Thermal-Mechanical Behavior of Compacted GMZ Bentonite

The THM behavior of compacted GMZ bentonite has been investigated using a suction-temperature controlled isotropic cell. The results obtained were compared with the existing results on other reference bentonites (MX80, FEBEX, FoCa, and Kunigel-V1). It has been observed that the coefficient of thermal expansion of the compacted GMZ bentonite is 2×10^-4°C^-1, similar to the values of compacted MX80 and FEBEX bentonites. The heating tests of the GMZ bentonite also show that the suction is an important parameter that governs the thermal volumetric behavior of unsaturated soils. Unlike temperature, suction has a significant effect on the compressibility parameters. Examination of the mineralogy of various bentonites showed that a good correlation can be generally established between the montmorillonite content and the cations exchange capacity (CEC) or the specific surface area (S). Nevertheless, both the basic geotechnical properties and the swelling potential seem to depend not only on the montmorillonite content but also on other factors such as the nature of base exchangeable cations. The quartz content of the GMZ bentonite is relatively high (11.7%). This could explain its relatively large values of thermal conductivity.     

高庙子膨润土及其混合材料导热性能研究

导热性能是高放废物地质处置库缓冲/回填材料的重要性能之一。采用瞬变平面热源法,研究了我国高放废物地质处置首选缓冲/回填材料高庙子膨润土,及以其为主料,添加不同含量石英砂、北山花岗岩碎屑组成的混合材料的导热性能。分析了添加剂种类和含量、干密度、饱和度等因素对导热系数的影响。研究结果表明:高庙子膨润土及其混合材料的导热系数、热扩散系数都随干密度和含水量的增大而增大;石英砂、北山花岗岩碎屑能够不同程度提高膨润土的导热系数,石英砂的作用优于北山花岗岩碎屑;饱和度对添加剂发挥其提高缓冲/回填材料导热性能的作用影响明显,饱和度越高,添加剂的作用越显著。     

氢氧根离子在膨润土中的弥散规律及其溶蚀作用

高放废物地质处置库中可能出现的碱性孔隙水,会对膨润土的缓冲封闭性能产生不良影响,尤其是碱性孔隙水中的OH^-离子。本文用NaOH溶液模拟碱性孔隙水,用蒸馏水模拟处置库现场的地下水,对初始干密度为1.70 g/cm³的高庙子(GMZ)膨润土试样开展弥散试验,研究OH^-离子在高压实GMZ膨润土中的弥散规律;用pH值为13和13.8的NaOH溶液模拟孔隙水侵蚀GMZ膨润土试样,研究碱性孔隙水侵蚀,GMZ膨润土的溶解规律。结果表明,非稳态条件下,OH^-离子在GMZ膨润土中的弥散系数为1.49×10^-11~1.89×10^-10 m²/s,且弥散系数随着试样两侧溶液浓度差的减小而降低;高pH值碱性孔隙水侵蚀,首先会造成膨润土中含Si和Al矿物的迅速溶解,溶解速率与时间呈近似线性增长关系,且溶液的pH值越高,溶解速率越快。     

高庙子膨润土膨胀力时效性试验研究

针对高庙子膨润土在不同含水率和不同干密度条件下膨胀力时效性进行了试验研究。首先采用静力压实法将3种不同含水率的高庙子膨润土粉末压实为两种不同密实状态的试样,随后在保持压实试样的体积和含水率不变的条件下,分别静置0,1,7,15,30和90 d,最后采用膨胀仪对完成静置试样的膨胀力进行量测;同时结合静置过程,完成了部分试样的扫描电镜（SEM）试验。试验结果表明：高庙子膨润土的膨胀力随静置时间的增长不断减小,且前期减小明显,后期逐渐趋于稳定;膨胀力的时效性与试样初始条件有关,试样含水率和干密度越大,膨胀力随静置时间的衰减越明显,即时效性越强。SEM试验结果表明,静置90 d后,高庙子膨润土内的蒙脱石发生了水化,集合体分解,颗粒相互黏结,微观孔隙结构趋于均质化,呈现点阵式的絮状结构;试样静置过程中不同微观结构层次之间的水分重分布导致的蒙脱石水化是高庙子膨润土静置过程中膨胀力降低的主要内在原因。     

