WILEY-VCH - 東京工業大学 · WILEY-VCH Author Proof Selective NMR Pulse Sequences for the Study of Solid Hydrogen-Containing Fluoropolymersa Shinji Ando,1 Robin K. Harris,*2

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Author ProofAuthor ProofFeature Article: Magic-angle spinningNMR spectroscopy provides a great dealof information about semicrystalline poly-mers.Akeyaspect of suchwork is the abilityto tailor pulse sequences so as to selectsubspectra appropriate to amorphous andcrystalline domains separately. This articlediscusses the basis of such work (whichinvolves differences in molecular-level mo-bility), describes relevant sequences, andillustrates their use for the special case offluorine-19 NMR of hydrogen-containingfluoropolymers (see Figure). & pleasecheck&

Selective NMR Pulse Sequences for the Studyof Solid Hydrogen-ContainingFluoropolymers

S. Ando, R. K. Harris,* P. Hazendonk, P.Wormald

Macromol. Rapid Commun. 2005, 26, 345–356

marc.200400517C

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Author ProofAuthor Proof

Selective NMR Pulse Sequences for the Study of

Solid Hydrogen-Containing Fluoropolymersa

Shinji Ando,1 Robin K. Harris,*2 Paul Hazendonk,3 Philip Wormald4

1Department of Organic and PolymericMaterials, Tokyo Institute of Technology, Ookayama,Meguro-ku, Tokyo 152-8552, Japan2Department of Chemistry, University of Durham, South Road, Durham DH1 3LE, UKFax: (þ44) 191-384-4737; E-mail: [email protected]

3Department of Chemistry and Biochemistry, University of Lethbridge, 4401 University Drive W, Lethbridge,Alberta T1K 3M4, Canada

4School of Chemistry, University of St. Andrews, Purdie Building, St. Andrews, Fife KY16 9ST, UK

Received: October 26, 2004; Revised: December 17, 2004; Accepted: December 20, 2004; DOI: 10.1002/marc.200400517

Keywords: domain structure; fluoropolymers; NMR; pulse sequences; relaxation

Introduction

Synthetic polymers form an extremely important class of

materials, which has been extensively studied by NMR

methods, applied to both solutions and solids. The first

experiments combining cross-polarization (CP), magic-

angle spinning (MAS), and high-powered proton decou-

pling (HPPD) were applied to obtain high-resolution 13C

spectra of three solid polymers.[1] Indeed, in the first decade

of the use of theCP/MAS/HPPDsuite of techniques,[2] solid

polymers formed a high proportion of the samples studied,

Summary: Fluorine-19 NMR spectra of solids have somespecial features, which are discussed in this article. Inparticular, they generally contain two abundant spin baths(protons and fluorine nuclei). This situation throws up somespecial operational requirements, as does the study of hetero-geneous samples. The relaxation characteristics of heteroge-neous systems, which are briefly described herein, frequentlypermit the use of specific pulse sequences to obtain subspec-tra for individual components. Various possible selectivesequences for use in fluorinated heterogeneous organicsolids are listed and their actions rationalized on the basisof molecular mobility. Semicrystalline hydrogen-containingfluoropolymers form especially suitable systems for suchoperations, and in order to understand their domain structuresit is essential to obtain subspectra of the amorphous andcrystalline domains. Examples are given of the use of selec-tive pulse sequences for studying fluoropolymers, especiallyfor poly(vinylidene fluoride) (PVDF) and the copolymerP(VDF75/TrFE25) (TrFE¼ trifluoroethylene).

DIVAM/CP spectra of the vinylidene fluoride/trifluorethy-lene copolymer as a function of the minipulse angle used.Top: Unfiltered spectrum. Middle: the amorphous domain.Bottom: the crystalline domain.&Q1 please check legend&

Macromol. Rapid Commun. 2005, 26, 345–356 DOI: 10.1002/marc.200400517 � 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

marc.200400517

Feature Article 345

a Based on a lecture given at the MACRO 2004 conference inParis, June 2004, and the SPSJ meeting in Sapporo, September2004.

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Author ProofAuthor ProofShinji Ando (homepage: http://www.op.titech.ac.jp/polymer/lab/sando/index.htm) received his B.E.,M.E., and Ph.D. degrees in polymer science and engineering from the Tokyo Institute of Technology in1984, 1986, and 1989, respectively. His work for the Ph.D was an investigation of the conformationdependence and the hydrogen-bond length dependence of 13C chemical shifts in oligo- and poly-peptides. He served as a research scientist at the Nippon Telegraph and Telephone Corporation from1989 to 1995, where he was engaged in analysis of optical properties and the development of thermallystable fluoropolymers applicable to optical micro-components and planar lightwave circuits. In 1995,he transferred to the department of organic and polymeric materials at the Tokyo Institute of Technologyas an associate professor. He commenced structural analysis and developments of novel fluoropolymersfor electronic and optical applications using solid-state NMR spectroscopy, optical spectroscopies, andcomputational chemistry. He stayed at the University of Durham, UK, as a visiting scientist from 1998 to1999, working with Prof. R. K. Harris. He analyzed the cross-polarization dynamics between 1H and 19Fnuclei in semicrystalline and amorphous fluoropolymers. He also investigated the morphology andmolecular motions of semicrystalline fluoropolymers such as PVDF, PVF, ETFE and so on. Recently,based on knowledge from 19F NMR spectroscopy, density functional calculations, and spectroscopies, hedeveloped highly fluorescent fluorinated polyimides. His research interests include the analysis andprediction of optical properties and electronic structures of thermally stable and functionalfluoropolymers and the structural analysis of semicrystalline and amorphous fluoropolymers usingsolid state 19F NMR spectroscopy.

