Shale primary porosimetry based on 2D nuclear magnetic resonance of T_(1)-T_(2)

Porosity,a key parameter in assessing the physical properties of shale reservoirs and the reserves,is of great significance to the selection and evaluation of shale sweet spots.There are many methods at present to characterize shale porosity,most of which are aimed at post-core cleaning shale,such as those involving helium and saturated fluid(namely liquid-involved porosimetry).However,due to the low efficiency of shale core cleaning and the possible damage to pore structure during the core cleaning process,it's hard to guarantee the accuracy of porosity measurement.In this regard,we resort to the two-dimensional(2D)nuclear magnetic resonance(NMR)technology of T1-T2 in characterizing the primary shale porosity with samples taken from pressure coring in the 4th member of Shahejie Formation(Sha 4 Member)in well Fanxie 184 in the Jiyang Depression.Moreover,comparative experiments of shale porosity measurement by three methods,namely the simultaneous distillation extraction(SDE),helium and fluid measurement,are carried out simultaneously.The results show that the values obtained by SDE,gas and liquid measurement are similar,which are about 0.6 times of 2D NMR porosimetry.Core cleaning efficiency tends to seriously affect the results involving gas and liquid.In addition,the core cleaning treatment is bound to change the shale pore structure,and this is especially true in clay which tends to swell;consequently,porosity results are to be distorted by gas and liquid methods.It is thereby recommended to utilize the 2D NMR technology to characterize the primary total porosity of shale samples without core cleaning.The effective porosity of samples from pressure coring is determined by T2 cutoff value of around 0.3 ms.

Estimation of unfrozen water content of saturated sandstones using nuclear magnetic resonance, mercury intrusion porosimetry, and ultrasonic tests

The unfrozenwater content(UWC)is a crucial parameter that affects the strength and thermal properties of rocks in relation to engineering construction and geological disasters in cold regions.In this study,three different methods were employed to test and estimate the UWC of saturated sandstones,including nuclear magnetic resonance(NMR),mercury intrusion porosimetry(MIP),and ultrasonic methods.The NMR method enabled the direct measurement of the UWC of sandstones using the free induction decay(FID).The MIP method was used to analyze the pore structures of sandstones,with the UWC subsequently calculated based on pore ice crystallization.Therefore,the MIP test constituted an indirect measurement method.Furthermore,a correlation was established between the P-wave velocity and the UWC of these sandstones based on the mixture theory,which could be employed to estimate the UWC as an empirical method.All methods demonstrated that the UWC initially exhibited a rapid decrease from 0C to5C and then generally became constant beyond20C.However,these test methods had different characteristics.The NMR method was used to directly and accurately calculate the UWC in the laboratory.However,the cost and complexity of NMR equipment have precluded its use in the field.The UWC can be effectively estimated by the MIP test,but the estimation accuracy is influenced by the ice crystallization process and the pore size distribution.The P-wave velocity has been demonstrated to be a straightforward and practical empirical parameter and was utilized to estimate the UWC based on the mixture theory.This method may be more suitable in the field.All methods confirmed the existence of a hysteresis phenomenon in the freezing-thawing process.The average hysteresis coefficient was approximately 0.538,thus validating the GibbseThomson equation.This study not only presents alternative methodologies for estimating the UWC of saturated sandstones but also contribute to our understanding of the freezing-thawing process of pore water.

Utilization of nuclear magnetic resonance (NMR) in the determination of water status on rice seeds

The relation between seed viability and waterstatus in seed was studied.The experimentwas carried out at Zhongshan University.Seeds of hybrid rice Shanyou 63 were collectedfrom Guangdong Academy of Agriculture Sci-ences in 1993 and then stored for one year inopen air or with silica gel.Before and afterstorage,the relative content of free water andbound water in seeds were measured with

Application of nuclear magnetic resonance technology to carbon capture,utilization and storage:A review

Carbon capture,utilization and storage (CCUS) is considered as a very important technology for mitigating global climate change.Carbon dioxide (CO2) injected into an underground reservoir will induce changes in its physical properties and the migration of CO2 will be affected by many factors.Accurately understanding these changes and migration characteristics of CO2 is crucial for selecting a CCUS project site,estimating storage capacity and ensuring storage security.In this paper,the basic principles of nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) technologies are briefly introduced in the context of laboratory experiments related to CCUS.The types of NMR apparatus,experimental samples and testing approaches applied worldwide are discussed and analyzed.Then two typical NMR core analysis systems used in CCUS field and a self-developed high-pressure,low-field NMR rock core flooding experimental system are compared.Finally,a summary of the current deficiencies related to NMR applied to CCUS field is given and future research plans are proposed.

