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。     

Swelling pressure of compacted MX80 bentonite/sand mixture prepared by different methods

Compacted bentonite/sand mixture have been considered as possible sealing/backfilling material in the deep geological disposal of high-level radioactive nuclear waste. The swelling pressure of the compacted bentonite/sand mixture is of significance in the design of the geological repository, which requires good consistency between data obtained by laboratory and field measurement. In this work, a series of swelling pressure tests were performed on compacted MX80 bentonite/sand specimens prepared by methods commonly adopted in laboratory (As-compacted, Transferred) and those mimicking the real block manufacturing process (Trimmed, Inserted). Results shown that with identical dry density (especially when the dry density was larger than 1.70 Mg/m³), largest swelling pressure was obtained in specimens prepared by method Inserted, followed by method As-compacted, Transferred and Trimmed. The distinct difference between the swelling pressure could be largely attributed to the effects of residual post-compaction lateral stress. More interestingly, specimens prepared by methods Trimmed and Transferred followed a similar swelling pressure-dry density relationship. From this point of view, method Transferred without causing mass loss, change of bentonite content and possible technological voids effect was recommended in lieu of method Trimmed for specimen preparation in laboratory.     

缓冲材料热-水-力耦合模型试验研究

高放废物深地质处置采用多重屏障设计体系,缓冲材料是位于废物罐和围岩之间的一道重要的人工屏障。在放射性衰变热、地下水入侵和围岩应力等作用下,缓冲材料经历复杂的热-水-力耦合过程,评价其长期性能对高放废物地质处置库的稳定运行至关重要。缓冲材料模型试验是研究膨润土在多场耦合环境下性能变化的重要途径。中型实验台架是大型实验台架(China-Mock-up)的重要补充,用来模拟与大型实验台架边界相同的环境下,即热量和水分别从缓冲材料的不同侧向另一侧传递和渗透的条件下膨润土的行为特征。通过实时监测缓冲材料在长期加热和加水条件下的温度、相对湿度、力学等特征参数,揭示了在热-水-力耦合条件下缓冲材料的性能变化规律,同时对台架进行了拆解,对拆解样品的含水量、干密度和微观结构等进行了分析测试,研究结果可为高放废物处置库缓冲材料的工程设计提供参数支持。     

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。     

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.     

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。     

圆饼状高压实膨润土膨胀力各向异性特征研究

针对作为我国缓冲/回填材料的高压实高庙子膨润土，采用自主研制的膨胀力-渗透性一体化测试仪器开展膨胀力试验，分别测定圆饼状试样的轴向膨胀力和径向膨胀力发展规律，研究试样初始干密度、初始吸力和尺寸效应对其膨胀力各向异性特征的影响。试验结果显示，轴向膨胀力和径向膨胀力均随着试样初始干密度的增加呈指数增大，膨胀力各向异性特征愈加显著。轴向膨胀力和径向膨胀力均随着试样初始吸力的增加而呈减小趋势；相同初始吸力条件下，径向膨胀力均大于轴向膨胀力，但是膨胀力各向异性系数随着初始吸力增大而不断减小。试样尺寸对膨胀力有显著影响，增加试样高度，轴向膨胀力不断增加，径向膨胀力增加到某一数值后不再随高度增加，膨胀力各向异性系数随着试样高度的增加逐渐减小。最后，基于膨润土膨胀机理、压实效应和尺寸效应，分析了膨胀力各向异性特征的形成机理。     

高放废物处置库中COx黏土岩回填材料压缩特性研究

 高放废物处置库中回填材料需要预先压缩到一定密实度,其压缩特性对处置库的设计和安全性有重要影响。目前,粉碎后的Callovo-Oxfodian(COx)黏土岩(法国)被考虑为可选的回填材料之一。通过开展一维压缩试验,研究2种不同粉碎工艺下获得的粗/细COx土样的压缩特性,结果表明：压缩曲线受粒度成分的影响非常明显,为获得同等压实度,细粒土所需的压实功能较粗粒土高,除此之外,细粒土的压缩指数也高于粗粒土,表现出较强的压缩性;随着土样压实密度的增加,粗/细土样的压缩曲线逐渐靠拢,粒度成分对压实功能影响逐渐减弱;土样卸荷时回弹指数随干密度的增加而增加,受粒度成分的影响不明显;高压实(rd = 2.0 g/cm3)粗粒土样在7 MPa的轴向应力下饱和时,体积发生明显的塌陷现象,饱和后土样的压缩指数小于饱和前,而回弹指数则较饱和前高。     

