Research on properties of hollow glass microspheres/epoxy resin composites applied in deep rock in-situ temperature-preserved coring

Deep petroleum resources are in a high-temperature environment.However,the traditional deep rock coring method has no temperature preserved measures and ignores the effect of temperature on rock porosity and permeability,which will lead to the distortion of the petroleum resources reserves assessment.Therefore,the hollow glass microspheres/epoxy resin(HGM/EP)composites were innovatively proposed as temperature preserved materials for in-situ temperature-preserved coring(ITP-Coring),and the physical,mechanical,and temperature preserved properties were evaluated.The results indicated that:As the HGM content increased,the density and mechanical properties of the composites gradually decreased,while the water absorption was deficient without hydrostatic pressure.For composites with 50 vol%HGM,when the hydrostatic pressure reached 60 MPa,the water absorption was above 30.19%,and the physical and mechanical properties of composites were weakened.When the hydrostatic pressure was lower than 40 MPa,the mechanical properties and thermal conductivity of composites were almost unchanged.Therefore,the composites with 50 vol%HGM can be used for ITPCoring operations in deep environments with the highest hydrostatic pressure of 40 MPa.Finally,to further understand the temperature preserved performance of composites in practical applications,the temperature preserved properties were measured.An unsteady-state heat transfer model was established based on the test results,then the theoretical change of the core temperature during the coring process was obtained.The above tests results can provide a research basis for deep rock in-situ temperature preserved corer and support accurate assessment of deep petroleum reserves.

In-situ pressure-preserved coring for deep exploration:Insight into the rotation behavior of the valve cover of a pressure controller

In-situ pressure-preserved coring(IPP-Coring)is considered to be the most reliable and efficient method for the identification of the scale of oil and gas resources.During IPP-Coring,because the rotation behavior of the pressure controller valve cover in different medium environments is unclear,interference between the valve cover and inner pipe may occur and negatively affect the IPP-Coring success rate.To address this issue,we conducted a series of indoor experiments employing a high-speed camera to gain greater insights into the valve cover rotation behavior in different medium environments,e.g.,air,water,and simulated drilling fluids.The results indicated that the variation in the valve cover rotation angle in the air and fluid environments can be described by a one-phase exponential decay function with a constant time parameter and by biphasic dose response function,respectively.The rotation behavior in the fluid environments exhibited distinct elastic and gravitational acceleration zones.In the fluid environments,the density clearly impacted the valve cover closing time and rotation behavior,whereas the effect of viscosity was very slight.This can be attributed to the negligible influence of the fluid viscosity on the drag coefficient found in this study;meanwhile,the density can increase the buoyancy and the time period during which the valve cover experienced a high drag coefficient.Considering these results,control schemes for the valve cover rotation behavior during IPP-Coring were proposed for different layers and geological conditions in which the different drilling fluids should be used,e.g.,the use of a high-density valve cover in high-pore pressure layers.

Design and development of the deep-rock in-situ condition-preserved coring calibration platform

To systematically validate and calibrate the theory and technology of the deep in-situ conditionpreserved coring, the in-situ conditions at different depths should be simulated, and the full-size coring tests should be carried out in this simulated environment. Therefore, a deep-rock in-situ conditionpreserved coring calibration platform was designed and developed. The self-tightening sealing structure and the quick-disassembly structure were designed on the basis of an innovative segmented nonuniformdiameter structure, which was a breakthrough from the traditional high-pressure vessel frame and was verified by finite element simulation and actual testing under extreme working conditions, respectively.To simulate the actual deep in-situ environment with a temperature of 150℃ and pressure of 140 MPa for a large Φ450 mm×H1400 mm core, temperature and pressure control systems were designed by coupling, and a pre-embedded high-pressure-resistant temperature sensor was designed. Finally, highprecision assembly automation, complex movement coordination of the coring device with the platform,and rotary dynamic sealing were achieved by utilizing the combination of adaptive cabin body servo control and an adaptive mechanical structure in a limited space, laying a solid foundation for the calibration of in-situ condition-preserved coring.

Research progress and application of deep in-situ condition preserved coring and testing