Swelling pressure characteristics of compacted Chinese Gaomiaozi bentonite GMZ01

Gaomiaozi bentonite (GMZ01) has been decided upon as the first option for use as buffer/backfill materials in the deep disposal of high-level radioactive waste in China. The basic functions of the materials used in the waste repositories request among others a sufficient swelling pressure and low hydraulic conductivity in order to provide long-term stability to the barrier system under environmental pressure and behavior of the waste loads. As such, it is necessary to investigate the influence of initial dry density on the swelling properties of Gaomiaozi bentonite (GMZ01) in order to achieve better design of buffer/backfill materials. In this study the swelling pressure of GMZ01 has been studied and analyzed by multi and one-step wetting constant volume tests with five different dry densities (1.15, 1.35, 1.50, 1.60 and 1.75 mg/m³). Results show that swelling pressure changes with time nonlinearly, while there is a linear relationship between time/swelling pressure and time. Curves of swelling pressure and the amount of absorbed water varying with time can be classified into typical phases. For the GMZ01 tested here, the initial dry density is an important factor influencing the swelling pressure. The results show that there is an exponential relationship between swelling pressure and dry density. Moreover, comparison was done between the experimental swelling pressure results of used GMZ bentonite in this study and other bentonites cited in literature: (i) other GMZ׳s and (ii) different types of bentonites proposed as buffer/backfill materials (i.e., MX80, Kunigel, Montigel, and Calcigel). The effect on the microstructure of the density and the wetting under the constant volume condition (after the swelling pressure test) has been investigated by studying the results of pore size distribution for GMZ01 by using the mercury intrusion porosimetry (MIP) test and the environmental scanning electron microscope (ESEM) photos. Finally, two different theoretical concepts were used to estimate the swelling pressure (the modified DDL and thermodynamics approaches). The results of the two methods show that the swelling pressure results compare relatively well with the experimental data for the GMZ bentonite.     

高碱性溶液对高庙子膨润土溶蚀作用的研究

 在高放性核废物地质处置库中,碱性孔隙水长期入渗可能会对膨润土的缓冲封闭性能产生不良影响。为了研究高碱性溶液对膨润土的溶蚀作用及其机制,本文用NaOH溶液模拟高碱性孔隙水,对初始干密度为1.70 g/cm3的高庙子膨润土试样进行渗透侵蚀,并借助X射线衍射(XRD)和能谱分析(EDS)测试,对侵蚀后各试样的矿物成分和Mg元素含量的变化进行测定分析。结果表明：高庙子膨润土含有蒙脱石、石英、斜长石和微斜长石(或方石英),且主要有效组分为蒙脱石;在试验过程中,经高碱性溶液的侵蚀,试样的主要原生矿物的种类没有减少,也没有检测到新物质生成,但膨润土试样中的蒙脱石和Mg元素的含量随着侵蚀碱性溶液浓度的增大而降低,这说明在高碱性溶液的侵蚀作用下,膨润土中的蒙脱石发生溶解。因此,碱性孔隙水的长期入渗会对膨润土产生溶蚀作用,进而降低膨润土的膨胀性能,增大膨润土的有效孔隙比和渗透性,最终削弱了膨润土的缓冲封闭性能。     

压实膨润土膨胀应变时效性试验及模型研究

本文对高庙子膨润土试样竖向膨胀应变时效性进行了试验和理论研究。首先,3种不同含水率的高庙子膨润土粉末被压实到2种不同干密度,然后保持试样含水率不变分别静置0、1、7、15、30和90天,最后利用膨胀变形仪对静置完成后的试样的水化膨胀变形进行了测量,试验结果表明:试样的水化膨胀曲线呈双曲线型,水化初期膨胀明显,之后逐渐稳定;竖向膨胀应变随初始干密度的增加而增大,与初始含水率关系不明显;最大竖向膨胀应变随静置时间的增长不断衰减,且静置前期衰减明显,后期趋于稳定;基于试验成果,通过类比,建立了压实膨润土的膨胀应变时效性经验模型,拟合结果表明该模型能够较好地反映静置时间对高庙子膨润土膨胀应变的影响。     

