Hydrate phase transition and seepage mechanism during natural gas hydrates production tests in the South China Sea:A review and prospect

Natural gas hydrates(NGHs)are globally recognized as an important type of strategic alternative energy due to their high combustion efficiency,cleanness,and large amounts of resources.The NGHs reservoirs in the South China Sea(SCS)mainly consist of clayey silts.NGHs reservoirs of this type boast the largest distribution range and the highest percentage of resources among NGHs reservoirs in the world.However,they are more difficult to exploit than sandy reservoirs.The China Geological Survey successfully carried out two NGHs production tests in the Shenhu Area in the northern SCS in 2017 and 2020,setting multiple world records,such as the longest gas production time,the highest total gas production,and the highest average daily gas production,as well as achieving a series of innovative theoretical results.As suggested by the in-depth research on the two production tests,key factors that restrict the gas production efficiency of hydrate dissociation include reservoir structure characterization,hydrate phase transition,multiphase seepage and permeability enhancement,and the simulation and regulation of production capacity,among which the hydrate phase transition and seepage mechanism are crucial.Study results reveal that the hydrate phase transition in the SCS is characterized by low dissociation temperature,is prone to produce secondary hydrates in the reservoirs,and is a complex process under the combined effects of the seepage,stress,temperature,and chemical fields.The multiphase seepage is controlled by multiple factors such as the physical properties of unconsolidated reservoirs,the hydrate phase transition,and exploitation methods and is characterized by strong methane adsorption,abrupt changes in absolute permeability,and the weak flow capacity of gas.To ensure the long-term,stable,and efficient NGHs exploitation in the SCS,it is necessary to further enhance the reservoir seepage capacity and increase gas production through secondary reservoir stimulation based on initial reservoir stimulation.With the constant progress in the NGHs industrialization,great efforts should be made to tackle the difficulties,such as determining the micro-change in temperature and pressure,the response mechanisms of material-energy exchange,the methods for efficient NGHs dissociation,and the boundary conditions for the formation of secondary hydrates in the large-scale,long-term gas production.

Charge density wave states in phase-engineered monolayer VTe_(2)

Charge density wave(CDW)strongly affects the electronic properties of two-dimensional(2D)materials and can be tuned by phase engineering.Among 2D transitional metal dichalcogenides(TMDs),VTe_(2)was predicted to require small energy for its phase transition and shows unexpected CDW states in its T-phase.However,the CDW state of H-VTe_(2)has been barely reported.Here,we investigate the CDW states in monolayer(ML)H-VTe_(2),induced by phase-engineering from T-phase VTe_(2).The phase transition between T-and H-VTe_(2)is revealed with x-ray photoelectron spectroscopy(XPS)and scanning transmission electron microscopy(STEM)measurements.For H-VTe_(2),scanning tunneling microscope(STM)and low-energy electron diffraction(LEED)results show a robust 2√3×2√3CDW superlattice with a transition temperature above 450 K.Our findings provide a promising way for manipulating the CDWs in 2D materials and show great potential in its application of nanoelectronics.

Phase engineering of two-dimensional transition metal dichalcogenides

Two-dimensional(2D) transition metal dichalcogenides(TMDs) have gained much attention in virtue of their various atomic configurations and band structures.Apart from those thermodynamically stable phases, plenty of metastable phases exhibit interesting properties. To obtain 2D TMDs with specific phases, it is important to develop phase engineering strategies including phase transition and phaseselective synthesis. Phase transition is a conventional method to transform one phase to another, while phase-selective synthesis means the direct fabrication of the target phases for2D TMDs. In this review, we introduce the structures and stability of 2D TMDs with different phases. Then, we summarize the detailed processes and mechanism of the traditional phase transition strategies. Moreover, in view of the increasing demand of high-phase purity TMDs, we present the advanced phase-selective synthesis strategies. Finally, we underline the challenges and outlooks of phase engineering of 2D TMDs in two aspects-high phase purity and excellent controllability. This review may promote the development of controllable phase engineering for 2D TMDs and even other2D materials toward both fundamental studies and practical applications.