Robin K. Harris obtained his Ph.D. (and, later, a Sc.D.) from the University of Cambridge (U.K.) andthen spent two years as a postdoctoral fellow in independent research at the Mellon Institute, Pittsburgh.On his return to the U.K. he was appointed to a lectureship at the new University of East Anglia(Norwich). He spent 20 years there, rising to a full professorship, before transferring to the University ofDurham (U.K.) in 1984, where he is now an Emeritus Professor. His interests in the first 20 years of hisresearch work were concentrated on solution-state NMR spectroscopy and its applications to manychemical topics (inter alia to silicones and silicates using 29Si NMR spectroscopy), including the use ofspectral analysis and the development of relevant computer programs. This began to change in the late1970s, when he set up, in collaboration with Professor K. J. Packer, the first CPMAS spectrometer inEurope. Gradually his research evolved to concentrate on solid-state NMR methods and their use in awide range of chemical areas, from ceramics and synthetic polymers to pharmaceutical polymorphism.He has been especially involved with the analysis of spinning sidebands and second-order effects inspin-½ spectra. In the 1990s he pioneered the use of 19F CPMAS NMR spectroscopy with high-powerproton decoupling, which led to applications to fluoropolymers. He has published around 500 scientificpapers, reviews, and also a textbook on NMR spectroscopy. He co-edited a monograph on ‘‘NMR andthe Periodic Table’’ in 1978. More recently, he has been co-editor-in-chief for the 9-volumeEncyclopedia of NMR spectroscopy.

Paul Hazendonk obtained his undergraduate degree in Chemistry from the University of Winnipeg,Canada, in 1993. He started his graduate studies in High-Resolution Nuclear Magnetic ResonanceSpectroscopy with T. Schaefer at the University of Manitoba, Winnipeg, obtaining his M.Sc. in 1995. Hecontinued his research with A. D. Bain, at McMaster University, Hamilton, Ontario, obtaining his Ph.D.in 2000. His thesis work was concerned primarily with dynamic NMR spectroscopy in solution andsolid-state. Over the next two years he served as a postdoctoral research fellow at the University ofDurham, Durham, U.K., with Professor R. K. Harris, working on solid-state NMR spectroscopy offluoropolymers. He investigated cross-polarization dynamics between multiple abundant spin systemssuch as occur between 19F and 1H nuclei in non-perfluorinated polymers. He is now an AssistantProfessor at the University of Lethbridge, Canada, where his research focuses on solid-state NMRspectroscopy of fluorine-containing materials such as organic and inorganic fluoropolymers andinorganic fluorides. One of the main objectives of his research is to provide a mechanistic understandingof the macroscopic properties of these materials at a molecular level, and to develop new solid-statefluorine NMR experiments to study these materials. He has authored and coauthored 25 peer-reviewedjournal articles and has presented 30 papers at national and international conferences.

346 S. Ando, R. K. Harris, P. Hazendonk, P. Wormald

Macromol. Rapid Commun. 2005, 26, 345–356 www.mrc-journal.de � 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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and they continue to be highly investigated by MAS

NMR.[3] There are a number of reasons for this situation, in

particular: (i) the ability of NMR to obtain detailed chem-

ical information from amorphous as well as crystalline

materials; (ii) the remarkable versatility of NMR, exempli-

fied by the wide range of pulse sequences which can be

chosen to produce specific results.[2]

Most MAS work on polymers has, naturally, concen-

trated on the ubiquitous 13C nucleus,[3,4] but of course, a

number of different NMR-active nuclides are present in

particular polymeric systems,[3,5] for instance 15N, 29Si, and31P. These nuclei are also amenable to the CP/MAS/HPPD

combination of techniques. For 1H high-resolution spectra

of solids, one must generally use either very fast MAS[6]

or else multiple-pulse operation combined with MAS

(‘‘CRAMPS’’)[7–9] in order to overcome the strong homo-

nuclear (1H, 1H) dipolar interactions. The 19F nuclide is also

a special case. In several ways it is very suitable for high-

resolution NMR spectroscopy. Thus as it exists in 100%

natural abundance and has a high magnetic moment (in fact

the third highest of spin-½ nuclides after 3H and 1H), it has a

very high receptivity (0.834 of that of 1H, 4.90� 103 times

that of 13C).[10] Unlike 1H, however, it has a large chemical

shift range and so the spectra can be highly resolved (and

therefore, chemically informative). Arguably, then, 19F

NMR is to be preferred to either 1H or 13CNMR for suitable

cases, though clearly the three nuclides can be studied

together. Therefore, one would expect high-resolution 19F

NMR spectroscopy of solids to be very popular. However,

the same properties that give advantages also confer pro-

blems. For instance, for perfluorinated systems, the strong

(19F, 19F) dipolar interactions have (at least until recently)

required the use of CRAMPS,[11] which is technically

demanding. Moreover, for fluorinated materials that also

contain protons (to which the rest of this article is dedi-

cated), high-power proton decoupling has been considered

necessary (again, at least until very recently), and this is not

entirely straightforward because of the proximity of 1H

and 19F resonance frequencies (differing by only ca. 6%).

