Swelling characteristics of Gaomiaozi bentonite and its prediction

Gaomiaozi （GMZ） bentonite has been chosen as a possible matrix material of buffers/backfills in the deep geological disposal to isolate the high-level radioactive waste （HLRW） in China. In the Gaomiaozi deposit area, calcium bentonite in the near surface zone and sodium bentonite in the deeper zone are observed. The swelling characteristics of GMZ sodium and calcium bentonites and their mixtures with sand wetted with distilled water were studied in the present work. The test results show that the relationship be- tween the void ratio and swelling pressure of compacted GMZ bentonite-sand mixtures at full saturation is independent of the initial conditions such as the initial dry density and water content, hut dependent on the ratio of bentonite to sand. An empirical method was accordingly proposed allowing the prediction of the swelling deformation and swelling pressure with different initial densities and bentonite-sand ratios when in saturated conditions. Finally, the swelling capacities of GMZ Na- and Ca-bentonites and Kunigel Na-bentonite are compared.

Soil-water characteristics of Gaomiaozi bentonite by vapour equilibrium technique

Soil-water characteristics of Gaomiaozi(GMZ)Ca-bentonite at high suctions(3–287MPa)are measured by vapour equilibrium technique.The soil-water retention curve(SWRC)of samples with the same initial compaction states is obtained in drying and wetting process.At high suctions,the hysteresis behaviour is not obvious in relationship between water content and suction,while the opposite holds between degree of saturation and suction.The suction variation can change its water retention behaviour and void ratio.Moreover,changes of void ratio can bring about changes in degree of saturation.Therefore,the total change in degree of saturation includes changes caused by suction and that by void ratio.In the space of degree of saturation and suction,the SWRC at constant void ratio shifts to the direction of higher suctions with decreasing void ratio.However,the relationship between water content and suction is less affected by changes of void ratio.The degree of saturation decreases approximately linearly with increasing void ratio at a constant suction.Moreover,the slope of the line decreases with increasing suction and they show an approximately linear relationship in semi-logarithmical scale.From this linear relationship,the variation of degree of saturation caused by the change in void ratio can be obtained.Correspondingly,SWRC at a constant void ratio can be determined from SWRC at different void ratios.

Determination of full-scale pore size distribution of Gaomiaozi bentonite and its permeability prediction

Gaomiaozi(GMZ)bentonite is a potential buffer/backfill material for a deep geological disposal of highlevel radioactive waste.It has a wide pore size distribution(PSD)with sizes ranging from several nanometers to more than one hundred microns.Thus,properly characterizing the pore structures of GMZ bentonite is a challenging issue.In this study,pressure-controlled porosimetry(PCP),ratecontrolled porosimetry(RCP),and scanning electron microscopy(SEM)were used to investigate the PSD of GMZ bentonite,The results indicate that each method has its limitation,and a combined use of PCP and RCP is suitable to obtain the full-scale PSD of GMZ bentonite.Moreover,we also compared the full-scale PSD with nuclear magnetic resonance(NMR)result.It is found that there is no significant difference in the range of PSD characterization between NMR and mercury intrusion method(PCP and RCP).However,in a ce rtain range,the detection accuracy of NMR is higher than that of mercury injection method.Finally,permeability prediction based on PCP and SEM data was conducted,and both of the two methods were found to be able to predict the permeability.The combined method is effective to obtain the full-scale PSD of GMZ bentonite,which is the key to estimation of the sealing ability of bentonite buffer.

Quantitative two/three-dimensional spatial characterization and fluid transport prediction of macro/micropores in Gaomiaozi bentonite

The sealing performance of a bentonite barrier is highly dependent on its seepage characteristics, which are directly related to the characteristics of its pore structure. Based on scanning electron microscopy(SEM) and focused ion beam-SEM(FIB-SEM), the pore structure of bentonite was characterized at different scales. First, a reasonable gray threshold was determined through back analysis, and the image was binarized based on the threshold. In addition, binary images were used to analyze bentonite’s pore structure(porosity and pore size distribution). Furthermore, the effects of different algorithms on the pore structure characterization were evaluated. Then, permeability calculations were performed based on the previous pore structure characteristics and a modified permeability prediction model. For permeability prediction based on the three-dimensional model, the effect of pore tortuosity was also considered. Finally, the accuracy of numerical calculations was verified by conducting macroscopic gas and alcohol permeability experiments. This approach provides a better understanding of the microscale mechanism of gas transport in bentonite and the importance of pore structures at different scales in determining its seepage characteristics.