Recent advances of phase engineering in group VI transition metal dichalcogenides

As the crystal quality and phase structure of two-dimensional(2D)transition metal dichalcogenides(TMDs)have significant impacts on their properties such as electroconductivity,superconductivity and chemical stability,the precise synthesis,which plays an important role in fundamental researches and industrial applications,is highly required.Group VI TMDs,such as MoS_(2),usually exhibit diverse polymorphs including semiconducting 1H and metallic 1T phases.Even great efforts are devoted to revealing the structure-dependent physicochemical nature of TMDs by modulating their phases from the stable to the metastable at the atomic scale,there are still challenges on the phase-controlled synthesis of Group VI TMDs with metallic or semimetal properties.In this review,methods such as ion intercalation,chemical doping,strain engineering,defect triggering,and electric-field treatment are examined in detail.Finally,challenges and opportunities in this research field are proposed.

Studies on thermoresponsive polymers:Phase behaviour,drug delivery and biomedical applications

The present review aims to highlight the applications of thermoresponsive polymers.Thermo-responsive polymers show a sharp change in properties upon a small or modest change in temperature.This behaviour can be utilized for the preparation of so-called‘smart’drug delivery systems,which mimic biological response behaviour to a certain extent.Such materials are used in the development of several applications,such as drug delivery systems,tissue engineering scaffolds and gene delivery.Advances in this field are particularly relevant to applications in the areas of regenerative medicine and drug delivery.This review addresses summary of the main applications of thermoresponsive polymers which are categorized based on their 3-dimensional structure;hydrogels,interpenetrating networks,micelles,films and particles.The physico-chemical behaviour underlying the phase transition is also discussed in brief.

Restructuring of 4H Phase Au Nanowires and its Catalytic Behavior toward CO Electro-oxidation

Au nanowires in 4H crystalline phase(4H Au NWs)are synthesized by colloid solution methods.The crys-talline phase and surface structure as well as its performance toward electrochemical oxidation of CO be-fore and after removing adsorbed oleylamine molecules(OAs)intro-duced from its synthesis are evaluat-ed by high-resolution transmission electron microscopy(HR-TEM),X-ray diffraction(XRD),underpoten-tial deposition of Pb(Pb-upd)and cyclic voltammetry.Different methods,i.e.acetic acid cleaning,electrochemical oxidation cleaning,and diethylamine replacement,have been tried to remove the adsorbed OAs.For all methods,upon the removal of the adsorbed OAs,the morphology of 4H gold nanoparticles is found to gradually change from nanowires to large dumbbell-shaped nanoparticles,accompanying with a transition from the 4H phase to the face-centered cubic phase.On the other hand,the Pb-upd results show that the sample sur-faces have almost the same facet composition before and after removal of the adsorbed OAs.After electrochemical cleaning with continuous potential scans up to 1.3 V,CO electro-oxida-tion activity of the 4H Au sample is significantly improved.The CO electro-oxidation activi-ty is compared with results on the three basel Au single crystalline surfaces reported in the lit-erature,possible origins for its enhancement are discussed.

急倾斜脉群钨矿开采过渡区围岩力学环境变化特征研究

随着现代化采矿工艺的发展,急倾斜脉群矿体正由传统的浅孔留矿法向更高效的阶段矿房法转变,采区围岩力学环境扰动规律也随之改变,特别是在2种采矿方法接替的开采过渡区,可能存在围岩力学环境分布规律的盲区。基于声发射测定的初始地应力采用FLAC3D软件模拟研究了过渡区开采中段采区围岩的力学环境变化特征。结果表明:①上部采区经浅孔留矿法回采出矿后,采区上下盘围岩受到拉应力作用且存在采场边帮松脱的趋势,单脉采场间围岩受应力作用不均匀导致上下端位移交错分布,采区上下盘围岩及单脉采场间围岩以剪切塑性区为主,有发生剪切破坏的风险。②下部采区经阶段矿房法回采出矿后,采区的应力集中现象更加明显,采场顶板出现沉降趋势,采区上下盘围岩向竖直方向变形且两采区位移较连续,采区的顶底板主要为拉伸塑性区且上下盘围岩存在较大范围的剪切塑性区,预示着采区围岩可能同时存在张拉和剪切破坏风险。③对采空区及时进行废石嗣后充填能够有效抑制应力集中现象。矿山在开采过渡区生产时应严格控制上下部相邻采场的开采、充填时序,避免超前开采,进而最大程度抑制应力集中导致的围岩变形、失稳等不利影响。

Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system

Ferroelastic hybrid perovskite materials have been revealed the significance in the applications of switches,sensors,actuators,etc.However,it remains a challenge to design high-temperature ferroelastic to meet the requirements for the practical applications.Herein,we reported an one-dimensional organicinorganic hybrid perovskites(OIHP)(3-methylpyrazolium)CdCl_(3)(3-MBCC),which possesses a mmmF2/m ferroelastic phase transition at 263 K.Moreover,utilizing crystal engineering,we replace-CH_(3) with-NH_(2) and-H,which increases the intermolecular force between organic cations and inorganic frameworks.The phase transition temperature of(3-aminopyrazolium)CdCl_(3)(3-ABCC),and(pyrazolium)CdCl_(3)(BCC)increased by 73 K and 10 K,respectively.Particularly,BCC undergoes an unconventional inverse temperature symmetry breaking(ISTB)ferroelastic phase transition around 273 K.Differently,it transforms from a high symmetry low-temperature paraelastic phase(point group 2/m)to a low symmetry high-temperature ferroelastic phase(point group ī)originating from the rare mechanism of displacement of organic cations phase transition.It means that crystal BCC retains in ferroelastic phase above 273 K until melting point(446 K).Furthermore,characteristic ferroelastic domain patterns on crystal BCC are confirmed with polarized optical microscopy.Our study enriches the molecular mechanism of ferroelastics in the family of organic-inorganic hybrids and opens up a new avenue for exploring high-temperature ferroic materials.

难处理金矿预氧化过程中载金包裹体的相变与重构研究进展

这是一篇矿业工程领域的论文。在“双碳”和难处理金矿资源“压舱石”背景下,预氧化是难处理金矿高效提金的有效预处理方法。有效破坏微细浸染金包裹体,消除或避免有害物质对金的钝化、劫金或二次包裹作用,是决定难处理金矿中金回收率高低的关键和瓶颈问题。明晰预氧化过程中载金物质的相变重构演化规律,对定向破坏载金包裹体和高效浸金至关重要。本文概述了难处理金矿的典型特征与现有预氧化技术,总结了焙烧氧化、热压氧化、生物氧化、化学氧化及其他预氧化过程中载金包裹体的相变重构研究进展。结果表明,载金硫化物通过预氧化主要转变为铁(砷)氧化物和硫(砷)酸盐,受氧化温度、气氛或含氧量、酸碱环境、氧化还原电位、菌种特性等多因素耦合作用,也可能转变为单质硫、氧化硫、硫代硫酸盐、黄钾铁矾和臭葱石等次生产物,黄钾铁矾、氧化铁和硫酸钙等是导致金二次包裹的主要固相物质。低温低压中性热压氧化,高效嗜热嗜碱耐砷菌种驯化、多因素耦合下的细菌氧化过程强化,绿色高效氧化剂筛选、基于多场耦合的化学氧化等预氧化工艺开发与微观机制仍需系统深入研究。矿石特性、预氧化过程反应、载金物质相变重构与金回收率之间的耦合关系及调控是未来难处理金矿绿色高效预氧化领域的研究热点与难点。

障碍物长度对两相爆震起爆特性影响的研究

为了探究障碍物长度对气液两相爆震起爆特性的影响,以汽油和富氧空气作为燃料和氧化剂,在使用不同长度障碍物的爆震管中进行了工作频率为20 Hz的无阀式多循环实验研究.研究结果表明,障碍物长度为管径4倍至8倍的孔板、Shchelkin螺旋、环形凹槽和螺旋凹槽均可实现爆震的起爆;增加障碍物长度可以缩短DDT距离和DDT时间;气液两相DDT过程中,火焰加速至产物声速左右,可能会马上起爆,也可能维持在产物声速左右继续传播一段距离后再起爆;在火焰达到产物声速左右的位置下游布置障碍物可以增加爆震马上起爆的概率.