高庙子膨润土微观结构时效性试验研究

针对高庙子膨润土在不同含水率和不同干密度条件下的微观孔隙结构时效性进行了试验研究。首先采用静力压实法将3种不同含水率条件下的高庙子膨润土粉末压实到2种不同密实状态,压实结束后保持试样体积和含水率不变分别静置1,30,90d,然后分别采用压汞仪法和扫描电镜法对静置不同时间后试样的微观孔隙结构进行量测。试验结果表明,高庙子膨润土集合体间大孔隙随静置时间增加逐渐减少,而集合体内孔隙和小于压汞仪最小探测粒径的极小孔隙逐渐增多;随着静置时间的延续,膨润土微观孔隙结构趋于均匀化。产生上述现象的主要原因是：试样静置过程中,为达到吸力平衡,试样各微观孔隙结构中水分子重分布,导致层叠体内水分子层数增多,蒙脱石水化;随着水化的进行,层叠体晶层间水分子层数逐渐增多,同时厚的层叠体逐渐裂开成薄的层叠体,导致集合体内小孔隙增多;在体积不变条件下,集合体间大孔隙不断被挤压填充,孔隙体积逐渐减少。     

高庙子膨润土的土水特征曲线

近年来，用于高放废物深地质处置工程屏障的高压密膨润土越来越受到关注。经过全国范围内的比较和筛选，内蒙古兴和县高庙子膨润土矿床被确定为我国高放废物处置库缓冲材料的首选矿床。采用渗析法和水汽平衡法来控制吸力技术，通过上水特征曲线测定试验、环境扫描电镜和乐汞试验，研究高庙子高压密膨润土在不同吸力下的持水特性及其微观结构特征。利用压汞试验结果推算膨润土在恒体积条件下的土水特征曲线，并与实测数据进行比较。研究结果表明：在不同吸力作用下，膨润土的持水特性与其微观结构之间有着密切关系。     

Bentonite transformations in strongly alkaline solutions

Strongly alkaline solution pH causes changes to the mineralogy of bentonites which might impact on their performance as environmental barriers. The long term effect of solution pH on the performance of bentonite barriers such as in Geosynthetic Clay Liners needs to be studied from the viewpoint of solubility and stability of the mineral phases present at extreme pH values. Changes to bentonite mineralogy brought about by extended reaction with 1 M sodium hydroxide solutions at 20–25 °C reveal that certain components of bentonites, namely smectite, opaline silica and quartz, are subject to dissolution in alkaline solution. Associated with dissolution is the formation of hydrous hydroxy-aluminosilicate as well as hydrous carbonate mineral phases. It is postulated that these precipitates, formed from reaction of bentonite with alkaline leachates can result in pore filling, which is responsible for recently measured lower hydraulic conductivity of some bentonites to high pH leachates.     

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.     

温度对GMZ膨润土的膨胀性能影响研究

在25℃,40℃,60℃和90℃的蒸馏水中对高庙子(GMZ)膨润土进行了膨胀性能试验。由于在试验条件下渗透膨胀占主导地位,GMZ膨润土的膨胀性能随温度的升高而增大,其中最大膨胀率随温度线性增加,而膨胀力随温度呈指数增加。压实GMZ膨润土的膨胀性能可用em=Kp^D-3表示。N2吸附试验结果表明温度对GMZ膨润土的表面分维D基本没有影响。在渗透膨胀条件下,采用扩散双层模型计算发现膨胀系数K与温度T_c之间存在线性关系,并且通过GMZ膨润土和Bikaner膨润土的膨胀试验进行了验证。将K–T_c线性关系与e_m–p分形关系相结合,提出了温度作用下GMZ膨润土膨胀性能的一种简便定量评价方法。     

