ADVANCES IN MICROMECHANICAL PROPERTIES OF HYDRATE-BEARING SOILS
摘要: 天然气水合物作为一种资源储量大、分布范围广、能量密度高的清洁能源, 受到了国内外的广泛关注, 竞相研究安全高效、持续可控的开采方法. 充分掌握含天然气水合物土的力学特性并厘清其在开采过程中的动态演化规律, 是实现天然气水合物资源产业化开发的重要前提. 含天然气水合物土的力学响应行为本质上是其内部结构演化的宏观反映, 相关的微观力学特性研究对于深化含天然气水合物土力学特性认识具有重要的意义. 本文从天然气水合物晶体、天然气水合物与土颗粒界面、含天然气水合物土3个尺度对含天然气水合物土微观力学特性的研究现状进行了总结, 系统归纳了天然气水合物的晶体结构类型及天然气水合物的孔隙微观赋存模式; 重点介绍了计算机断层扫描、扫描电子显微镜、X射线衍射及原子力显微镜等微观测试技术原理与特点; 简述了与计算机断层扫描联用的三轴剪切实验、颗粒流程序模拟及分子动力学模拟在天然气水合物微观力学特性研究方面的最新进展; 综合现有研究结果对含天然气水合物土内颗粒界面剪切机理及微观力学理论模型进行了概述分析; 最后探讨了含天然气水合物土微观力学研究目前仍存在的不足与挑战, 并给出了针对性的建议以期促进含天然气水合物土的力学特性研究发展.Abstract: As one kind of clean and unconventional energy resources, natural gas hydrates have drew enormous interests worldwide due to their high energy density, large reserves, and wide distribution in nature, and lots of countries have tried their best to develop suitable methods for gas hydrate production with acceptable safety, efficiency, continuity, and controllability. Industrialized production of gas hydrates basically needs to deeply understand mechanical properties of hydrate-bearing soils and fully clarify how these mechanical properties evolve during gas hydrate production. Mechanical properties of hydrate-bearing soils are inherently governed by their micro structures inside, and great efforts have been made to study macro mechanical properties of hydrate-bearing soils from the micro perspective, which is of great significance to deep understandings of how mechanical properties of hydrate-bearing soils evolve during gas hydrate production. In this study, advances in mechanical properties of gas hydrate crystal, interface cementation between gas hydrate and soil particles, and bulk hydrate-bearing soils are summarized. Gas hydrate crystal structures and pore-scale hydrate morphologies in hydrate-bearing soils are briefly introduced. Then, fundamental principles and advantages of microscopic testing techniques such as computed tomography (CT), scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and atomic force microscopy (AFM) applied to mechanical property characterizations are emphasized. Then, up-to-date researches performed by using triaxial shearing tests combined with CT, particle flow code (PFC) and molecular dynamics (MD) numerical simulations are reviewed, and the shearing mechanism as well as constitutive models of hydrate-bearing soils are analyzed. At last, challenges in current studies on micromechanical properties of hydrate-bearing soils are discussed, and corresponding suggestions are subsequently proposed to further studies on mechanical properties of hydrate-bearing sediments.
Parameters sI sII sH small(X) big(Y) small(X) big(Y) small(X) medium(Y) big(Z) structure (crystal cavity) 512 51262 512 51264 512 435663 51268 number 2 6 16 8 3 2 1 molecular formula 2X·6Y·46H2O 16X·8Y·136H2O 3X·2Y·1Z·34H2O hydration number 5.75 5.67 5.67 average radius /nm 0.391 0.433 0.391 0.473 0.391 0.406 0.571 molecular size to hold /nm < 0.52 0.52 ~ 0.69 0.75 ~ 0.90 crystal structure cube diamond hexahedron
表 2 近期水合物晶体MD模拟研究汇总
Table 2. Summary of recent MD research on hydrate crystals
Year Focus Remark Ref. 2015 Mechanical instability of monocrystalline and polycrystalline methane hydrates. The monocrystalline hydrate is brittle failure, while the polycrystalline is ductile.
The mechanical stability of polycrystalline methane hydrate is closely related to the particle size and morphology.
 2017 Thermodynamic properties of propane or tetrahydrofuran mixed with carbon dioxide or methane in Structure-II clathrate hydrates. The lattice parameter at a constant pressure or a constant temperature varies as a function of the guest type and guest coupling interaction.
The thermodynamic properties of hydrates largely depend on the enclathrated compounds.
 2018 Mechanical properties of methane hydrate: Intrinsic differences from ice. The crystal direction has little effect on the tensile response.
Both types of crystals show brittle fracture behavior, but the specific failure forms are different.
 2018 Role of guest molecules on the mechanical properties of clathrate hydrates. Tensile strength and Young’s modulus of CHs depend not only on the size and shape of guest molecules but also on their polarity.
Strain-induced variation in structural characteristics of H-bonds pronouncedly depends on their locations and orientations.
 2018 Guest-host interactions in mixed CH4–CO2 hydrates. Thermodynamic interaction energies, broken down between guest species and cage type, CO2 has a much stronger interaction with the hydrate framework than CH4 and that CO2 prefers the large cage while CH4 is energetically preferential to the small cage.  2019 The dynamic behavior of gas hydrate dissociation by heating in tight sandy reservoirs. During hydrate dissociation, the undecomposed hydrate core shrank in a stepwise manner with a curved dissociation front.