Local engineering of topological phase in monolayer MoS2

Monolayer transition metal dichalcogenides(TMDCs) with the 1 T0 structure are a new class of large-gap two-dimensional(2 D) topological insulators, hosting topologically protected conduction channels on the edges. However, the 1 T0 phase is metastable compared to the 2 H phase for most of 2 D TMDCs, among which the 1 T0 phase is least favored in monolayer MoS2. Here we report a clean and controllable technique to locally induce nanometer-sized 1 T0 phase in monolayer 2 H-MoS2 via a weak Argon-plasma treatment,resulting in topological phase boundaries of high density. We found that the stabilization of 1 T0 phase arises from the concerted effects of S vacancies and the tensile strain. Scanning tunneling spectroscopy(STS) clearly reveals a spin-orbit band gap(~60 meV) and topologically protected in-gap states residing at the 1 T0-2 H phase boundary, which are corroborated by density-functional theory(DFT) calculations.The strategy developed in this work can be generalized to a large variety of TMDCs materials, with potentials to realize scalable electronics and spintronics with low dissipation.

Optimizing strain response in lead-free(Bi_(0.5)Na_(0.5))TiO_(3)-BaTiO_(3)-NaNbO_(3)solid solutions via ferroelectric/(non-)ergodic relaxor phase boundary engineering

Lead-free bismuth sodium titanate(Bi_(0.5)Na_(0.5))TiO_(3)(BNT)and related solid solutions are potential piezoelectric materials for such applications as actuators and transducers if their excellent strain responses and piezoelectric properties can be optimized.In this work,a large strain response of 0.61%is achieved in lead-free(0.94-x%)(Bi_(0.5)Na_(0.5))TiO_(3)-0.06BaTiO_(3)-x%NaNbO_(3)(x=0 e6,BNT-6BT-xNN)ceramics with the composition of x=3.5 in a pseudo-cubic structure.Coexistence of ferroelectric(FE)and relaxor(RE)domain structures is observed in all the unpoled ceramics and the enhanced strain response is believed to be related to the evolution of the ergodic relaxor(ER)and non-ergodic(NR)states thanks to the substitution of antiferroelectric NN.BNT-6BT-3.5NN is a critical composition near the FE/NR/ER phase boundary close to room temperature(RT)and its high strain response arises from a synergistic combination of a reversible electric-field-induced phase transition and an active domain switching in the mixed NR/ER state.This work provides new insights into the dynamic interplay between mesoscopic domains and macroscopic electrical properties in the BNT-based piezoceramics.

Enhanced thermoelectric performance of two dimensional MS2(M=Mo,W)through phase engineering

The potential application of monolayer MS2(M?Mo,W)as thermoelectric material has been widely studied since the first report of successful fabrication.However,their performances are hindered by the considerable band gap and the large lattice thermal conductivity in the pristine 2H phase.Recent discoveries of polymorphism in MS2s provide new opportunities for materials engineering.In this work,phonon and electron transport properties of both 2H and 1T0 phases were investigated by first-principle calculations.It is found that upon the phase transition from 2H to 1T0 in MS2,the electron transport is greatly enhanced,while the lattice thermal conductivity is reduced by several times.These features lead to a significant enhancement of power factor by one order of magnitude in MoS2 and by three times in WS2.Meanwhile,the figure of merit can reach up to 0.33 for 1T0eMoS2 and 0.68 for 1T0eWS2 at low temperature.These findings indicate that monolayer MS2 in the 1T0 phase can be promising materials for thermoelectric devices application.Meanwhile,this work demonstrates that phase engineering techniques can bring in one important control parameter in materials design.

