黏土岩温度-渗流-应力耦合特性试验与本构模型研究进展

高放废物处置库、垃圾填埋场等工程中常常涉及到温度场（T）、渗流场（H）和应力场（M）的耦合作用的问题。从试验和理论模型两个角度综述国内外黏土岩温度-渗流-应力耦合特性的研究进展,主要包括其传热特性、温度影响下的渗流特性、变形、强度、蠕变特性。在此基础上,重点分析了黏土岩水-热迁移模型以及热-力耦合本构模型的适应性。基于上述认识,通过试验研究了比利时Boom clay在温度作用下的强度、渗透性、蠕变性等特征。结果表明：随着温度升高,Boom clay的强度有所降低,渗透性显著增强,蠕变速率明显加快。提出了适用于Boom clay的THM耦合弹塑性损伤模型,计算结果验证了模型能合理反映温度的影响。最后,探讨了黏土岩THM耦合机理研究的不足和今后的研究方向。     

Micromechanical approach to swelling behavior of capillary-porous media with coupled physics

A detailed multiscale analysis is presented of the swelling phenomenon in unsaturated clay-rich materials in the linear regime through homogenization. Herein, the structural complexity of the material is formulated as a three-scale, triple porosity medium within which microstructural information is transmitted across the various scales, leading ultimately to an enriched stress-deformation relation at the macroscopic scale. As a side note, such derived relationship leads to a tensorial stress partitioning that is reminiscent of a Terzaghi-like effective stress measure. Otherwise, a major result that stands out from previous works is the explicit expression of swelling stress and capillary stress in terms of micromechanical interactions at the very fine scale down to the clay platelet level, along with capillary stress emerging due to interactions between fluid phases at the different scales, including surface tension, pore size, and morphology. More importantly, the swelling stress is correlated with the disjoining forces due to electrochemical effects of charged ions on clay minerals and van der Waals forces at the nanoscale. The resulting analytical expressions also elucidate the role of the various physics in the deformational behavior of clayey material. Finally, the capability of the proposed formulation in capturing salient behaviors of unsaturated expansive clays is illustrated through some numerical examples.     

Illite-smectite Mixed-layer Minerals in the Alteration Volcanic Ashes under Submarine Environment

The clay mineralogy of the clay intervals interbedded with siliceous mudstones across the Permian-Triassic boundary (PTB) in Pengda, Guiyang, Guizhou province, was investigated by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The clay mineral assemblages of the sediments are mainly I/S clays and minor smectite, kaolinite, and illite as reveled by XRD analyses. The peak-shape parameters BB1 and BB2 of I/S clays of the representative clay bed PL-01 are 4.7° and 4.4°, and the peak position of the low angle reflection is at 6.8° 2θ (13.6 ), suggesting that the I/S clays has a IS type of ordering. However, the presence of multi-order reflections and their intensities are different from those of completely ordered 1∶1 mixed-layer I/S clay rectorite, indicating that I/S clays of the Pengda section have partially ordered IS structures. HRTEM observations show that most of the I/S clays exhibit an IS stacking ordering. However, in some areas within a IS particle, smectite layer is observed in doublets, triplets, and quartets, which are interstratified by various amounts of illite layers, suggesting the presence of other irregular stacking in addition to the major 1∶1 IS ordered stacking. Transformation of smectite layer into illite layers is also observed in the I/S clays, suggesting that the Pengda I/S clays are derived from smectite illitization, in good agreement with the clay mineral assemblage. The I/S clays of the Pengda section contain up to 45% to 95% smectite layer, the notably higher contents of smectite layer relative to those of other PTB stratigraphic sets in south China can be attributed to difference in alteration and smectite illitization processes due to different sedimentary environments.     

