Effects of synthetic site water on bentonite-concrete system for a potential nuclear waste repository

In high-level nuclear waste(HLW)repositories,concrete and compacted bentonite are designed to be employed as buffer materials,which may raise a problem of interactions between concrete and bentonite.These interactions would lead to mineralogy transformation and buffer performance decay of bentonite under the near field environment conditions in a repository.A small-scale experimental setup was established to simulate the concrete-bentonite-site water interaction system from a potential nuclear waste repository in China.Three types of mortars were prepared to correspond to the concrete at different degradation states.The results permit the determination of the following:(1)The macroproperties of Gaomiaozi(GMZ)bentonite(e.g.swelling pressure,permeability,the final dry density,and water content of reacted samples);(2)The composition evolution of fluids from the synthetic site water-concrete-bentonite interaction systems;(3)The sample characterization including Fourier transform infrared spectroscopy(FTIR)and X-ray powder diffraction(XRD).Under the infiltration of the synthesis Beishan site water(BSW),the swelling pressure of bentonite decreases slowly with time after reaching its second swelling peak.The flux decreases with time during the infiltrations,and it tends to be stable after more than 120 d.Due to the cation exchange reactions in the BSW-concrete-bentonite systems,the divalent cations(Ca and Mg)were consumed,and the monovalent cations(Na and K)were released.The dissolution of minerals in the bentonite such as albite causes Si increasing in the pore water.It was concluded that the hydro-mechanical property degradation of bentonite takes place when it comes into contact with concrete mortar,even under low-pH groundwater conditions.The soil dispersion,the uneven water content,and the uneven dry density in bentonite samples may partly contribute to the swelling decay of bentonite.Therefore,the direct contact with concrete has an obvious effect on the performance of bentonite.

Effect of drying cracks on swelling and self-healing of bentonite-sand blocks used as engineered barriers for radioactive waste disposal

Experiments were conducted to evaluate the healing of drying cracks in air-dried bentonite-sand blocks after hydration and swelling in groundwater,providing justifications to simplify the protection of blocks prior to installation in a high-level radioactive waste repository.Synthetic groundwater was prepared to represent the geochemistry of Beishan groundwater,and was used to hydrate the blocks during the swelling pressure and swelling strain measurements,as Beishan is the most promising site for China's repository.Healing of the surface cracks was recorded by photography,and healing of the internal cracks was visualized by CT images and hydraulic conductivity of air-dried blocks.The results indicate that the maximum swelling pressure and swelling strain are primarily affected by the geochemistry of Beishan groundwater,but not affected by the drying cracks.The maximum swelling pressure and swelling strain of air-dried blocks are comparable to or even higher than the pressure and strain of fresh blocks.The maximum swelling pressure measured in strong(i.e.high ion strength)Beishan groundwater was 44%of the pressure measured in deionized(DI)water,and the maximum swelling strain was reduced to 23%of the strain measured in DI water.Nevertheless,the remained swelling of the blocks hydrated in strong Beishan groundwater was sufficient to heal the surface and internal drying cracks,as demonstrated by the pictures of surface cracks and CT images.The hydraulic conductivity of the air-dried block permeated with strong groundwater was comparable(3.7×higher)to the hydraulic conductivity of the fresh block,indicating the self-healing of drying cracks after hydration and swelling in groundwater.A simplified method of protecting the block with plastic wraps before installation is recommended,since the remained swelling of the block hydrated in Beishan groundwater is sufficient to heal the drying cracks.

Fluorographene with Narrow Lateral Size and Thickness Distributions Prepared for Enhancing Lubrication Performance of Bentonite Grease

Fluorographene(FG)with narrow lateral size and thickness distributions was prepared by a liquid-phase exfoliation method,based on liquid cascade centrifugation.The Rtec MFT-5000 tribo-meter was used to investigate the lubricating performance of bentonite grease enhanced by the as-prepared FG.The results showed that the coefficient of friction and the wear volume of bentonite grease with 0.3 wt%FG were decreased by 20.4%and 44.9%,respectively,as compared to those of the base grease.The main reason is that FG can promote the formation of the tribo-chemical reaction film consisting of complex carbon oxide,Fe_(2)O_(3)and FeF_(3)on the friction surface,which can remarkably improve the performance of friction reduction and prevent the appearance of severe wear.