Experimental research on water retention and gas permeability of compacted bentonite/sand mixtures

Highly compacted bentonite-based materials are often considered as buffer or sealing materials for deep high-level radioactive waste repositories. In situ, the initial state of bentonite-based materials is only partially saturated, which has a very high suction that will promote water absorption from the host rock. In addition, a gradient of water saturation will be formed between the external part and the central part of the compacted bentonite blocks. In this paper, water retention tests, under both constant-volume and free-swelling conditions, were performed to investigate the suction behavior of a compacted bentonite/sand mixture. In order to investigate the sealing ability of the partially saturated bentonite/sand mixture, gas permeability tests were also carried out under the in situ confining stress. It was found that the confining conditions have a limited effect on the water retention capacity of the compacted bentonite/sand mixture at lower levels of relative humidity (RH), while this influence is significant at higher RH levels. The results of gas permeability tests show that gas permeability is very sensitive to the water content and the confining pressure. When the sample (stable at RH=98%) was subjected to a in situ confining pressure (7–8 MPa), the gas permeability was very low (1.83×10^–14 m/s) which indicates that gas tightness can be obtained even though the sample is not fully saturated.     

High-level radioactive waste disposal in China: update 2010

For geological disposal of high-level radioactive waste (HLW), the Chinese policy is that the spent nuclear fuel (SNF) should be reprocessed first, followed by vitrification and final disposal. The preliminary repository concept is a shaft-tunnel model, located in saturated zones in granite, while the final waste form for disposal is vitrified high-level radioactive waste. In 2006, the government published a long-term research and development (RD) plan for geological disposal of high-level radioactive waste. The program consists of three steps: (1) laboratory studies and site selection for a HLW repository (2006–2020); (2) underground in-situ tests (2021–2040); and (3) repository construction (2041–2050) followed by operation. With the support of China Atomic Energy Authority, comprehensive studies are underway and some progresses are made. The site characterization, including deep borehole drilling, has been performed at the most potential Beishan site in Gansu Province, Northwestern China. The data from geological and hydrogeological investigations, in-situ stress and permeability measurements of rock mass are presented in this paper. Engineered barrier studies are concentrated on the Gaomiaozi bentonite. A mock-up facility, which is used to study the thermo-hydro-mechano-chemical (THMC) properties of the bentonite, is under construction. Several projects on mechanical properties of Beishan granite are also underway. The key scientific challenges faced with HLW disposal are also discussed.     

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。     

自由膨胀条件下高压密膨胀粘土微观结构随吸力变化特征

核废料处置问题是世界各国安全利用核能所关心的重大问题。作为用于封堵通往地下处置库的通道,以隔断处置库内核废料与外界环境联系的首选隔绝用材料——膨胀性粘土的特性正越来越受到岩土工程界的关注。利用压汞测试法和电镜扫描法方法,对吸力控制条件下高压密蒙脱石充分自由水化后微结构变化特征展开平行对比试验,以研究高压密蒙脱石在不同吸力条件下的体积变化特征。吸力的控制采用了渗析(液相)法。试验对不同密实度的压密膨胀土随吸力变化特征的进行了研究。研究结果表明:(1)压实膨胀土水化过程中的膨胀势与初始压实密度有关,初始压实密度越大,膨胀势越大;(2)体积膨胀量与水化过程的控制吸力之间存在近似的半对数衰减关系,且随着控制吸力的增大,衰减速率减弱;(3)体积的膨胀主要来源于膨胀土集合体结构中集合体之间的大孔的扩张。     

Effect of synthetic Beishan site water and cement solutions on the mineralogy and microstructure of compacted Gaomiaozi(GMZ) bentonite

The mineral alteration and microstructure evolution of compacted GMZ bentonite was investigated during the long-term in the Beishan area, a candidate for a high-level radioactive waste repository in China. The compacted GMZ bentonite samples at initial dry densities of 1.5 and 1.7 Mg/m³ were infiltrated by synthetic Beishan Site Water (BSW) and two synthetic cement solutions (Young Cement Water -YCW and Evolved Cement Water - ECW) under constant volume conditions for about 2 months in this study. X-Ray diffractometry (XRD), mercury intrusion porosimetry (MIP) and scanning electron microscope (SEM-EDS) tests were carried out to observe the mineralogy and microstructure of the specimens after experiencing the three types of pore solutions.There is evidence of cation exchange reactions, some zeolites and C-S-H in the GMZ bentonite after the infiltration of alkaline solutions. The hydration of alkaline solutions and mineralogy alteration result in changes to the microstructure of compacted GMZ bentonite. The generated secondary mineral on the surface of montmorillonite leads to the clogging of inter-aggregate pores. In the case of high dry density, this resulted in pore occlusion.     