不同粘土矿物对赖氨酸的吸附行为对比研究

以皂石、高岭石、绿泥石和伊利石为原材料,分别与赖氨酸进行反应,研究赖氨酸在上述粘土矿物上的吸附行为, 并运用粉末X-射线衍射技术（XRD）、傅里叶变换红外吸收光谱术（FTIR）和热重（TG）等分析方法,表征反应前后粘土 矿物的变化。实验结果表明,不同粘土矿物对赖氨酸的吸附等温线均符合Freundlich等温方程,且不同粘土矿物对赖氨酸的 饱和吸附量大小顺序为：皂石>蒙脱石>绿泥石>高岭石>伊利石;XRD结果表明皂石对赖氨酸的吸附发生在矿物层间,而绿 泥石、高岭石和伊利石对赖氨酸的吸附主要在矿物表面进行;FTIR和TG结果表明赖氨酸主要取代粘土矿物层间吸附水,以 氢键的形式与Si-O-Si(IVAl)键合。实验结果将有助于进一步探明环境中粘土矿物对有机质的吸附机理。     

海相沉积软黏土的弹塑性本构模型研究

在深入探讨海相沉积原状软黏土压缩、变形等力学特性和详细分析加载屈服面随荷载情况变化的基础上,确认了海相沉积原状软黏土的强度、变形特性与结构屈服应力密切相关。即当固结压力小于结构屈服应力时,其力学特性与超固结重塑土的力学特性类似;当固结压力大于结构屈服应力时,其力学特性与正常固结重塑土的力学特性类似。为描述海相沉积原状软黏土的上述力学特性,将姚仰平等提出的超固结重塑土本构模型引入到海相沉积软黏土弹塑性本构模型的构建中。在本构模型构建过程中,考虑了海相沉积原状软黏土具有的抗拉强度及其演化规律,软黏土强度包线的特点及其进一步修正的表达式,使模型更符合海相原状软黏土的强度、变形特性。最后,将3种不同海相沉积软黏土固结排水剪切试验得到的应力-应变-体变曲线与模型预测结果进行对比。比较结果显示,本文提出的弹塑性本构模型能很好地描述海相沉积原状软黏土的剪缩硬化、剪胀软化以及变形的应力水平依存性等力学特性。     

CHEMO-PLASTICITY OF CLAYS SUBJECTED TO STRESS AND FLOW OF A SINGLE CONTAMINANT

Isothermal chemo-elasto-plasticity of clays is discussed, to describe strains induced in clay by permeation of it with a low dielectric constant organic contaminant, in the presence of stress. The strain is crucial in controlling permeability changes in chemically affected clay barriers of landfills and impoundments. The theory encompasses chemical softening or yield surface reduction, coefficient of chemical reversible expansion or contraction due to mass concentration increase, as well as chemical sensitivity of bulk plastic modulus. The experiments on chemistry and stress dependent permeability of Sarnia clay performed by Fernandez and Quigley (1985, 1991) are interpreted using this model. The numerical representations of the chemo-plastic softening function and the chemo-elastic strain function, as well as plastic bulk modulus sensitivity to concentration are evaluated for dioxane and ethanol. Specific requirements for the tests for chemo-plastic behavior of clays are discussed. © 1997 by John Wiley & Sons, Ltd.     

The microstructure and internal architecture of shear bands in sand–clay sequences

The microstructures of cm-scale displacement faults offsetting unlithified sequences of finely interbedded sands, silts and clays from outcrops in Denmark have been examined. A variety of shear band types are recognised based on their grain-scale deformation mechanism and internal structure. Shear bands in a Jurassic sequence exposed along the coastline of Bornholm are characterised by intense cataclasis of both sand and clay layers. This deformation mechanism is accompanied by extensive grain scale mixing along discrete shear bands to give a fault rock composition that reflects the relative amount of sand and clay within the faulted sequence. In contrast, shear bands at Nr. Lyngby and Jensgaard, both on the Jutland coast, are characterised by granular flow within the sand units. Grain scale mixing is subdued at these locations so that layers maintain their integrity across the shear band to form a layered internal structure of sand, silt and clay smears. In some instances, particularly at Nr. Lyngby, clays have deformed in a brittle manner so that they do not contribute material to the shear band, which is then comprised exclusively of coarser-grained components. The different deformation mechanisms and internal structures of shear bands are thought to be controlled by burial depth at the time of faulting.     