Anisotropic swelling pressures of compacted GMZ bentonite infiltrated with salt solutions

In the high-level radioactive waste(HLW)deep geological repository,bentonite is compacted uniaxially,and then arranged vertically in engineered barriers.The assembly scheme induces the initial anisotropy,and with hydration,it develops more evidently under chemical conditions.To investigate the anisotropic swelling of compacted Gaomiaozi(GMZ)bentonite and the further response to saline effects,a series of constant-volume swelling pressure tests were performed.Results showed that dry density enhanced the bentonite swelling and raised the final anisotropy,whereas saline inhibited the bentonite swelling but still promoted the final anisotropy.The final anisotropy coefficient(ratio of radial to axial pressure)obeyed the Boltzmann sigmoid attenuation function,decreasing with concentration and dry density,converging to a minimum value of 0.76.The staged evolution of anisotropy coefficient was discovered,that saline inhibited the rise of the anisotropy coefficient(Dd)in the isotropic process greater than the valley(d1)in the anisotropic process,leading to the final anisotropy increasing.The isotropic stage amplified the impact of soil structure rearrangement on the macro-swelling pressure values.Thus,a new method for predicting swelling pressures of compacted bentonite was proposed,by expanding the equations of Gouy-Chapman theory with a dissipative wedge term.An evolutionary function was constructed,revealing the correlation between the occurrence time and the pressure value due to the structure rearrangement and the former crystalline swelling.Accordingly,a design reference for dry density was given,based on the chemical conditions around the pre-site in Beishan,China.The anisotropy promoted by saline would cause a greater drop of radial pressure,making the previous threshold on axial swelling fail.

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 bentoniteesand 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 rangedtwo 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.

On the installation of an in situ large-scale vertical SEALing (VSEAL) experiment on bentonite pellet-powder mixture

Recently,the Institute for Radiological protection and Nuclear Safety(IRSN)has launched VSEAL(Vertical SEALing)project to investigate the impact of gas migration on the long-term performance of bentonite based vertical sealing systems(VSS).The first VSEAL in situ test was emplaced in IRSN’s Underground Research Laboratory(URL)in Tournemire(France)in 2019 and was equipped with 76 wired and wireless sensors.The test is still in progress,but the collected set of data provides already valuable information of the hydro-mechanical behavior of VSS during hydration.The swelling core consists of a mixture of highdensity pellets and powder of MX80 bentonite in a ratio of 80/20(in dry mass).An innovative method was adopted to drill a 1-m diameter and w10-m deep shaft in order to minimize the rock perturbation at the sidewalls.Because a specific protocol was adopted to install the bentonite mixture together with a careful characterization of the core during construction,VSEAL 1 constitutes the unique in situ sealing test with a well-known initial structural distribution of the pellets and the powder.Some heterogeneities occurred within the experiment during the installation process:a damaged zone developed around the shaft walls due to the interruption of the installation operations caused by COVID19 lockdown in France;a technological gap with a variable thickness between the last pellets layer and the top confining lid and a heterogeneous distribution of the bentonite powder at some layers inducing large inter pellets voids close to the bentonite-rock interface.Artificially injected water volume,relative humidity,water content and swelling pressure in both radial and axial directions were monitored.Comparison of the results showed that the presence of installation-induced heterogeneities led to the generation of preferential flow paths that influenced the swelling pressure evolution at radial and axial directions.