Relaxation study of cement based grouting material using nuclear magnetic resonance

Aiming at actual condition of poor effect of hole sealing for the reason of poor cement paste fluidity in the process of coal mine gas drainage,by adding a water reducing agent,cement paste for hole sealing was produced.The changes of initial distribution,weighted average values and total relaxation signal intensity of transverse relaxation time(T 2) of water in pure cement paste and water reducing agent added cement paste were studied with low field proton nuclear magnetic resonance(NMR).The results show that there are four peaks in T2 distribution curves of cement paste:the first peak is related to the bound water in flocculation,the second and the third peaks are related to the water in flocculation,water reducing agent makes it extending towards the long relaxation time,increasing its liquidity,and the fourth peak is related to the free water.By using weighted average values of T2 and total relaxation signal intensity,hydration process of cement pastes could be roughly divided into four stages:the initial period,reaction period,accelerated period and steady period.By analyzing the periods,it makes sure that the grouting process should be completed in the reaction period in the site,and the drainage process should be started in the steady period.The results have great guiding significance to the hole sealing and methane drainage.

基于LF-NMR研究双孢菇远红外辅助热泵干燥过程中水分迁移规律及品质变化

为研究双孢菇远红外辅助热泵干燥过程中水分分布规律及品质变化,采用低场核磁共振及成像技术分别对干燥过程的双孢菇进行弛豫特性及质子密度成像分析,并研究干燥前、后双孢菇微观结构和品质的变化。结果表明:在热泵温度分别为45,55,65℃时,双孢菇到达干燥终点的时间分别为510,420,390 min。双孢菇的T2反演谱有3个不同的弛豫峰:T21(3~23 ms)、T22(25~155 ms)和T23(155~1084 ms),分别代表双孢菇中的结合水、不易流动水和自由水。干燥初期,T23左迁幅度很大,干燥后期,左迁幅度变小,随着干燥时间的延长,自由水的流动性降低。干燥结束时,T23对应的弛豫峰下降约99.8%,只剩下部分T21和T22对应的峰,说明自由水几乎被完全去除,双孢菇内仅剩结合水和少量不易流动水。低场核磁共振图像显示,65℃条件下,干燥360 min,水分基本被脱除,而55℃和45℃处理组分别在干燥390 min和450 min才基本脱除。双孢菇外侧的水分先被脱除,内部的水分向外迁移,并且温度越高,内部水分迁移速率越快。另外,65℃条件下的双孢菇的BI值分别比45℃和55℃条件下的BI低30.55%和22.69%,说明65℃更能维持双孢菇原有的色泽。65℃条件下干燥的双孢菇的抗坏血酸、总酚、总黄酮含量分别比干燥前下降84.62%,55.80%和36.78%,与45℃和55℃相比,65℃下双孢菇营养成分的损失最小。本研究表明低场核磁共振及成像技术为双孢菇干燥过程中水分的变化提供了直观的参考依据,也可为双孢菇的远红外辅助热泵干燥工艺优化干燥参数、提高产品质量提供理论参考。

Investigation of reinforcement of the modified carbon black from wasted tires by nuclear magnetic resonance

Pyrolysis has the potential of transforming waste into recyclable products. Pyrolytic carbon black (PCB) is one of the most important products from the pyrolysis of used tires. Techniques for surface modifications of PCB have been developed. One of the most significant applications for modified PCB is to reinforce the rubber matrix to obtain high added values. The transverse relaxation and the chain dynamics of vulcanized rubber networks with PCB and modified PCB were studied and compared with those of the commercial carbon blacks using selective 1H transverse relaxation (T2) experiments and dipolar correlation effect (DCE) experiments on the stimulated echo. Demineralization and coupling agent modification not only intensified the interactions between the modified PCB and the neighboring polyisoprene chains, but also increased the chemical cross-link density of the vulcanized rubber with modified PCB. The mechanical testing of the rubbers with different kinds of carbon blacks showed that the maximum strain of the rubber with modified PCB was improved greatly. The mechanical testing results confirmed the conclusion obtained by nuclear magnetic resonance (NMR). PCB modified by the demineralization and NDZ-105 titanate coupling agent could be used to replace the commercial semi-reinforcing carbon black.