Stabilization of swelling clays by Mg(OH)2. Changes in clay properties after addition of Mg-hydroxide

Stabilization of the swelling clay structure is attempted by intercalation of Mg(OH)₂ and the development of a brucite interlayer between the clay layers. The properties of the product obtained by applying the technique, formulated as described in a previous work, are considered here. The materials used were Wyoming bentonite (USA), Fuller's Earth (UK), kaolinite, illite, lignite, and silica gels. The Mg(OH)₂-clay products were examined by the methylene blue dye test, X-ray diffraction analysis (XRD), differential thermal analysis (DTA), and derivative thermogravimetry analysis (DTGA). From the results obtained it is concluded that: the Mg-hydroxide is adsorbed by swelling clays both on their external and internal surface, whereas it is adsorbed on the external surface by non-swelling clays. The internally adsorbed phase of Mg-hydroxide forms an ill-defined interlayer of brucite, retarding swelling, whereas the external phase covers the particles modifying drastically their surface properties, like the adsorption of the MB dye. The material produced after precipitation of Mg-hydroxide on swelling clays (smectites) did not re-expand on wetting or after glycolation. The adsorption of MB dye was also reduced by some 80–90%, due to coating effect, preventing the measurements of the external surface area of the clay by polar molecules. The principal forces involved in the process are believed to be physical adsorption on the external surface, along with chemisorption and some chemical bonding, mostly in the internal surface. Cementation due to crystallization and, in the long term, some pozzolanic reactions take also place. Internal adsorption of the Mg-hydroxide is postulated to be in the form of positively charged mono- and/or small polymers and it is, chiefly, diffusion controlled. Since Mg-hydroxide is internally adsorbed by swelling clays, whereas Ca-hydroxide(lime) is not, and the (Mg, Ca)-clay aggregates are more stable than the Ca-clay or the Mg-one, the combination of the two hydroxides could give better results in soil stabilization than each hydroxide alone.     

The development of a multi-surface soil speciation model for Cd (II) and Pb (II): Comparison of two approaches for metal adsorption to clay fractions

The mobility of toxic metals in soils or sediments is of great concern to scientists and environmentalists since it directly affects the bioavailability of metals and their movement to surface and ground waters. In this study, a multi-surface soil speciation model for Cd (II) and Pb (II) was developed to predict the partition of metals on various soil solid components (e.g. soil organic matter (SOM), oxide mineral, and clay mineral). In previous study, the sorption of metal cations on SOM and oxide minerals has been evaluated by thermodynamically based surface complexation model. However, metal binding to soil clay fractions was normally treated in a simplistic manner: only cation exchange reactions were considered and exchange coefficient was assumed unity. In this study, the binding of metals onto clays was described by a two-site surface sorption model (a basal surface site and an edge site). The model was checked by predicting the adsorption behavior of Cd (II) and Pb (II) onto three selected Chinese soils as a function of pH and ionic strengths. Results showed that the proposed model more accurately predicted the metal adsorption on soils under studied condition, especially in low ionic strength condition, suggesting that adsorption of metals to soil clay fractions need to be considered more carefully when modeling the partition of trace elements in soils. The developed soil speciation model will be useful when evaluating the movement and bioavailability of toxic metals in soil environment.     