However, in the mid-1990s commercial probes capable of19F-{1H} double resonance, involving high powers in the

proton channel but with efficient filtering, became avail-

able, so that work in this area began.[12–19] There is a

residual oddity in that, at relatively low applied magnetic

fields, high-power proton decoupling results in the appea-

rance of the Bloch–Siegert effect,[20,21] which causes an

apparent chemical shift on 19F resonances,[13,18] as shown

in Figure 1 and expressed in Equation (1).

DdðBSÞ ¼ ðgFB1HÞ2=ðo2F � o2

HÞ ð1Þ

where gF is the magnetogyric ratio of 19F, B1H is the proton

radiofrequency magnetic field strength, oF is the 19F

resonance frequency, and oH is the 1H ‘‘decoupling’’ fre-

quency. However, once this is recognized, it poses no

difficulties for chemical shift measurement. All that is

required is the use of the same 1H radiofrequency (RF)

Philip Wormald obtained his undergraduate degree in Chemistry at the University of Stockholm,Sweden in 1989, after which, he worked on solid-state nuclear magnetic resonance of ligno-cellulosicmaterials at the Swedish Paper and Pulp Research Institute and the Royal Swedish Institute ofTechnology. In 1998 he moved to the University of Durham, UK, were he worked in the Solid-StateNMR Research Service for other UK universities (funded by the Engineering and Physical SciencesResearch Council) and for industry. During this time he continued research with Professor R. K. Harris,obtaining his Ph.D. in 2005. His thesis work was primarily concerned with 19F and 1H relaxation invinylidenefluoride-based polymers and the relationship of their macroscopic properties to themolecular level. Since 2002 he has been a senior research fellow in solid-state NMR spectroscopy at theUniversity of St Andrews, Scotland, and was made an honorary lecturer there in 2004. His researchinvolves: solid-state NMR spectroscopy of novel microporous and battery materials, as well asfluoropolymers. In the former case, the main objectives are the development of Multiple-QuantumMagic-Angle Spinning (MQMAS) methodologies and the structural determination of microporousmaterials such as zeolites and catalysts. For fluoropolymers, the work involves high-resolution solid-and solution-state NMR spectra of modifiable low-molecular-weight systems for structuraldetermination and to further understand macroscopic properties at the molecular level of thesematerials. He has authored and coauthored 13 peer-reviewed journal articles and contributed to twobooks in solid-state NMR spectroscopy.

Figure 1. 188MHz 19F CPMAS spectra without and with high-power proton decoupling, showing the Bloch–Siegert shift(ca., 2.8 ppm) example.

Selective NMR Pulse Sequences for the Study of Solid Hydrogen-Containing Fluoropolymers 347


WILEY-VCH

Author ProofAuthor Proofpower during 19F observation of the reference sample (e.g.,

liquid C6F6) as when the sample of interest is examined.[22]

The Bloch–Siegert effect is avoided by 19F CRAMPS

operation with synchronized p pulses on the proton channelproviding the heteronuclear decoupling.[19] Moreover, the

effect is not significant for spectrometers operating at 7.1 T

and above. However, for observation of 19F spectra of

proton-containing fluoropolymers, increasing B0 provides

no advantages in dispersion and requires higher spin rates to

minimize the occurrence of spinning sidebands.

There are some other residual problems. For instance,

geminal (19F, 19F) isotropic indirect (i.e., scalar) couplings

are significant (ca. 280 Hz) for CF2 groups, for example, in

P(VDF/TrFE)[23] (VDF¼ vinylidene fluoride, TrFE¼ tri-

fluoroethylene) and in principle cause splittings in spectra.

Moreover, partly for this reason and partly not fully

understood, linewidths in 19FMAS spectra of solids remain

relatively high (e.g., hundreds of Hz)[15] even for well-

crystallized samples. In addition, the large 19F shielding

anisotropies can make some specialized pulse sequences

inefficient or complex.[19]

With the relatively recent advent of high-speed

(>20 kHz) MAS, HPPD appears to be no longer essential

for obtaining high-resolution 19F spectra[24–26] of some

fluorinated solids that also contain protons. However, such

spin rates can cause substantially higher increases in sample

temperature unless controlled. Moreover, there remains a

number of advantages of using CP from protons, and this is

generally more efficient at somewhat lower spin rates (e.g.,

ca. 15 kHz), which then also requires HPPD during signal

acquisition.Whereas the gain in sensitivity relative to direct

polarization is rather small (gH/gF¼ 1.062),[10] CP dis-

criminates against compounds in a heterogeneous sample

which are perfluorinated. This also applies to probe com-

ponents, which frequently involve poly(tetrafluoroethene)

(PTFE) and consequently lead to background signals (albeit

broad) for MAS-only operation for some spectrometer/

probe combinations (see Figure 2).[13,16] More importantly,

CP is involved in a number of specialized pulse sequences,

as described below, including some two-dimensional

experiments.

