the surface was seen under an optical microscope. Little leaching of any element has been recognized by analyses using an electron microprobe analyzer. Secondary ion mass spectrometry analysis, however, indicates significant hydration which may dominantly be a permeation of molecular water.As an indicator of durability of glass against groundwater a normalized mass loss of Si (NL_Si) has been evaluated for the volcanic glass based on free energy for hydration. The difference between estimated NL_Si of the volcanic glass and that of a simulated waste glass is within one order so that the volcanic glass may be analogous to a waste glass with respect to durability to water. The argillaceous rock is analogous to the compacted bentonite with respect to physical properties such as dry-density, unconfined compression strength, porosity, and hydraulic conductivity. The ambient physical and chemical conditions surrounding the volcanic glass have been also investigated: temperature was in the range from 4 to 30°C due to the burial history of the volcanic glass. Over most of the past 1 Ma the volcanic glass has been in contact with groundwater originating from seawater. Thermodynamic calculations indicate (1) pH (=7.74–7.94) of the groundwater has mainly been controlled by dissolution of carbonate minerals, (2) the redox potential (Eh=−34–−73 mV) of the groundwater has dominantly been controlled by decomposition of organic materials to produce CH₄(g), and (3) activity of aqueous silica of the groundwater was in equilibrium with SiO₂ amorphous. Because of the equilibrium between aqueous silica and SiO₂ amorphous, the volcanic glass did not dissolve during the burial.Vitrified nuclear waste sealed in compacted bentonite, therefore, will not dissolve significantly if buried in an environment as mentioned above.     

Coupled thermo-hydro-mechanical modelling of bentonite buffer material

Mechanistic model development and numerical analyses were carried out on coupled thermo-hydraulic-mechanical processes in bentonite-based buffer material for the geological disposal of high-level radioactive waste with small-scale laboratory experiments and a full-scale test. The mechanism of water movement in compacted bentonite was identified by applying theoretical equations to the experimental results. The application clearly explained the observed results of the temperature dependence of the hydraulic conductivity in the saturated state and the water diffusivity in the unsaturated state for the compacted bentonite and the dry density dependence of the diffusivity. The full-scale coupled test, BIG-BEN, was conducted at PNC (Power Reactor and Nuclear Fuel Development Corporation) Tokai Works. The results of the numerical analyses for the full-scale test which are based on the present knowledge of coupled processes and our small-scale experiments were in good agreement with the measured results except for mechanical phenomena. Copyright © 1999 John Wiley & Sons, Ltd.     

高庙子膨润土中蒙脱石碱性溶蚀的矿物学证据

高放废物地下处置库运营过程中,衬砌混凝土在地下水作用下产生的强碱性溶液,会扩散进入膨润土缓冲屏障,长期将使屏障性能发生退化。采用不同 pH 值的 KOH 溶液模拟衬砌混凝土溶出的碱性溶液,在室内进行为期一年的常温接触扩散试验,开展X射线荧光光谱（X-ray fluorescence spectroscopy,简称XRF）、X射线衍射（X-ray diffraction,简称 XRD）、扫描电镜（scanning electron microscope,简称 SEM）和能谱（energy dispersive spectrometry,简称 EDS）试验,研究强碱性溶液缓慢扩散对高庙子膨润土矿物的影响。XRF试验结果表明,当 KOH 溶液的 pH>12.6时,膨润土中 Si 元素的含量开始减少,即含Si 矿物蒙脱石、石英、方石英等发生了溶解;同时,K元素含量增多,表明膨润土与碱溶液发生离子交换反应,溶液中大量的K⁺进入蒙脱石层间。XRD 试验结果表明,在 pH=12.6时,蒙脱石矿物的 001峰开始右移、变宽,峰值强度大大减弱;在pH>13时,衍射角θ整体向右偏,晶面间距由原始膨润土样的1.385 3 nm（13.853 Å）减小为1.221 0 nm（12.210 Å）,表明蒙脱石矿物晶层被压缩。随着 KOH 溶液 pH 值增大,膨润土中蒙脱石、石英等矿物的含量明显减少,长石类矿物的含量逐渐增加,伊利石和斜发沸石的含量也呈现略微增多的趋势。SEM 试验结果表明,随着溶液 pH 的增大,蒙脱石部分晶层会发生重叠,进而产生部分裂隙和孔洞,加速蒙脱石的溶蚀进程。在为期一年的接触扩散试验中,pH=13.8的 KOH 溶液扩散深度超过7.5 mm,并且在碱溶液与膨润土接触面上观察到新生成的伊利石微晶,证实强碱性溶液会导致蒙脱石溶解及伊利石化。     