Investigation of long-wavelength elastic wave propagation through wet bentonite-filled rock joints

The saturation of the compacted bentonite buffer in the deep geological repository can cause bentonite swelling,intrusion into rock fractures,and erosion.Inevitably,erosion and subsequent bentonite mass loss due to groundwater inflow can aggravate the overall integrity of the engineered barrier system.Therefore,the coupled hydro-mechanical interaction between the buffer and rock during groundwater inflow and bentonite intrusion should be evaluated to guarantee the long-term safety of deep geological disposal.This study investigated the effect of bentonite erosion and intrusion on the elastic wave propagation characteristics in jointed rocks using a quasi-static resonant column test.Jointed rock specimens with different joint conditions(i.e.joint surface saturation and bentonite filling)were prepared using granite rock discs sampled from the Korea Underground Research Tunnel(KURT)and Gyeongju bentonite.The long-wavelength longitudinal and shear wave velocities were measured under different normal stress levels.A Hertzian-type power model was used to fit the wave velocities,and the relationship between the two fitted parameters provided the trend of joint conditions.Numerical simulations using three-dimensional distinct element code(3DEC)were conducted to better understand how the long-wavelength wave propagates through wet bentonite-filled rock joints.

Influence of relative compaction and degree of saturation on the deformation characteristics of bentonite under freeze-thaw cycles

Bentonite,consisting of clay minerals of the montmorillonite group,has been widely used as an adsorbent and backfill material in nuclear waste disposal and groundwater remediation.It is challenging to use bentonite as a filling material in cold regions since bentonite is highly sensitive to thermal environmental changes,during which its bulk volume and microstructure change significantly.In this study,a series of one-dimensional and three-dimensional freeze-thaw tests were carried out within a closed system to investigate the influencing factors of the deformation of bentonite under freeze-thaw cycles.Results show that the initial soil water content greatly impacts bentonite's deformation during freeze-thaw cycles.For an initial higher degree of saturation(Sr),the expansion caused by the formation of ice lenses has a greater impact than the shrinkage induced by dehydration,ice-cementation,and so on.Conversely,bentonite tends to shrink at a lower degree of saturation during freezing.And the critical degree of saturation that determines bentonite's behavior of frost heave or frost shrinkage seems to be roughly 0.8.As the number of freeze-thaw cycles rises,initially uncompacted bentonite clay becomes more compacted,and initially compacted bentonite clay remains unchanged.

Preparation of Iron-Pillared Bentonite/Oyster Shell Composite and Phosphate Adsorption in Water

Iron-pillared bentonite(FB)was prepared by Fe(III)modified bentonite,and then the composites(FB-OS)were prepared by iron-pillared bentonite and oyster shell powder.The composites were characterized by FTIR,SEM,TGA,and EDS,and the phosphorus removal test was carried out.The results showed that FB-OS contained a large amount of CaO.Its structure was compact,but there were gaps in it.The maximum bending stress and compressive strength were 43.7 N and 0.927 MPa,respectively.The phosphorus removal test showed that the phosphorus removal rate of FB-OS was more than 90%,and measured the maximum adsorption capacity was 48.31 mg/g.A large amount of spherical products were produced on the surface and inside of FB-OS after phos-phorus removal,it was speculated that spherical products were amorphous calcium phosphate in the paper.Ana-lysis indicated that there was chemical adsorption during phosphorus removal.The kinetic equation of phosphorus adsorption by FB-OS was qt=10:193t/1+2:574t (R^(2)=0.995).The adsorption rate was mainly controlled by outerfilm diffusion and intraparticle diffusion.