Phase engineering two-dimensional nanostructures for electrocatalytic hydrogen evolution reaction

Hydrogen(H2)is considered to be a promising substitute for fossil fuels.Two-dimensional(2D)nanomaterials have exhibited an efficient electrocatalytic capacity to catalyze hydrogen evolution reaction(HER).Particularly,phase engineering of 2D nanomaterials is opening a novel research direction to endow 2D nanostructures with fascinating properties for deep applications in catalyzing HER.In this review,we briefly summarize the research progress and present the current challenges on phase engineering of 2D nanomaterials for their applications in electrocatalytic HER.Our summary will be of significance to provide fundamental understanding for designing novel 2D nanomaterials with unconventional phases to electrochemically catalyze HER.

Improved multiferroic in EuTiO_(3) films by interphase strain engineering

Interphase strain engineering provides a unique methodology to significantly modify the lattice structure across a single film,enabling the emergence and manipulation of novel functionalities that are inaccessible in the context of traditional strain engineering methods.In this work,by using the interphase strain,we achieve a ferromagnetic state with enhanced Curie temperature and a room-temperature polar state in EuO secondary phase-tunned EuTiO_(3) thin films.A combination of atomic-scale electron microscopy and synchrotron X-ray spectroscopy unravels the underlying mechanisms of the ferroelectric and ferromagnetic properties enhancement.Wherein,the EuO secondary phase is found to be able to dramatically distort the TiO_6 octahedra,which favors the non-centrosymmetric polar state,weakens antiferromagnetic Eu-Ti-Eu interactions,and enhances ferromagnetic Eu-O-Eu interactions.Our work demonstrates the feasibility and effectiveness of interphase strain engineering in simultaneously promoting ferroelectric and ferromagnetic performance,which would provide new thinking on the property regulation of numerous strongly correlated functional materials.

沉积相变岩体声波速度特征的试验研究

声波测试技术发展至今已有30多年的历史,但对声波速度与岩石力学特性相关联的问题研究还只是处于起步阶段。以淮南潘三矿区地质条件为研究背景,以相似物理模拟试验和数值模拟技术为主要研究手段,研究潘三矿区沉积相变岩体声波速度特征及其影响因素,得出岩体中相变体的存在改变岩体应力分布特征:在相变体上部一般为承压区,端部为应力集中区。相变体的存在也使模型中声波速度产生新的分布,相变体上部声波速度较其下部速度大,相变体中声波速度一般较低,经过相变介质声波速度受相变体影响速度变小。研究结果对地下工程声波探测及煤田地震进行精细构造勘探具有重要意义。

热力耦合作用下无烟煤煤体变形特征的试验研究

利用自主研制的"600℃20MN伺服控制高温高压岩体三轴试验机"系统,研究φ200mm×400mm大尺寸无烟煤试样在恒定500m原岩应力状态(轴压12.5MPa、围压15MPa),以10℃/h的升温速率从20℃升至600℃过程中的变形规律。试验结果表明:随着温度的升高,无烟煤煤体的变形可分为3个阶段,即20℃～200℃热膨胀阶段、200℃～400℃缓慢压缩阶段和400℃～600℃剧烈压缩阶段。其中,400℃～450℃为无烟煤煤体变形由脆性机制转变为韧性机制的临界温度范围,温度和压力是影响无烟煤煤体变形脆-韧性转变的主要因素,且具有明显的温压等效性,即较高的临界温度所需转化压力较低。热力耦合作用和热解产气是影响煤体变形的关键因素,尤其在高温阶段,热解产气对变形起到主控作用。