北山花岗岩岩屑-膨润土混合材料导热性能研究

高放废物地质处置库缓冲/回填材料的重要作用之一是传导和散失高放废物衰变热,在膨润土中添加石英砂、石墨、花岗岩岩屑等导热性能较好的添加剂是提高缓冲/回填材料导热性能的主要方法。选用北山花岗岩岩屑为添加剂,与高庙子钠基膨润土GMZ01组成混合材料,制备不同含水率、不同密度的试样。使用Hot Disk TPS2500s热常数分析仪测定样品的导热系数,分析其与花岗岩岩屑含量、干密度、饱和度等参数的关系,并运用多种混合物热传导模型分析预测导热系数。研究结果表明,花岗岩岩屑能够有效提高缓冲/回填材料的导热性能,混合材料的导热系数分别与其饱和度、气体体积存在线性关系;Maxwell方程能够较好预测北山花岗岩岩屑-膨润土混合材料的导热系数。     

Mechanisms and Models for Bentonite Erosion Used for Geologic Disposal of High Level Radioactive Waste: A Review

The performance of the bentonite buffer in nuclear waste repository concept relies to a great extent on the buffer surrounding the canister having sufficient dry density. Loss of buffer material caused by erosion remains as the most significant process reducing the density of the buffer. In the worst case, the process is assumed to last as long as the free volume between the pellets in the pellets filled regions is filled with groundwater. Erosion rate and mass erosion are calculated based on the erosion model, and the measures are presented to prevent the geological disaster due to bentonite erosion. The groundwaters may solubilise the smectite particles in the bentonite and carry them away as colloidal particles. A dynamic model is developed for sodium gel expansion in fractures where the gel soaks up groundwater as it expands. The model is based on a force balance between and on smectite particles, which move in the water. Attractive van der Waals forces, repulsive electric diffuse layer (DDL) forces, gravity and buoyancy forces and forces caused by the gradient of chemical potential of the particles act to move the particle in the water. The effect of the fracture width and the frictions between particles and water and surrouding rock is analysed based on erosion model. The DDL forces strongly depend on the type of clay minerals and the type of ion and concentration in the water surrounding the particles. In the designed safe use of nuclear waste disposal (tens of thousands of years to hundreds of thousands of years), the safety of nuclear waste disposal is affected by the hydrodynamic and chemical effects, and bentonite erosion. Due to the bentonite erosion, the buffer/backfill layers become loose, and their permeability increases, which causes the nuclear element diffusion and convection, and even the nuclear disaster. In this paper, the mechanisms, models, experiments and control measures of bentonite erosion were systematically summarized. The current deficiencies of bentonite erosion were pointed out, and new methods were put forward to carry out the research for bentonite erosion. The measures were presented to prevent the geological disaster due to bentonite erosion through changes. The project is not only academic innovation, but also has a large practical significance. The research results of this project can be widely applied to the design, construction and maintenance of the bentonite buffer in nuclear waste repository.     

Plutonium diffusivity in compacted bentonite

Measurements on plutonium diffusivity in water-saturated compacted bentonite were carried out. Representative specimens of sodium bentonite were taken from the Tsukinuno and Kuroishi mines situated in northeast Japan. Tsukinuno bentonite was divided into three types: raw type, purified Na-type, and H-type which was prepared by treating Na-type bentonite with hydrochloric acid. Kuroishi bentonite contained chlorite as impurity. H-type bentonite was used as reference for the convenience of profile measurement in bentonite, since plutonium diffusivity in H-type bentonite was considered to be larger than that in Na-type bentonite because of low pH and low swelling pressure of H-type bentonite.

Sampled bentonite was compacted into pellets of 20 mm in diameter and 20 mm in height. Bulk densities of these specimens were 1200–1800 kg/m³ for purified Na-type and H-type bentonite and 1600 kg/m³ for raw type bentonite.

Plutonium profiles obtained in H-type bentonite can be explained by diffusion equation with constant concentration source. Diffusivity ranges from 10^-13 to 10¹² m²/s for H-type and Kuroishi impure sodium bentonite. Diffusivity in both raw type and purified Tsukinuno bentonite was was estimated to less than 10^-14 M²/s. Diffusivity in H-type bentonite showed a tendency to decrease with increasing density. Influence of in bentonite was also studied. Quartz content up to 50% or hematite content up to 1% did not influence diffusivity significantly in H-type bentonite.

The chemical species of plutonium in pore water of Na-type and H-type were estimated Pu(OH)₃^-; and PuO₂^- , respectively.     

Evaluation of a compacted bentonite/sand seal for underground waste repository isolation

This study investigates the performance of an optimum compacted bentonite/sand mixture seal for the isolation of underground waste repositories. Engineering geological tests such as compaction, flow, swelling, mechanical and shear strength tests have been conducted to select an optimum mixture and to recommend a stable bentonite/sand seal length-to-radius ratio (L/a) as far as the factor of safety (F) is concerned. The results of the compaction permeameter tests led to a recommendation to select an optimum compacted bentonite/sand mixture possessing a bentonite content of about 20% to satisfy the minimum regulatory hydraulic conductivity requirement. Engineering geological analysis of the seal/rock mechanical interaction with regard to reduce the possibility of seal slip led to a recommendation to utilize a seal L/a of at least 25.     