Review of nuclear magnetic resonance studies on iron-based superconductors

The newly discovered iron-based superconductors have triggered renewed enormous research interest in the condensed matter physics community. Nuclear magnetic resonance （NMR） is a low-energy local probe for studying strongly correlated electrons, and particularly important for high-Tc superconductors. In this paper, we review NMR studies on the structural transition, antiferromagnetic order, spin fluctuations, and superconducting properties of several iron-based high-Tc superconductors, including LaFeAsOl_xFx, LaFeAsOl_x, BaFe2As2, Bal_xKxFe2As2, Cao.23Nao.67Fe2As2, BaFe2（Asl_xPx）2, Ba（Fel_xRux）2As2, Ba（Fel_xCox）2As2, Lil＋xFeAs, LiFel_xCoxAs, NaFeAs, NaFel_xCoxAs, KyFe2_xSe2, and （T1,Rb）yFe2_xSe2.

Three dimensional structure prediction and proton nuclear magnetic resonance analysis of toxic pesticides in human blood plasma

The purpose of this study was to investigate the nuclear magnetic resonance （NMR） assignments of hydrolyzed products extracted from human blood plasma. The correlations between chemical, functional and structural prop- erties of highly toxic pesticides were investigated using the PreADME analysis. We observed that toxic pesticides possessed higher molecular weight and, more hydrogen bond donors and acceptors when compared with less toxic pesticides. The occurrence of functional groups and structural properties was analyzed using ~H-NMR. The ~H- NMR spectra of the phosphomethoxy class of pesticides were characterized by methyl resonances at 3.7-3.9 ppm （8） with the coupling constants of 11-16 Hz （Je-cns）. In phosphoethoxy pesticides, the methyl resonance was about 1.4 ppm （8） with the coupling constant of 10 Hz （Je-cH2） and the methylene resonances was 4.2-4.4 ppm （8） with the coupling constant of 0.8 Hz （Jp-cH3）, respectively. Our study shows that the values of four parameters such as chemical shift, coupling constant, integration and relaxation time correlated with the concentration of toxic pesticides, and can be used to characterise the proton groups in the molecular structures of toxic pesticides.

Nuclear magnetic resonance measurement station in SECUF using hybrid superconducting magnets

Nuclear magnetic resonance （NMR） is one of the most powerful tools to explore new quantum states of condensed matter induced by high magnetic fields at a microscopic level. High magnetic field enhances the intensity of the NMR signal, and more importantly, can induce novel phenomena. In this article, examples are given on the field-induced charge density wave （CDW） in high-To superconductors and on the studies of quantum spin liquids. We provide a brief introduction to the high magnetic field NMR platform, the station 4 of the Synergetic Extreme Condition User Facility （SECUF）, being built at Huairou, Beijing.

A model of unfrozen water content in rock during freezing and thawing with experimental validation by nuclear magnetic resonance

The unfrozen water content of rock during freezing and thawing has an important influence on its physical and mechanical properties.This study presented a model for calculating the unfrozen water content of rock during freezing and thawing process,considering the influence of unfrozen water film and rock pore structure,which can reflect the hysteresis and super-cooling effects.The pore size distribution cu rves of red sandsto ne and its unfrozen water conte nt under different temperatures during the freezing and thawing process were measured using nuclear magnetic resonance(NMR) to validate the proposed model.Comparison between the experimental and calculated results indicated that the theoretical model accu rately reflected the water content change law of red sandstone during the freezing and thawing process.Furthermore,the influences of Hamaker constant and surface relaxation parameter on the model results were examined.The results showed that the appropriate magnitude order of Hamaker constant for the red sandstone was 10J to 10J;and when the relaxation parameter of the rock surface was within 25-30 μm/ms,the calculated unfrozen water content using the proposed model was consistent with the experimental value.

Characterization of Average Molecular Structure of Heavy Oil Fractions by ~1H Nuclear Magnetic Resonance and X-ray Diffraction

The chemical structure of heavy oil fractions obtained by liquid-solid adsorption chromatography was character-ized by 1 H nuclear magnetic resonance and X-ray diffraction.The molecular weight and molecular formula of asphaltene molecules were estimated by combining 1 H nuclear magnetic resonance and X-ray diffraction analyses,and were also ob-tained from vapor pressure osmometry and elemental analysis.Heteroatoms,such as S,N,and O atoms,were considered in the construction of average molecular structure of heavy oils.Two important structural parameters were proposed,including the number of alkyl chain substituents to aromatic rings and the number of total rings with heteroatoms.Ultimately,the av-erage molecular structures of polycyclic aromatics,heavy resins and asphaltene molecules were constructed.The number of α-,β-,γ-,and aromatic hydrogen atoms of the constructed average molecular structures fits well with the number of hydro-gen atoms derived from the experimental spectral data.