高放废物处置库缓冲材料导热性能研究

 缓冲材料是高放废物深地质处置库中的重要工程屏障,其导热性能参数是高放废物处置系统设计的关键参数之一。利用ISOMET导热仪,研究内蒙古高庙子天然钠基膨润土GMZ01与石英砂和石墨混合材料GMZM不同压实密度和不同含水量样品的导热性能。结果表明,GMZM的导热系数、热容量和热扩散系数随压实密度的增大而显著增大,随着含水量的增大而增大;与GMZ01的导热性能相比,随着压实密度的增大,石英砂和石墨作为添加剂可以明显提高缓冲材料的导热性能和热扩散性能,但对比热没有显著影响。压实干密度大于1.8 g/cm3后,GMZM的导热系数和热扩散系数比GMZ01的导热系数和热扩散系数均提高20%以上。缓冲材料的导热性能与其含水量、干密度、矿物组成和微结构等有关,导热系数随着含水量和干密度的增大而增大,但是导热系数与含水量和压实干密度不具有一致的线性关系。当GMZ01的饱和度大于20%时,不同压实干密度样品的导热系数、比热、热容量、热扩散系数均与饱和度具有线性关系。     

Deterioration of swelling pressure of compacted Gaomiaozi bentonite induced by heat combined with hyperalkaline conditions

Compacted bentonite has been considered a suitable engineered barrier material for high-level radioactive waste (HLW) repositories for several decades. However, hyperalkaline groundwater produced by cementitious materials, combined with the heat generated by nuclear decay during the long-term storage of waste canisters, may cause the deterioration of the swelling properties of compacted bentonite. In this study, a series of swelling pressure tests and scanning electron microscopy (SEM) tests were performed on compacted Gaomiaozi (GMZ) bentonite (dry density 1.7 Mg/m³) to investigate the deterioration of the swelling pressure. Results indicated that the deterioration of the swelling pressure was facilitated by the temperature when the same concentration of NaOH solution was infiltrated, and a model of swelling pressure deterioration was developed to predict the long-term swelling pressure. Furthermore, the dissolution of montmorillonite and some silicate minerals, as well as the formation of non-expanding secondary minerals, led to transformations of the agglomeration patterns of the soil particles and structural damage to the bentonite, which controlled the long-term deterioration of the swelling pressure. Therefore, for the long-term operation of an HLW repository, the deterioration of the swelling pressure of compacted bentonite should be monitored, and safety assessments should account for the effects of heat and alkalinity.     

高庙子膨润土在高温高压下的强度特性研究

高庙子膨润土是中国高放废物地质库的首选缓冲/回填材料,将长期在高温(100℃左右)高压(数十兆帕)条件下工作。为了探讨高庙子膨润土在高温高压条件下的强度特性,使用高温高压土工三轴仪,共做了81个三轴不排水剪切试验,系统研究了干密度、围压、温度和含水率对其强度特性的影响。研究结果表明:(1)围压和干密度对高庙子膨润土的破坏形态的影响很大;(2)高庙子膨润土的强度随含水率增大而减小;温度和干密度对其强度的影响比较复杂,干密度较低时,偏应力–轴向应变曲线的位置随温度升高而上移;但干密度较高时的情况则完全相反;(3)分别建立了高庙子膨润土的黏聚力和内摩擦角随干密度、含水率和温度变化的公式。本文的研究成果为分析缓冲材料的热–水–力耦合性状提供了科学依据。     

温控下高压实膨润土持水特性及预测研究

高庙子膨润土是我国核废料深地质处置的首选材料。作为缓冲密封材料,在使用过程中,会受到核素衰变放热的影响而改变土的持水特性、渗透性和力学特性,其工作性能也随之改变。为研究高温下高庙子膨润土的持水特性,文中采用在80℃侧限条件下进行实验研究。实验采用渗析法和水汽平衡法来控制吸力,测得在不同吸力点的含水量,从而得出土水特征曲线。对于特定吸力点的土样进行压汞试验,分析不同吸力点的孔隙特点,并由压汞试验得到PSD曲线来预测其土水特征曲线,并在PSD预测中考虑温度影响。最终将PSD预测曲线与实测曲线对比研究,发现考虑温度的PSD预测比较接近于真实的土水特征曲线。     

