氯化聚乙烯辐射效应的NMR研究

用¹H NMR,¹³C NMR谱,二维谱,FT-IR等方法研究了氯化聚乙烯（CPE）在室温下限量空气中经⁶⁰Co γ射线辐照后的辐照效应. 结果表明CPE在辐照过程中以发生裂解反应为主,在裂解反应过程中伴随着HCl脱出,HCl的脱出量随着辐照剂量的增加而增加. 辐照后CPE样品的大分子结构发生相应变化,序列结构为CH₂CHClCHClCH₂CHCl,CH₂CH₂CHClCH₂CH₂,CHClCH₂CHClCH₂CH₂,CHClCH₂CHClCH₂CHCl的单元数量减少,但没有形成新的序列结构类型,T₁ 和T₂值给出了有关辐照前后分子运动变化的信息.     

基于核运动效应下的H同位素双原子分子的解析势能函

在加入核运动效应修正下的Born-Oppenheimer近似电子能量的基础上, 采用QCISD(T)/ aug-cc-pvqz方法计算出H同位素双原子分子（H₂, HD, HT, D₂, DT,T₂）的势能函数参数, 获得体现H同位素分子质量差异下的势能函数。 并在此基础上导出H同位素分子的力常数和光谱数据。 同时对于OH, OD和OT分子采用QCISD/aug-cc-pvtz方法计算, 同样获得了这些分子对应的势能函数、 力常数和光谱数据。Based on the correction of the electron energy under Born Oppenheimer approximation using nuclear motion effect, the parameters of potential energy functions for hydrogen isotopic diatomic molecules (H₂, HD,HT,D₂, DT,T₂) are calculated with QCISD (T) method and aug-cc-pvqz basis set,and those potential energy functions that indicate the differences from the masses of hydrogen isotopic atoms are obtained. The force constants and spectroscopic data of those molecules are calculated as well. The potential energy functions, force constants, and spectroscopic data of the isotopic diatomic molecules OH, OD,and OT are also derived using QCISD method and aug-cc-pvtz basis set.     

核磁共振二维谱反演

核磁共振二维谱包含扩散系数 D 和横向弛豫时间 T₂ 的信息,利用核磁共振仪来测量多孔介质中物质的信息,根据其弛豫时间和扩散系数的差别来区分不同物质;利用全局反演方法,提出了核磁共振二维谱反演的物理模型和数学模型;介绍了传统的奇异值分解（SVD）和改进的奇异值分解反演算法;采用改进的奇异值分解法对核磁共振二维谱进行反演,其反演算法具有计算速度快和二维谱分布连续等优点. 它适合于信噪比较高的数据反演,当原始数据信噪比SNR≥100时,可以对二维谱图进行定量分析;当60≤SNR<100时,可以对二维谱图进行定性分析. 核磁共振二维谱可以一次性直接区分油和水,为核磁共振测井提供了新的科学技术.     

超支化高分子桥联聚倍半硅氧烷复合物的NMR研究

以三羟甲基丙烷(TMP)为内核,二羟甲基丙酸(DMP)为支化单元用准一步法合成了重均分子量为12100的第四代端羟基脂肪族超支化聚酯(HBPE-G4),用3-异氰酸酯基丙基三乙氧基硅烷(TPIC)对它进行了端基改性,并以其为桥联剂,与聚倍半硅氧烷(PMSQ)复合制备出超支化高分子桥联聚倍半硅氧烷复合物．利用固体核磁共振(NMR),傅立叶红外(FI-IR),分子纳米粒度分析等方法表征了改性超支化高分子和复合物的结构和反应程度,并通过测量¹³C T₁,¹H T₂,¹H T_1ρ研究了体系中各组分的运动性能,以及超支化高分子与聚倍半硅氧烷之间的相容性．     

