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Diffusion NMR of Confined Systems
Fluid Transport in Porous Solids and Heterogeneous Materials
Published on 12 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782623779-FP001
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New Developments in NMR
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Diffusion NMR of Confined

Systems
Fluid Transport in Porous Solids and

Heterogeneous Materials
Edited by
Rustem Valiullin
Leipzig University, Leipzig, Germany
Email: valiullin@uni-leipzig.de
Published on 12 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782623779-FP001 View Online
New Developments in NMR No. 9
Print ISBN: 978-1-78262-190-4

PDF eISBN: 978-1-78262-377-9
EPUB eISBN: 978-1-78262-970-2
ISSN: 2044-253X
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r The Royal Society of Chemistry 2017
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Preface
As reflected in its title ‘‘Diffusion NMR of confined systems’’, this book

addresses phenomena at the intersection of three very broad research areas.
These are diffusion, an essentially ubiquitous process in nature, nuclear
magnetic resonance, one of the most versatile experimental techniques, and
confined systems, exhibiting a particular wealth of dynamic and thermo-
dynamic behaviors. Special focus is put on fluids, gases and liquids, con-
fined to holes and voids created in solid materials. Although the content of
most chapters is indeed concerned with the transport of simple molecular
species in porous solids, the basic physical principles dealt with have a much
broader impact and may be deployed in related research areas. To illustrate
this, the collection also contains several chapters demonstrating the impact
achieved by combining the methodology developed in diffusion NMR for
porous media research with more complex systems.
Within such an attractive field of research it does not come as a surprise
that many of the covered aspects have already been addressed in the
literature and, in particular, several textbooks. But there remains a strong
need for a comprehensive presentation. The present book project was,
correspondingly, scheduled to demonstrate the impressive progress in the
field over the last few decades both in methodological development and in
broadening the scope of applications. Indeed, the collection of chapters
included shows the truly multidisciplinary character of the field as seen from
various perspectives. From the point of view of fundamental science, syn-
ergistic contributions from physicists and chemists were prerequisite for
deepening our understanding of fluid behavior under confinement.
Advances in the methodology were driven by the diversity of applications
ranging from the exploration of oil-bearing shales to the human brain
to water migration in plant cells and to energy storage by zeolites.

Diffusion NMR of Confined Systems: Fluid Transport in Porous Solids and
Edited by Rustem Valiullin
Published by the Royal Society of Chemistry, www.rsc.org
v
View Online
vi Preface
The intention of this book was, therefore, two-fold—to report the recent
advances and to enlighten the diversification and broadening of the fields of
application.
The chapters included in this book were written by experts in the different
sub-fields of NMR and porous media research, both from academia and
industry. They represent, therefore, a balanced selection between funda-
mentals and applications. All fundamental phenomena discussed are
contained in several chapters with increasing complexity, making it thus
especially useful for undergraduate and postgraduate studies. At the same
time, the collection of chapters presents the state-of-art, reporting on the
forefront of active research and indicating the perspective areas for future
research. Thus, it will also be useful as a reference book for active scientists.
I would like to mention that the preparation of this book was inspired
by the success of the ongoing Bologna Conference series on Magnetic
Resonance in Porous Media. For many years it has provided and continues to
provide an excellent framework for promoting this area of research, for
exchanging ideas, and for attracting and supporting talented students.
I am very thankful to the Royal Society of Chemistry and its editors for
proposing us to edit this book within the series ‘‘New Developments in
NMR’’ and to coordinate the editorial work from Leipzig. In fact, Leipzig has
very intimate links with most of the phenomena discussed throughout this
book. Thus, being famous for its publishing industry, it is no surprise that
the breakthrough papers on diffusion from Fick, Einstein, and Knudsen first
appeared in the Annalen der Physik (und Chemie) published in Leipzig. The
development of the ideas of nuclear magnetism by Felix Bloch started, in
some way, at the University of Leipzig during his doctorate with Werner
Heisenberg and continued and developed to a vibrant research landscape of
NMR across many disciplines. It comes therefore as a fortunate coincidence
that this book is published on the same year with the establishment of the
Felix Bloch Institute at the University of Leipzig, memorizing his contri-
butions to physics in general, and to NMR, in particular.
Rustem Valiullin
Leipzig, Germany
Contents
Chapter 1 NMR under Confinement: Roots in Retrospect 1

Robert J. S. Brown, Paola Fantazzini, Jörg Kärger and
Rainer Kimmich
References 12
Chapter 2 Fundamentals of Diffusion Measurements

using NMR 16
Scott A. Willis, Tim Stait-Gardner, Allan M. Torres and
William S. Price
2.1 What is Diffusion? 16

2.1.1 Self-diffusion, Mutual Diffusion, Flow and
Dispersion 16
2.1.2 Free and Restricted Diffusion 18
2.1.3 Diffusion in General Porous Media 28
2.2 How to Measure Diffusion using Magnetic
Resonance 30
2.2.1 Radiofrequency Pulses and Gradients 30
2.2.2 Pulsed Gradient Diffusion Sequences 32
2.2.3 The Torrey-Bloch Equations and Application
to the PGSE Sequence 33
2.2.4 Anisotropic Systems with Uniform
Orientation 35
2.2.5 Anisotropic Systems with Powder
Distributions 38

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viii Contents
2.3 Experimental Measurements 40

2.3.1 An ‘Ideal PGSE’ Experiment and Analysis 40
2.3.2 Optimising PGSE Experiments 41
2.3.3 Real Experiments, Complications and
Solutions 44
References 46
Chapter 3 From the Microstructure to Diffusion NMR, and Back 52

Denis S. Grebenkov
3.1 Introduction 52
3.2 Mathematical Background 53
3.2.1 Bloch–Torrey Equation 53
3.3 Boundary Conditions 55
3.4 Diffusion-weighting Magnetic Field 58
3.5 Characteristic Scales 62
3.6 Solutions of the Bloch–Torrey Equation 64
3.7 Theoretical Approaches 66
3.7.1 Narrow-pulse Approximation 66
3.7.2 Gaussian Phase Approximation 70
3.8 Diffusion in Multi-compartmental Tissue 79
3.8.1 Multi-exponential and Distributed Signals 80
3.8.2 Bi-exponential Model 81
3.8.3 Kärger Model 84
3.8.4 Anomalous Diffusion Models 86
3.8.5 Effective Medium Theory 87
3.9 Towards Microscopic Geometric Models 88
3.10 Towards High Gradients 89
3.11 Conclusions and Perspectives 94
References 96
Chapter 4 Two-dimensional NMR of Diffusion and Relaxation 111

Yi-Qiao Song, Lalitha Venkataramanan, Ravinath Kausik
and Nick Heaton
4.1 Introduction 111

4.2 Basic Pulse Sequence Building Blocks and
Experiments 112
4.2.1 Relaxation Correlation Experiments 114
4.2.2 Diffusion–Relaxation Correlation
Experiments 115
4.2.3 Correlation Experiments in Static Field
Gradients 116
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Contents ix
4.2.4Correlation Experiments in RF Field

Gradients 116
4.2.5 Mixed Diffusion and Relaxation
Experiment 117
4.2.6 Diffusion Time Correlation Experiment 117

4.2.7 Diffusion Anisotropy Correlation 120
4.2.8 DDIF-CPMG 120
4.2.9 Fast Acquisition of 2D NMR 121
4.2.10 Summary 122
4.3 Diffusion Dynamics in Porous Media 122
4.3.1 Theory 122
4.3.2 NMR Experiments 123
4.4 Laplace Inversion 125
4.4.1 General Theory 126
4.4.2 Data Compression 126
4.4.3 Mellin Transform 128
4.4.4 Max Entropy Method 130
4.4.5 Monte Carlo Inversion 133
4.4.6 Time-domain Analysis 135
4.4.7 Summary 136
4.5 Applications 136
4.5.1 Well-logging 136
4.5.2 Water Saturation 136
4.5.3 Drilling Fluid Invasion 138
4.5.4 Oil Composition Measurement 139
4.5.5 Surface Relaxivity 139
4.5.6 Diffusion Correlation 141
4.5.7 Pore Structure 141
4.5.8 Nanoporous Shales 143
4.5.9 Biological Materials 145
4.5.10 Food Materials 146
4.5.11 Cement and Other Materials 146
4.5.12 Environmental Sciences 147
4.6 Instrumentation 147
4.7 Summary 148
References 148
Chapter 5 Transport in Structured Media: Multidimensional

