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.

A new permeability calculation method using nuclear magnetic resonance logging based on pore sizes: A case study of bioclastic limestone reservoirs in the A oilfield of the Mid-East

It is difficult to accurately obtain the permeability of complex lithologic reservoirs using conventional methods because they have diverse pore structures and complex seepage mechanisms.Based on in-depth analysis of the limitation of classical nuclear magnetic resonance(NMR)permeability calculation models,and the understanding that the pore structure and porosity are the main controlling factors of permeability,this study provides a new permeability calculation method involving classifying pore sizes by using NMR T_2 spectrum first and then calculating permeability of different sizes of pores.Based on this idea,taking the bioclastic limestone reservoir in the A oilfield of Mid-East as an example,the classification criterion of four kinds of pore sizes:coarse,medium,fine and micro throat,was established and transformed into NMR T_2 standard based on shapes and turning points of mercury intrusion capillary pressure curves.Then the proportions of the four kinds of pore sizes were obtained precisely based on the NMR logging data.A new NMR permeability calculation model of multicomponent pores combinations was established based on the contributions of pores in different sizes.The new method has been used in different blocks.The results show that the new method is more accurate than the traditional ones.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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。

Classification of tight sandstone reservoirs based on NMR logging

The traditional reservoir classification methods based on conventional well logging are inefficient for determining the properties,such as the porosity,shale volume,J function,and flow zone index,of the tight sandstone reservoirs because of their complex pore structure and large heterogeneity.Specifically,the method that is commonly used to characterize the reservoir pore structure is dependent on the nuclear magnetic resonance(NMR)transverse relaxation time(T2)distribution,which is closely related to the pore size distribution.Further,the pore structure parameters(displacement pressure,maximum pore-throat radius,and median pore-throat radius)can be determined and applied to reservoir classification based on the empirical linear or power function obtained from the NMR T2 distributions and the mercury intrusion capillary pressure ourves.However,the effective generalization of these empirical functions is difficult because they differ according to the region and are limited by the representative samples of different regions.A lognormal distribution is commonly used to describe the pore size and particle size distributions of the rock and quantitatively characterize the reservoir pore structure based on the volume,mean radius,and standard deviation of the small and large pores.In this study,we obtain six parameters(the volume,mean radius,and standard deviation of the small and large pores)that represent the characteristics of pore distribution and rock heterogeneity,calculate the total porosity via NMR logging,and classify the reservoirs via cluster analysis by adopting a bimodal lognormal distribution to fit the NMR T2 spectrum.Finally,based on the data obtained from the core tests and the NMR logs,the proposed method,which is readily applicable,can effectively classify the tight sandstone reservoirs.

Molecular structure characterization of middle-high rank coal via^(13)C NMR,XPS,and FTIR spectroscopy

Elemental analysis,nuclear magnetic resonance carbon spectroscopy(^(13)C-NMR),X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)experiments were carried out to determine the existence of aromatic structure,heteroatom structure and fat structure in coal.MS(materials studio)software was used to optimize and construct a 3D molecular structure model of coal.A method for establishing a coal molecular structure model was formed,which was“determination of key structures in coal,construction of planar molecular structure model,and optimization of three-dimensional molecular structure model”.The structural differences were compared and analyzed.The results show that with the increase of coal rank,the dehydrogenation of cycloalkanes in coal is continuously enhanced,and the content of heteroatoms in the aromatic ring decreases.The heteroatoms and branch chains in the coal are reduced,and the structure is more orderly and tight.The stability of the structure is determined by theπ-πinteraction between the aromatic rings in the nonbonding energy EN.Key Stretching Energy The size of EB determines how tight the structure is.The research results provide a method and reference for the study of the molecular structure of medium and high coal ranks.

A Novel Model of Predicting Archie's Cementation Factor from Nuclear Magnetic Resonance(NMR) Logs in Low Permeability Reservoirs

The resistivity experimental measurements of core samples drilled from low permeability reservoirs of Ordos Basin, Northwest China, illustrate that the cementation factors are not agminate, but vary from 1.335 to 1.749. This leads to a challenge for the estimation of water and hydrocarbon sa- turation. Based on the analysis of Purcell equation and assumption that rock resistivity is determined by the parallel connection of numerous capillary resistances, a theoretical expression of cementation factor in terms of porosity and permeability is established. Then, cementation factor can be calculated if the parameters of porosity and permeability are determined. In the field application, porosity can be easily obtained by conventional logs. However, it is a tough challenge to estimate permeability due to the strong heterogeneity of low permeability reservoirs. Thus, the Schlumberger Doll Research （SDR） model derived from NMR logs has been proposed to estimate permeability. Based on the analysis of the theoretical expressions of cementation factor and SDR model, a novel cementation factor prediction model, which is relevant to porosity and logarithmic mean of NMR T2 spectrum （T21m）, is derived. The advantage of this model is that all the input information can be acquired from NMR logs accurately. In order to confirm the credibility of the novel model, the resistivity and corresponding laboratory NMR measurements of 27 core samples are conducted. The credibility of the model is confirmed by compar- ing the predicted cementation factors with the core analyzed results. The absolute errors for all core samples are lower than 0.071. Once this model is extended to field application, the accuracy of water and hydrocarbon saturation estimation will be significantly improved.

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.