Deformation and water/gas flow properties of claystone/bentonite mixtures

As a potential engineered barrier material for disposal of radioactive waste in clay formations,claystone aggregate excavated from the Opalinus clay(OPA),its mixture with bentonite MX80 in a mass ratio of 7/3,and pure bentonite were extensively investigated with respect to the hydro-mechanical properties and performances.With these materials,a series of parallel experiments was performed under sequentially applied conditions of hydration with synthetic porewater of the clay formation,consolidation and water flow under increased stresses,and gas injection into the water-saturated and compacted materials under loading.Significant responses of the clay mixtures were observed.Main findings include:(1) the hydration and induced swelling of the mixtures are mainly dominated by bentonite content and dry density;(2) the consolidation decreases the porosity and water permeability exponentially by 2-3 orders of magnitude to low values of 10~(-18)-10~(-20) m~2 at stresses of 2-5 MPa,depending upon bentonite content;and(3) the gas penetration in the water-saturated and compacted bentonite is characterised by a cyclic pressure rising/dropping process limited in between the upper breakthrough and lower shut-off boundaries,whereas the compacted claystone and claystone/bentonite mixture allow for gas release at low and moderate pressures.The results are helpful for design of the engineered barriers for safe isolation of radioactive waste in repositories.     

Modelling the effects of test conditions on the measured swelling pressure of compacted bentonite

In the current concept of repositories for radioactive waste disposal, compacted bentonite and bentonite-based materials with low hydraulic conductivity are being used as engineered barriers to inhibit the migration of radioactive nuclides. To ensure low hydraulic conductivity, the swelling characteristics of compacted bentonite are also important. However, previous studies have shown that swelling pressure measurements vary considerably and that this variation may be attributable to the differences in testing apparatuses. This variability increases the uncertainty in the design of the facilities. Thus, in this study, an improved stress–strain model for bentonite materials during the saturation process is proposed. The validity of the model is confirmed by comparing the experimental results obtained using several test methods with the simulated results from the model. Consequently, it is found that the swelling pressure test results of compacted bentonite, which are affected by several factors, such as the stiffness of the test cell, the height of the specimen, and the initial degree of saturation, can be numerically simulated using the proposed model. Thus, the effects of these factors on the test results can be evaluated quantitatively using the proposed model.     

Effect of water chemistry on the hydro-mechanical behaviour of compacted mixtures of claystone and Na/Ca-bentonites for deep geological repositories

In the French deep geological disposal for radioactive wastes, compacted bentonite/claystone mixtures have been considered as possible sealing materials. After emplacement in place, such mixtures are hydrated by the site solution as well as the cement solution produced by the degradation of concrete. In this study, the effects of synthetic site solution and cement solution on the hydro-mechanical behaviour of compacted mixtures of claystone and two types of bentonites (MX80 Na-bentonite and Sardinia Ca-bentonite) were investigated by carrying out a series of swelling pressure, hydraulic conductivity and mercury intrusion porosimetry (MIP) tests. It was found that for the MX80 bentonite/claystone mixture hydrated with synthetic site solution, the swelling capacity was reduced compared to the case with deionised water owing to the transformation of Na-montmorillonite to multi-cation dominant montmorillonite by cation exchanges. For the Sardinia bentonite/claystone mixture, the similar increasing rate of swelling pressure was observed during the crystalline swelling process for different solutions, suggesting insignificant cation exchanges. Additionally, the cations in the synthetic site solution could reduce the thickness of diffuse double layer and the osmotic swelling for both MX80 bentonite/claystone and Sardinia bentonite/claystone mixtures. The large-pore volume increased consequently and enhanced water flow. In the cement solution, the hydroxide could also dissolve the montmorillonite, reducing the swelling pressure, and increase the large-pore volume, facilitating the water flow. Furthermore, the decrease of swelling pressure and the increase of hydraulic conductivity were more significant in the case of low dry density because of more intensive interaction between montmorillonite and hydroxide due to the high permeability.     