All these considerations clearly apply to NMR studies of

hydrogen-containing fluoropolymers.[12,13] Such synthetic

macromolecules are important industrially because of their

excellent stability against chemical degradation under a

variety of conditions and because of their special properties

(e.g., piezoelectricity, ferroelectricity, pyroelectricity,

etc.).[27] Moreover, they are frequently complex in physical

structure and are thus of intrinsic interest. They are gene-

rally semicrystalline so their domain structures require

study. Several of them exhibit polymorphism of their

crystalline domains so that characterization methods are

necessary and their phase transition behavior becomes

important in practical usage. Such polymorphism is fre-

quently of the conformational type, and variable conforma-

tion also characterizes amorphous domains. As with many

polymers, especially those produced commercially, the

nature of the end-groups is relevant, as are any chemical

defects in the polymer chains. Such defects, arising from an

occasional reversal in the ordering of a monomer unit in a

chain, are common[28–31] in samples of poly(vinylidene

fluoride), PVDF. Finally, mobility at the molecular level, as

always for polymers, conveys distinctive properties, which

are temperature dependent. These motions can be analyzed

by measurement of NMR relaxation times.

Relaxation in Homogeneous andHeterogeneous Samples

One of the most powerful attributes of solid-state NMR

spectroscopy is its ability to address heterogeneous systems

and, in particular, to separately obtain subspectra relating

to different components by use of specialized pulse

sequences. This ability is clearly of value not only in cases

where heterogeneities correspond to different chemical

components but also, as in the situations considered here,

for samples that are chemically uniform but physically

diverse, that is, for domain structures of pure polymers. This

property of NMR renders it very unusual, if not unique,

among characterization methods, especially as it extends to

amorphous as well as crystalline domains (in contrast to all

diffraction tools). NMR discrimination methods rely on the

versatility of NMR as expressed in the immense range of

pulse sequences that are possible. These can be tailored to

give specific results. Their effective operation in terms of

selectivity must rely on differences in the properties of the

various physical domains that are under investigation.

The property that readily distinguishes solid samples

even of the same material but in different physical form (or

of domains of samples of chemically homogeneous mate-

rials) is molecular-level mobility. This is, of course, a

complex property. Its extent shows a strong dependence on

the motional frequency considered, and it varies greatly

Figure 2. Fluorine-19 MAS spectra[16] of a physical mixture ofPTFE (95%) and PVDF (5%). (a) Direct polarization. (b)1H! 19F cross polarization. The PVDF is severely discriminatedagainst in (b).



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Author ProofAuthor Proofwith temperature as well as with molecular environment in

the solid state. In particular, amorphous domains, which are

unordered and, therefore, generally less tightly packed than

the ordered crystalline domains, are usually the more mo-

bile. Theirmobility normally increases significantlywhen a

sample is heated through the glass-transition temperature.

Any molecular motion causes modulation (leading to

partial averaging) of nuclear dipole–dipole interactions and

hence affects relaxation times and related parameters.

Relaxation can also be caused by re-orientation of the

shielding tensor, the anisotropy ofwhich is often substantial

for 19F. A number of different relaxation times may be

measured by NMR spectroscopy and influence the opera-

tion of NMR experiments in different ways. In order to

provide a reasonable background to the present review

article, the relevant parameters are described briefly below,

but for further detail the reader is referred to references

[2,32,33]. The relaxation parameters in question include:

(i) Spin-lattice (also known as longitudinal) relaxation.

The characteristic time T1 is generally of the order of

seconds for abundant spins such as 1H or 19F in solids

(though it can be significantly longer). It governs the

return of magnetization in the direction of the applied

field (Bo) to its equilibrium value following a

perturbation and responds to motions in the region of

the NMR frequency, that is, hundreds of MHz. It

therefore influences the delay between repetition of

pulse cycles in the NMR experiment.

(ii) Spin-lattice relaxation in the rotating frame. The

characteristic time is designated T1r and usually lies in

the tens of ms range for solids. It governs return of

magnetization perpendicular to Bo but under the

influence of a radiofrequency field B1, to equilibrium

following establishment of a significantmagnitude. Its

value is influenced by motions at the nutation

frequency related to B1 (i.e., to gB1/2p), which is

usually in the tens of kHz range. It influences the

operation of the CP experiment.

(iii) Spin–spin relaxation, perhaps better denoted as

transverse relaxation. The characteristic time T2relates to the return of magnetization perpendicular

to Bo to zero (in the absence of B1) following the

establishment of a non-zero value. Its magnitude is

influenced by low-frequency motions, and for rela-

tively rigid solids (static samples) it is generally a few

tens of ms. It governs the observed free-induction

decay and hence the linewidth of resonances. It may

have a complicated dependence on MAS rate.

(iv) Cross-polarization rate (characteristic time THF). In

the CP experiment (Figure 3), the contact time, t, is avariable. The magnetization in the observed nucleus

first increases as a function of t at a rate governed by

THF and then decays as it leaks to the lattice by a T1rprocesses. The value of THF is generally in the region

of tens or hundreds of ms.

Whereas linewidths tend to decrease, and transverse rela-

xation rates tend to increase, monotonically as increasing

temperature promotes more molecular mobility, T1 and T1rpass through one or more minima. Hence the effect of

temperature change on T1 and T1r is sometimes difficult to

predict and measurements at a single temperature can be

misleading. Of course, for amorphous polymer domains,

passing through the glass-transition temperature induces

substantial changes in molecular mobility and, hence, in

relaxation times.