Pu在膨润土层中的反应性迁移模拟研究(1)——地下水-膨润土体系演化的地球化学模拟

在某区含Pu高放废物处置系统的性能评价中,需要分析水-岩相互作用下蒙脱石、孔隙度、pH值等演化过程对膨润土材料性能及Pu反应性迁移的影响,为此,本文以工程屏障系统中厚度为1 m的柯尔碱膨润土回填材料为研究对象,基于地下水入渗景象,采用TOUGHREACT模拟了地下水-膨润土体系的地球化学演化。结果表明:膨润土完全饱和约需20年;膨润土中蒙脱石的伊利石化作用很弱,而去白云石化过程(白云石溶解、方解石形成)相对明显,这使得水中Ca^(2+)浓度减小、Mg^(2+)和HCO_(3)^(-)浓度增大、pH值呈弱碱性且维持在8.1~10.3范围内;膨润土的孔隙度和渗透率变化不明显(变化量不到2%)。这些演化过程将有利于维持膨润土的膨胀性,阻滞核素向外迁移。

高庙子膨润土胶体释放影响因素试验研究

高放废物处置库中缓冲回填材料膨润土与地下水相互作用时会释放出胶体,而胶体会直接影响放射性核素的迁移行为,因此,膨润土遇水释放胶体研究是处置库系统安全评价的重要内容之一。本文以高庙子膨润土为研究对象,通过室内试验,获得了离子种类、离子强度、pH、温度与浊度的关系曲线,并对这些因素影响胶体释放的机理进行了分析。结果表明:阳离子种类抑制膨润土释放胶体排序依次为Li^(+)<Na^(+)<K^(+)<NH_(4)^(+)<Zn^(2+)<Mg^(2+)<H+<Ca^(2+);阴离子中除OH-对胶体释放有显著促进作用外,其他阴离子基本对胶体释放影响不大;溶液离子强度越大,抑制膨润土胶体释放的能力越强;膨润土在中性条件下更容易释放胶体;在20~50℃之间,升高温度有利于膨润土胶体的释放。

Pu在膨润土层中的反应性迁移模拟研究(2)——Pu的种态分布及反应性迁移分析

为评估柯尔碱膨润土工程屏障材料的安全性能,采用考虑渗流扩散、溶解-沉淀、表面配位吸附、放射性衰变等多过程动态耦合的反应性迁移模拟方法,综合运用TOUGHREACT等程序开展了Pu在柯尔碱膨润土层中反应迁移的数值模拟,结合地下水-膨润土体系演化模拟分析了Pu的种态分布特征,叠加表面配位模型预测分析了Pu的长期迁移规律。结果表明:地下水中Pu主要以难迁移的Pu(OH)_(4)(aq)形式存在;由于膨润土的低渗透性和强吸附性,正常情景下Pu的扩散范围很小而将长期滞留于1 m厚膨润土中;在忽略强吸附阻滞作用的保守情景下,Pu在渗流作用下可扩散迁移出膨润土层;考虑到长时间尺度下不可避免存在的不确定性,建议重视渗流扩散为主导的其他过程和情景研究。

氨氮在膨润土改性黄土衬垫层中的吸附和扩散行为研究

膨润土改性黄土可以用作生活垃圾填埋场底部衬垫层。然而,污染物在膨润土改性黄土衬垫层中的吸附和扩散行为尚不明晰,无法对该类衬垫层的截污性能进行准确评价。研究向黄土中掺入质量占比为15%和30%的膨润土,通过开展批式吸附试验和扩散试验,研究氨氮在改性衬垫层中的吸附和扩散行为。研究结果显示:当膨润土的掺入量为15%时,氨氮在改性衬垫层上的吸附量与纯黄土衬垫层相比没有明显变化,但扩散速率下降了400%;当膨润土的掺入量达到30%时,氨氮在改性衬垫层上的吸附量增加了1.25倍,而扩散速率下降了420%。Pollutev7.0的模拟计算结果表明,在对膨润土改性黄土衬垫层的截污性能进行评价时,如果不考虑污染物的扩散行为,评价结果将产生3.50~4.75倍误差;而不考虑污染物的吸附行为,则将产生334~382倍误差。研究成果可为膨润土改性黄土衬垫层的截污性能评价提供理论依据。