Coupled effects of saline solutions and temperature on the swelling deformation property of GMZ bentonite-sand mixtures

Based on the results of one-dimensional free swelling tests, the coupled effects of NaCl-Na₂SO₄ solutions and temperature on the swelling deformation property of compacted GMZ bentonite-sand mixtures were analyzed. The concentrations of the NaCl-Na₂SO₄ solutions were 0, 0.008, 0.04, 0.08 and 0.16 mol/L, the temperatures were 20 °C, 40 °C, 60 °C, 80 °C and 90 °C and the sand contents were 0, 30 and 50%. X-ray diffraction (XRD) and mercury intrusion porosimetry (MIP) tests were also performed to find the influences of the temperature, solution concentration and sand content on the mineral composition and microstructure. The results showed that the maximum swelling strain of the specimens increased with an elevated temperature, while it decreased with increases in the solution concentration and sand content. The swelling process was accelerated by the rising temperature. The XRD tests indicated that the combined effect of a high temperature and a high solution concentration may have caused more Na⁺ from the saline solutions to enter the interlayer, partly displacing the divalent cations. The MIP tests demonstrated that adding sand to the bentonite could reduce the amount of inter-granular pores and increase the intra-aggregate pores. These findings are advantageous to the transfer of heat and pour fluid in the specimens; and thus, the swelling deformation capacity of the bentonite-sand mixtures was higher than that of pure bentonite under the same conditions.     

钠钾盐梯度循环作用下高压实膨润土膨胀力衰变特性

高放废物深地质处置库近场环境中,高压实膨润土将长期遭受含盐地下水的循环化学作用,导致其膨胀性能不断衰变。针对干密度为1.7 g/cm3的高压实高庙子(GMZ)膨润土,分别开展了0.5 mol/L和1.0 mol/L两种盐梯度、Na Cl-水-KCl和Na Cl-水不同循环路径下的恒体积膨胀力试验,探讨盐梯度循环化学作用下其膨胀力的衰变特性。结果表明:盐梯度循环作用下,膨润土膨胀力的发展与离子种类、浓度和循环次数等因素有关。盐化阶段膨胀力不断降低,淡化阶段膨胀力有所提高;低盐度梯度循环下各阶段的稳定膨胀力均高于高盐度梯度循环时的膨胀力。随着循环次数的增加,稳定膨胀力逐渐下降,入渗溶液浓度越高,降幅越大,且衰减幅度随着循环次数的增加而减小。KCl溶液的入渗会引起膨润土发生矿物相变,膨胀力显著降低;当KCl溶液浓度达到一定值时,蒙脱石的充分溶解导致膨润土丧失膨胀能力。     

石英砂掺量对混合型缓冲回填材料抗剪强度的控制机制

高放废物深部地质处置工程中,向膨润土中加入一定比例的石英砂可以优化缓冲回填材料的热传导性和可施工性。从"混合土"的概念出发,设计干密度和含水率相同、掺砂率不同的压实膨润土-砂混合物试样,通过剪切试验揭示掺砂率对抗剪强度的控制机制。试验材料选用内蒙古高庙子膨润土(GMZ001膨润土),石英砂按照质量0%～50%的比率添加。剪切试验结果表明:随着掺砂率的增大,压实混合物由应变软化型向应变硬化型过渡,黏聚力及内摩擦角逐渐减小,即抗剪强度降低。基于混合土孔隙结构假说,通过类比分析,对黏土-砂混合物抗剪强度的界限掺砂率进行估计,提供孔隙结构的扫描电镜证据。引入有效黏土密度和有效含水率的概念,描述石英砂颗粒之间的黏土基质的物理状态,阐释石英砂掺量对混合型缓冲回填材料抗剪强度的控制机制。     

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.