页岩油气层核磁共振评价技术综述

对于常规储层,核磁共振是一项十分有效的解释-评价技术,它既能评价岩石物性与孔隙结构,又能评价孔隙流体分布与饱和度,且具有快速、无损、经济等特点;而对于页岩储层,其核磁共振受纳米级孔隙、复杂矿物成分、特殊孔隙结构、较高有机质含量、超低渗透性及内部梯度和受限扩散等因素的影响,面临探测分辨率低、解释模型不适用等瓶颈．为了发挥该项技术在页岩油气勘探开发中的作用,将国内外的页岩油气层核磁共振分析、评价技术与相关的页岩油气层实验室微观分析成果相结合,进行了系统梳理,从探测分辨率的提高、孔隙结构与岩石物性评价模型的建立、孔隙流体分布与识别模型的建立等方面进行了综述,提出需加强纳米孔的核磁共振弛豫机理和提高 D-T₂二维谱分辨率两个基础研究,在此基础上,进一步完善岩石物理及孔隙流体两个评价模型．
     

丙烯酰胺-甲基丙烯酸共聚物结构的NMR研究

用¹H NMR谱,¹³C NMR谱,DEPT谱,gHMQC,gHMBC二维谱和质子弛豫时间等方法研究了在紫外光辐照条件下丙烯酰胺(AM) -甲基丙烯酸(MAA)共聚合反应,讨论了AM-MAA共聚合反应时间与转化率的关系、共聚单体的连接方式、共聚物序列结构以及不同辐照时间下形成的共聚物链运动. 结果表明在紫外光辐照条件下,AM-MAA共聚物链节中同时存在多种连接方式,当反应时间为45 min时,共聚合转化率可达100%. 从自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）测定中得出,在辐照1小时范围内,时间越长聚合物长链分子运动速度越快,但主链的链段运动变化不明显.     

实验不可分辨的Voigt线型重叠谱线的压致展宽线宽的偏差确定

通过仿真和拟合Voigt线型重叠谱线,讨论了将实验上不可分辨的两条谱线重叠后视为单条谱线时所得到的压致展宽线宽与其实际值的相对误差ε,分析了该误差与两谱线的中心位置距离δν₀和实际的压致展宽线宽δν0_Ｌ的变化规律。发现ε在谱线的压致展宽线宽远小于多普勒线宽δν_Ｄ时显得很大,与δν₀和δν0_Ｌ的变化规律较复杂;当δν0_Ｌ可与δν_Ｄ比拟时,ε随δν₀的变化趋于呈光滑的二次项函数曲线,但曲线的斜率在δν0_Ｌ小于δν_Ｄ情况下为负,而在δν0_Ｌ大于δν_Ｄ时为正。整体来说,随着δν0_Ｌ对总线宽的影响越大,ε越小。所有这些结论和相应关系数据为修正压致展宽线宽的拟合值具有积极的参考价值,并且为进一步从实验上不可分辨的重叠谱线确定精确的压致展宽系数提出了极有意义的方法和思路。     

常温高压下碳酸根离子的拉曼谱峰标定压力初探

在准静水压的条件下,利用碳化硅压腔和显微拉曼光谱原位测量技术,在0～1.7 GPa压力范围测定22 ℃高压下三种不同的H₂O-Na₂CO₃体系(1.5,2.0,2.5 mol·L-1)中CO2-₃的对称伸缩振动ν_{1 066}拉曼谱峰的变化。结果表明,在室温条件下,碳酸根的ν_{1 066}峰的拉曼位移随着压力的增大而线性增加。三种浓度下ν_{1 066}峰的拉曼位移与压力的拟合直线彼此接近,斜率误差小于1%,偏差小于系统误差,因此在实验误差范围内碳酸根浓度对ν_{1 066}峰随压力变化的行为不存在影响。经过数据拟合得到公式：p/MPa=174.13 Δν_{1 066}/cm-1—59.03(Δν_{1 066}=ν_{1 066}-ν_{1 066}0,ν_{1 066}0为体系零压时碳酸根离子ν_{1 066}峰的拉曼位移)。此公式可以用于常温下在含有纯碳酸钠体系中的压力标定。     