PFG-NMR Applied to Diffusion and Flow Processes 156
Siegfried Stapf
5.1 Introduction: Diffusion vs. Transport 156

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x Contents
5.2 Theoretical Background 158

5.2.1 Encoding of Transport Properties 158
5.2.2 Two- and Higher-dimensional Sequences 161
5.3 Examples for Flow and Correlations in
Displacements 164
5.3.1 Velocity EXchange SpectroscopY (VEXSY) 164
5.3.2 Diffusion EXchange SpectroscopY (DEXSY) 167
5.3.3 Two- and Three-dimensional Propagators 170
5.3.4 Local Anisotropy of Diffusion 179
5.4 Velocity Encoding and Imaging: Recent
Developments 181
5.5 Summary 190
References 190
Chapter 6 Real Time PGSE NMR Through Direct Acquisition of

Averaged Propagators in the Time Domain Using Pulsed
Second Order Magnetic Fields 194
Wilfred Kittler, Sergei Obruchkov, Mark Hunter and
Petrik Galvosas

6.1.1 General Background 194
6.1.2 PGSE NMR for Diffusion and Flow 196
6.2 Time Domain Signal as the Averaged Propagator 197
6.2.1 The Conventional PGSE Experiment 197
6.2.2 The PGSE Experiment using Second Order
Magnetic Fields 199
6.3 Applications 208
6.3.1 Real Time Propagator Measurements 208
6.3.2 Single-shot Surface-to-volume Ratios for
Porous Materials 215
6.4 Conclusions 220
References 221
Chapter 7 NMR Methods for Studying Microscopic Diffusion

Anisotropy 226
Daniel Topgaard

7.2 Tensors 228
7.2.1 Tensor Size and Shape 229
7.2.2 Tensors with Axial Symmetry 231
7.2.3 Alternative Measures of Tensor Anisotropy 232
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Contents xi
7.3 Ensembles of Diffusion Tensors 233

7.3.1 Diffusion Tensor Distributions 233
7.3.2 Size and Shape Distributions 234
7.3.3 Means and Variances 234
7.3.4 Orientation Distributions and

Order Tensors 235
7.3.5 Ensemble-averaged Diffusion Tensor 237
7.4 NMR Methods and Application Examples 238
7.4.1 Diffusion Encoding with Magnetic Field
Gradients 238
7.4.2 Method Classification Based on the Shape
of the b-Tensor 239
7.4.3 General Principles for Designing
Measurement Protocols 242
7.4.4 Signal from Powders 242
7.4.5 Powder-averaging of the Signal 245
7.4.6 Detecting Microscopic Diffusion
Anisotropy 246
7.4.7 Cumulant Expansion of the Signal 247
7.4.8 Variance of Isotropic Diffusivities and
Mean-square Anisotropy from the 2nd
Moment 248
7.4.9 Model-free Estimation of the 2nd Moment 249
7.4.10 Mapping the Variance of Isotropic
Diffusivities and Mean-square Anisotropy 250
7.4.11 Mapping Microscopic Diffusion Tensors
and Orientational Order Tensors 251
7.4.12 Microscopic Anisotropy Parameters for
Clinical MRI 251
7.4.13 Removing the Need for Powder Averaging:
The Covariance Tensor 253
7.4.14 2D Size-shape Diffusion Tensor
Distribution 253
7.5 Conclusions 255
Acknowledgements 255
References 255
Chapter 8 Beyond the Limits of Conventional Pulsed Gradient Spin

Echo (PGSE) Diffusometry: Generalization of the
Magnetization-grating Principle 260
Ioan Ardelean and Rainer Kimmich

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xii Contents
8.2 Diffusometry using the B0 Gradients of the Fringe

Field of Magnets 262
8.2.1 Formalism for the Fringe-field SGSE
Technique 264
8.2.2 Determination of the Size of Polymeric

Capsules with the Aid of the Fringe-field
SGSE Technique 269
8.3 Diffusometry using B1 Gradients 271
8.3.1 Stimulated Rotary Spin Echo 271
8.3.2 Nutation Spin Echo 275
8.3.3 MAGROFI 277
8.3.4 Applications of Rotating-frame Techniques
for Diffusion Studies 280
8.4 Laboratory-frame Diffusometry Based on Non-linear
(or ‘‘multiple’’) Stimulated Echoes 283
8.4.1 The Demagnetizing Field 284
8.4.2 Formation of Non-linear Stimulated Echoes
and Evaluation of Diffusion Coefficients 285
8.5 Conclusions 289
References 292
Chapter 9 Probing Exchange and Diffusion in Confined Systems

by 129Xe NMR Spectroscopy 294
Julia Hollenbach, Ben Anger and Jörg Matysik
9.1 Introduction to the Use of 129Xe NMR to Investigate

the Structure and Transport Phenomena in
Confined Systems 294
9.2 Theoretical Background and Hardware 296
9.2.1 Factors Influencing the Chemical Shift
of 129Xe 296
9.2.2 The Spin Exchange Optical Pumping
Method 299
9.2.3 Hardware Aspects 301
9.3 NMR Experiments and their Application 305
9.3.1 EXSY-experiments 306
9.3.2 The Hyperpolarized Tracer Exchange
Experiment 311
9.3.3 The HyperCEST Approach 313
9.4 Summary 314
References 314
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Contents xiii
Chapter 10 Diffusive Dynamics in Porous Materials as Probed by

NMR Relaxation-based Techniques 318
J.-P. Korb

10.2 Limiting Nuclear Magnetic Relaxation Processes of
a Liquid in Pores 320
10.3 Nuclear Magnetic Relaxation Dispersion of
Longitudinal Relaxation Rate in Calibrated
Micropores 323
10.3.1 Theory 323
10.3.2 Application to Aprotic Liquids 327
10.3.3 Application to Protic (Water) Liquid 328
10.4 Continuous Multi-scales NMR Relaxation
Investigation of Microstructure Evolution of
Cement-based Materials 330
10.5 Direct Probing of the Nano-wettability of
Plaster Pastes 335
10.6 Dynamical Surface Affinity of Diphasic Liquids as a
Probe of Wettability of Multimodal Macroporous
Petroleum Rocks 341
10.7 Dynamics and Wettability of Oil and Water in the
Dual Organic and Mineral Porosity of Shales Oils 345
10.7.1 Samples 345
10.7.2 Methods 345
10.7.3 Interpretation of the Nuclear Magnetic
Relaxation Dispersion Data 347
10.8 Conclusion 350
References 350
Chapter 11 Industrial Applications of Magnetic Resonance Diffusion

and Relaxation Time Measurements 353
Jonathan Mitchell

11.2 NMR Petrophysics 355
11.2.1 Magnetic Resonance Well Logging 355
11.2.2 Laboratory Core Analysis 357
11.2.3 Relaxation Time Distributions 358
11.2.4 Diffusion as a Contrast Mechanism 359
11.2.5 Internal Gradients 362
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xiv Contents
11.3 Rock Lithology 364

11.3.1 Sandstone 364
11.3.2 Carbonates 366
11.3.3 Unconventionals 368
11.4 Advanced NMR Petrophysics 371

11.4.1 Wettability 371
11.4.2 Capillary Pressure 373
11.4.3 Hydrodynamics 374
11.4.4 Oil Recovery 377
11.5 Applications in Other Industries 381
11.6 Summary 383
References 384
Chapter 12 Confined Fluids: NMR Perspectives on Confinements and

on Fluid Dynamics 390
Rustem Valiullin and Jörg Kärger

12.2 Basic Properties of Confined Fluids 391
12.2.1 Phase State 391
12.2.2 Diffusion Mechanisms 393
12.2.3 Trajectory Analysis for Multi-phase
Systems 395
12.2.4 Restricted Diffusion 398
12.2.5 Potentials of NMR for Delivering
Complementary Information 399
12.3 Structural Information Accessible by Diffusion
NMR 401
12.3.1 Tortuosity of the Pore Space 401
12.3.2 Surface-to-volume Ratio 404
12.3.3 Pore Size in Closed and Interconnected
Pore Systems 408
12.3.4 Pore Space Anisotropy 412
12.3.5 Hierarchical Pore Spaces 413
12.3.6 Pore Space Organization 418
12.4 Fluid Behavior in Confined Spaces 419
12.4.1 Surface Diffusion 419
12.4.2 Global Equilibration Dynamics 422
12.4.3 Memory Effects in Confined Fluids 424
12.4.4 Ergodicity Theorem for Diffusion 426
12.5 Conclusions and Perspectives 428
References 428
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Contents xv
Chapter 13 NMR and Complementary Approaches to Establishing