The typical times mentioned above are those appropriate

for abundant spins such as 1H and 19F. The behavior of spin-

lattice relaxation, both in the laboratory and the rotating

frame, is generally single-exponential for a homogeneous

sample, but transverse relaxation is a more complex pheno-

menon, which may be difficult to fit mathematically.[34,35]

The time T2 may therefore have a meaning that depends on

the circumstances. For a heterogeneous sample with large

domain sizes, spin-lattice relaxation may be treated inde-

pendently for the various domains (i.e., the total magnetiza-

tion will relax as the sum of two exponentials, if there are

two domains, with coefficients appropriate to the domain

concentrations), as may spin-lattice relaxation in the rotat-

ing frame and transverse relaxation. However, the pheno-

menon of spin diffusion spreadsmagnetization in a random-

walk fashion such that the degree of spread is governed by

time. Hence, in typical times, themagnetization of different

Figure 3. (a) Standard CP sequence. (b) Delayed-acquisition CP(dipolar dephasing/non-quaternary suppression) sequence. (c)Delayed CP sequence.



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Author ProofAuthor Proofdomains can be averaged if the domains are small enough.

In such cases, single values of T1 (and of T1r) will be

observed even for heterogeneous samples. The critical

domain size for these events is of the order of nano-

meters.[36] Moreover, T1 is more readily averaged than T1r.

Relaxation behavior in the critical region is complex[34,35]

and, whilst sums of exponentials may be used, the various

T1 values will be distorted from those intrinsic to the various

domains and the coefficients will not correspond to the

concentrations of the domains. Transverse relaxation is

virtually unaffected by spin diffusion. The effects of spin-

diffusion on T1r in heterogeneous systems can be

minimized[37,38] by spin-locking at the magic angle.[39,40]

Discriminating Experiments in19F Solid-State NMR Spectroscopy

As stated above, pulse sequences can be devised to discri-

minate between various domains in a heterogeneous poly-

mer. These are primarily based on differences in mobility,

which cause changes in the various relaxation times by both

dipolar and shielding anisotropy mechanisms. Since the

relationship between mobility and relaxation is not simple,

a variety of responses to the NMR experiment in question

can occur. Therefore, whereas in some cases T1 may differ

greatly between two domains (and an experiment based on

T1 differentiation will work well), in others it will prove to

be better to discriminate by T1r or T2. Moreover, such a

choice will be temperature dependent. In addition, whereas

sometimes the relaxation of 19F itself may provide a good

opportunity for selectivity, in other cases it will prove to be

better to use differentiation based on 1H relaxation, byCP to19F. Hence there are many possibilities, and therefore, a

range of appropriate pulse sequences is described briefly

here.

Firstly, the cross-polarization pulse sequence (Figure 3)

is itself selective. This is because the 19F magnetization

variation with contact time (Figure 4) has the functional

form[41] of Equation (2):

MFðtÞ / � expð�t=THF*Þ þ expð�t=T1r*Þ ð2Þ

where THF* and T1r* are themselves functions of THF (the

cross-polarization time), T1r(H) and T1r(F). (The cross-

polarization dynamicswill bemore complexwhen there are

resolved 19F resonances for a given domain such that there

are several distinct fluorine spin baths.[42] In addition, dipo-

lar oscillations are often seen at short contact times.[43–45])

The values of both T�HF and T

�1r will depend on local mole-

cular mobility. CP rates depend on the strength of (H,F)

dipolar interactions which are weakened by molecular

mobility. Therefore, CP with short contact times generally

favors crystalline domains. However, the same molecular

mobility also frequently causes T1r(H) for amorphous

domains to be significantly shorter, which means that

crystalline domains may also be selected by long contact

times. Figure 4 shows schematically the contact-time

dependence for a system containing two domains (labelled

A and B) with equal amounts of the observed nuclide but

with CP and relaxation characteristics of crystalline (A) and

amorphous (B) materials. It can be seen that, in general, CP

favors crystalline domains, especially at short contact times

(when CP toA is efficient and the signal is large) and at very

long times (when domain Bmay be undetectable because of

the noise level).

Discriminating CP experiments, which depend on T1(H)

or T1(F), involve an inversion-recovery component, of 1H

magnetization pre-contact or of 19F magnetization post-

contact, respectively (Figure 5). In each case, the recovery

time can be set so as to nullify the magnetization of one

domain, resulting in only the signal of the other domain

being observed. The null condition for a simple systemwith

relaxation time T1 requires the recovery time, t, to be T1ln

2¼ 0.693 � T1. For the inversion-recovery experiment on19F, the magnetization after the CP must first be placed in

Figure 4. Schematic plot of variable-contact-time CP intensity,S, for two domains with very different CP rates and effective T1r.The detectability level would be determined by the noise.

Figure 5. (a) Pre-CP inversion-recovery sequence. (b) Post-CPinversion-recovery sequence.



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Author ProofAuthor Proofthe –z direction by a 90x

8 pulse and then brought back to the y

direction (to be measured) after the relevant nulling time.