基于T2截止值的幂函数构建毛管压力曲线

岩心核磁共振（NMR）T₂谱和毛管压力曲线都在一定程度上反映了岩石孔隙结构，理论分析表明可利用T₂谱构建毛管压力曲线，由此快速获取储层孔隙结构的信息．本文对18块岩样T₂分布和毛管压力曲线进行了分析，提出将T₂截止值作为幂函数的分段点，采用分段幂函数方法构建岩样的NMR毛管压力曲线，并与采用不分段幂函数方法获得的毛管压力曲线进行了对比．研究结果表明，与不分段幂函数方法相比，分段幂函数方法得到的结果和压汞实验测定的毛管压力曲线吻合度更高，平均拟合度（R²）达到0.943 1，并且论证了T₂截止值作为分段点进行分段幂函数法构建NMR毛管压力曲线的合理性和可靠性．T₂截止值的引入提高了幂函数法构建NMR毛管压力曲线的精度，是利用NMR T₂谱构建岩样毛管压力曲线的有价值探索．     

2 μm附近CO2谱线参数测量及应用

吸收光谱技术用于痕量气体浓度监测,特别是在气体分子稳定同位素丰度探测中,吸收谱线参数的准确性非常重要,目前普遍使用的HITRAN数据库中给出的各项参数具有一定的不确定性。为利用2.0 μm激光波段进行CO₂浓度及其同位素丰度探测,需要对该波段的CO₂吸收谱线参数进行校准,采用窄线宽分布反馈式二极管激光器作为光源,结合自行搭建的谱线参数测量系统,采集了2.0 μm波段10条CO₂吸收谱线,获得了各谱线的位置、强度、自加宽系数和N₂加宽系数,并与HITRAN2012数据库中相应的数据进行对比发现两者之间吻合较好,CO₂谱线强度和自加宽系数相对偏差均小于2%。实测实验室大气的CO₂浓度为440 ppm,13CO₂的丰度值δ为-9‰。测量结果为该波段应用于CO₂浓度及13CO₂同位素丰度的实时在线探测提供了重要参考依据。     

An NMR-Based Analysis of Soil–Water Characteristics

Both direct and indirect methods for determining soil–water characteristic curves rely on determination of some empirical coefficients, which may not necessarily represent real microscopic mechanisms. Proton nuclear magnetic resonance (NMR) is a powerful tool for investigating water content and their interaction with solid particles in porous media. The NMR technique is widely used in food science and petroleum. In the present study, proton NMR spin–spin relaxation time (T ₂) distribution measurement is integrated with a Tempe apparatus to characterize the hydraulic processes of unsaturated soils, shedding insights into the microscopic mechanisms of pore water distribution and migration in the soil during hydraulic cycles. It is revealed that during a drying process the drainage of pore water occurs sequentially from larger pores to smaller pores, whereas in a wetting process the water invades into the soil sequentially from smaller pores to larger pores. A new procedure is developed which can be used to determine the pore size distribution of the soil based on the NMR T ₂ distribution measurements; compared to the traditional methods, the new method is rapid and non-destructive. The new procedure is validated by comparing the new result with the measurement of the mercury intrusion porosimetry.     

pH对血清影响的1H NMR研究

维持血液的pH在7.35～7.45范围内,是生命的基本需要. 人体生理状态的改变往往会伴随或者引发血液pH的变化. 本文通过扩散加权、横向弛豫加权以及饱和转移差谱等¹H NMR方法,对pH 7.0～7.8的血清体系进行研究,观察其中大分子和小分子代谢物的变化. 实验结果表明 pH的改变不仅能够引起血清中一些小分子代谢物化学位移的改变,还会影响小分子代谢物与蛋白的相互作用,引起这些小分子结合态和游离态含量的变化. 此外,没有观察到血清蛋白信号的明显变化,仅血清白蛋白赖氨酰信号随pH增高有高场位移.     