危险废物渗滤液阳离子和应力作用下膨润土化学相容性研究

膨润土因其优异的防渗性能被用于危险废物填埋场防渗屏障的构筑,但其防渗性能通常会受到渗滤液和应力的影响。通过渗滤液采样分析设置不同浓度阳离子溶液,系统探究实际渗滤液组分对膨润土防渗性能的影响规律;选用Ca^(2+)作为特征阳离子研究不同应力条件下膨润土渗透系数变化规律;同时结合Zeta电位和DLVO理论计算,阐明渗滤液组分和应力作用对膨润土化学相容性影响规律。结果表明,渗滤液中Al^(3+)、Fe^(3+)、Zn^(2+)、Ni^(2+)、Cu^(2+)、Fe^(2+)、Mn^(2+)浓度为0~0.20 mmol/L时,对膨润土膨胀特性和渗透特性影响较小。Mg^(2+)、Ca^(2+)、K^(+)、Na^(+)浓度为0.20~50 mmol/L时,Ca^(2+)对膨润土膨胀特性和渗透特性影响较大,Ca^(2+)浓度由1 mmol/L上升到50 mmol/L时,渗透系数由1.15×10^(−7)cm/s急速上升到6.34×10^(−6)cm/s。Ca^(2+)浓度和应力通常通过影响水化后膨润土孔隙比进而影响其渗透特性,相同Ca^(2+)浓度条件下,渗透系数随应力增加而逐渐降低。Zeta电位和DLVO理论分析表明,Ca^(2+)浓度增大会导致膨润土表面负电势减弱,引起膨润土双电层厚度减小,使膨润土中蒙脱石的层间距变小,导致膨润土膨胀特性和渗透特性降低。因此,填埋过程中应优化危险废物固化稳定化工艺,从源头减少渗滤液中Ca^(2+)浓度;同时还应研发新型膨润土复合材料,提高膨润土在Ca^(2+)等高浓度盐溶液中的防渗性能,防控危险废物填埋场渗漏风险。

膨润土浆液及其自凝灰浆黏度微观机理研究

不同厂家生产的钠基膨润土在相同配比要求下制备的自凝灰浆黏度差别很大,其本质是材料微观组分、结构不一致。基于SEM、XRD、EDS与NMR等微观试验,对两个厂家生产的同类钠基膨润土(简称湘源土和玉龙土)及其所制自凝灰浆进行试验分析,并据此对其黏度微观机理进行研究。结果如下:湘源土和玉龙土浆液黏度具有触变性,“卡片宫”的建立与Q~4结构的生成会促使其黏度上升,剪切作用会破坏微观结构使其黏度降低;湘源土蒙脱石含量高于玉龙土的,所以其浆液黏度整体高于玉龙土浆液。搅拌与低剪切作用促进蒙脱石颗粒小片层分散,小片层分散越多,停止剪切后膨润土浆液黏度越高。对于膨润土所制自凝灰浆,其黏度的变化主要依赖于内部电荷吸附与水化反应的程度,水化反应生成的C-S-H凝胶会促进浆液黏度提高。自凝灰浆在凝结过程中生成的碳硫硅酸钙不利于C-S-H凝胶生成,湘源土自凝灰浆碳硫硅酸钙含量高于玉龙土自凝灰浆的,所以其整体黏度低于玉龙土自凝灰浆的。