Fluid identification and tight oil layer classification for the southwestern Mahu Sag,Junggar Basin using NMR logging-based spectrum decomposition

The intricate distribution of oil and water in tight rocks makes pinpointing oil layers challenging.While conventional identification methods offer potential solutions,their limited accuracy precludes them from being effective in their applications to unconventional reservoirs.This study employed nuclear magnetic resonance(NMR)spectrum decomposition to dissect the NMR T_(2)spectrum into multiple subspectra.Furthermore,it employed laboratory NMR experiments to ascertain the fluid properties of these sub-spectra,aiming to enhance identification accuracy.The findings indicate that fluids of distinct properties overlap in the T_(2)spectra,with bound water,movable water,bound oil,and movable oil appearing sequentially from the low-value zone to the high-value zone.Consequently,an oil layer classification scheme was proposed,which considers the physical properties of reservoirs,oil-bearing capacity,and the characteristics of both mobility and the oil-water two-phase flow.When applied to tight oil layer identification,the scheme's outcomes align closely with actual test results.A horizontal well,deployed based on these findings,has produced high-yield industrial oil flow,underscoring the precision and dependability of this new approach.

Nuclear magnetic resonance study of the formation and dissociation process of nature gas hydrate in sandstone

In this work,the authors monitored the formation and dissociation process of methane hydrate in four different rock core samples through nuclear magnetic resonance(NMR)relaxation time(T_(2))and 2D imaging measurement.The result shows that the intensity of T_(2) spectra and magnetic resonance imaging(MRI)signals gradually decreases in the hydrate formation process,and at the same time,the T_(2) spectra move toward the left domain as the growth of hydrate in the pores of the sample accelerates the decay rate.The hydrate grows and dissociates preferentially in the purer sandstone samples with larger pore size and higher porosity.Significantly,for the sample with lower porosity and higher argillaceous content,the intensity of the T_(2) spectra also shows a trend of a great decrease in the hydrate formation process,which means that high-saturation gas hydrate can also be formed in the sample with higher argillaceous content.The changes in MRI of the sample in the process show that the formation and dissociation of methane hydrate can reshape the distribution of water in the pores.

Progress of novel diluted ferromagnetic semiconductors with decoupled spin and charge doping: Counterparts of Fe-based superconductors

Diluted ferromagnetic semiconductors（DMSs） that combine the properties of semiconductors with ferromagnetism have potential application in spin-sensitive electronic（spintronic） devices. The search for DMS materials exploded after the observation of ferromagnetic ordering in Ⅲ-Ⅴ（Ga,Mn）As films. Recently, a series of DMS compounds isostructural to iron-based superconductors have been reported. Among them, the highest Curie temperature TCo f 230 K has been achieved in（Ba,K）（Zn,Mn）2As2. However, most DMSs, including（Ga,Mn）As, are p-type, i.e., the carriers that mediate the ferromagnetism are holes. For practical applications, DMSs with n-type carriers are also advantageous. Very recently,a new DMS Ba（Zn,Co）2As2 with n-type carriers has been synthesized. Here we summarize the recent progress on this research stream. We will show that the homogeneous ferromagnetism in these bulk form DMSs has been confirmed by microscopic techniques, i.e., nuclear magnetic resonance（NMR） and muon spin rotation（μSR）.

Further discussion of CO_(2) huff-n-puff mechanisms in tight oil reservoirs based on NMR monitored fluids spatial distributions

Due to the poor physical properties of tight reservoirs,CO_(2) huff-n-puff(HNP)is considered a potential enhanced oil recovery(EOR)method after primary depletion.Optimization plays a critical role in the effective implementation of CO_(2) huff-n-puff.But the optimization requires a good understanding of the EOR mechanisms.In this work,the spatial distribution of oil saturation under different experimental conditions was analyzed by the NMR method to further discuss the HNP mechanisms.According to the variation of 1D frequency signal amplitude,we divided the core into the hardly movable area and movable area,the region with the obvious signal decline was defined as the movable area,and the hardly movable area was the region with limited signal decline.Based on that the recovery characteristics of different scenarios were evaluated.Firstly,the necessity of the soaking stage was studied,where three scenarios with different soaking times were carried out.Secondly,the injection pressure was adjusted to investigate the effect of the pressure gradient.The T_(2) spectra show that soaking has significantly improved the production of crude oil in small pores,and higher oil recovery in a single cycle is observed,but it is lower when the elapsed time(total operation time)is the same.31.03% of oil can be recovered after 3 cycles HNP,which increases to 33.8% and 37.06% for the 4 cycles and 6 cycles cases.As the pressure gradient increases,more oil is removed out of the matrix,and the oil in the deep part of the reservoir can be effectively recovered.During the CO_(2) huff-n-puff process,the oil distributions are similar to the solution gas drive,the residual oil is distributed at the close end of the core and the range that the oil can be efficiently recovered is limited.