泥页岩主要黏土矿物组分甲烷吸附实验

为了从深层次揭示控制黏土矿物天然气吸附能力的主要因素, 选择不同来源和成因的泥页岩中的常见黏土矿物进行了甲烷等温吸附实验.分析显示不同类型的黏土矿物气体吸附能力差异明显, 各种黏土矿物甲烷吸附容量次序为蒙脱石＞＞伊蒙混层＞高岭石＞绿泥石＞伊利石＞粉砂岩＞石英岩.黏土矿物结晶结构决定了矿物片层之间的层间孔隙和聚合体颗粒之间粒间孔隙的形态和大小, 从而决定着其表面积和气体吸附性能.黏土矿物甲烷吸附能力与电镜扫描所反映的微孔隙发育程度密切相关.研究表明, 黏土矿物的气体吸附能力不仅与黏土类型有关, 而且明显受成岩演化程度和岩石成因的影响.此外, 随粒度减小孔隙连通性和内表面积的不断增加, 黏土矿物气体吸附能力有所升高.      

Molecular dynamics modeling of a partially saturated clay-water system at finite temperature

The mechanical and hydraulic properties of unsaturated clay under nonisothermal conditions have practical implications in geotechnical engineering applications such as geothermal energy harvest, landfill cover design, and nuclear waste disposal facilities. The water menisci among clay particles impact the mechanical and hydraulic properties of unsaturated clay. Molecular dynamics (MD) modeling has been proven to be an effective method in investigating clay structures and their hydromechanical behavior at the atomic scale. In this study, we examine the impact of temperature increase on the capillary force and capillary pressure of the partially saturated clay-water system through high-performance computing. The water meniscus formed between two parallel clay particles is studied via a full-scale MD modeling at different elevated temperatures. The numerical results have shown that the temperature increase impacts the capillary force, capillary pressure, and contact angle at the atomic scale. The capillary force on the clay particle obtained from MD simulations is also compared with the results from the macroscopic theory. The full-scale MD simulation of the partially saturated clay-water system can not only provide a fundamental understanding of the impact of temperature on the interface physics of such system at the atomic scale, but also has practical implication in formulating physics-based multiscale models for unsaturated soils by providing interface physical properties of such materials directly through high-performance computing.     

热-应力-损伤耦合作用下深埋隧洞围岩稳定性分析

以热力学和弹塑性力学理论为基础,分析岩石热-力完全耦合作用及其对力学参数和热特性参数的影响,建立了岩石热-力-损伤耦合模型及其参数演化方程,以ABAQUS软件为平台对其进行二次开发,并通过典型算例验证了岩石热-力完全耦合的重要性。然后以某深埋软岩隧洞为例,研究温度和开挖卸载共同作用下的隧洞围岩力学行为和损伤过程。计算结果表明：温度对岩石的力学性质和损伤演化过程影响显著,开挖损伤和热应力诱发的损伤对围岩热力学参数的影响不可忽略;所提出的力学模型可以有效反映围岩损伤演化、调热圈演化以及热力学参数演化,具有一定的借鉴作用。     

大同盆地砷中毒病区沉积物中砷的吸附行为和影响因素分析

沉积物对砷的吸附-解吸作用是控制砷在地下水中的迁移和转化的决定性因素。对砷中毒重病区大同盆地山胡县沉积物中砷的吸附行为和影响因素研究结果表明,沉积物对砷的吸附符合Freundlich吸附等温模式,吸附量主要与沉积物颗粒大小、黏土矿物质量分数和类型、铁铝氧化物质量分数以及沉积物中As的质量分数有关,有机质质量分数对砷的吸附量影响需进一步深入研究。铝硅酸盐、铁铝氧化物质量分数较高且颗粒较细的黏土和亚黏土类沉积物对砷的吸附性较强;而铝硅酸盐、铁铝氧化物质量分数较低且颗粒较粗的细砂和粉砂类沉积物对砷的吸附性较差,其所处的含水层也是形成高砷地下水的主要含水层。pH值为5．5～8．0时,砷的吸附量最大。大同盆地高砷地下水pH条件非常不利于沉积物中砷的吸附,易形成高砷地下水。该区地下水10℃左右的温度条件非常有利于沉积物对砷的吸附,但由于影响因素较多,且地下水的温度在不同季节会发生一定的变化,其产生的影响还有待进一步研究。     