With the depletion of shallow resources,the exploration of deep earth resources has become a global strategy.The study of the different patterns in the physical mechanical properties of rocks at different occurrence depths is the basis for exploring deep into the earth,with the core and premise being the acquisition and testing of deep in-situ core specimens.Based on the original idea of deep in-situ condition preserved coring(ICP-Coring)and testing,combined with theoretical modeling,numerical analysis,test platform development,indoor testing and engineering application,the principles and technologies of deep ICP-Coring are developed.This principle and technology consists of five parts:in-situ pressurepreserved coring(IPP-Coring),in-situ substance-preserved coring(ISP-Coring),in-situ temperaturepreserved coring(ITP-Coring),in-situ light-preserved coring(ILP-Coring),and in-situ moisturepreserved coring(IMP-Coring).The theory and technology of temperature and pressure reconstruction at different occurrence depths and in different environments are proposed,and prototype trial production was completed by following the principle of displacement and tests based on the in-situ reconstructed environment.The notable advances are as follows:(1)Deep in-situ coring system:A pressure-preserved controller with an ultimate bearing capacity greater than 140 MPa,highperformance(temperature-resistant,pressure-resistant,and low thermally conductive)temperaturepreserved materials,an active temperature control system,and high-barrier quality-preserved membrane materials were developed;a deep ICP-Coring capacity calibration platform was independently developed,a deep in-situ coring technology system was developed,and the acquisition of deep in-situ cores was realized.(2)In-situ storage displacement system:Following the dual-circuit hydraulic design idea,a single-drive source push-pull composite grabbing mechanism was designed;the design of the overall structure for the deep in-situ displacement storage system and ultrahigh pressure cabin structure was completed,which could realize docking the coring device and core displacement in the in-situ reconstructed environment.(3)Test analysis system:A noncontact acoustic-electric-magnetic test system was developed under the in-situ reconstructed environment,and the errors between the test results and traditional contact test results were mostly less than 10%;a detachable deep in-situ core true triaxial test system was developed,which could perform loading tests for deep in-situ cores.The relevant technological achievements were successfully applied to the exploration and development of deep resources,such as deep mines,deep-sea natural gas hydrates,and deep oil and gas.The research results provide technical and equipment support for the construction of a theoretical system for deep in-situ rock mechanics,the development of deep earth resources and energy,and the scientific exploration of different layers and occurrence depths(deep and ultradeep)of the Earth.

Engineering behaviour of in situ cored deep cement mixed marine deposits subjected to undrained and drained shearing

The deep cement mixing(DCM)is used to improve the capacity and reduce the settlement of the soft ground by forming cemented clay columns.The investigation on the mechanical behaviour of the DCM samples is limited to either laboratory-prepared samples or in-situ samples under unconfined compression.In this study,a series of drained and undrained triaxial shearing tests was performed on the in-situ cored DCM samples with high cement content to assess their mechanical behaviours.It is found that the drainage condition affects significantly the stiffness,peak and residual strengths of the DCM samples,which is mainly due to the state of excess pore water pressure at different strain levels,i.e.being positive before the peak deviatoric stress and negative after the peak deviatoric stress,in the undrained tests.The slope of the failure envelope changes obviously with the confining pressures,being steeper at lower stress levels and flatter at higher stress levels.The strength parameters,effective cohesion and friction angle obtained from lower stress levels(c′0 andφ′0)are 400 kPa and 58°,respectively,which are deemed to be true for design in most DCM applications where the in-situ stress levels are normally at lower values of 50-200 kPa.Additionally,the computed tomography(CT)scanning system was adopted to visualize the internal structures of DCM samples.It is found that the clay pockets existing inside the DCM samples due to uneven mixing affect markedly their stress-strain behaviour,which is one of the main reasons for the high variability of the DCM samples.

Hollow glass microspheres/silicone rubber composite materials toward materials for high performance deep in-situ temperaturepreserved coring

Deep petroleum resources are stored under high temperature and pressure conditions,with the temperature having a significant influence on the properties of rocks.Deep in-situ temperature-preserved coring(ITP-coring)devices were developed to assess deep petroleum reserves accurately.Herein,hollow glass microspheres(HGMs)/silicone rubber(SR)composites that exhibit excellent thermal insulation properties were prepared as thermal insulation materials for deep ITP-coring devices.The mechanism and process of heat transfer in the composites were explored,as well as their other properties.The results show that the HGMs exhibit good compatibility with the SR matrix.When the volume fraction of the HGMs is increased to 50%,the density of the HGMs/SR composites is reduced from 0.97 to 0.56 g/cm^(3).The HGMs filler introduces large voids into the composites,reducing their thermal conductivity to 0.11 W/m·K.The addition of HGMs into the composites further enhances the thermal stability of the SR,wherein the higher the HGMs filler content,the better the thermal stability of the composites.HGMs significantly enhance the mechanical strength of the SR.HGMs increase the compressive strength of the composites by 828%and the tensile strength by 164%.Overall,HGMs improve the thermal insulation,pressure resistance,and thermal stability of HGMs/SR composites.