Structure–Transport Relationships in Disordered Porous
Solids 435
Sean Patrick Rigby

13.2 Surface Diffusion 437
13.2.1 NMR Studies of Surface Diffusion 437
13.2.2 Structure–Transport Model for Surface
Diffusion Validated by NMR 438
13.3 Pore Diffusion 448
13.4 Structural Characterization and its Validation 448
13.4.1 Gas Sorption 448
13.4.2 Pore–Pore Co-operation Effects 451
13.4.3 Cryoporometry 452
13.4.4 Application of NMR Diffusometry to
Improving Structural Characterization 452
13.5 Conclusion 462
References 462
Chapter 14 NMR Diffusometry for the Study of Energy-related Soft

Materials 464
L. A. Madsen and J. Hou
14.1 Introduction to Energy-related Soft Materials 464

14.1.1 Soft Materials: Polymers, Ionic Liquids,
Plastic Crystals, Liquid Crystals, Gels 465
14.1.2 Morphology vs. Molecular Features that
Influence Transport 468
14.2 How Can NMR Diffusometry Help Us Understand
Soft Materials? 469
14.2.1 Overview: Chemical Selectivity and
Tunable Translational Time/Length Scale 469
14.2.2 Signal Analysis: SGP and GPD
Approximations 471
14.2.3 Restricted Diffusion in Polymer
Membranes 473
14.2.4 Activation Energy: A Window into
Molecular Motion on B1 nm Scales 474
14.3 Key Challenges and Experimental Aspects in
Nanostructured Soft Materials 476
14.3.1 Lower Length-scale Limit, Short T2, and
Signal Loss 476
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xvi Contents
14.3.2 Artifacts When Using High Gradients to

Observe Slow Diffusing Species 477
14.3.3 Pre-averaging over Small Length Scale
Heterogeneity 480
14.3.4 Fruitful Combinations of NMR

Techniques: Multimodal NMR 481
14.4 Key Applications in Energy-related Soft
Materials 482
14.4.1 Nanostructured Ionic Polymer
Membranes: Nanochannel Alignment
and Diffusion Anisotropy 482
14.4.2 Ionic Liquids Inside Nanostructured
Polymers: Ion Associations 486
14.4.3 Organic Ionic Plastic Crystals 488
14.4.4 Ion Motions in Polymer-gel Battery
Electrolytes 490
14.5 Conclusion and Outlook 493
References 494
Chapter 15 Diffusion Magnetic Resonance Imaging in

Brain Tissue 497
Farida Grinberg, Ezequiel Farrher and N. Jon Shah

15.1.1 Diffusion Basics 498
15.1.2 How are dMRI Experiments
Performed? 500
15.2 Water Diffusion in Brain Tissue 503
15.2.1 Complex Brain Microstructure and the
Apparent Diffusion Coefficient 503
15.2.2 Diffusion Tensor Imaging 507
15.2.3 Non-Gaussian Diffusion 510
15.3 Selected Applications of dMRI 513
15.3.1 Diffusion Contrast in Ischemic Stroke 513
15.3.2 Diffusion Changes in Development and
Aging 515
15.3.3 Fibre Tractography and Human
Connectomics 517
15.4 Conclusions 519
References 520
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Contents xvii
Chapter 16 Surface Effect Dominates Water Diffusion at Nanoscopic

Length Scales 529
Brendan W. Allison, John M. Franck, Chi-Yuan Cheng and
Songi Han

1
16.2 H ODNP Theory and Analysis of Local Water
Diffusivity 535
16.2.1 Moving from x to Dbulk/Dlocal 535
16.2.2 Experimentally Determining x 537
16.3 Results: ODNP Case Studies 538
16.3.1 Translational Diffusivity of LUV Surface
Water and Its Activation Energy 538
16.3.2 Decoupling of Surface Water Dynamics on
LUV from Bulk Solvent Viscosity 542
16.3.3 LUV Bilayer-internal Water Diffusion and
Its Activation Energy 546
16.3.4 Lipid Membrane Integrity Relies on Stable
Hydration Shell 551
16.3.5 Effect of Confinement in a Biological
GroEL/GroES Chaperone on Water 554
16.3.6 Heterogeneous Water Dynamics within
Nafions Inner Membranes 556
16.4 Conclusion 563
References 563
Subject Index 568

Published on 12 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782623779-FP007 View Online
Published on 12 December 2016 on http://pubs.rsc.org | doi:10.1039/9781782623779-00001
CHAPTER 1
NMR under Confinement:

Roots in Retrospect
ROBERT J. S. BROWN,a PAOLA FANTAZZINI,a
JÖRG KÄRGER*b AND RAINER KIMMICH*c
a
University of Bologna, Department of Physics and Astronomy, Viale Berti
Pichat 6/2, Bologna, Italy; b University of Leipzig, Faculty of Physics and
Earth Sciences, Linnestr. 5, 04103 Leipzig, Germany; c University of Ulm,
89069 Ulm, Germany
*Email: kaerger@physik.uni-leipzig.de; rainer.kimmich@uni-ulm.de
Nuclear magnetic resonance (NMR) has provided us with many beneficial

opportunities for science and technology. Its continued use in novel fields
has yielded impressive strength and attractiveness for nearly a century. This
is particularly true with regards to the topic of this book, the exploration of
‘‘Fluid Transport in Porous Solids and Heterogeneous Materials’’.
Here, the benefit of NMR in being able to look ‘‘from the outside’’ into
a system becomes particularly evident. NMR operates as an ‘‘ideal spy’’,
providing information without interfering with internally occurring phe-
nomena. NMR is able to give information on pore spaces as well as anything
that might happen within them. This wide-range of information that is
accessible is illustrated by the examples in this book. The origin of some
of these developments can, most remarkably, be traced back over many
decades, to the very beginning of NMR research. In this chapter we will
recollect some of the roots of the challenges we face today with applying
NMR to studying ‘‘Fluid Transport in Porous Solids and Heterogeneous
Materials’’—albeit with some bias by personal experiences and impressions.

1
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2 Chapter 1
The output of nuclear magnetic relaxation on pore space architecture and

guest dynamics in porous materials is, generally, based on model assump-
tions. These assumptions are, as a rule, well established and supported by
experimental evidence. In its early years, however, NMR was used for
studying molecular diffusion. The information gained stands on its own.

Hahn’s seminal paper in 19501 provided us with an opportunity that, in
subsequent years, has been extensively exploited for diffusion measure-
ments with liquids.2 With the application of pulsed field gradients by
Stejskal and Tanner,3 the gradient intensity could be chosen large enough so
that, eventually, diffusion measurements with porous materials have be-
come possible. In his seminal paper of 19654 John Tanner introduced
the technique under the title ‘‘Pulsed Field Gradients for NMR Spin-Echo
Diffusion Measurements’’. Since then, the method has found application in
quite a number of different communities. Its widespread use might have
contributed to a diversification in nomenclature, with currently two names
in common use: pulsed field gradient (PFG)5–9 and pulsed gradient spin
echo (PGSE)10–12 NMR. In either case, Tanner’s original wording is easily
recognized.
The development of NMR was, essentially from its very beginning, closely
related with the search for its application to petrophysical studies. The oil
industry became aware of the potential of this novel source of information
and vigorously promoted research on logging projects. The data in Table 1.1,
taken from the paper of Kleinberg and Jackson,13 illustrate this intense and
most rewarding partnership from its beginning until 2000.
In 1948, two years after the discovery of NMR in condensed matter by
Bloch14 and Purcell,15 the thesis of Bloembergen and the classical paper by
Bloembergen, Purcell and Pound (BPP theory16) explained many features of
the relaxation of NMR signals in bulk liquids by interpreting the dependence
of the relaxation times on parameters related to molecular motion, including
temperature, viscosity and distance between spins. A retrospective article by
Bloembergen gives a review of NMR attempts before 1946 and of early work
on relaxation.17 It has also been recognized that fluid molecules can be
adsorbed near a solid surface, resulting in a decrease in their mobility. The
existence and influence of pore walls were later found to appear in the re-
laxation patterns of NMR. The application of the BPP theory to the adsorbed
layers could have caused researchers to think that the relaxation times of
molecules in the adsorbed layers could have been decreased and so de-
creasing the relaxation times of fluids inside the pore space of porous media;
but it seems that nobody had that intuition.
However, the idea was raised to build a device to be lowered inside the
wells to get the signals of oil and water from the porous rock formation
outside the borehole at depths of thousands of meters. Russel Varian had
demonstrated that it was possible to observe NMR by free precession (at
about 2 kHz) in the Earth’s field. Numerous studies about the feasibility of
the application of Nuclear Magnetic resonance for well Logging (NML) by
Varian Associates18–20 followed. In those pioneering researches, the now
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NMR under Confinement: Roots in Retrospect 3