粘土矿物钝化改性和钝化机理初步研究

在岩土工程中,进行灾害防治和软基处理的一个核心问题是把粘土矿物由亲水性改造成疏水性,抑制和降低其含水量,使得粘土遇水后不再吸水膨胀,从而保持土壤的稳定性。岩土力学工程中以保持土壤稳定性为目的对粘土的改性称为“钝化”。所谓钝化就是用 钝化剂与粘土矿物表面发生反应,改变粘土矿物的表面结构,提高憎水性,增加粘土整体的力学性质,从而达到稳定土体的目的。在粘土矿物钝化中表面活性剂是一个重要的组成部分 ,但是表面活性剂在固液界面的吸附,除决定于其本身的性质外,还决定于固体的性质、溶 液的pH值和温度等。因此,研究粘土矿物表面结构和性质以及与钝化剂的相互作用是提高粘 土矿物钝化效果的重要途经。利用近代分析方法（XRD、IR、Raman、MAS NMR、TEM、AFM和S EM）,对粘土矿物（高岭石、蒙脱石和伊利石）钝化前后的表面结构和性质进行了系统研究 ,并结合相关的土力学、工程力学参数的测定,阐明粘土矿物钝化的机理,剖析和研制粘土 矿物钝化剂,为解决各类工程和灾害问题中的土壤稳定提供理论依据。     

Critical issues in modelling the long-term hydro-thermomechanical performance of natural clay barriers

Performance assessment of deep repositories for heat-generating radioactive waste requires the capability of predicting reliably the evolution of the system during a time period commensurate with the hazardous life of the waste. In many repository designs clay barriers represent important elements of the waste isolation system.

In order to provide reasonable assurance that clay barriers will ensure long-term waste isolation, it is essential to understand their behaviour under a variety of conditions. Due to the variability of argillaceous materials, to the complexity of the phenomena that might take place in a waste repository and to the longevity of the required isolation, an adequate understanding of the behaviour and the capability to model the evolution of the clay barriers are not easy tasks. The factors that need to be understood and modelled include stress evolution, long-term strain or creep, thermal effects on solid skeleton, on interstitial fluids and on mineralogy. The difficulty of the task is increased by the facts that many effects are coupled, that their rates must be extremely low, in order to be realistic, and that the time period to be modelled defies the possibility of direct experimental observation. Several critical issues are identified and discussed briefly, such as: constitutive law to describe the thermo-mechanical behaviour of the clay skeleton, modelling of the fluid phase in clays and its response to heating, thermal fracturing and healing. Strategies are suggested for a rational approach to the experimental investigation of some relevant processes. The study of suitable natural analogues, for example the thermo-metamorphic halo occurring at Orciatico in Tuscany, could provide valuable insights in the thermal effects of heating clay barriers. It is conceivable that models describing a variety of relevant phenomena, such as dehydration, fracturing and permeability changes could be tested through the study of the Orciatico analogue.

In the end performance assessments of clay barriers would benefit through improvements in modelling: this would involve progress in understanding the basic phenomena and their coupled nature, improved conceptual and mathematical models and increased reliability for their calibration/validation. The improved understanding of phenomena requires additional experimental activities on various levels: molecular, microscopic, macroscopic, medium scale and in situ.     

超固结粘土的二元介质模型

为了分析超固结粘土边坡的变形和稳定的需要,在岩土破损力学的框架内建议了一个适用于这类土的二元介质模型。该模型考虑了土体内在的不均一性,把它看作由结构块和结构带组成的复合体,两者共同分担外荷载,模型包含10参数,并拟定了这些参数的测定方法。通过模拟三轴试验的计算表明,该模型可以反映London粘土的应力-应变特征。     