Sealing performance of compacted block joints backfilled with bentonite paste or a particle-powder mixture

Technology gaps are inevitable parts of the buffer barriers in the high-level radioactive waste (HLW) repositories. The mechanical properties, permeability and water-solute-radionuclide migration of buffer barrier are different when considering the gaps. The present study was designed to investigate the sealing effect of joint between the compacted blocks with two types of sealing materials, a bentonite paste (P) and a bentonite particles and powder mixture (P/P) both from the macro- and micro-aspects.A series of laboratory test was conducted to study the hydro-mechanical properties of bentonite blocks after backfilling the joint between blocks. Both the intake and outflow water volume, and the pressure on radial and axial direction were monitored during the hydration. Following the permeability test, the joint’s sealing was evaluated by a final dry density, water content distribution and microstructure evolution. The results showed that the axial and radial pressure of blocks backfilled with bentonite P and bentonite P/P mixture were higher than that of blocks with a blank joint. Pressure preferentially increased in the low-stress areas (the joint areas), contributing to sealing of the joint. The hydraulic conductivities for backfilled bentonite blocks were almost on the same order of magnitude as to intact bentonite blocks, revealing a clear sealed hydraulic behavior. The final dry density decreased in the block area and increased in the joint area after hydration, forming a transition zone with a certain width. A smaller difference was found between the block and joint area in the backfilled block. The mercury intrusion porosimetry (MIP) test and scanning electron microscope (SEM) test showed that backfill decreased the numbers of inter-aggregates pores ranged between 8 and 15 μm compared with that in the blank joint. The comprehensive data showed that a joint backfilled with a bentonite P/P mixture has a higher swelling capacity, lower permeability, and denser structure compared with joint backfilled with bentonite P. The results suggested that joint backfilling improved the integrity of the blocks and enhanced the swelling property and impermeability compared with that of the non-backfilled blocks. Both bentonite P and bentonite P/P has satisfactory sealing performance of compacted block joints, with better effect of the later.     

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.     

Microstructure and anisotropic swelling behaviour of compactedbentonite/sand mixture

Pre-compacted elements(disks,torus) of bentonite/sand mixture are candidate materials for sealing plugs of radioactive waste disposal.Choice of this material is mainly based on its swelling capacity allowing all gaps in the system to be sealed,and on its low permeability.When emplaced in the gallery,these elements will start to absorb water from the host rock and swell.Thereby,a swelling pressure will develop in the radial direction against the host rock and in the axial direction against the support structure.In this work,the swelling pressure of a small scale compacted disk of bentonite and sand was experimentally studied in both radial and axial directions.Different swelling kinetics were identified for different dry densities and along different directions.As a rule,the swelling pressure starts increasing quickly,reaches a peak value,decreases a little and finally stabilises.FOr some dry densities,higher peaks were observed in the radial direction than in the axial direction.The presence of peaks is related to the microstructure change and to the collapse of macropores.In parallel to the mechanical tests,microstructure investigation at the sample scale was conducted using microfocus X-ray computed tomography(μCT).Image observation showed a denser structure in the centre and a looser one in the border,which was also confirmed by image analysis.This structure heterogeneity in the radial direction and the occurrence of macro-pores close to the radial boundary of the sample can explain the large peaks observed in the radial swelling pressure evolution.Another interesting result is the higher anisotropy found at lower bentonite dry densities,which was also analysed by means of μCT observation of a sample at low bentonite dry density after the end of test It was found that the macro-pores,especially those between sand grains,were not filled by swelled bentonite,which preserved the anisotropic microstructure caused by uniaxial compression due to the absence of microstructure collapse.     

Saturated hydraulic conductivity of compacted bentonite–sand mixtures before and after gas migration in artificial seawater

To understand the self-healing property of an engineered barrier for radioactive waste disposal, the hydraulic conductivity of compacted bentonite–sand mixtures saturated with artificial seawater (SW) before and after gas migration was examined. Na- and Ca-bentonites were mixed with fine sand at a ratio of 70% bentonite in dry weight. Two aspects were considered during the experiment: the hydraulic conductivity of the specimen that was resaturated after gas migration and the distribution of water content immediately after gas migration to study gas migration pathways. The gas migrated through the entire cross-section of the specimen, and gas breakthrough occurred in the equilibrium swelling pressure range approximately. Subsequently, the gas flow rate reached a sufficient large value when the gas pressure was approximately twice the equilibrium axial pressure (the sum of swelling and confining pressures), which excluded the back pressure. Although the gas migration pathway was not visible when the specimen was observed immediately after gas migration, the water content distribution showed that several parts of the specimen with lower water content were connected in the direction of gas migration. After resaturation, the change in permeability was within a limited range—two to three times larger than that before gas migration for each type of bentonite in SW. This slight change suggests that gas migration creates a pore structure that cannot be sealed via crystalline swelling of montmorillonite in SW, even if highly compacted bentonite is used under a constant-volume condition.