Table 1.1 Timeline of NMR Logging. Reproduced with permission from ref. 13.
Copyright r 2001 John Wiley & Sons, Inc.
1946 Discovery of NMR by Bloch (Standford) and Purcell (Harvard)
1948 Russell Varian files patent for Earth’s-field NMR magnetometer
1950 Spin echo, Hahn (U. Of Illinois)

1952 Russell Varian files patent for Earth’s-field NMR well logging
1953 Nobel Prize in physics awarded to Bloch and Purcell
1954 Carr and Purcell devise spin-echo pulse train
Harold Schwede (Schlumberger) files patent application for permanent
magnet well logging tool
1956 Discovery of reduced fluid relaxation time in porous media by Brown, Fatt
and others
1960 First Earth’s-field NML tool – Chevron Research Lab and collaborators
1960s Laboratory and theoretical studies in various university and petroleum
laboratories of the effect of restricted diffusion of T1 and relationship of
T1 and permeability
1960s Several companies offer NML commercial logging service
NML fails to live up to advance billing; NML gains bad reputation in
petroleum industry
1978 Schlumberger introduces new, improved NML tool
1978 Jackson at Los Alamos, invents first ‘inside-out’ pulsed RF NML logging
technique
1980 Laboratory demonstration of Los Alamos technique
1983 Proof-of-principle demonstration of Los Alamos logging technique at
Houston API test pit
1984 NUMAR formed to commercialize advances in medical NMR technology
Schlumberger begins development of permanent magnet/pulsed NMR
technique
1985 NUMAR obtains license for Los Alamos inside-out NMR patent
1985 NUMLOG demonstrates increased S/N for new magnet/RF scheme in
laboratory scale model
1989 First field test of full scale NUMAR logging tool in Conoco test hole, Ponca
City, OK
1990 NUMAR announces commercial availability of MRIL logging service based
on Series B single frequency tool
1992 Schlumberger starts field test of skid-type pulsed NMR tool
1993 Numar and Western Atlas sign cooperative agreement for MRIL services
1994 NUMAR introduces dual frequency MRIL Series C tool
Western Altas logs MRIL in combination with conventional tools
1995 Schlumberger announces commercial introduction of CMR tool
Peoples Republic of China purchases two logging systems from Western
Altas, including MRIL
1996 NUMAR and Halliburton sign cooperative agreement for MRIL services
1997 Halliburton buys NUMAR
1990s Laboratory and theoretical studies of the effect of restricted diffusion on T2
(most NMR logging data use T2)
2000 NMR logging-while-drilling prototype
widespread use and importance of the NMR single-sided NMR devices,21

that led to the evolution of the concept of compact and mobile devices,22
able to detect NMR signal outside the magnet, outside the laboratory, in a
non-destructive way, regardless of the sample sizes emerged. The key feature
of NML was intended to be the possibility to exploit the different relaxation
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4 Chapter 1
times of bulk oil and water (10 times larger for water than for oil) to dis-
tinguish their signals. Since water and oil have about the same 1H nuclei
density, the fraction of water and oil could have been determined by their
signal ratio and the porosity of the rock formation by the total signal, and all
this at depths of thousands of meters. Three NML research projects started

at that time: Varian with Byron-Jackson, Schlumberger in Ridgefield, and
what is now Chevron; nuclear Magnetic Resonance studies for fluids in
Porous Media (MRPM) also started at Shell and Magnolia (later Mobil) to
understand the properties of fluids in porous media for the purpose of
characterizing reservoir rocks.
When it was found that surface effects shortened water relaxation times to
where water could not be distinguished from oil or even to where it could not
be observed, it appeared that NML might not be very useful. However, it was
soon realized that relaxation times inversely proportional to pore surface
areas gave information on pore size distributions, thereby giving infor-
mation on the permeability of the rock to the flow of pore fluids, even more
important than the original objectives.23–25
In the 1950s many kinds of data were interpreted to suggest thick reduced-
mobility liquid layers of water or other fluids adsorbed on surfaces including
those of rock grains. Field dependent relaxation measurements at Chevron
(from a micro-Tesla to a Tesla) did not support this and even showed that the
postulated ice-like layers in DNA did not exist.26 The enhanced pore fluid
relaxation comes mainly from a single adsorbed liquid layer at the surface.
In the late 1950s it was well understood that the local relaxation times for
fluids were greatly shortened in not much more than one molecular layer at
the solid surface. It was shown23 that if a pore is small enough that diffusion
maintains nuclear magnetization uniform inside the pore, the rate of the
observed relaxation time of the fluid in the pore is 1/T ¼ 1/Tb þ (Vs/V)/(Ts þ t),
where Tb is the relaxation time of the bulk fluid, Vs the volume of the surface
layer, V the pore volume, Ts the relaxation time of the surface layer, and t the
residence time of a molecule in the surface layer. In 1956 Henry Torrey,
Jan Korringa and Bob Brown wrote a U.S. Patent where many of the most
basic features of MRPM were summarized, including relaxation for water
and oils of different viscosity, and their behavior inside porous media at
different temperatures. The first experimental NML was run in 1960 and
limited commercial earth’s-field NML service became available, and useful
applications were found.
The effects of pore sizes and surface properties on relaxation were in-
vestigated at Shell.27,28 Wettability effects had already been noted by Brown
and Fatt.29 Most of the papers used the longitudinal relaxation time T1, but
also the transverse relaxation time T2 started to be studied.30,31
The porosity of a water- or oil-saturated porous material can be deter-
mined from the NMR signal, with proper calibration. Other properties can
be related to T1 or T2 relaxation curves. It was assumed that signal with T1
less than some ‘‘cutoff’’ time was ‘‘irreducible water’’ and that only fluid
with longer relaxation times would be produced. Timur32 found a cutoff time
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of about 12 ms. Studies on the determination of water and oil when both
phases are present in the pore space led also to the proposals of NMR
estimates of the residual oil saturation.33 Permeability estimates from
relaxation data were developed by Seevers34 and by Timur32 and later by
Kenyon et al.35 The coming of MRI contributed to the understanding of oil