Nanochemomechanical assessment of shale: a coupled WDS-indentation analysis

Establishing the links between the composition, microstructure and mechanics of shale continues to be a formidable challenge for the geomechanics community. In this study, a robust methodology is implemented to access the in situ chemomechanics of this sedimentary rock at micrometer length scales. Massive grids of coupled wave dispersive spectroscopy (WDS) and instrumented indentation experiments were performed over representative material surfaces to accommodate the highly heterogeneous composition and microstructure of shale. The extensive datasets of compositional and mechanical properties were analyzed using multi-variate clustering statistics to determine the attributes of active phases present in shale at microscales. Our chemomechanical analysis confirmed that the porous clay (PC) mechanical phase inferred by statistical indentation corresponds to the clay mineral phase defined strictly on chemical grounds. The characteristic stiffness and hardness behaviors of the PC are realized spatially in regions removed from silt inclusions of quartz and feldspar. At the microscale shared by indentation and WDS experiments, a consistent chemomechanical signature for shale emerges in which the heterogeneities of the PC are captured by the standard deviations of indentation properties and concentrations of chemical elements. However, these local behaviors are of second order compared to the global trend observed for mean mechanical properties and the clay packing density, which synthesizes the relative volumes of clay and nanoporosity in the material. The coupled statistical indentation and WDS technique represents a viable approach to characterize the chemomechanics of shale and other natural porous composites at a consistent scale below the macroscopic level.     

有机粘土的特性及其对肥料养分的缓释作用

本研究表明 ,表面活性剂 2号不仅可以吸附在蒙脱石、高岭石和凹凸棒石的表面上 ,还可进入蒙脱石的层间 ,将其晶层撑开 ,并以双层小于 65°角斜交于蒙脱石的晶片之间 ,同时有极少量的表面活性剂 2号以单层方式直立于晶片上 ,形成石蜡质构型。由于粘土矿物对表面活性剂 2号的吸附作用 ,使其热性质发生变化 ,去除吸附水的温度降低并出现放热峰。此外 ,还使得有机粘土的含水量和吸湿率较原土有显著降低。有机粘土应用于肥料工业的复混肥生产中 ,不仅可以使其有效成粒率提高 3 0 % ,还可使其养分释放具有显著的缓释效果。     

吕梁山西麓复兴剖面红黏土的磁性地层学研究

吕梁山西麓中上新世的一套厚层红黏土层记录了吕梁山前盆地的演化和吕梁山新近纪的隆升。山前不同的构造部位,各异的古地貌特征导致红黏土的堆积特征差别较大,柳林复兴地区黏土层的下部常含有数层化石层和薄厚不等的砾石层。本文对复兴地区的红黏土进行了岩石磁学和磁性地层学研究,得出了复兴地区红黏土及所含砾石层和化石层的古地磁年龄,并通过野外沉积特征以及粒度等指标探讨了复兴地区红黏土的形成过程。岩石磁学结果表明,红黏土中特征剩磁的载体为磁铁矿和赤铁矿。古地磁和生物化石显示复兴剖面的年龄为7.1～2.6Ma。其中所含厚层砾石层的古地磁年龄约为5.2Ma。两层化石层的年龄分别为～6.8Ma和～7.1Ma。剖面野外沉积特征和粒度变化显示柳林复兴地区红黏土堆积初期有水流作用的参与。     

Numerical study of localization in soil systems

A numerical study of the mechanical behavior of heterogeneous soil systems, consisting of a bulk of sand with embedded stiff gravel inclusions or soft clay inclusions, is performed. A solution scheme using parallel computing is employed when analyzing two different categories of problems. First, a homogenization problem is studied, where use of a single representative volume element subjected to plane strain compression offers the possibility to investigate the coupling between the response at a local scale and at a global scale. Second, a plane strain footing problem with different heterogeneous soil systems is analyzed using a traditional finite element formulation. The material model utilized for the soil is a large deformation formulation of non-associated elasto-plasticity with an isotropic hardening law, able to represent dilation. It was found that the shape of the gravel or clay inclusions in the systems had no significant effect on the global responses, whereas the strain localizations in the two different soil systems, sand–gravel and sand–clay, were found to have different character. The effect of the initial density on the response was clearly observed in the localization patterns.