Research on in-situ condition preserved coring and testing systems

As shallow resources are increasingly depleted,the mechanics'theory and testing technology of deep insitu rock has become urgent.Traditional coring technologies obtain rock samples without retaining the in-situ environmental conditions,leading to distortion of the measured parameters.Herein,a coring and testing systems retaining in-situ geological conditions is presented:the coring system that obtains in-situ rock samples,and the transfer and testing system that stores and analyzes the rocks under a reconstructed environment.The ICP-Coring system mainly consists of the pressure controller,active insulated core reactor and insulation layer and sealing film.The ultimate bearing strength of 100 MPa for pressurepreservation,temperature control accuracy of 0.97%for temperature-retained are realized.CH_(4)and CO permeability of the optimized sealing film are as low as 3.85 and 0.33 ppm/min.The average tensile elongation of the film is 152.4%and the light transmittance is reduced to 0%.Additionally,the pressure and steady-state temperature accuracy for reconstructing the in-situ environment of transfer and storage system up to 1%and±0.2 is achieved.The error recorded of the noncontact sensor ring made of lowdensity polymer is less than 6%than that of the contact test.The system can provide technical support for the deep in-situ rock mechanics research,improving deep resource acquisition capabilities and further clarifying deep-earth processes.

Contact performance analysis of pressure controller's sealing interface in deep in-situ pressure-preserved coring system

The sealing performance of contact interfaces plays the most important role in the design and operation of the in-situ pressure-preserved coring system.To meet the demand of ultra-high pressure-retained coring for oil and gas exploration in deep reservoirs,a quantitative analysis of the contact mechanical behavior of the pressure controller was performed.Based on the micro-contact theory of rough surfaces,a three-dimensional numerical model of the rough contact interface between the valve cover and the valve seat was constructed,and the micro-contact behavior of the metal contact surfaces was comprehensively studied.The results show that the actual contact area of the valve interface increases with the increase of surface roughness before the critical contact point,but decreases after that.Compared with the real contact model with double rough surfaces,although the simplified hard-contact model with a single rough surface can reflect the micro-contact behavior of the rough surface to a certain extent,it cannot truly reveal the microchannel morphology between the sealing interfaces under pressure.Therefore,the realistic double-rough-surface model should be recommended to evaluate the sealing performance of coring tools,particularly for high pressure conditions.The material properties of valves have a significant effect on the contact characteristics of rough surfaces,which suggested that the actual contact area decreases with the increase of the elastic modulus of the contact material under the same loading conditions.The knowledge of this work could help to enhance the seal design of pressure controllers for in-situ pressure-preserved coring.

Deep original information preservation by applying in-situ film formation technology during coring

Accurately obtaining the original information of an in-situ rock via coring is a significant guiding step for exploring and developing deep oil and gas resources.It is difficult for traditional coring technology and equipment to preserve the original information in deep rocks.This study develops a technology for insitu substance-preserved(ISP),moisture-preserved(IMP),and light-preserved(ILP)coring.This technology stores the original information in real time by forming a solid sealing film on the in-situ sample during coring.This study designed the ISP-IMP-ILP-Coring process and tool.In addition,an ISP-IMP-ILPCoring process simulation system was developed.The effects of temperature,pressure,and film thickness on the quality of the in-situ film were investigated by performing in-situ film-forming simulation experiments.A solid sealing film with a thickness of 2-3 mm can be formed;it completely covers the core sample and has uniform thickness.The film maintains good ISP-IMP-ILP properties and can protect the core sample in the in-situ environment steadily.This study verifies the feasibility of“film formation during coring”technology and provides strong support for the engineering application of ISP-IMP-ILPCoring technology.

Development of a pressure coring system for the investigation of deep underground exploration

To provide a more accurate evaluation of the scale of deep underground resources,a new pressure coring system was carefully developed and its strength and safety of the engineering were verified by theoretical analyses and numerical simulation.The designed pressure coring system can obtain cores with length of 3 m and diameter of 50 mm at 70 MPa.The results of the ball-drop operation experiment demonstrate that differential motion assembly can effectively cut a safety pin by applying a tensile force of 4852 N,and it can lift the core tube through the center pole to complete a series of mechanical actions to seal the pressure.Additionally,by maintaining pressures at 70 MPa for 30 min,the pressure sealing capacity of the system was proven.Furthermore,a core sample with a diameter of 50 mm was obtained through a core drilling experiment and the coring performance of the pressure coring system was verified.This study can not only enrich the existing onshore coring technology but also provide a theoretical guide and design criteria for the development of similar pressure coring systems to meet the demand for deeper underground exploration.

High-brightness green InP-based QLEDs enabled by in-situ passivating core surface with zinc myristate

The performance of red InP and blue ZnTeSe-based quantum dots(QDs)and corresponding QD light emitting diodes(QLEDs)has already been improved significantly,whose external quantum efficiencies(EQEs)and luminances have exceeded 20%and 80000 cd m-2,respectively.However,the inferior performance of the green InP-based device hinders the commercialization of full-color Cd-free QLED technology.The ease of oxidation of the highly reactive InP cores leads to high non-radiative recombination and poor photoluminescence quantum yield(PL QY)of the InP-based core/shell QDs,limiting the performance of the relevant QLEDs.Here,we proposed a fluoride-free synthesis strategy to in-situ passivate the InP cores,in which zinc myristate reacted with phosphine dangling bonds to form Zn–P protective layer and protect InP cores from the water and oxygen in the environment.The resultant InP/ZnSe/ZnS core/shell QDs demonstrated a high PL QY of 91%.The corresponding green-emitting electroluminescence devices exhibited a maximum EQE of 12.74%,along with a luminance of over 175000 cd m^(-2)and a long T50@100 cd m^(-2)lifetime of over 20000 h.