industry applications.36
Many porous media have a wide distribution of pore sizes, the distribution
of classes of fluids with a distribution of relaxation times, possibly in dif-
ferent regimes of exchange, can determine a multi-exponential relaxation.
A stochastic theory for the relaxation in heterogeneous systems with many
exchanging water phases was proposed in 1957 by Zimmerman and Brittin.37
It started in an oil industry laboratory, to justify the behavior of T1 and T2 in
water systems adsorbed on silica gel, and had great success in the study of
systems also of biological interest, that for many aspects can be considered
as porous media. An example is given by the study on DNA water reported
by Brown.26 After some examples of sporadic interest for NMR relaxation
in biological systems,38 interest grew significantly with the appearance of
an NMR study on HeLa cells (the first ‘‘immortal’’ human cells grown in
a lab39), and the Damadian paper40 that indicated the possibility to
detect tumors by increased relaxation times for the first time. Let’s not
forget that the papers, posing the basis for Magnetic Resonance Imaging
(MRI), appeared around the same time41,42 with a clear focus on biological
systems.
The two fields of petrophysical and biological studies enjoyed reciprocal
advantages by exchange of experiences, methods, and theories, given by the
MRPM studies. A clear example of this is given by the seminal work of
Brownstein and Tarr43 that gave the interpretation of the multi-exponential
behavior by classical diffusion in the presence of relaxation sinks on the
confining surfaces, without the need of the assumption of different water
phases. Written for cell water, later this theory influenced the interpretation
of multi-exponential relaxation for porous media of any nature, including
rocks.44 In any case, it became clear that the observed multi-exponential
relaxation, giving rise to distributions of relaxation times strongly depended
on the diffusion regimes in the complex network of the pore space. In a real
porous medium, with the same surface properties, in the case of a fast dif-
fusion regime, one would observe a single exponential decay only if the
diffusion is fast enough inside each pore and among the pores to make
the magnetization uniform inside the whole pore space, or, of course if the
diffusion is fast and the pores are all the same. However, if the diffusion is
fast inside each pore, but slow among pores, the relaxation will be multi-
exponential.45,46 Algorithms have been developed to invert multi-exponential
curves to distributions of relaxation times.47 An algorithm was proposed
with a smoothing coefficient varying along the relaxation time distribution,
in order to maintain uniform the penalty.48
Over time these methods have been exploited to study the pore size dis-
tributions of porous media of different nature and for different applications.
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6 Chapter 1
Simple methods to separate solid and liquid components on the free in-
duction decay, combined with quasi-continuous analysis of the two data
sets, have been exploited to follow the kinetics of Portlandite and liquid
component formation in hydrate cements.49 In coral skeletons, the pore-
sizes can be analyzed, with a single NMR measurement, at multiple length

scales. The effect of increasing acidity on increasing the macro-scale por-
osity, whilst the linear extension rate remained the same, revealed the ac-
climation of the corals in a warming acidifying ocean.50
Later, algorithms were developed for two-dimensional (2D) inversion
of experimental 2D data,51 in order to obtain Relaxation–Relaxation
and Diffusion–Relaxation correlation functions or pore-to-pore exchange
parameters (for more details see Chapter 4).52–54 It is clear that caution is
needed to interpret multi-exponential relaxation in terms of pore-size
distributions, especially for T2, for water subjected to diffusion inside field
gradients. Not only large scale gradients can be present, but also internal
gradients inside the pore due to the susceptibility difference between water
and the solid material. For water diffusing inside a constant gradient, for
unrestricted diffusion, the dependence of 1/T2 on the half-echo time in a
CPMG sequence is expected to be quadratic.55 In many porous media it was
found to be linear instead of quadratic, and this was interpreted as due to a
distribution of correlation times for molecular diffusion.56
Shortly after, NMR with pulsed field gradients enabled diffusion meas-
urements of water in zeolites,57 probably the most important representative
of ‘‘microporous’’ materials.58 Pore sizes of such substances are known to be
of molecular dimensions. Transverse nuclear magnetic relaxation times of
guest molecules in such host materials are generally very small so that, as a
rule, NMR diffusion studies necessitate the use of ‘‘pulsed’’ field gradients.
As a most astonishing outcome of these studies, water diffusion in zeolites
was found to be only slightly exceeded by that in the neat liquid.
This puzzling result gave rise to an in-depth study of molecular diffusion
in zeolites in the very place where Felix Bloch was working as the first PhD
student of Werner Heisenberg. Owing to the activities of Artur Lösche and
Harry Pfeifer and their groups,59 Leipzig was now on the way to becoming a
place which Richard Ernst, during a talk in Leipzig in 1992, referred to as
the ‘‘East Pole of Magnetic Resonance’’.60 Benefitting from being part of the
Eastern hemisphere, researchers in Leipzig had access to probably the
largest zeolite crystals available at this time, synthesized in the famous la-
boratory of Sergey Petrovitch Zhdanov in Leningrad. In this way, by a pur-
poseful variation of the diffusion path lengths in relation to the crystal sizes,
the high diffusivities reported in ref. 57 could be attributed to ‘‘long-range’’
diffusion, i.e. to mass transfer in free space between the individual zeolite
crystallites. Water diffusivities in the micropores, however, was determined
to be notably smaller, in complete agreement with the expected behavior.61
The application of diffusion NMR to beds of zeolite crystals gave rise to the
development of two concepts of data analysis,62 which have become part of
the general tool box of NMR, namely the formalism of two-range
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63,64
diffusion for taking account of mass exchange between different com-
partments65 such as biological cells66 and the introduction of the ‘‘mean’’
propagator.67
The diffusion of guest molecules in zeolites was (so far) mainly based on
the measurement of transient uptake and release curves initiated by a

pressure step in the surrounding atmosphere. Diffusivities were determined
with the understanding that these phenomena were controlled by the guest
diffusivity within the zeolite pore space. It came as a great surprise, there-
fore, when in many cases the intracrystalline diffusivities—now directly
measured owing to the potentials of NMR—proved to exceed the so far
generally accepted values by several orders of magnitude.68 As the only so-
lution of the problem, mass transfer in such crystals had to be required to be
controlled by additional transport resistances on the external crystal surface
or in intracrystalline space rather than by exclusively the diffusional resist-
ance of the genuine pore space as so far generally implied.69 NMR diffusion
studies did thus provide evidence of these barriers long before they became
an object of high-resolution electron microscopy70 and initiated a paradigm
shift in the understanding of mass transfer in nanoporous materials.71
In a sense, the invention of MRI brought about a revolution of thinking in
the NMR community. Being used to associate spatial resolution with phe-
nomena like optical holography or scattering of particles or electromagnetic
waves, the pioneers in the field soon realized striking analogies. In par-
ticular, the signal patterns recorded with the standard MRI technique,
i.e. ‘‘spin-warp imaging’’,72 were identified as representations in reciprocal-
space just as known with optical holograms. That is, real-space images can
be rendered by two- (or three-) dimensional Fourier transformations of the
NMR signal intensities as functions of the respective wave-vector com-
ponents. Reciprocal-space variables (wavenumbers) are converted in this way
to conjugate real-space coordinates.
This analogy can be extended to diffusion NMR. It was mainly Paul
Callaghan and his group who put this idea forward.73 Again, a real-space/
reciprocal-space notion was employed. The spin-echo attenuation function
due to translational diffusion is actually the Fourier conjugate to the real-
space distribution of molecular displacements, where one is normally
dealing with Gauss functions for both space-representations. By definition,
the reciprocal-space variable, the ‘wavenumber’, is determined by the
strength and duration of the effective field gradient pulse acting on the
evolution of the precessing transverse magnetization.
As a matter of course, the effect of field gradients in MRI or NMR diffu-
sometry experiments has little to do with travelling electromagnetic or
matter ‘waves’. One is therefore tempted to discount the analogy as some-
thing entirely formal. However, the resemblance between real wave scenarios
and magnetization-evolution effects in the presence of field-gradient goes
much further. The wavelength defining the wavenumber turns up again as
the pitch of the so-called helix of the spatial distribution of transverse
magnetization after a gradient pulse. In the stimulated-echo variant of NMR
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8 Chapter 1
74,75
diffusometry, this helix is temporarily and partially converted to a si-
nusoidal modulation of the longitudinal magnetization along the gradient
axis with just the ‘wavelength’ attributed to the relevant wavenumber.
There is even more to it than that. The phenomena most characteristic for
waves are scattering and diffraction. As shown in ref. 76, there is a formal
coincidence of the diffusive echo-attenuation function with the incoherent
dynamic structure factor defined for scattering experiments. That is, field-
gradient NMR diffusometry extends the accessible wavenumber range of
quasi-elastic neutron scattering, for instance. Entirely distinct techniques for
studies of molecular dynamics can thus be combined in a most favorable
way as extensively outlined in ref. 77.
The second and most striking finding in this context is that diffraction
patterns can be observed in diffusion experiments. Callaghan et al.78 dem-
onstrated that exactly the same intensity patterns as in optical diffraction
experiments appear for echo attenuation when the field-gradient induced
‘wavelength’ matches structural lengths of a confining matrix such as a
porous medium. The relevant length scale is usually in the order of a
few micrometers. Striking applications of this kind of ‘NMR diffusion
diffraction’ to aqueous erythrocyte suspensions have been reported by
Kuchel et al.79
In terms of wavenumbers, the determination of very low diffusion co-
efficients with field-gradient techniques requires as large values as possible.
An optimal efficiency in this respect can be achieved by using firstly steady
instead of pulsed gradients, secondly the stimulated-echo variant, and thirdly
the particularly strong and stable gradients of the fringe field of super-
conducting magnets80 (see also Chapter 8). With such a set-up it was even
possible to reach the ultimate physical low-end limit of any field-gradient
NMR diffusometry measurement, namely immaterial spin-diffusion medi-
ated by flip-flop spin transitions. The direct assessment of this limiting spin-
diffusion coefficient was reported in ref. 81 for polymers.
A further result obtained with the fringe-field NMR technique is the
evaluation of the before mentioned incoherent dynamic structure factor for
polymers diffusing in nanoporous matrices. Referring to the well-known
tube/reptation concept,82 it was shown that the echo attenuation function is
non-Gaussian in this case.83 It depends on the pore diameter in a charac-
teristic way. That is, pore diameters have consistently been determined with
the aid of diffusion experiments.84 Remarkably, these results exceed the
diffusion time and wavenumber ranges accessible by quasi-elastic neutron
scattering by far.
Fluid transport through porous media can be mediated by molecular
diffusion, hydrodynamic flow, and—between these two extremes—by
hydrodynamic (or Taylor/Aris) dispersion. The latter contains elements both
of potentially tortuous but coherent flow, and diffusive displacements in a
superimposed manner.85
It has long been predicted that the incoherent part of displacements
should be sub-diffusive if diffusion prevails and super-diffusive in cases
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where tortuous flow dominates in random porous media. The crossover

