低场核磁共振流体分子结构在线探测技术（英文）

流体分子结构的探测是了解其物理、化学性质的基础.目前主要采用的实验室内分子结构探测技术包括光谱法和波谱法等,但这类测量方法具有测量效率低、需添加化学试剂、实验可重复性差等局限.基于低场核磁共振(NMR)技术进行流体组分的探测技术已十分成熟.该文提出进一步将该技术应用于烃类化合物流体分子结构的检测方法,并研发一种快速二维核磁共振驰豫测量脉冲序列和一套低场核磁共振流体在线检测系统.最终实现了一种快速、无损、清洁、有效的流体组分探测技术.     

优化重聚脉冲提高梯度场核磁共振信号强度

缩短射频脉冲宽度, 有助于解决脉冲电力消耗大、样品吸收率高、信噪比低等极端条件核磁共振探测的关键问题. 本文首先分析射频脉冲角度对核磁共振自旋回波信号强度的影响机理, 基于Bloch方程推导了回波信号幅度与扳转角、重聚角的关系. 在特制核磁共振分析仪上采用变脉冲角度技术, 分别在均匀磁场和梯度磁场条件下实现对扳转角和重聚角与回波信号强度关系的数值模拟和实验测量. 结果表明, 梯度场中, 扳转角为90°、重聚角为140°的射频脉冲组合获得最大首波信号强度, 比180°脉冲对应的回波幅值提高13%, 能耗降低至78%. 选用该重聚角(140°) 优化设计饱和恢复脉冲序列探测流体的纵向弛豫时间T₁特性, 准确获得 T₁分布.该结果对于低电力供应、且对信噪比有较高要求的核磁共振测量, 如随钻核磁共振测井和在线核磁共振快速检测等, 具有重要意义. 关键词： 核磁共振 信号强度 重聚脉冲角度 Bloch方程     

一种基于组分补偿的二维核磁共振测井数据高精度处理方法

二维核磁共振技术能够对储层中各类含氢流体进行无损、快速、定量的测量和表征，但受限于采集方式和参数，核磁共振设备在对页岩油等致密储层中的有机质、沥青等超快弛豫组分进行检测时，经常出现由于信号采集不完整所导致的二维谱中流体组分缺失或不准的问题.本文提出了基于超快弛豫组分补偿技术的T₂-T₁二维谱高精度反演方法，该方法将一维核磁共振前端信号补偿技术进行推广，通过在二维核磁数据反演前对回波数据进行组分补偿，能够有效解决二维核磁共振测井前端信号漏失的问题.实验及测井数据的应用表明，该方法在页岩油等富含快弛豫组分信号的储层中，可以得到更加精准和完整的储层信息.     

基于高温超导SQUID的低场核磁共振研究

采用一高温超导射频量子干涉器(HTS rf-SQUID)作为信号探测器件,研究了多种液体样品的低场核磁共振信号。通过改变测量场(简称Bm)的大小,可以探测到质子拉莫频率(简称fL)从2Hz到40kHz的信号。由于在低场核磁共振中,Bm的均匀性能很好的得到满足,因而可能得到很窄的谱线宽度。实验发现,对自来水样品,在7μT以下均可接近谱线的自然宽度。同时,在低场核磁共振条件下,样品的化学位移很小以至于消失,因而可以研究"纯"的异核间的自旋耦合谱。作者研究了低场下2,2,2-三氟乙醇的低场自旋耦合谱。另外,作者首次采用SQUID在户外探测到地球磁场下的核磁共振现象,并研究了地球磁场的涨落对测量的影响,为SQUID的低场核磁共振研究开辟了一个新的研究方向。     

基于小波滤波的低场NMR纤维上油率检测新方法

针对目前低场核磁共振纤维上油率检测存在的问题,提出了一种基于小波变换的纤维上油率检测新方法. 首先,用低场核磁共振采集标准纤维自由感应衰减信号进行线性拟合得到定标曲线;然后,用测试纤维采集多组叠加次数不同的核磁共振信号,并分别进行小波软阈值滤波;最后,将滤波后的多组结果代入定标曲线计算纤维的上油率. 检测结果和实际应用表明小波软阈值滤波可有效去除纤维FID信号中的噪声并大幅缩短检测时间. 此方法可为低场核磁共振纤维上油率快速、准确检测奠定基础.     

