Nuclear Magnetic Resonance in Modern Technology

610 Pages·1994·24.153 MB·English

by  E. W. Randall (auth.), Gary E. Maciel (eds.)

Nuclear Magnetic Resonance
in Modern Technology
NATO ASI Series
Advanced Science Institutes Series
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Series C: Mathematical and Physical Sciences -Vol. 447
Nuclear Magnetic Resonance
in Modern Technology
edited by
Gary E. Maciel
Department of Chemistry,
Colorado State University,
Fort COllins, Colorado, U.S.A.
Springer-Science+Business Media, B.V.
Proceedings of the NATO Advanced Study Institute on
Nuclear Magnetic Resonance in Modern Technology
Sarigerme Park (Dalaman), Turkey
August 16 - September 4, 1992
A C.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-94-010-4325-0 ISBN 978-94-011-0756-3 (eBook)
DOI 10.1007/978-94-011-0756-3
Printed on acid-free paper
AII Rights Reserved
© 1994 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1994
Softcover reprint of the hardcover 1st edition 1994
No part of the material protected by this copyright notice may be reproduced or
utilized in any torm or by any means, electronic or mechanical, including photo
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TABLE OF CONTENTS
Preface vii
Introduction
G. E. Maciel ix
Chapter 1. Introduction to NMR and Modern Technology
E.W. Randall 1
Chapter 2. Foundations and Strategies of Multidimensional NMR
R. Freeman 23
Chapter 3. Applications of High-Resolution NMR to Soluble Polymers
A. Zambelli, A. Proto and L. Oliva 57
Chapter 4. High Resolution NMR: Applications to Biological Systems
L.W. Jelinski 73
Chapter 5. Line Broadening in Solids
R. Dupffie 87
Chapter 6. Basic Cross Polarization Magic Angle Spinning
C.S. Yannoni 105
Chapter 7. NMR Studies of Solid Polymers and Resins: An Introduction
G.R. Hatfield 127
Chapter 8. NMR Characterization of Solid Fossil Fuels. Coal and Oil Shale
G.E. Maciel and O. Erbatur 165
Chapter 9. NMR in Industrial Process Control and Quality Control
G.E. Maciel 225
Chapter 10. Solid State NMR Investigation of Zeolites and Related
Materials
C.A. Fyfe and G.T. Kokotailo 277
VI
Chapter 11. NMR Study of Glasses ad Ceramics
R. Dupree 339
Chapter 12. Averaging Effects in NMR
J.S. Waugh 359
Chapter 13. NMR in the Study of Surfaces; H CRAMPS and 29Si CP-MAS
1
Studies of Silica
G.E. Maciel 401
Chapter 14. Cross-Polarization Processes Involving Less Common Pairs of
Nuclei
C.A. Fyfe, K.T. Mueller and K.C. Wong-Moon 447
Chapter 15. NMR of Polymer Composites and Blends
W.S. Vee man 483
Chapter 16. Applications of NMR Spectroscopy to Surfaces and Catalysts:
Acidic Sites and Adsorbed Species
H. Pfeifer 499
Chapter 17. Introduction to DOR NMR
A. Samoson 525
Chapter 18. NMR Imaging: Introduction and Survey
L.W. Jelinski 547
Chapter 19. High Resolution NMR Imaging of Solids
W.S. Veeman 563
Index 593
PREFACE
This volume represents the primary lectures of the NATO
Advanced Study Institute (ASI) on "Nuclear Magnetic Resonance in
Modern Technology," which was held at Sarigerme Park (near the
Dalaman Airport) on the southern Aegean shore of Turkey from
August 23 to September 4, 1992. As indicated in the title, this ASI
was aimed at examining, displaying, and perhaps influencing, the
role of nuclear magnetic resonance (NMR) in modern technological
activity. The lectures summarized in this volume and the numerous
short contributed talks and posters were primarily aimed at the
question, "What is NMR doing in support of modern technology?"
During the main discussion periods and the numerous small
scheduled meetings of specific interest groups this same topic was
also addressed, along with questions like, "What could or should NMR
be doing in support of modern technology?" With this kind of subject
orientation, the organizers attempted to include a large
participation at the ASI from scientists and engineers from diverse
private industries in which NMR does, or perhaps should, play a