between such mean square displacement laws deviating from Einstein’s
linear relationship has indeed been observed with the aid of pulsed field-
gradient NMR for the first time.86 Moreover, a rotational analogue of Taylor/
Aris dispersion has been concluded in a field-cycling NMR relaxometry study

of flow along inner surfaces of porous media.87 This suggests a kind of
interfacial slip including intermittent adsorption/desorption hopping cycles
along the pore walls instead of the no-slip boundary condition frequently
anticipated for viscous flow.
Studies of anomalous diffusion, i.e. of the sub- or super-diffusive mean
squared displacement laws for disordered porous media, require experi-
mental access to a time scale as wide as possible. The incoherent dynamic
structure factors determined with the aid of quasi-elastic neutron scattering
on the one hand, and—in the form of echo-attenuation functions—by
steady- or pulsed-field gradient NMR techniques on the other leave a dif-
fusion time gap from about 100 ns to about 100 ms.77 This gap can be
bridged by evaluating the inter-molecular contribution to spin-lattice relax-
ation as detected by field-cycling NMR relaxometry experiments. Inter-
molecular spin-lattice relaxation directly reflects translational diffusion.
It can be distinguished from the intramolecular counterpart by isotopic
dilution. That is in particular by partially replacing proton containing mol-
ecules by perdeuterated species. In combination, an enormous, hitherto
unprecedented range of seven orders of magnitude of the diffusion time
becomes accessible in this way.88,89
As outlined above, a very important information source exploited with
well-logging NMR is based on nuclear magnetic relaxation of the liquids
confined in porous rocks. Porous rock and building materials such as ce-
ment usually contain electron-paramagnetic impurities that can act as effi-
cient relaxation sinks in addition to diamagnetic mechanisms.90 Irrespective
of the relevant spin interactions dominating spin-lattice relaxation, the
strong increase of relaxation rates in pores suggests correlation times longer
by orders of magnitude than in the bulk-liquid state.
The first idea to explain this was that a kind of immobilization takes place
at the pore walls. One even spoke of ‘‘irrotationally bound’’ molecules.
However, quite amazingly it turned out that the translational mobility for
example in hydration layers of adsorbing surfaces is only moderately re-
duced. Geometrical constraints may even be more restrictive than binding
forces. Not unlike the findings for zeolites,62,68 field-gradient NMR studies
reveal that translational diffusion of adsorbate molecules at surfaces is un-
expectedly fast. This was demonstrated for instance in so-called ‘‘non-
freezing’’ surface layers,91 with crystal water in myoglobin single crystals92
and at silica surfaces.93
Before this background, the most intriguing question arose, how could the
retardation of molecular reorientations in porous media by up to eight orders
of magnitude relative to bulk conditions be reconciled with the almost
bulk-like translational diffusivities at short displacement length scales?
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10 Chapter 1
The answer is that adsorbate molecules probe diamagnetic surfaces via

translations from adsorption site to adsorption site. The mechanism is
called bulk mediated surface diffusion (BMSD) and was identified as a kind of
Lévy walk along pore walls.94,95 That is, molecular reorientation at surfaces is
a matter of the topology. The correlation of molecular orientations is

maintained as long as the sites probed by the molecules are correlated with
respect to surface orientations. Thus, reorientation is mediated by transla-
tional displacements along the surface (RMTD process).96
Apart from porous rock, hydrated cement or mortar at its various
processing stages turned out to be one of the media where electron-
paramagnetic ‘‘impurities’’ can act as relaxation sinks (see Chapter 10). This
especially refers to iron ions that are known to be incorporated in the
respective pore walls at random. Again, surface diffusion is an essential
element of the relaxation process. Korb et al.90,97 developed a model of 2D
adsorbate diffusion providing the interaction contacts to the paramagnetic
relaxation centers. Characteristic material properties such as the specific
surface area, for instance, have been determined on this basis. Relaxation-
based findings can be compared with results from field-gradient NMR
diffusion studies referring to much longer time and displacement length
scales.98 In this context, it should also be noted that electron paramagnetic
centers such as nitroxide free radicals can also be incorporated artificially in
otherwise diamagnetic materials for just the purpose to determine local
diffusivities of solvents.99,100
The diffusion studies so far referred to, concern porous media saturated
with liquids. Mainly as a consequence of the geometrical restrictions in the
pore network, the self-diffusion coefficient in the pore network tends to be
reduced relative to the bulk fluid. However, in pores only partially filled with
liquids, a quite puzzling phenomenon arises. The effective diffusivities
measured under these circumstances can exceed the values for bulk liquids
by up to an order of magnitude.101,102 Depending on the vapor pressure, this
is a consequence of the contribution of the vapor phase in the pores. It re-
veals itself in spite of the three orders of magnitude lower density of the
vapor. The diffusion coefficient in the vapor is four orders of magnitude
larger than in the respective liquid phase. Molecular exchange between the
two phases on the time scale of the experiment thus leads to more or less
averaged diffusivities. These are largely determined by the vapor contri-
bution, whereas—notabene—the NMR signal is still dominated by the li-
quid. Whether molecular exchange between the two phases is fast or slow
relative to the diffusion time, that is, how the vapor-diffusion enhancement
effect discloses itself in experiments, was shown to be a question of the
pore size.103,104 Furthermore, and provided the vapor pressure is high en-
ough, vapor-enhanced diffusion along surfaces also contributes to the
RMTD process mentioned above for spin-lattice relaxation as demonstrated
in ref. 105.
A retrospective view on science over the last few decades would be in-
complete without reference to the particular conditions of a world divided
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into two power blocks, and to the beneficial influence of science ensuring
mutual contacts even across the ‘‘iron curtain’’. It was the existence of these
contacts which, eventually, accelerated and facilitated the re-establishment
of unlimited international exchange after the fall of the Berlin Wall. This is
particularly true with the field of MRPM. At the end of the 1980s the number
of groups working on NMR for porous media independently and, as a rule,
by very different routes attained such a level that the time was ripe for a
direct exchange of their experiments and ideas, as stated by the organizers in
the proceedings of the first conference on MRPM.106 In 1988 the idea came
out to organize an international meeting on NMR in porous media. The
meeting took place in 1990, devoted to the progress in magnetic resonance
in porous media and in understanding porous media themselves and on
the behavior of fluids inside. It was also an opportunity to stimulate contacts
among researchers from various parts of academia and industry. The
Bologna meeting was the first of a long series that continues today, as
summarized in the Table 1.2.
The seventh conference was the first one without Giulio Cesare Borgia, the
co-founder and promoter of these conferences, who died unexpectedly in
September 2002. The seventh conference was an important event from the
point of view of the future of the MRPM community and of this conference
series. The growing vitality and interest in these conferences and the con-
sideration that the community, which the conference series served
had grown considerably covering all continents, discussed how the future
of these meetings would be assured; it was decided that the community
would join the Groupement Ampere as the MRPM Division. The conferences,
which are now explicitly called the ‘‘Bologna MRPM Conferences,’’ became
Ampere Events and, in commemoration of the co-founder and promoter,
the ‘‘Giulio Cesare Borgia Award for Young Researchers’’ was established.
Thus, it is by far not incidental to find some of these awardees, notably
Denis S. Grebenkov, Jonathan Mitchell and Rustem Valiullin, among the
contributors to this book.
Table 1.2 Timeline of the International Bologna Conferences on Magnetic Reson-