电阻式核磁共振测量的最新进展

电阻式核磁共振(RDNMR)测量是1988年由德国马普所的von Klitzing研究小组针对GaAs二维电子气中少量核自旋的探测而提出的一种具有超高灵敏度的实验技术. 目前, RDNMR已经成为研究单层或双层GaAs二维电子气核自旋和电子自旋特性的重要手段. 由于为实现电阻式核磁共振测量所建立的动态核极化方法强烈依赖于GaAs特有的材料属性, 至今这一技术一直没有扩展应用到其他半导体低维系统中. 最近,本研究小组发展了一种动态核极化新方法,成功实现了对典型窄带半导体锑化铟(InSb) 二维电子气的电阻式核磁共振测量.本文在介绍电阻式核磁共振测量工作原理及已建立的典型动态核极化方法的基础上,着重讨论所提出的动态核极化新方法的机理、 实验结果以及对今后研究的展望.     

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．
     

随钻核磁共振测井仪探测特性研究

随钻核磁共振测井是继电缆核磁共振测井之后的重要进步,具有直接探测原状地层孔隙度、束缚水、渗透率和流体饱和度等特点,受到广泛关注. 随钻核磁共振测井需要在更加恶劣的环境下作业,对探头尤其是对磁体有更高的要求. 该文研究随钻核磁共振测井的探测特性. 基于测量环境和工作方式,分析了随钻核磁共振测井静磁场设计中的特殊问题;利用有限元方法,分别模拟了MRIL-WD（哈里伯顿）、proVISION（斯伦贝谢）和MagTrak（贝克休斯） 3种随钻核磁共振测井仪的静磁场分布;根据数值模拟结果,提出可以抑制仪器随钻具运动（轴向转动、纵向钻进和径向振动）对测量的影响的随钻核磁共振测井静磁场方案,为自主随钻核磁共振测井仪器的设计、实现和优化提供了思路和注意事项.     

流水式核磁共振实验系统介绍

简述了流水式核磁共振的原理,利用自制的流水式核磁共振实验装置测量了纯水的纵向驰豫时间、强磁场(检测场)的强度、弱磁场(空间场)的三维分量的大小,对章动现象进行了观察和解释.     

流动速度对核磁共振在线测量的影响及校正

流体流动的核磁共振（NMR）在线测量是一种高效、无损的探测方式,可广泛应用于管道流体输送过程、化学反应动态流程、河流流动等具有时移变化特点的过程在线检测.但是流动状态下样品流速会对NMR测量造成诸如磁化时间不充分、采集信号损失等不容忽视的影响.通过量化分析流动状态对NMR测量的影响因素,提出回波串校正方法,实现流动状态下的NMR流体测量.     

Correlating fast and slow chemical shift spinning sideband patterns in solid-state NMR

An experiment is presented that enables the measurement of small chemical shift anisotropy tensors under fast magic-angle spinning (MAS). The two-dimensional spectra obtained give a fast MAS sideband pattern in the directly observed dimension with the spinning sideband intensities equivalent to the chemical shift anisotropy scaled by a factor of N, or equivalently the sample spinning frequency scaled by 1/N, in the indirectly observed dimension. The scaling factor may be arbitrarily varied by changing the number and timings of the rotor synchronized pi-pulses used. Desirable features of the experiment include a fixed length pulse sequence and efficient sampling of the indirectly observed dimension. In addition, neither quadrature detection in the indirect dimension nor storage periods are required, consequently no signal intensity is discarded by the pulse sequence. The experiment is demonstrated using (31)P NMR of sodium phosphate and (13)C NMR of fumaric acid monoethyl ester for which a scaling factor of N=10.2 was employed.     

A method for detection of spectral spin diffusion from minor peaks, and its application to F MAS NMR of antimony(III)-doped fluorapatite

A new technique for detecting spectral spin diffusion in solids under MAS NMR conditions that is particularly well suited for accurately measuring cross-relaxation from minor spectral components is presented. The pulse sequence, SINK (Saturation Inter-Nuclear Kinetics), selectively saturates the magnetization of a minor spectral component with a series of rotor-synchronized DANTE pulse trains and monitors spin diffusion to other peaks with a non-selective 90° pulse. We have used SINK with ¹⁹F MAS NMR on samples of calcium fluorapatite doped with Sb³⁺ to measure spin diffusion between a weak peak at 68.6 ppm due to fluoride ions associated with Sb³⁺ and other peaks in the spectrum. The SINK experiment clearly demonstrates that spin diffusion from the former peak to the main resonance of fluorapatite at 64.0 ppm is faster than spin diffusion to a second antimony-related peak at 65.6 ppm. These results strengthen our previous conclusion that antimony(III) occupies a phosphate site in the apatite lattice, with an SbO₃³⁻ group replacing a PO₄³⁻ group. The SINK experiment also enables the detection of a “hidden” peak at approximately 62.9 ppm that is otherwise obscured by the intense main peak at 64.0 ppm.     