The nanobubbles formed on the silica surfaces are not stable but also merge during the simulation process.
 2020 Mechanical response of nanocrystalline ice-contained methane hydrates. There is a crossover in the tensile strength and average compressive flow stress due to the presence of ice.
Reveals the dissociation and reformation of various water cages due to mechanical deformation.
 2020 The dynamic process of N2–CO2 replacement for natural gas hydrate. The molecular dynamics method was used to systematically study the structural evolution, molecular number distribution, radial distribution function, hydrate free energy and diffusion process of the system. 
表 3 近期含水合物土CT联用三轴剪切实验汇总
Table 3. Summary of current triaxial shearing tests combined with CT conducted on hydrate-bearing soils
Year Focus Remark Ref. 2013 Development of innovative triaxial testing system.
Capture the motion and local deformation of a specimen.
Experimental system is stable and reliable.
Toyoura sand indicate a barrel-type deformation which is the first visual observation under high confining and pore water pressure.
 2015 Mechanical behavior of hydrate-bearing pressure-core sediments visualized under triaxial compression. Sediments containing natural gas hydrate exhibit brittle failure and hydrate-free sediments is ductile failure.
With the increase of hydrate saturation, the local stiffness tends to increase.
 2016 Large strain behavior of hydrate-bearing sediments with different saturations. With the increase of saturation, the peak strength increases and presents a brittle failure mode.
The shear band thickness decreased with increasing hydrate saturation.
 2019 Development of low temperature and high pressure triaxial apparatus based on X-ray. System capabilities are demonstrated using the in-situ formation of hydrate within a glass bead sample.
Hydrate occurrence under triaxial stress and the evolution of local deformation along with strain are study by CD triaxial test.
 2019 Development of testing assembly that
combines pore-scale visualization and
triaxial test capability of methane
The equipment will improve the understanding of geomechanical behavior of these hydrate-bearing sediments under stress and its dependency on hydrate saturation, hydrate pore habits, and distribution patterns.  2020 Microstructure evolution of hydrate-bearing sands during thermal dissociation and ensued impacts on the mechanical and seepage characteristics. Hydrate covering the sand particle surface dissociates first and then at the menisci between sand particles.
Hydrate dissociation could cause fabric changes in hydrate-bearing sands, resulting in a more isotropic orientation distribution of sand particles.
 2020 Pore-scale investigation of methane hydrate-bearing sediments under triaxial condition. Hydrate enables the sand skeleton to bear additional loads, the potential of sand crushing upon hydrate dissociation also increases.
Strength of hydrate-bearing sediments decreases as pressure-temperature condition approaches hydrate phase boundary.
Hydrate-bearing sediments creep and heal with time.
 2020 Microscopic analysis of hydrate failure in CD triaxial test. In the linearity region, the hydrate-cemented clusters moved as a whole while small hydrate particles would aggregate to the periphery of the clusters.
Localized deformation occurred perfectly exhibit an antisymmetric bifurcation pattern.
表 4 含水合物土微观本构模型分类及特点
Table 4. Classification and characteristics of microscopic constitutive models of hydrate-bearing soils
Classification Year Modeling basic Characteristic Applicability Ref. elastic-plastic models 2016 Critical state constitutive model. A simple bonding and debonding law issued to describe the evolution of the hydrate-induced bonding. The model can capture the stress–strain and volume change behaviors of hydrate-bearing soils (HBS) with the range of saturations, confining pressures and densities.  2017 MCC model and the concept of the effective degree of saturation. Nonassociative flow rule. The model can capture the enhancements of stiffness, strength and dilatancy, and the hydrate occurrence habits.  2017 The hiss critical-state framework, subloading concepts and hydrate enhancement factors. Bonding and damage effects are considered. The model can well describe the improvement of strength and stiffness, and dilatancy characteristics.  2020 CSUH model and the filling and bonding effects of hydrates. A compressive hardening parameter and a bonding parameter are put forward. The model can describe the strength, stiffness, shear dilation and strain-softening of HBS.  statistical damage models 2012 Mesomechanics mechanism perspective of composite material
and principles of damage mechanics.
The whole process of the stress-strain curve can be obtained only by obtaining the peak stress and strain values. The model can well reflect the change process of stress-strain curve of gas hydrate bearing sediments.  2019 The theory of micromechanics mixing rate of composite and the
rock pore damage theory.
Weibull statistical distribution and the Drucker-Prager criterion are used to describe micro elements. The model can well simulate the whole process of hydrate sediment deformation under different confining pressures.  2019 The continuous damage theory and the Weibull distribution of three parameters. The influence of damage threshold and residual strength are considered. The model can reflect the multi-field (thermo-hydro-mechanical-chemical) coupling characteristics of hydrate.  other models 2017 The concept of partition stress and inelastic mechanisms. Hydrate and soil skeleton adopt different mechanical models respectively. This constitutive model is especially well suited to simulate the behavior of HBS upon dissociation.  2020 Bounding surface model and
the slip theory of plasticity.
A micro stress–strain relationship and a micro stress–dilatancy relationship are established. The model comprehensively describes the consolidation, hardening, softening, dilatation, collapse, and non-coaxial characteristics of hydrate. 
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