ance in Porous Media.
MRPM1 1990 University of Bologna, Bologna, Italy
MRPM2 1993 University of Kent, UK
MRPM3 1995 Université Catolique of Louvain-la-Neuve, Belgium
MRPM4 1997 Statoil Research Center, Trondheim, Norway
MRPM6 2002 University of Ulm, Ulm, Germany
MRPM7 2004 Ecole Polytechnique, Palaiseau, France
MRPM9 2008 Schlumberger Research Center, Cambridge, USA
MRPM10 2010 University of Leipzig, Leipzig, Germany
MRPM11 2012 University of Surrey, Guildford, UK
MRPM12 2014 Victorial University of Wellington, Wellington, New Zealand
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de Neve, 141
Nicolaas, 192, 210, 228, 251
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Nieneven, Ninove, 76
Nieske, 132, 133
Nieupoort, 76, 78
Nieuwe-Diep, 63
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Nine, Nynke, 217, 251
Ninove, 73, 76, 78
Nittert, Nidhart, 201
Niukerke, Niwkerka, 116
Nolle, 180
Noord-Beveland, 83
Nordahn, Norda, 122
Nordernei, 88
Nordkerke, 116
Notecraeckers van Orchies, 76
Notgrim, 201
Nye Gerryt, 263
Nynke, Nine, 217, 251
Oaljekoeken van Bolsward, 14, 16, 20
Oanbreide hoasen van Ureterp, 35
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Ocko, Ocke, Okke, 262, 273, 284, 288
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Oebele, 214, 221, 226, 229
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Oene, 212, 230
Oentje, 214
Oentse, 215
Oentsje (Oentje), 215
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Oepkje, 203
Oesinga, Oesingha, 238, 239 [317]
Oeswalt Kokenmester, Koeckenmeester, 268
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Orchies, 76
Ork, 202
Orseltsje, Osseltsje, 282
Os, 67
Osborne, 117
Ose, Osi, 239
Osinga, Osenga, Ozinga, 237, 238, 239, 240, 244
Osinga-hûs, 238
Osinga-huzen, Oessingahuyssen, Oedsyngahuysen, 238

Osinga-state, 238
Ostkerke, 116
Ostraet, 120
Oswin, 134
Otte, 212
Otterfretters van Gaast, 37, 50
Otlinga Saxonica, 110
Otrange, 160
Oude Bildtzijl, 36
Oudemonstre, 118
Oudenaarde, 73, 76, 79
Oudenburgh, 77
Ouderkercke, 116
Ouderwijk, Ouderwick, 114
Oudewater, 66
Oudeweg, 121
Oudewog, Oudewoghe, 120
Oudezele, 114
Ouistreham, 110, 111
Overahn, 122
Overmoedighe van Ronsse, 77, 79
Oye, 119
Pabe, 212
de Pachtere, 140
Paddelanders van Zuid-Beveland, 83
de Paepe, 140
Paesche Backer, 267
Paesche, Paeske, Paschasius, 274
Palingstroopers van Mendonk, 73
Pallington, 129
Panne, 249, 251
de Pannemaecker, 139
Papbuiken van St.-Oeden-Rode, 67
Papenwoge, 120
Pap-eters van Denterghem, 71, 77
Pastei-eters van Kortrijk, Pastey-eters van Curtrycke, 71, 74, 76, 78, 79
de Pauw, 143
Pauwels, 146, 147
Peasens, 34
Peer, 71, 73
Peerdenprossers van St.-Nicolaas, 73
Peeters, 146, 147
Peevreters van Noord-Beveland, 83
Pekelsma, 237, 238, 245

Pelincthun, 103, 129
Pellemans, 193
Pelserstraat, Pelsterstraat, 267
Pelsmakers van Meenen, 71, 81
Pelsnaaien van Ninove, Pelsnaeyers van Nieneven, 76, 78
Peperloock-eters van Eecloo, 77
Pepernoten van Elburg, 60
Peren van Cadzand, 67
Peter Art Peter Meeussoens soen, 177
Peter Casteleyn, 268
Peter Corstken Lemmens dochter, 185
Peter Janz, 258
Peter Kamingh, 261
Peter Kamminga, 257, 260
Peterken, Pietertje, Pietje, Petronella, 185
Peter Lambertz, 258
Petermannen van Leuven, 72
Peter Michiels, 178 [318]
Peter Moelker, 268
Peter Pedelmans, 182, 194
Peter Scutmaker, 269
Peter Stippelmans, 182, 194

Peter Trap, 272
Peter Tyeusker, 268
Peter van den Doseldonck, 181
Peter van Eyndhouts, 182
Peter van Harlingen, 271
Peter Willem Luppensoen van Bakel, 177
Peting, 146
Petrick, Pietrikje, 274
Petrus, 228
Peuplingue, 96
Pezerikken van Loenhout, 72

Pibbe, 210, 217, 218, 250, 251
Pibe, 212, 249, 250, 252
Pickaert, 143, 144
Pier, 147, 228
Pieren van Halle, 73
Pieren van Liezele, 72
Piers, 146, 147
Pieter, Piet, 176
Pieter Cammingha, Pieter Kamminga, 261
Pieters, 146, 147
Pike, 250
Pim, 150, 249, 252
Pingjum, 35, 36, 37
Pinnekenmakers van Arendonk, 72
Pittendal, 117
Plaetevoet, 134
Plasschaert, 144
Platpooten van Purmerland, 63
Platte gesellen van Sleedingen, 81
Plattekèèsboeren van Opdorp, 71, 73

Pletinckx, Plettinckx, 146
Ploegsma, 245
Po, 250
Poai, Poi, 250
Poehoannen van ’t Heerenveen, 37, 54
Poepen, 83
Poepen van Deventer, 59, 85
Poepen van Onderdendam, 56
Poggen van Aurik, 5, 57, 58
Pohlenga, 115
Poi, 217, 218
Pole, 115
Polincove, 114
Pollema, 139, 246
Pomme, 217, 218
Pompsma, 237, 238, 245
de Poorter, 134, 141
Poorters van Brugge, 76, 79
Pootenvreters van Haasrode, 73
Poperingen, Poperynghe, 74, 76, 79, 81
Popke, Popco, 215, 230
Popma, 241
Poppe, Poppo, 212, 230, 241
Poppel, 72
Poppen, 236
Potatenboeren van Esschene, 71, 73
Poteerddabbers van Ramsel, 72
Potestraet, 120
Potigny, 110
Potschijters van Emden, 5, 7, 57
de Potter, 139
Powels Olyslager, 268
Powels Tymmerman, 267
Praamsma, 245
de Praeter, 141
de Prince, 140
Prom-iters, Prommen van Hilaard, 36, 38
de Proost, 140
Pruiksma, 245
Pruimsma, 245
Prunkers van Burhafe, 57
Puieraars van Leiden, 66
Puiers van den Briel, 66
Purmerland, 63
Putoor-eters van Waestene, 77
Puutfangers van Sillensted, 57
de Puydt, 143
Pybe Rogdrager, 266
Pynaert, 144
Pypaert, 144
Pyttsje (Pietje), 218, 250
Quaesaet, 137
Raapkoppen van St.-Anna-Parochie, 36
Rabout heeren Raboutssoen van Vloedorp, 179
Rabout, Radbout, Radbold, Redbald, 189
Radbald, Radbad, Radbod, Rabbod, Rabbold, Radbout, 201
Radcot, 128
Raeckelboom, 134
Raepeters van Waes, 76, 78
de Raeve, 143
Raginwulf, Reinolf, 162
Rakkers van Gouderak, 66
Rakkers van St.-Anthonius, 72
Rambrectesgat, 121
Ramkama, Ramkema, 237, 238
Rammevreters van St.-Jacobi-Parochie, 36