ASSURE-NMR-HSQC实验检测保健食品中西地那非类物质

本研究通过使用灵敏度增强的带梯度形状脉冲进行异核单量子相干(HSQC)实验检测保健食品中违法添加的西地那非类物质。待测样品以甲醇溶解超声辅助提取,减压浓缩后以氘代DMSO溶解上机测试;利用Assure-NMR软件将得到的未知样品异核单量子相干(Heteronculear Single Quantum Coherence)谱图与已知西地那非类物质谱图进行模拟匹配。本方法检出限可以达到200μg·kg-1,能快速有效的对保健食品中西地那非类物质的违法添加侦察识别。该方法简便快捷,可以为食品安全监管部门提供一种新颖便捷的那非类物质监管稽查参考办法。

基于干燥动力学结合LF-NMR分析的不同干燥过程中天麻切片水分变化

为探究天麻(Gastrodia elata Blume)切片干燥过程中水分迁移变化规律,并建立其量化表征方法,本研究采用低场核磁共振(Low-Field Nuclear Magnetic Resonance, LF-NMR)技术分析热风干燥(Hot Air Drying, HAD)和微波干燥(Microwave Drying, MWD)过程中不同热风温度(60、70、80℃)和不同微波功率密度(2、3、4 W/g)条件下的天麻切片,结合干燥特性曲线建立基于LF-NMR参数的天麻切片含水量预测模型。结果表明,MWD速率远大于HAD,在热风温度(60-80℃)和微波功率密度(2-4 W/g)范围内,高温、高功率密度有利于提高干燥速率,缩短干燥时间。Logarithmic模型可以准确描述天麻切片HAD和MWD过程中含水量的变化。经LF-NMR技术分析,在HAD和MWD过程中,天麻切片的横向弛豫时间曲线整体上呈现左移的趋势,各状态水的弛豫峰信号强度不断降低;干燥结束时天麻切片中的自由水完全被脱去,仅存少量的不易流动水和结合水。无论是HAD还是MWD,弛豫峰总面积A_(2)和天麻片的干基含水量相关性均在0.99以上。研究结果可为阐明天麻切片干燥机制和干燥工艺参数的优选提供参考。

酸化对高阶煤不同层理方向增透效果影响研究

为了研究酸化对寺河矿高阶煤垂直、平行两个层理方向的增透效果,开展了多组分酸煤粉和煤柱溶蚀试验,优选出了合适的酸液体系,分析了两个层理方向煤柱不同酸化时长下的溶蚀效果,并进行了两个层理方向煤柱的煤岩三轴吸附-解吸-渗流试验和低场核磁共振试验,对比了酸化前后的渗透率、孔隙度、孔径分布变化。结果表明:(1)寺河矿酸化选用质量分数2%HCl+2%CH3COOH+5%HF的酸液配比溶蚀效果最优;(2)酸化使垂直层理方向煤柱的孔隙率增幅更大,而平行层理方向煤柱达到最大增幅用时更短;(3)酸化后两个层理方向煤柱的渗透率、孔隙度均提升,垂直层理方向煤柱孔隙度增幅更大,渗透率增幅则小于平行层理方向煤柱,且二者的渗透率增幅都在滑脱效应拐点处最小;(4)酸化使两个层理方向煤柱的瓦斯吸附孔占比下降,其中平行层理方向煤柱降比更大,且酸化前后中大孔占比也都更高;确定了寺河矿酸化后以煤样平行层理方向作为钻孔瓦斯抽采方向能更好地提高瓦斯抽采率。

二维核磁共振评价页岩流体饱和度实验仿真

二维核磁共振(2D NMR)T_(1)-T_(2)测量在页岩油勘探中具有重要优势,但其数据处理与解释过程复杂,涉及抽象的理论知识。设计了一套基于Matlab图形用户界面的2D NMR T_(1)-T_(2)谱储层流体识别与饱和度评价实验仿真。仿真系统包括地层T_(1)-T_(2)谱模型构建、回波数据正演、回波数据反演以及流体识别与饱和度评价模块。通过输入不同参数,模拟得到页岩地层的T_(1)-T_(2)谱模型、回波数据、T_(1)-T_(2)谱反演结果以及页岩储层流体识别与饱和度评价结果。实验以直观、实用的方式向学生展示了基于2D NMR T_(1)-T_(2)谱的页岩储层流体识别与饱和度评价过程,增强学生对NMR数据处理与解释方法的理解,提高NMR教学效果。