Feasibility of using fly ash,lime, and bentonite to neutralize acidity of pore fluids

Acidic groundwater resulting from the poorly planned use of acid sulfate soils has become a major environmental issue in coastal Australia over the last several years. Use of permeable reactive barriers (PRBs) designed to generate alkalinity by promoting sulfate reduction has recently become popular as an alternative solution to this problem. However, recent studies have also revealed that the long-term performance of such PRBs can be significantly undermined by chemical precipitation and clogging of pore space, which would decrease the buffer capacity and hydraulic conductivity of the reactive material. This study seeks to explore the feasibility of using bentonite in addition to lime and fly ash to form mixtures with a high buffer capacity and permeability that would enable groundwater flow through PRBs over a substantial period of time. A series of laboratory experiments, including buffer capacity and leaching tests, were performed on different mixtures of fly ash with lime and bentonite using acidic fluids of low pH. It was found that the ability of such mixtures to neutralize acidic fluids was mostly controlled by the content of lime. Laboratory data also showed that an addition of bentonite to lime—fly ash mixtures could decrease the buffer capacity of soil. Compaction tests indicated that the presence of bentonite would increase the dry density of mixtures at the optimum moisture content. A series of hydraulic conductivity tests were carried out to study changes in the coefficient of permeability of lime—fly ash mixtures with different contents of bentonite permeated with acidic liquids. The obtained results revealed that the coefficient of permeability of the specimens tended to increase over a period of time, likely due to the changes in the diffuse double layer of bentonite particles.     

高压实膨润土的非饱和渗透膨胀模型

高放废弃物深地质处置库中,作为缓冲/回填材料的高压实膨润土的设计功能是,遇水吸湿导致土体膨胀变形,以密封高压实膨润土块体砌置时形成的块体与块体之间和块体与围岩之间的施工缝隙以及围岩中因处置库开挖卸载引起的裂缝,形成阻障围岩中地下水渗入内库引起核素迁移,与库内高放废物的辐射扩散的人工屏障。高压实膨润土在自由膨胀条件下的膨胀应变和非饱和渗透系数由渗透试验测得;孔隙比和吸力的关系由压汞试验测得。吸力和含水率的函数关系可由土-水特征曲线测试试验得到。因此,自由膨胀条件下膨润土的非饱和渗透膨胀模型由膨胀应变、非饱和渗透系数和孔隙比与吸力的函数关系建立。结果表明：渗透系数和体积应变都随吸力减小而增加,因为吸力减小会导致孔隙比增加。这一发现有助于设计高放废物的最终处置方案。     

高压实膨润土热湿耦合效应实验室模拟

本文研究了作为高放废物深地质处置库最后一道人工屏障－缓冲层在热湿耦合艇下的宏观表现,通过自行设计的实验,得到了一些有益的启示,初步认为在本研究涉及的时间范围内,水势场对高压实膨润土中温度场分布影响较小,而温度场对其中水分运移有一定影响。文中介绍了有关实验设计、实验步骤,实验结果与分析,对多孔介质中传热传质研究及高放废物深地质处理有一定参考价值。．     

膨润土性能温度效应研究进展

通过文献调研、资料总结和分析,阐述了温度对膨润土诸多性状的影响。膨润土中孔隙水的化学成分因温度变化而发生改变,温度的增加使膨润土中内水、外水的含量发生改变,从而影响土的水合力大小。以OPHELIE膨润土实验为例,介绍了温度对膨润土内部孔隙大小的影响。此外,还对目前膨润土持水能力与膨胀力的温度效应进行了阐述。     

Numerical modelling on water retention and permeability of compacted GMZ bentonite under free-swelling conditions

In this study, a solid–liquid–gas coupled equation was established to simulate water retention characteristics of highly compacted GMZ bentonite. Then, modelling results were compared with laboratory test results. Results indicate that GMZ bentonite has a strong moisture expansion (or a limit drying shrinkage) characteristic. The control equation can simulate the water absorption and deformation characteristics very well at high relative humidity (or low suction). Environmental scanning electron microscope (ESEM) observation reveals the course grain soil texture of the surface under low relative humidity (RH), while the surface of GMZ bentonite becomes smooth (more fine-grained soil texture) as RH increases. Differences were found between the porosities calculated by macroexperiment results and microscopic observations with ESEM method. This is because only the interaggregate pores can be observed by ESEM photographs. Additionally, we find that the simulated effective porosities are close to the results calculated by microscopic tests, while the effective porosity is considered as the main flow channel of flow. Further, the intrinsic permeability, the effective water and gas permeability are calculated based on the proposed model. The modelling results coincide well with the laboratory experimental results and support the reliability of the proposed model.     