工程尺度缓冲材料热-水-力多场耦合数值模拟研究

缓冲材料作为填充在废物罐与地质体之间重要的人工屏障,对高放废物处置库的长期安全至关重要。以工程尺度缓冲材料热-水-力多场耦合大型模型试验系统(China-Mock-up)为研究对象,采用有限元数值模拟软件LAGAMINE,考虑试验过程中复杂的边界条件与材料属性,实现了近5 a试验数据的定量模拟。模拟结果可准确预测试验系统内部不同特征点温度随室温周期性波动及线性增长这一动态变化规律;能够较好反映不同特征点相对湿度随时间的行为演化趋势,在加热器附近区域呈现出先干燥后饱和的现象,远离加热器区域则逐渐增大;模拟的总应力与实测试验数据间表现较好地一致性,能够反映试验台架内部不同特征点的总应力随时间逐渐增大这一演化过程。揭示了多场耦合条件下缓冲材料(膨润土)温度、湿度及应力的相互作用关系,为深入认识处置库环境下缓冲材料行为演化特征提供了重要的参考依据。

Selection and Basic Properties of the Buffer Material for High-Level Radioactive Waste Repository in China

Radioactive wastes arising from a wide range of human activities are in many different physical and chemical forms, contaminated with varying radioactivity. Their common features are the potential hazard associated with their radioactivity and the need to manage them in such a way as to protect the human environment. The geological disposal is regarded as the most reasonable and effective way to safely disposing high-level radioactive wastes in the world. The conceptual model of geological disposal in China is based on a multi-barrier system that combines an isolating geological environment with an engineered barrier system. The buffer is one of the main engineered barriers for HLW repository. It is expected to maintain its low water permeability, self-sealing property, radio nuclides adsorption and retardation properties, thermal conductivity, chemical buffering property, canister supporting property, and stress buffering property over a long period of time. Bentonite is selected as the main content of buffer material that can satisfy the above requirements. The Gaomiaozi deposit is selected as the candidate supplier for China＇s buffer material of high level radioactive waste repository. This paper presents the geological features of the GMZ deposit and basic properties of the GMZ Na-bentonite. It is a super-large deposit with a high content of montmorillonite （about 75 %）, and GMZ-1, which is Na-bentonite produced from GMZ deposit is selected as the reference material for China＇s buffer material study.

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。

高压实高庙子膨润土GMZ01的膨胀力特征

高放废物深地质处置中,缓冲/回填材料系统起着工程屏障、水力学屏障、化学屏障、传导和散失放射性废物衰变热等重要作用,是高放废物地质处置库长期安全性和稳定性的有效保障。前人研究表明,膨润土是理想的缓冲/回填材料。在归纳总结压实膨润土膨胀力的室内试验研究成果的基础上,采用恒体积试验法研究高压实高庙子膨润土GMZ01的膨胀力特性,该膨润土已经被确定为我国高放废物地质处置库首选缓冲材料。结果表明,高压实高庙子膨润土GMZ01膨胀力随时间的变化曲线是一条渐近线,而时间/膨胀力与时间之间存在很好的线性关系;膨胀力发展过程曲线与吸水量曲线具有明显的阶段性特征;高压实高庙子膨润土的膨胀力和干密度之间存在指数关系,干密度是影响膨胀力的一项重要的因素。所取得的膨胀力特性成果,对于高庙子膨润土膨胀性能的正确判定具有非常重要的意义。

两种高庙子钠基膨润土膨胀特性比较研究

对两种高庙子钠基膨润土(简称GMZ001和GMZ07)在不同初始干密度下进行膨胀力试验、常压力下的膨胀变形试验以及压缩试验。试验结果表明,GMZ001的膨胀能力要比GMZ07的大,并且GMZ001比GMZ07更难压实。对饱和后两种膨润土进行压汞试验和扫描电子显微镜测试后发现,在相同孔隙比下,GMZ07集聚体间孔隙较多,并且GMZ001集聚体的水化程度大于GMZ07。结合土工和微观试验的结果,认为导致两者力学性能差异的主要原因是由于颗粒粒径大小的差异以及蒙脱石含量的不同。最后利用蒙脱石孔隙比的概念对两种膨润土的浸水膨胀试验结果进行归一化,并对膨润土的膨胀特性进行了预测。