锁磷剂与增氧剂联用去除沉积物中砷的效果与机制

为研究锁磷剂(LMB)与增氧剂CaO_(2)联合应用对富营养化湖泊沉积物中砷(As)污染的去除效果,理清联用技术对沉积物水界面As的去除机制,以太湖梅梁湾底泥为研究对象开展模拟试验。结果表明:LMB与CaO_(2)联用对沉积物中的As的去除效果优于LMB、CaO_(2)单独使用;在试验第45天,LMB与CaO_(2)联用对沉积物溶解态As去除率最大,为39.31%,在试验第90天,LMB与CaO_(2)联用对As的去除效果较差;为实现沉积物中As的高效去除,可在加入LMB和CaO_(2)45 d后对LMB和CaO_(2)进行回收;LMB与CaO_(2)联用去除As的主要机制为LMB和CaO_(2)中的La^(3+)、Ca^(2+)与砷酸根离子络合形成LaAsO_(4)和Ca_(3)(AsO_(4))2沉淀以及Fe(Ⅲ)、Mn(Ⅳ)氧化物的协同吸附作用;Fe和Mn氧化还原在控制沉积物As的释放中起着关键作用。

甘蔗渣/膨润土基复合高吸水性树脂性能及应用研究

采用微波法,以蔗渣和膨润土为基质,与丙烯酸(AA)和丙烯酰胺(AM)共聚合成甘蔗渣/膨润土复合高吸水性树脂(B/BCSAR)。选取辐射时间、膨润土用量、AM/AA(质量比)及中和度四个因素,利用正交试验得到树脂的最佳制备条件,即AM/AA=0.5,中和度为60%,膨润土用量为6%,辐射时间为3min时,产品的吸水倍数和吸盐水倍数最大,分别为402.65g/g和86.14g/g。通过对B/BCSAR性能研究,结果表明,B/BCSAR吸附速率先快后慢,8h时吸水倍数最大,达到吸附平衡,且保水能力良好,有一定的机械强度,耐热耐寒及耐光照性能良好。B/BCSAR应用实验结果表明,作为土壤掺杂剂,当B/BCSAR的掺杂量为4g时,应用效果最好,发芽率达到80%,平均茎长为6.13cm;作为种子包衣剂,当包衣比为1∶30时,应用效果最好,发芽率为100%,平均茎长为7.58cm。二者相比,后者对植物发芽及前期生长更有利。

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。

不同品位高庙子膨润土用于钻井泥浆的试验研究

钻井泥浆是膨润土应用占比较大的市场之一,通过试验测试,研究不同品位高庙子膨润土用于钻井泥浆的可行性,以便充分开发和利用高庙子膨润土矿床。研究结果表明:不同位置开采的未经处理的高庙子天然钠基膨润土不符合钻井泥浆的使用性能要求,必须对其进行增效处理;通过添加增效剂羧甲基纤维素(CMC),发现高庙子天然钠基膨润土在添加2%的增效剂后,蒙脱石含量为70%左右的膨润土均达到国家标准规范要求的钻井级膨润土的要求。但应综合考虑天然钠基膨润土的开采成本和增效剂的成本,筛选出既满足技术要求,又能控制成本的样品类型。

碱-热条件下膨润土缓冲材料导热系数演化及微观特征

碱-热条件下膨润土缓冲层材料的导热性能是核废物深地质处置库设计的一个关键因素。对MX80膨润土粉末进行不同碱-热工况预处理,采用热针法探讨碱-热条件下膨润土缓冲材料导热系数的演化规律;选取代表试样分别进行X射线衍射(XRD)、扫描电镜(SEM)、压汞(MIP)和热重分析(TGA)等试验,揭示出碱-热作用对膨润土试样矿物成分、微观形貌、孔隙结构和结合水形态等演化特征的影响机制,阐释碱-热条件下膨润土缓冲材料导热系数演化的微观机理。试验结果表明:碱-热条件下,膨润土试样的导热系数λ随碱液p H值的递增而减小,随环境温度T的升高而增大,在高碱性溶液(pH=13.0~14.0)和高温环境(T=60℃~90℃)中这一特性表现得尤为显著;根本原因在于试样中原有矿物成分在碱液作用下发生不同程度的溶蚀现象,表现为蒙脱石和石英含量的减少、方沸石含量的增加,导致试样中固体成分减少、孔隙率增加、表观干密度减小、吸水性能变弱,而环境温度在该过程中起到良好的促进作用。