Ramsel, 72
Randolf, 201
Rapenplukkers van Heiloo, 63
Rappoltsweiler, 110
Ratger, Redger, 201
Ratsma, 287
Ratten van Kolhorn, 63
Rattekot, 128
Rauwerd, Rauwerda, 236, 246
Ravenstiene, 121
de Reade Hel, 283, 288
Readhel, Reahel, Rahel, Rohel, 283, 288
Readtsjerk (Roodkerk), 283
Reberg, 116 [319]
Redle, 214
Redlef, 201
Redward, 201
Regina, Ragina, 231, 233
Reginhald, Reginald, Reinold, Reinout, 162
Reginhart, Reinhart, Reinaert, 162
Regino, Ragin, 233
Reichmann, 100
Rein, Reino, 233
Reina, 163, 231, 233
Reinbern, 201, 202
Reindert, 227, 233
Reinema, 163
Reiner, Reinder, 189
Reinert, 233
Reinger, Regingar, 203
Reinhard, Reinhart, Reinert, Reindert, Reginhart, 201, 203
Reinharda, 233
Reinhusen, 164
Reiningh, Reinink, 163
Reinkens, 163
Reinou, 201, 202, 225
Reins, 163
Reinseel, 164
Reinske, Reynsck, 233, 272
Reinskje, 203, 233
Reintsje (Reintje), 163, 205, 225, 231, 233
Reintjens, 163
Reitse, 215, 221, 249, 252
Reltjo, 216
Rem, Remmertje, 185
Renick Drager, 269
Renick Eminga, 261
Renick Pelazer, 267
Renick, Rienk, 274
Reningessem, 126
Rentjo, 216
Reppelmonde, 77
Rethy, 72
Reye, 249, 252
Reyn, 132, 162, 163
Reynen, 163
Reyner, Reinier, Raginheri, 189
Reyner van den Wintmoelen, 181
Reynier Haengreve, 181, 189
Reyninga, 163
Reyn Kannemaker, 269
Reyns, 146, 158, 162, 163
Reynsck, Reinske, 272
Ribbekliuwers van Staveren, 14, 30
Ribeauvillé, 111
Ricbald, 201
Ricbern, 201, 202
Ricbert, 100
Ricfred, 201
Richard, 100, 150, 210
Richolt, 201
Richtje, 132
Rickmansworth, 100
Ricman, 99, 100
Ricmaninghen, 96, 97, 99, 106
Ricolf, 100
Ricout, 100
Ricward, 201
Ricwin, 100
Ricwold, 100
de Ridder, 140
Riechmann, 100
Riede, 121
Riemer, 132
Riemke, 220
Rients, 221
Rijkhard, 100
Rijklof, 100
Rijkman, 99
Rijkmans, 100
Rikaert, Richard, Richaert, 167
Rikert, 100
Riklef, 201
Rikmenspoel, 100
Rikou, 201, 202
Rink, Rinke, 185, 215
Rinne, 241
Rinnert, 233
Rinse, Rinso, 203, 214, 223, 229, 241
Rinske, Rins, 184, 203, 220, 227, 250
Rinsma, 241
Rinsumageest, 36, 39
Rinthie Sibrenz, 258
Rintse, 132
Rintsje (Rintje), 220, 258, 273
Rinxent, 126
Rioerd, Ruurd, 274
Ripperda, Ryperda, 274
Ritse, 221
Ritsert, Richard, Rikhart, 201

Rix, 132
Robarsdal, 121
Robbe, Robbert, Hrodbrecht, 176
Robert, 150, 155, 210
Robet, Hrodbald, 201
Rocthun, 113
Rodbern, 201, 202
Rodbrecht, 155
de Rode, 134
Rodelant, 120
Rodger, 155
Rodmer, Rudimer, Hrodmar, 155, 201
Roeckaert, 144
Roef Alartssoen uten Vehuse, 174
Roef Gheryt Janssoens soen van Boerdonc, 176
Roef, Rodfred, 174, 191
Roekefretters van Holwerd, 35, 50
Roel, 162, 163, 191
Roelandts, 146
Roelant, 145, 149
Roela-sate, 164
Roelck, 275
Roelens, 146
Roelfentje, 164
Roelfina, 228
Roelfke, 227
Roeling, Roelink, 164
Roelinga, Roelenga, 164
Roelke, 163
Roelof, Rolof, Rodlof, Rodolf, Rudolf, Hrodolf, 162, 191, 233
Roels, 146, 158, 162, 163, 164
Roelsma, 164 [320]
Roeltje, 163
Roever Godart Meeussoens soen, 176
Roger, Rogier, 155
Rog-eters van Munnikereede, Rocheters van Muenickeree, 76, 78, 79
Rogstekers van Weert, 6, 67, 69
Roland, 146, 149
Rolof, 252
Roloff Schriver, 269
Rolof Gryp, 272
Rombrecht, Rommert, 233
Rombrechta, 234
Romelia, 208, 227

Textbook Diffusion NMR of Confined Systems Fluid Transport in Porous Solids and Heterogeneous Materials Rustem Valiullin Ebook All Chapter PDF

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Diffusion Nmr of Confined Systems

Fluid Transport in Porous Solids and

The Molecular Theory of Adsorption in Porous Solids 1st

Multiphase Fluid Flow in Porous and Fractured

Modeling Phenomena of Flow and Transport in Porous

Divided Solids Transport 1st Edition Jean-Paul

The NMR Probe of High Tc Materials and Correlated

Physicochemical Fluid Dynamics in Porous Media

Adsorption and Diffusion in Nanoporous Materials,

Computational Homogenization of Heterogeneous Materials

New Developments in NMR

Titles in the Series:

How to obtain future titles on publication:

For further information please contact:

Diﬀusion NMR of Confined

Fluid Transport in Porous Solids and

New Developments in NMR No. 9

Print ISBN: 978-1-78262-190-4

r The Royal Society of Chemistry 2017

All rights reserved

Published by The Royal Society of Chemistry,

Registered Charity Number 207890

For further information see our web site at www.rsc.org

As reflected in its title ‘‘Diﬀusion NMR of confined systems’’, this book

New Developments in NMR No. 9

Chapter 1 NMR under Confinement: Roots in Retrospect 1

Chapter 2 Fundamentals of Diﬀusion Measurements

2.1 What is Diﬀusion? 16

New Developments in NMR No. 9

2.3 Experimental Measurements 40

Chapter 3 From the Microstructure to Diﬀusion NMR, and Back 52

Chapter 4 Two-dimensional NMR of Diﬀusion and Relaxation 111

4.1 Introduction 111

4.2.4Correlation Experiments in RF Field

4.2.6 Diﬀusion Time Correlation Experiment 117

Chapter 5 Transport in Structured Media: Multidimensional

5.1 Introduction: Diﬀusion vs. Transport 156

5.2 Theoretical Background 158

Chapter 6 Real Time PGSE NMR Through Direct Acquisition of

6.1 Introduction 194

Chapter 7 NMR Methods for Studying Microscopic Diﬀusion

7.1 Introduction 226

7.3 Ensembles of Diﬀusion Tensors 233

7.3.4 Orientation Distributions and

Chapter 8 Beyond the Limits of Conventional Pulsed Gradient Spin

8.1 Introduction 260

8.2 Diﬀusometry using the B0 Gradients of the Fringe

8.2.2 Determination of the Size of Polymeric

Chapter 9 Probing Exchange and Diﬀusion in Confined Systems

9.1 Introduction to the Use of 129Xe NMR to Investigate

Chapter 10 Diﬀusive Dynamics in Porous Materials as Probed by

10.1 Introduction 318

Chapter 11 Industrial Applications of Magnetic Resonance Diﬀusion

11.1 Introduction 353

11.3 Rock Lithology 364

11.4 Advanced NMR Petrophysics 371

Chapter 12 Confined Fluids: NMR Perspectives on Confinements and

12.1 Introduction 390

Chapter 13 NMR and Complementary Approaches to Establishing

13.1 Introduction 435

Chapter 14 NMR Diﬀusometry for the Study of Energy-related Soft

14.1 Introduction to Energy-related Soft Materials 464

14.3.2 Artifacts When Using High Gradients to