Determination of mining-induced stresses using diametral rock core deformations

Knowledge of ground stresses is crucial for ground control activities such as the design of underground openings,selec-tion of support systems,and analysis for stability.However,it is a known fact that far field stresses experience changes in orientation and magnitude due to the presence of geological structures and due to the excavations created by mining activi-ties.As a result,in-situ stresses around drifts,ramps,and stopes in underground mines are quite different from far field or pre-mining stresses.The purpose of this research is to develop a simple and practical methodology for determining in-situ stresses.Stress relief occurs once the rock core is drilled off.Such relief is a function of the surrounding stress field.This study uses exploration rock cores that are drilled off for the purpose of orebody definition in the underground mine.The method measures and analyzes the diametral core deformations in laboratory.Two case studies from operating underground mines are presented for demonstration.In these case studies,rock core deformations are measured with a customized test apparatus and rock samples were prepared and tested for Young's modulus and Poisson's ratio.The differential stress,namely the difference between the local principal stresses in the plane perpendicular to the core rock axis is calculated.It is shown that this methodology is useful for determining the brittle shear ratio in the rock mass,which is of primary interest to ground control studies.

Dual-ion pre-inserted Mo glycerate template for constructing NiMo-OS core–shell structure with boosting performance in zinc ions hybrid supercapacitors

Zinc ion hybrid supercapacitors(ZHS)have received much attention due to the enhanced potential window range and high specific capacity.However,the appropriate positive materials with high electrochemical performance are still a challenge.Herein,NH_(4)^(+)and glycerate anions pre-inserted Mo glycerate(N-MoG)spheres are synthesized and serve as the template to form NH_(4)^(+)intercalated Ni_(3)S_(2)/Ni_(3)O_(2)(OH)_(4)@MoS_(2)core–shell nanoflower(N-NiMo-OS)in-situ grown on nickel foam(NF)(N-NiMo-OS/NF)by sulfurization treatment.Compared with the product using traditional MoG as a template,N-NiMo-OS/NF inheriting a larger core structure from N-MoG delivers enhanced space for ions transport and volume expansion during the energy storage process,together with the synergistic effects of multi-components and the heterostructure,the as-prepared N-NiMo-OS/NF nanoflower exhibits excellent performance for the battery-type hybrid supercapacitors(BHS)and ZHS devices.Notably,the ZHS device delivers superior electrochemical performance to the BHS device,such as a higher specific capacity of 327.5 mAh·g^(−1)at 1 A·g^(−1),a preeminent energy density of 610.6 Wh·kg^(−1)at 1710 W·kg^(−1),long cycle life.The in-situ Raman,ex-situ X-ray photoelectron spectroscopy(XPS),theoretical calculation demonstrate the extra Zn^(2+)insertion/extraction storage mechanism provides enhanced electrochemical performance for ZHS device.Therefore,the dual-ion pre-inserted strategy can be extended for other advanced electrode materials in energy storage fields.

原位液相转变制备多孔h-MoO_3@C纳米线用于锂/钠离子储存（英文）

基于金属氧化物存储机制,MoO_3比MoO_2具有更高的理论容量.本文通过热的硝酸氧化MoO_2@C纳米线成功制备出具有400.2 m2g^-1高比表面积的多孔h-MoO_3@C纳米纤维,且碳壁没有明显破坏.作为锂离子电池的负极,与MoO_2@C纳米线相比多孔h-MoO_3@C纳米纤维电极表现出更好的性能,其中在2 Ag^(-1)的电流密度下500循环后展现出302.9 mAhg^-1的可逆容量.作为钠离子电池的负极,h-MoO_3@C电极同样具有很好的倍率性能.在2 Ag^(-1)的电流密度下500循环后仍具有108.9 mAhg^-1的容量,并且在2 Ag^(-1)的电流密度下1200循环后还能保持91 mAhg^-1的容量.由于碳壁可以维持结构的完整性且可提高导电性;同时h-MoO_3的隧道结构可作为分离电子孔并为Li+/Na+嵌入脱出提供更多的特有位置,使得该复合纳米线作为电极材料表现出更好的性能.本工作为合成具有高价的过渡金属氧化物/碳复合材料在电池和催化剂领域的运用提供了依据.