substantial role in supporting or optimizing technology. Perhaps
because of a combination of worldwide industrial contractions and
residual corporate nervousness regarding the then recent Gulf War
(which caused a one-year postponement of this ASI), the
participation from private industry was numerically disappointing.
We hope that this book will serve to bring the role of NMR in modern
industry to the attention of numerous industrial scientists and
engineers who were unable to attend the AS!.
vii
viii
For the success of the ASI, we are grateful to many people.
This certainly includes the lecturers for providing excellent
lectures, notes and ultimately chapters, the students and other
participants for the stimulation that they
provided, and Dr. Oktay Erbatur and Dr. Gaye Erbatur and their
assistants, who handled all of the local arrangements in Turkey. The
AS! arrangements and the site were outstanding, and the Turkish
hospitality was superb. Of course, we are grateful to NATO for the
basic grant that made possible the AS! on "Nuclear Magnetic
Resonance in Modern Technology." We also thank the U.S. National
Science Foundation for travel grants to graduate students, the U.S.
Naval Research European Office for co-sponsoring this AS! with a
substantial grant, and the following private companies (listed in
alphabetical order), whose financial contributions substantially
enhanced the quality of the ASI in all respects: BP International,
Doty SCientific, DSM Research, IBM, Nabisco Brands, Otsuka
Chemagnetics, Unilever, Union Carbide, and W. R. Grace. I also wish
to thank Cheryl Tyler, Barbara Wilson and Vicky Pan for their help in
preparing the final manuscript.
Gary E. Maciel,
Fort Collins, Colorado, USA
INTRODUCTION
GARY E. MACIEL
Department of Chemistry
Colorado State University
Fort Collins, CO 80523 USA
This book covers a variety of very fundamental topics in
chemistry and physics, in most cases with the aim of preparing the
reader to understand technological applications of NMR that are
described in this volume or elsewhere. With a publication date that
comes at approximately the fiftieth anniversary of the discovery of
NMR,' this book is timely, in the sense of providing an excellent
view of the substantial role that this maturing, yet dynamic
phenomenon/technique is having in modern technology.
The level of most of the coverage in this volume is
approximately that which would be appropriate for a graduate
chemistry student with an elementary introduction in the following
basic principles of NMR:
1. The NMR spectrum (Fig. 1 B) of a sample is its frequency
response, due to nuclear spin transitions (Fig. 1 A), induced by a
radiofrequency (rf) radiation field (B1) in the presence of a static
magnetic field (8 2 In "high resolution" experiments the spectrum
0).
is typically dominated by the chemical shift, a measure of the
shielding (0) of a nucleus from the unadulterated effect of the
applied static field Bappl due to the local field generated by
circulations of electrons induced by Bappl(Bo = BapPI(l- 0) ); and by
"indirect" (J) coupling between nuclei in a molecule, reflecting the
interaction between spins mediated (communicated) by the bonding
electrons involved with the coupled nuclei. 3
ix
x
A
hu
yh
~E =-2 B = hu
1t 0
J
B ~
J J
( )( )
G(m)
1
~
,
I
f-ro Ib roC
roa
COo
0 0
Figure 1. The NMR spectrum as a frequency response for transitions
of a spin-1/2 system in a magnetic field, Bo' A) Energy levels and
transitions, where Bo is the field experienced by the spins as a
result of a large static applied field, Bappl' B) Frequency response
NMR spectrum, showing three different chemical environments with
chemical shifts 0a' 0b' 0c (corresponding to shieldings O"a' O"b and o"c'
respectively, and resonance frequencies (J)~ (J)~ and (J)~), and J coupling
between the spins of environments band' c with a pattern that is
characteristic of protons in a ~C HC- CH% moiety.