Success for this experiment depends on T1 for the two

domains differing substantially. However, there is a

complication with these experiments since, in principle,

spin-lattice relaxation for a coupled heteronuclear system is

not single exponential unless the two types of spin are

decoupled during the time allowed for relaxation. Decou-

pling would, therefore, be desirable for significant periods

of time, which could cause probe damage. The method will

often work without decoupling but the appropriate condi-

tions are not readily determined. However, spin diffusion is

relatively efficient at averaging longitudinal relaxation

rates,[32] so discrimination based on T1 is not often

implemented for fluoropolymers.

Similar, but somewhat simpler pulse sequences are

available (Figure 6) for selectivity based on T1r(H) or

T1r(F). In the former case a 908(H) pulse is followed by a

spin-lock period that lies between the values of T1r(H) for

the two domains. A CP contact time follows immediately

the spin-lock period ends, no additional 908 pulse being

required. For the sequence based on T1r(F), the spin-lock

period (which must be between the values of T1r(F) for the

two domains) follows the CP contact time, and acquisition

of the signal occurs immediately the spin-locking ends. In

these cases, decoupling during the relaxation (spin-lock)

periods is scarcely feasible since it is essential to avoid CP

during these times, so the relaxation may, in practice, be

complex.

There are several pulse sequences based on discrimina-

tion by linewidths (i.e., transverse relaxation). The simplest

is the dipolar dephasing sequence (Figure 3b),[46] also

known as non-quaternary suppression[47,48] because of its

use for selecting 13C signals for quaternary carbons while

eliminating those fromCH andCH2 carbons. This sequence

involves a (non-observed) free induction decay period

during a decoupling window immediately after CP. Under

these conditions, 19F signals from crystalline domains

correspond to broad lines (because the polymer chains are

rigid, giving rise to strong heteronuclear and homonuclear

dipolar interactions) and so they decay quickly, leaving sig-

nals from amorphous domains (corresponding to relatively

sharp lines) to be detected following the end of the de-

coupling window. In fact, a post-CP delayed-acquisition

sequence with proton decoupling during the delay would

also give some discrimination because of the differences in

(F,F) homonuclear dipolar interactions. Another alterna-

tive, which often gives similar results for semicrystalline

polymers, is the delayed CP sequence (Figure 3c), which

relies on differences in proton bandwidths. In both the

delayed-acquisition and delayed-CP cases (especially the

former), it may be advantageous to introduce a p pulse into

the middle of the delay period, with rotor synchronization,

to refocus chemical shifts.

A further selective method based on differentiation

between strong and weak (i.e., partially averaged) homo-

nuclear dipolar interactions is the so-called dipolar filter

(DF) pulse sequence (Figure 7a).[49] This consists of a series

of 908 pulses with phase cycling. Weak dipolar couplings

are refocussed, but strong dipolar interactions are affected

less efficiently and consequently magnetization from rigid

regions tends to be eliminated by this pulse sequence.

Recently, a new method for obtaining selective

spectra based on proton transverse relaxation has been

Figure 6. (a) Pre-CP spin-lock sequence. (b) Post-CP spin-locksequence.

Figure 7. (a) Dipolar filter sequence. (b) DIVAM/CP sequence.(c) Direct DIVAM sequence.



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Author ProofAuthor Proofreported. This pulse sequence is called Discrimination

Induced by Variable Amplitude Minipulses (DIVAM)

(Figure 7b)[44,45,50] and consists of a series of (usually 12)

minipulses of constant phase but with pulse (nutation)

angles chosen to eliminate the magnetization from either

rigid or relatively mobile domains. During the minipulse

intervals My decays relatively slowly for the latter, so that

the net pulse angle gradually increases over the 12 pulses

whereasMy for the rigid regions is essentially lost between

the minipulses (but a substantial Mz is retained if the

minipulse angle is small). When the minipulse angle and

interval for 1H are set so as to give a net nutation of 908 forthe mobile domain magnetization, a final 908 pulse fol-

lowed by a CP contact time will give the 19F spectrum

selectively for the rigid domain. Alternatively, a CP contact

time immediately following the 12 minipulses (but without

the extra 908pulse)will give the 19F spectrummainly for the

mobile domain. This may also be obtained by use of larger

minipulse angles leading to, say, a net nutation angle of

3608 forM(mobile), by which timeM(rigid) may have been

lost (see Figure 8), so that CP (908 pulse plus contact time)

will yield a spectrum of the mobile region only. It will be

seen that this ability to obtain spectra of both rigid and

mobile domains selectively is an advantage of this method.

The DF method can only give selective spectra of mobile

regions, as does dipolar dephasing, and T1r filter methods

only yield spectra of the regionwith the longer T1r. It is true

that subtraction of a single selected spectrum from the full

spectrum can yield the complementary spectrum, but this is

often unsatisfactory in practice.

Several of the above discriminationmethods can, alterna-

tively, proceed using 19F direct polarization (DP) instead of1H! 19F cross polarization. Hence DP can involve inver-

sion-recovery (use of T1(F)), spin-locking (use of T1r(F)),

dipolar dephasing (which simply becomes delayed acquisi-

tion), and dipolar filter components in the pulse sequence.