基于PC机的脉冲序列发生器

为了降低谱仪的复杂性和成本，文中提出了基于PC机的脉冲序列发生器设计方案. 详细讨论了在Windows 98和Windows XP下通过关中断的方法来保证脉冲序列时序的精度和稳定性，通过实验给出了基于PC机的脉冲序列发生器的短期稳定度和长期稳定度，最后通过自旋回波实验直接验证了该方案的可行性.     

A New Approach of Two-Dimensional the NMR Relaxation Measurement in Flowing Fluid

Driven-equilibrium fast saturation recovery (DEFSR), as a new method for two-dimensional (2-D) nuclear magnetic resonance (NMR) relaxation measurement based on pulse sequence in flowing fluid, is proposed. The two-dimensional functional relationship between the ratio of transverse relaxation time to longitudinal relaxation time of fluid (T ₁/T ₂) and T ₁ distribution is obtained by means of DEFSR with only two one-dimensional measurements. The rapid measurement of relaxation characteristics for flowing fluid is achieved. A set of the down-hole NMR fluid analysis system is independently designed and developed for the fluid measurement. The accuracy and practicability of DEFSR are demonstrated.     

多维核磁共振波谱学

核磁共振波谱学自本世纪40年代中期诞生起,已走完了其光辉的50年历程,其间,它已完成了自连续波检测向脉冲傅里叶变换检测的过渡,并在此基础上率先将传统的一维谱的观测拓宽为多维谱的观测,不断提供了其它方法难以提供或无法提供的崭新信息,从而确立了它在分子结构和动力学研究中的独特地位,本文旨在以二维NMR为主,简述被称为现代核磁共振波谱学之核心的多维NMK的概况。     

Enhancement of SQUID-detected NMR signals with hyperpolarized liquid 129Xe in a 1 microT magnetic field

We report an enhancement of proton NMR signals by a factor of 10(6) by cross polarization with hyperpolarized liquid 129Xe in an ultralow magnetic field of 1 microT. The NMR signals from cyclopentane, acetone, and methanol are detected using a commercial high-T(c) SQUID magnetometer with a signal-to-noise ratio of up to 1000 from a single 90 degrees tipping pulse. This technique allows a wide range of low-field NMR measurements and is promising for the detection of intermolecular scalar spin-spin couplings. Scalar intermolecular couplings can produce a shift of the average NMR frequency in a hyperpolarized sample even in the presence of rapid chemical exchange.     

2D NMR技术在石油测井中的应用

近几年,2D NMR技术得到迅速发展,特别是在核磁共振测井领域. 该文将主要介绍2D NMR技术的脉冲序列、弛豫原理以及2D NMR技术在石油测井中应用. 2D NMR技术是在梯度场的作用下,利用一系列回波时间间隔不同的CPMG脉冲进行测量,利用二维的数学反演得到2D NMR. 2D NMR技术可以直接测量自扩散系数、弛豫时间、原油粘度、含油饱和度、可动水饱和度、孔隙度、渗透率等地层流体性质和岩石物性参数. 从2D NMR谱上,可以直观的区分油、气、水,判断储层润湿性,确定内部磁场梯度等. 2D NMR技术为识别流体类型提供了新方法.     

Sensitivity and resolution enhancement in solid-state NMR spectroscopy of bicelles

Magnetically aligned bicelles are becoming attractive model membranes to investigate the structure, dynamics, geometry, and interaction of membrane-associated peptides and proteins using solution- and solid-state NMR experiments. Recent studies have shown that bicelles are more suitable than mechanically aligned bilayers for multidimensional solid-state NMR experiments. In this work, we describe experimental aspects of the natural abundance (13)C and (14)N NMR spectroscopy of DMPC/DHPC bicelles. In particular, approaches to enhance the sensitivity and resolution and to quantify radio-frequency heating effects are presented. Sensitivity of (13)C detection using single pulse excitation, conventional cross-polarization (CP), ramp-CP, and NOE techniques are compared. Our results suggest that the proton decoupling efficiency of the FLOPSY pulse sequence is better than that of continuous wave decoupling, TPPM, SPINAL, and WALTZ sequences. A simple method of monitoring the water proton chemical shift is demonstrated for the measurement of sample temperature and calibration of the radio-frequency-induced heating in the sample. The possibility of using (14)N experiments on bicelles is also discussed.