Estimation of Saturation Exponent from Nuclear Magnetic Resonance (NMR) Logs in Low Permeability Reservoirs

The resistivity experimental measurements of 36 core samples, which were drilled from low permeability reservoirs of southwest China, illustrate that the saturation exponents are not agminate, but vary from 1.627 to 3.48; this leads to a challenge for water saturation estimation in low permeability formations. Based on the analysis of resistivity experiments, laboratory nuclear magnetic resonance (NMR) measurements for all 36 core samples, and mercury injection measurements for 20 of them, it was observed that the saturation exponent is proportional to the proportion of small pore components and inversely proportional to the logarithmic mean of NMR T ₂ spectrum (T _2lm). For rocks with high proportion of small pore components and low T _2lm, there will be high saturation exponents, and vice versa. The proportion of small pore components is characterized by three different kinds of irreducible water saturations, which are estimated by defining 30, 40 and 50 ms as T ₂ cutoffs separately. By integrating these three different kinds of irreducible water saturations and using T _2lm, a technique of calculating the saturation exponent from NMR logs is proposed and the corresponding model is established. The credibility of this technique is confirmed by comparing the predicted saturation exponents with the results from the core analysis. For more than 85 % of core samples, the absolute errors between the predicted saturation exponents from NMR logs and the experimental results are lower than 0.25. Once this technique is extended to field application, the accuracy of water saturation estimation in low permeability reservoirs will be improved significantly.     

Decoherence in crystal lattice quantum computation

Nuclear magnetic resonance (NMR) quantum computation in a crystal lattice holds more promise for scalability than its solution NMR counterpart, but dephasing is a severe concern. Pulse sequence refocusing can help bring the qubit dephasing time closer to the limit of the intrinsic decoherence time, but the intrinsic transverse relaxation time (T₂) and the longitudinal relaxation time (T₁) of the crystal must be sufficiently long for a successful implementation. We discuss these time scales and their relation to parameters relevant to quantum computation for several crystal types, discussing in detail the examples of CaF₂, MnF₂, and CeP. Included in the calculation of coherence times for CeP is the development of spin-wave spectra in a type-1 antiferromagnetic FCC lattice.     

Influential Factors of Internal Magnetic Field Gradient in Reservoir Rock and Its Effects on NMR Response

Nuclear magnetic resonance (NMR) plays a significant role in porous media analysis and petroleum exploration, but its response is significantly influenced by the internal magnetic field gradient in fluid saturated porous medium, which obviously limits the accuracy of rock core analysis and logging interpretation. The influential factors of the internal magnetic field gradient in formation and its influences on NMR response are studied in this paper, based on NMR mechanism through one- and two-dimensional core NMR experiments. The results indicate that the internal magnetic field gradient is positively correlated with the static magnetic field strength and the magnetic susceptibility difference between pore fluid and solid grains, while it presents negative correlation with pore radius. The internal magnetic field gradient produces an additional diffusion relaxation in hydrogen relaxation system and accelerates the attenuation of magnetization vector. As a result, T₂ spectrum shifts to the left and NMR porosity and diffusion coefficient of the fluid could be inaccurate. This research sets a foundation for the NMR porosity correction and fluid distribution on T₂-G maps based on the internal magnetic field gradient correction.     

Estimation of Permeability by Integrating Nuclear Magnetic Resonance (NMR) Logs with Mercury Injection Capillary Pressure (MICP) Data in Tight Gas Sands

It has been a great challenge to determine permeability in tight gas sands due to the generally poor correlation between porosity and permeability. The Schlumberger Doll Research (SDR) and Timur–Coates permeability models, which have been derived for use with nuclear magnetic resonance (NMR) data, also lose their roles. In this study, based on the analysis of the mercury injection experiment data for 20 core plugs, which were drilled from tight gas sands in the Xujiahe Formation of central Sichuan basin, Southwest China, two empirical correlations between the pore structure index ( $ \sqrt {{K \mathord{\left/ {\vphantom {K \varphi }} \right. \kern-0em} \varphi }} $ , defined by the square root of the ratio of rock permeability and porosity) and the R ₃₅ (the pore throat radius corresponding to 35.0 % of mercury injection saturation), the pore structure index and the Swanson parameter have been developed. To consecutively estimate permeability in field applications, based on the study of experimental NMR measurements for 36 core samples, two effective statistical models, which can be used to derive the Swanson parameter and R ₃₅ from the NMR T ₂ logarithmic mean value, have been established. These procedures carried out on the experimental data set can be extended to reservoir conditions to estimate consecutive formation permeability along the intervals with which NMR logs were acquired. The processing results of several field examples using the proposed technique show that the classification scale models are effective only in tight gas reservoirs, whereas the SDR and Timur–Coates models are inapplicable. The R ₃₅-based model is of significance in thin sands with high porosity and high permeability, but the predicted permeability curves in tight gas sands are slightly lower. In tight gas and thin sands, the Swanson parameter model is all credible.     