Recently, direct DIVAM (Figure 7c) has also been

utilized.[51] However, the direct DIVAM pulse sequence

appears to be more complicated in operation than CP/

DIVAM. The effects depend on offset and shielding aniso-

tropy (both ofwhich aremuch larger than the corresponding

parameters for protonNMR) but not significantly on dipolar

interactions. Gerstein et al. have shown[52] that significantly

delayed acquisition proton spectra can reveal the existence

of mobile moieties in a solid system even at a very low

concentration, though the cause of this effect is subject to

controversy.[53,54] DP methods are, naturally, available for

perfluorinated systems also. For fluoropolymers containing

protons, direct detection of their 1H spectra is also possible

(as well as 19F! 1H CP). However, 19F spectra contain the

big advantage of better resolution. Methods involving1H! 19F CP are often preferred because of the elimination

of background signals from fully protonated or fully

fluorinated components of the probe (and rotor caps).

Of course, any of the selective pulse sequences described

above may be used as a preliminary to further manipulation

of the magnetization of the selected domain. For instance,

they can be used in a Goldman–Shen[55] experiment to

utilize spin diffusion in order to obtain information on the

size of domains.[56] Combinationwith awideline separation

(WISE) pulse sequence[57] enables heteronuclear correla-

tion (two-dimensional) experiments to be carried out selec-

tively for crystalline and amorphous domains.[17]

All the pulse sequences described above involve ob-

servation of 19F subspectra. It is possible to use analogous

methods to obtain proton subspectra for amorphous and

Figure 8. Explanation of DIVAM, showing how magnetizations with short and longtransverse relaxation times behave during the operation of a succession of minipulsesof common phase. To obtain the pure subspectra, CP is used following the situationsshown at the bottom.Under the conditions illustrated, the ‘‘puremobile spectrum’’ (seebottom left) will usually contain a small contribution from the rigid domains unless asmall oppositely phased pulse is applied before the CP.



WILEY-VCH

Author ProofAuthor Proofcrystalline domains[44] (assuming the existence of two

abundant spin baths, 19F and 1H), but such procedures are

less attractive because fluorine spectra have a far superior

chemical shift dispersion than proton spectra.

Applications to Fluoropolymers

As far as we are aware, domain-selective measurements

based on T1 differences have not been implemented on

fluoropolymers, largely because typical domain sizes imply

substantial (usually complete) averaging caused by spin

diffusion. However, circumstances may occur for which

such methods are appropriate.

The first-reported domain-selective 19F-{1H} experi-

ments on a fluoropolymer (PVDF) involved using a T1r(H)

filter (i.e., a spin-locked delayed-contact CPMAS pulse

sequence) as an introduction to aWISE sequence.[17] Such a

filter is effective (Figure 9) at ambient probe temperature

because T1r(H) for the crystalline domains is significantly

longer than for the amorphous domains. Figure 9 shows

how this method can be used[12] to study the polymorphic

form of the crystalline domains in PVDF samples produced

by different processing methods. It should, however, be

noted that the precise values of the relevant relaxation

parameters are difficult to obtain accurately because of the

effects of spin diffusion and of cross-relaxation between

proton and fluorine spin baths. Moreover, it needs to be

recognized that CP dynamics are complicated when two

abundant spin nuclides are involved,[41,58] rendering the

variable-contact-time method for obtaining T1r difficult to

apply. In any case, all relaxation parameters will depend on

the nature of the sample (average molecular mass, disper-

sion, regio-irregularity, etc.) and on temperature. However,

the ratio of T1r(H) values for the crystalline and amorphous

domains for PVDF is found to be generally in the range of

2–3,[44,59,60] which suffices tomake the pre-CPproton spin-

lock an efficient tool to select the spectrumof the crystalline

domains. A similar situation applies to T1r(F), so that a

post-CP 19F spin-lock is equally effective in selecting such

domains. Figure 10[60] illustrates this fact and also shows

that the selectivity extends to the spinning sidebands. The

result suggests that some reverse units in PVDF occur in

rigid regions (possibly at the interface of amorphous and

crystalline domains). This has been confirmed by the use of

a post-CP 19F spin-lock as a preparation phase to a RFDR

experiment.[60] Experiments conducted at aorund 100 8Cshowed that T1r(F) values for both the crystalline and

amorphous domains of PVDFwere significantly lower than

those at approximately 60 8C but that the ratio remained

approximately the same, so that the T1r(F) filter selection

Figure 9. Fluorine-19 spectra (centreband signals only) of twosamples of PVDF, showing discrimination using a T1r(H) filter.The pre-CP proton spin-lock duration was 40 ms and a shortcontact time (50 ms) was used. The different polymorphic contentof the two samples is clearly shown.[13]

Figure 10. Fluorine-19 CPMAS spectra of a sample of PVDFusing the standard sequence (top) and a T1r(F) filter (bottom). Inthis case the full spectrum, including the spinning sidebands, isshown.

Figure 11. Fluorine-19 CPMAS spectra of PVDF showingselection of the amorphous subspectrum by dipolar dephasing.



WILEY-VCH


method was still viable at the higher temperature.[60] The19F DP/spin-lock method has been shown[61,62] to be

effective for selecting the subspectrum of the g-crystallineform of PVDF.