盐溶液饱和高庙子膨润土膨胀特性及预测

甘肃北山被首选为修建高放废物处置库的地区。考虑到该地区地下水中含有总溶解固体(TDS),选择NaCl-Na2SO4作为溶解固体。以高庙子钠基膨润土为试验材料,利用单向固结仪,进行不同TDS浓度盐溶液和蒸馏水饱和的膨胀试验。根据蒙脱石孔隙比的概念,统一整理了饱和高庙子膨润土在盐溶液和蒸馏水饱和下的膨胀特性。结果表明,当TDS浓度为12.3 g/L(预选处置库区的最高离子浓度)时,在双对数坐标中蒙脱石孔隙比与膨胀力关系和干密度与膨胀力关系均呈直线且平行于蒸馏水的试验结果;对于给定干密度试样,膨胀力的对数与TDS浓度呈线性关系。根据以上试验结果,给出了由高庙子钠基膨润土的设计干密度和离子浓度计算相应膨胀力和膨胀变形的表达式。

高庙子膨润土和砂混合物膨胀变形特性及其预测

以高庙子钠基膨润土为试验材料,利用单向固结仪进行一维浸水膨胀、浸水湿陷以及膨胀力试验,分析了该膨润土在不同掺砂率下浸水膨胀和湿陷变形特性等问题,并根据蒙脱石孔隙比的概念,分析了饱和时的膨润土及其掺砂混和物的变形特性.试验结果表明,在低掺砂率下充分吸水膨胀湿陷或不变形时,膨润土与砂混合物的蒙脱石孔隙比与垂直应力的关系在对数坐标系中是一条直线,并且可据此预测膨润土及膨润土掺砂混和物在不同的干密度、掺砂率下吸水至饱和时的变形量及膨胀力.分析砂骨架孔隙比对高掺砂率膨润土混合物的试验结果,可预测形成砂骨架时的垂直应力值.

高庙子膨润土强度时效性试验研究

本文用试验方法研究了静置时间对不同含水率高庙子钠基(GMZ07)膨润土强度的影响。在保持试样干密度和含水率不变的情况下,将初始含水率为10%、18%和24%(饱和)3组压实试样分别静置0、5、15、30、90 d,之后采用精度较高的直剪仪在400、800和1 600 k Pa垂直压力下进行剪切试验;同时完成了部分试样的压汞试验。结果表明:GMZ07膨润土的剪切强度随静置时间增长而减小;静置前期,强度下降较快;静置时间超过一定天数后,其剪切强度逐渐趋于稳定。根据3种含水率试样的强度包线可得到:随着静置时间增加,饱和试样的内摩擦角略微下降而黏聚力变化不大;含水率10%和18%试样的黏聚力明显变小而内摩擦角几乎不变。根据Alonso等提出的非饱和土有效应力,结合压实膨润土试样的孔径分布,认为集聚体内孔隙增多是非饱和膨润土强度随静置时间而变小的原因。

由天然钠基膨润土直接合成钛柱撑膨润土的研究

以高庙子天然钠基膨润土为原料,钛酸正丁酯在pH=2-5环境下水解聚合成柱撑剂,水热法制备了钛柱撑膨润土（Ti-pillaredclay,Ti-PILC）。采用X-射线粉晶衍射（XRD）、扫描电镜（SEM）、比表面积分析仪（BET）分析了产物的结构和形貌。探讨了制备Ti-PILC的工艺参数对结构的影响。结果表明：Ti-PILC呈片层桥结的多孔结构;钛柱撑剂撑开的d001层间距为1.860 8~2.481 3 nm;比表面积由31 m2/g增加到191 m2/g。柱撑最佳工艺参数为：钛/土比30 mmol/g,反应时间为3 h,反应温度为100℃。