边坡和采场围岩变形破裂响应特征的相似模拟试验研究

以云南磷化集团晋宁磷矿6#坑口东采区深部缓倾斜中厚磷矿层为研究对象,依据相似模拟原则,利用重庆大学资环学院矿山压力平面应力相似模拟试验台,进行晋宁磷矿6#坑口东采区深部缓倾斜中厚磷矿露天转地下开采的相似模拟模型试验。试验结果表明:(1)受地下采动影响后,露天矿边坡顶部、腰部和底部的应力分布进行重新调整,随着开挖范围的扩大,整体上呈受压—压缩应力增大—受拉伸的动态变化趋势。受境界顶柱的保护支承作用,开挖后其垂直下沉变形很小。(2)地下磷矿体开挖后,在采空场前后方顶板一定区域内形成顶板支承压力集中区,而在采空场上方靠近磷矿层的顶板区域形成卸压区,同时在采空场下方靠近磷矿层的底板区域则形成底板卸压区。随着采空场沿磷矿层倾斜延伸方向的推进,采空场顶板和底板卸压范围逐渐增大,顶板支承压力区动态前移。(3)受采动的影响,采空场附近顶底板围岩均有不同程度的变形,顶板岩层有不同程度的下沉,底板岩层有不同程度的隆起。顶板下沉和底板隆起最大点均位于采空场中点偏下部分,随着开挖的推进而动态前移,达到充分采动后岩层整体下沉和隆起曲线趋于稳定的碗状。以采空场为中心,随着距离其纵向和水平方向距离的增加,顶底板岩层位移变形量单调递减。(4)开挖推进至断层破碎带及其影响区域时,在采动应力的影响下,断层破碎带被"活化",沿断层接触面发生滑移和剪切破坏。该研究成果对云南磷化集团晋宁磷矿6#坑口东采区深部矿体及类似条件下矿山露天转地下开采现场工程实施有重要理论指导意义。

煤层中气水两相运移的NMRI试验研究

首次将先进的无损检测NMRI成像技术引入煤层中气水两相运移的研究领域,将自主设计研制的、可同时改变围压、轴压和孔隙压的、非磁性聚碳酸酯材料制成的三轴渗透仪置于NMRI成像仪磁体腔中,通过气驱水和水驱气NMRI试验实时观测了气水流动规律.主要以水驱气NMRI试验为例,详细介绍了核磁共振三轴渗透仪和型煤试件的研制,并重点阐述了水驱气试验过程和相关参数,利用NMRI技术实时观测得到了不同时间沿驱替方向型煤试件水平剖面的NMRI成像图,最后对试验结果进行了比较分析,揭示了一些新的规律认识:(1)水驱替前缘具有不一致性,从NMRI试验角度验证了前人甲烷类气体赋存形式主要以吸附在孔隙内表面为主的重要结论;(2)煤试件存在优势驱替路径,且这种优势路径在驱替过程中基本保持不变,水驱气的优势驱替路径易产生在煤试件边缘,即煤孔隙裂隙发育区;(3)水驱流量变化决定了水驱前缘的运移速度,且对水驱气效果具有滞后效应;(4)水驱气初次驱替效果好于二次驱替效果;(5)水驱替气的顺序为:主要大裂隙—周边裂隙—周边孔隙.

富氧条件下不同泄爆面积对CH4燃烧诱导快速相变的影响

为了研究富氧条件下不同泄爆面积对CH4燃烧诱导快速相变的影响,基于自主设计搭建的CH4燃烧诱导快速相变试验台,通过改变富氧系数和泄爆面积对CH4燃烧的压力振荡特性进行研究,分析了不同富氧系数E(0.21,0.3,0.4,0.6)及泄爆面积比(0,0.25,0.5,0.75,1)下CH4燃烧的压力峰值、到达压力峰值的时间及特征时间等参数的变化趋势。结果表明,随富氧系数增大,爆炸压力峰值逐渐增大。富氧系数E=0.21时,压力峰值低于相应的绝热压力,无压力振荡;当E=0.3时,压力峰值低于相应的绝热压力且伴随压力振荡。当E为0.4、0.6时,压力峰值高于相应绝热压力且伴随压力振荡;在泄爆条件下,随富氧系数增加,到达压力峰值的时间逐渐减小。通过分析不锈钢管道中的燃烧诱导快速相变现象,发现泄爆可以有效降低爆炸压力峰值,且随泄爆面积比增大,到达压力峰值的时间提前。