However, T1r filters only select for crystalline domains,

so they must be matched with other methods. The dipolar

dephasing pulse sequencewas the first one used to select the

spectrum of amorphous domains in PVDF (Figure 11),[59]

since it was found that the decay time of the magnetization

for these regions during the decoupling window was about

three times that for the crystalline domains. Figure 11[59]

illustrates this situation; the lower spectrum should be

Figure 12. Domain selection of PVDF in 19F direct-polariza-tion spectra.[60] Top: full spectrum. Middle: dipolar-filteredspectrum. Bottom: T1r(F)-filtered spectrum. In this case, T1r(F)for the principal amorphous peak is 3.5 ms, whereas for the high-frequency crystalline peak it is measured to be 9.5 ms, a sufficientdifference to give good selectivity, as shown in the bottomspectrum.

Figure 13. CPMAS spectra of PVDF, obtained using a Gold-man–Shen pulse sequence following selection of the crystallinesubspectrum.[56] The delay time allowed for spin diffusion is givenat the right-hand side. The signal for the amorphous phase can beseen to grow in as the delay time increases, analysis of whichallows domain sizes to be determined.

Figure 14. 19F–{1H} MAS spectra of P(VDF75/TrFE25) at68 8C, obtained by (a) direct polarization, (b) delayed CP(delay time 0.5 ms), and (c) short-contact CP (contact time0.1 ms).

Figure 15. DIVAM/CP spectra of the VDF/TrFE copolymer as afunction of the minipulse angle used. Top: Unfiltered spectrum.Middle: Selection of the amorphous domain. Bottom: Selection ofthe crystalline domain. The inter-pulse spacing was 6 ms, and theminipulse nutation angles used are indicated.



WILEY-VCH


compared with the upper one of Figure 9 for the crystalline

domains. Later,[56] the dipolar filter (DF) sequencewas also

used for this purpose (Figure 12, middle spectrum) and

proved to be very effective. The T1r(H) and DF methods

have been inserted before a Goldman–Shen pulse sequence

in order to determine the lamellar sizes of the two domains,

as is shown in Figure 13.[56]

Delayed-CP and short-contact CP can be readily used to

select for amorphous and crystalline regions respectively, as

is illustrated for a sample of P(VDF75/TrFE25) in Figure 14.

This clearly shows that the sample (as received from a

commercial source) contains both mobile (amorphous) and

rigid (crystalline) domains. The spectrum of the latter is

clearly depicted by the short-contactCP experiment,where-

as it is largely obscured in the DP experiment because the

resonances are broad and the crystallinity of the sample is

relatively low.

The DIVAM/CP method was first used[45] to select for

amorphous domains in the case of PVF, and was later appli-

ed[44] to PVDF. Its action was later explained in terms of a

simple dephasing process[50] and it was shown to also be

effective in selecting for crystalline domains in aVDF/TrFE

copolymer.[50] Figure 15 illustrates its use for selecting both

amorphous and crystalline domains merely by varying the

minipulse nutation angle. Domain selectivity for PVDF by

the direct DIVAM pulse sequence has been successfully

simulated and appears to be largely dependent on the differ-

ence in shielding anisotropy between the fluorine nuclei

in the crystalline and amorphous regions[51] (Figure 16). On

the other hand, the signal for the reverse units seems to be

governed primarily by the offset term. The effect of relaxa-

tion could not be simulated togetherwith the spin dynamics,

so one cannot rule out a role for transverse relaxation in the

selection process.

Neither the T1r(H) filter nor the dipolar dephasing me-

thod appeared to give[43] any significant selection for

p(TrFE). A combination of a T1r(F) filter with a short spin-

diffusion time[60] gave a DP spectrum of PVDF at 100 8Cwhich revealed the existence of a signal in the ‘‘reverse

unit’’ region that arose from a highly mobile group. This

signal was dramatically selected[60] in a delayed-acquisi-

tion spectrum obtained at 60 8C. It has been attributed to

–CF2H end groups occurring in only approximately 0.013%

concentration, as attested by a solution-state spectra of a

telomer.[63] The delayed-acquisition experiment has simi-

larly revealed the existence of verymobile groups in aVDF/

TrFE copolymer (Figure 17).[64]

Conclusion

It is shown herein that there are many ways to discriminate

effectively between 19F spectra of crystalline and amor-

phous domains for semicrystalline fluoropolymers. The

pulse sequences involved all rely on differences in magne-

tization relaxation between the domains. Since various

relaxation properties (linewidth, T1, T1r) may be involved,

Figure 16. Direct DIVAM measurements on PVDF. Left: normalized experimental results. Right:simulations. The value of the inter-pulse spacing was 6 ms.

Figure 17. Rotor-synchronized delayed-acquisition spectra ofP(VDF75/TrFE25).



WILEY-VCH

Author ProofAuthor Proofand either 1H or 19F relaxation can be used, the optimum

experiment must be carefully chosen in each case.

Acknowledgements: We thank Dr. Paolo Avalle for Figure 16,Dr. David Apperley for much assistance with obtaining spectra,Dr. Keitaro Aimi for work on g-PVDF and the copolymer, andN. Andres and T. Montina for their assistance in simulating thedirect DIVAM results.

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WILEY-VCH - 東京工業大学 · WILEY-VCH Author Proof Selective NMR Pulse Sequences for the Study of Solid Hydrogen-Containing Fluoropolymersa Shinji Ando,1 Robin K. Harris,*2