化学作用下高庙子膨润土屏障性能演化行为

深地质处置库运营过程中,受地下水化学成分、可能泄露的核素等近场化学条件影响,膨润土工程屏障性能可能发生衰减。围绕化学作用下膨润土屏障性能的演化行为,以我国北山处置库预选场地为工程背景,以内蒙古高庙子膨润土为研究对象,首先介绍了高庙子膨润土的基本物理性质及北山预选场地近场化学条件;在此基础上,详细总结了化学作用下高庙子膨润土水力、力学及阻滞等屏障性能演化行为相关研究成果。结果表明:化学作用对膨润土持水、渗透特性的影响可分别依据渗透吸力及双电层理论解释;化学作用下膨润土膨胀力的衰减与其水化膨胀机制有关,化-力耦合及化-水-力耦合作用下膨润土变形特性因渗透固结、化学软化效应而发生改变;膨润土的吸附与扩散特性受核素浓度、离子环境、pH值等因素影响。最后,提出化学作用下膨润土屏障性能演化研究应重点关注的方向。

内蒙古高庙子膨润土热学性能研究

膨润土的热学性能是评价膨润土作为高放废物深地质处置库缓冲/回填材料的重要参数。高庙子膨润土矿床初步确定为中国缓冲/回填材料的供应基地,本研究通过实验,获得了高庙子膨润土的导热系数。结果表明,在相同的压实密度条件下,随着膨润土含水率的增加,导热系数也增加。

Al_(13)柱撑膨润土的制备及柱化影响因素的研究

以钠化改型后的内蒙古高庙子膨润土为原料,Al13高聚体为柱化剂,采用水热离子交换法,合成了Al13高聚体柱撑膨润土(Al13 pillared Clay,Al13-PILC)。通过X-射线粉晶衍射(XRD),扫描电镜(SEM)分析了产物的结构和形貌,探讨了制备Al13-PILC的工艺参数对结构的影响。结果表明,钠化后的膨润土呈现大而薄的颗粒,铝柱撑膨润土颗粒仍保留了较完整的层状和片状结构;铝柱撑剂撑开的d(001)层间距可达1.889nm;最佳工艺参数为:铝/土比10mmol/g,水热反应温度90℃,柱撑老化时间72h。

两种膨润土的土-水特征曲线

用滤纸法和压力板法对Kunigel-V1和高庙子两种膨润土进行试验研究,量测不同孔隙比情况下的土-水特征曲线,研究土-水特征曲线与孔隙比之间的关系以及两种膨润土的土-水特性。试验结果表明:用吸力与含水率的关系表示土-水特征曲线时,在吸力较大的情况下,孔隙比对土-水特征曲线的影响不大;用吸力与饱和度的关系表示土-水特征曲线时,土-水特征曲线随着孔隙比的减小向右上方移动,即在吸力一定的情况下,饱和度随着孔隙比的减小而增加,并且此变化接近于线性变化。另外,孔隙比相同时,Kunigel-V1和高庙子膨润土的土-水特征曲线比较接近,即两种膨润土的持水特性比较相近。

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。

高庙子膨润土的土水特征曲线与渗透系数

在土水特征测定试验的基础上,分析了历史上提出的各种模拟土水特征曲线的方程与试验结果的拟合程度。在非饱和渗透系数试验结果的基础上,分析了由分维理论得到的非饱和渗透系数模拟方程与试验结果的拟合程度。得出以下结论:Fredlund and Xing土水特征曲线方程对于试验结果有较好的模拟效果;Brooks和Corey土水特征曲线方程与试验结果的曲线形状更为接近,但在模拟接近309MPa的吸力段的土水曲线时与试验结果有偏差。分维理论的修正公式能更好模拟非饱和渗透系数。

缓冲/回填材料-压实高庙子钠基膨润土的胀缩性试验研究

选用内蒙古高庙子钠基膨润土压实试样进行了室内膨胀力、膨胀变形以及收缩变形的实验。结果表明:高庙子膨润土具有高膨胀、低收缩的良好特性。试样的膨胀力随时间呈渐近线趋势增长,随含水量呈线性增长,随干密度呈指数增长;膨胀变形受初始干密度影响较大,收缩变形受初始含水量的影响较大;在高水分和干密度态下,试样膨胀力为0.85～4.64 MPa,无荷膨胀率为24.4%～40.8%,收缩系数为0.19～0.50。