Reservoir Pore Structure Classification Technology of Carbonate Rock Based on NMR T 2 Spectrum Decomposition

The carbonate reservoir has a number of properties such as multi-type pore space, strong heterogeneity, and complex pore structure, which make the classification of reservoir pore structure extremely difficult. According to nuclear magnetic resonance (NMR) T ₂ spectrum characteristics of carbonate rock, an automatic pore structure classification and discrimination method based on the T ₂ spectrum decomposition is proposed. The objective function is constructed based on the multi-variate Gaussian distribution properties of the NMR T ₂ spectrum. The particle swarm optimization algorithm was used to solve the objective function and get the initial values and then the generalized reduced gradient algorithm was proposed for solving the objective function, which ensured the stability and convergence of the solution. Based on the featured parameters of the Gaussian function such as normalized weights, spectrum peaks and standard deviations, the combinatory spectrum parameters (by multiplying peak value and normalized weight for every peak) are constructed. According to the principle of fuzzy clustering, the carbonate rock pore structure is classified automatically and the discrimination function of each pore structure type is obtained using Fisher discrimination analysis. The classification results were analyzed with the corresponding casting thin section and scanning electron microscopy. The study shows that the type of the pore structure based on the NMR T ₂ spectrum decomposition is strongly consistent with other methods, which provides a good basis for the quantitative characterization of the carbonate rock reservoir pore space and lays a foundation of the carbonate rock reservoir classification based on NMR logging.     

钯催化Csp-Csp3偶联反应的13C NMR定量研究

利用NOE（Nuclear Overhauser Effect）增强的¹³C NMR方法对钯催化C_sp-C_sp3偶联反应过程进行实时、定量监测. 通过制作浓度曲线的方法定量分析了反应过程中各组分的浓度变化. 实验表明,同一物质各个共振峰的NOE增强倍数基本不变. 结果证实了几个主要反应物和产物的含量变化之间具有相关性,提示这些物质同属一个反应过程,为早期提出的反应机理（Zhao Y S, et al. J Am Chem Soc, 2006, 128: 15 048-15 049）提供了实验证据. 说明¹³C NMR能准确地提供反应体系中各物质的浓度变化信息,是化学反应机理的有效研究手段.     

A field-cycling NMR study of nematic 4-pentyl-4′-cyanobiphenyl confined in porous glasses

The proton spin-lattice relaxation time T₁, in the nematic liquid crystal 4-pentyl-4′-cyanobiphenyl confined in a glassy porous matrix has been measured in a wide Larmor frequency range of 1 · 10²?2 · 10⁷ Hz employing the fast field-cycling NMR technique. A strong influence of the restricted geometry on the character of the T₁ dispersion was found. Our investigation clearly demonstrates the importance of the translationally induced molecular reorientations in inhomogeneous director field for the relaxation in the samples with 200 and 80 nm mean pore size. The experimental results are in a good agreement with the theoretical predictions. In the sample with 7 nm pore size the main contribution to the relaxation is ascribed to the slowing down of the molecular motion in the near-surface layer. Zero-field 1H NMR spectra of a microconfined liquid crystal are reported for the first time.     

二氧化硅纳米结构径向呼吸振动的理论研究

运用密度泛函理论的B3LYP方法,在6-31G(d)基组水平上,计算了由Si₂O₂二元环组成的准一维SiO₂纳米链及三元环(3MR)、四元环(4MR)、六元环(6MR)和八元环(8MR)组成的SiO₂纳米管的Raman振动光谱。从Raman光谱发现纳米链和纳米管的径向呼吸振动频率随链或管长的增加而频率移动相反,即分别发生红移和蓝移,但随着链和管趋于无限长频率趋近稳定值;同时,随着直径的增大,振动频率减小。在小尺寸时,由于结构内部的应力影响使频率移动更明显,进一步对键长和键角分析说明,结构应力的作用使频率随尺寸变化发生移动。