双电层理论与高庙子膨润土的体变特征

黏性土中土体颗粒（矿物颗粒）带有负电荷,周围存在电场。在静电引力与布朗运动（热运动）作用下,紧邻土体颗粒表面处静电引力最强,水化离子和极性分子牢牢地被吸附在颗粒表面附近形成固定层。由固定层向外,静电引力逐渐减小,水化离子和极性分子的活动性逐渐增大,形成扩散层。固定层和扩散层中的阳离子（反离子层）与土粒表面负电荷共同构成双电层。根据双电层理论,当给定两个黏土片层之间的距离时,渗透压力可以由两个片层中轴线处的离子浓度来求取。同样,对于给定的渗透压力和中轴线处的离子浓度,便可以确定两个片层之间的距离。采用渗析法吸力控制技术与压汞仪法（MIP）微观结构试验手段,研究了低吸力范围内、自由膨胀条件下高压实高庙子膨润土的土水特性与体变特征,同时采用双电层理论估算了高庙子膨润土水化过程中的自由膨胀量,并将估算值与试验实测值进行了对比分析。在使用孔率计法试验结果求取试样孔隙比时考虑了压汞仪出力能力影响,采用线性延伸方法估算了残余孔隙量。研究结果显示,低吸力范围内,由双电层理论,估算的高压实高庙子膨润土的自由体积膨胀量与试验数据吻合较好,但随着吸力的进一步减小,两者之间的误差有增大的趋势,文中对出现这一偏差的原因进行了分析探讨。     

碱−热环境下MX80膨润土导热性能试验研究

以美国怀俄明州钠基（MX80）膨润土为研究对象,采用热探针法测定碱−热环境下MX80膨润土的导热系数,探讨了温度、碱液强度和干密度对试样导热系数λ的影响规律,并选择部分试样进行了X射线衍射（X-ray diffraction,简称XRD）和扫描电镜（scanning electron microscope,简称SEM）试验,揭示了碱−热环境下MX80膨润土导热性能演变的微观机制。试验结果表明：MX80膨润土的导热系数λ随碱液含量和干密度的递增而增大;在不同碱液含量条件下,膨润土的导热系数均随温度升高而增大,且碱液含量越高,导热系数的温度效应越显著;干密度较小时,膨润土导热系数λ随温度升高而增大的影响越明显,主要原因是温度促进了试样内部的水汽潜热传输;同一温度和干密度条件下,热传导系数λ随着碱液pH值的升高而降低6,且pH值越高,则λ降幅越明显,主要原因是强碱溶液腐蚀了膨润土的蒙脱石成分,减少了试样内石英含量,增大了膨润土试样的孔隙率,进而降低了膨润土导热系数,这与测试试样的XRD和SEM结果相吻合。     

高压实膨润土热湿力性能测试

本文介绍了高压实样品的制样特点,测试了高压实膨润土样的导热系数,热膨胀系数,对高压实膨润土热湿力特性研究有较大参考价值。     

Diffusion of uranium in compacted sodium bentonite

Sorption and diffusion of uranium in sodium bentonite MX-80 were measured in aerobic conditions. The batch method was used for the sorption measurements and the steady state method for the diffusion measurements. Clear sorption was noticed only when high uranium concentrations were used so that the pH of the solution decreased.

The diffusivities of uranium were strongly dependent on the compaction of bentonite so that in the highly compacted samples the diffusion was very restricted. Uranium shows both features of ion-exclusion and sorption. Further studies are, however, needed to explain the diffusion mechanisms of uranium.     

考虑膨胀效应UH模型的有限元实现

高庙子膨润土已被确定为我国高放废物地质处置的首选缓冲/回填材料,进行其力学特性及应用模拟研究对合理设计处置库具有十分重要的意义。考虑膨胀效应的UH模型是在超固结非饱和土本构模型（非饱和土UH模型）的基础上提出的,因引入了土体团粒的吸水膨胀作用,使其适用于非饱和膨润土。基于有限元软件ABAQUS的二次开发平台,利用Fortran语言编制模型的UMAT（user-difined material）材料子程序,进行了考虑膨胀效应UH模型的有限元实现。然后针对高放废物处置概念模型,利用编制的模型子程序对高放废物处置系统进行了三维有限元模拟,并对渗流场和应力场的演化规律进行了初步探究。模拟结果显示处置系统中膨润土的内应力增加,土体的稳定性较好,说明选择高庙子膨润土作为缓冲/回填材料的合理性,也同时验证了程序的正确性。