6 NMRIMAGINGOFPOLYMERS

J. L. KOENIG
The J. Donnell Institute Professor, Departments of Macromolecular Science and
Chemistry, Case Western Reserve University, University Circle, Cleveland, OH
44102-7202, USA

6.1 INTRODUCTION
Nuclear magnetic resonance imaging (NMRI) is a technique for measuring
spatially resolved features of inhomogeneous samples. The technique has found
particular utility in the medical field, where it is used for diagnosis based on the
fact that the mobility of water in diseased tissue is different from that in normal
tissue. However, in recent years, NMRI has found its way into the field of
materials, particularly polymers.
NMRI has the capability of measuring inhomogeneities in finished articles by
a noninvasive and nondestructive method. Defect or nonuniform areas of the
polymeric materials will be clearly shown in the NMR image. NMRI may be
considered as a type of chemical microscope and, as such, the concept transcends
any other methodology for generating images.

6.1.1 BASIS O F N M R I M A G I N G

Nuclear magnetic resonance (NMR) [1] is based on the fact that many atomic
nuclei oscillate like tiny gyroscopes when in a magnetic field. In NMR, a sample is
placed in a magnetic field which forces the nuclei into alignment. The sample is
then bombarded with a radio wave. As the nuclei absorb the radio wave, they
topple out of alignment with the magnetic field. As they lose the absorbed energy
from the radio wave, they line up again. By measuring the specific radio
frequencies that are emitted by the nuclei and the rate at which the realignment
occurs, spectroscopists can obtain detailed information about the molecular
structure and motion of the sample they are studying.
Conventional NMR spectroscopy is used to determine chemical structure, as is
described in Chapter 4, but cannot locate the position of the stimulated nuclei.
NMRI is a method where the stimulating signal is spatially encoded so that an
image can be reconstructed showing the distribution of nuclei in the sample.
Polymer Spectroscopy. Edited by Allan H. Fawcett
© 19% John Wiley & Sons Ltd
Other than spatially encoding the signal, imaging works on the same principles as
standard NMR.
The NMRI technique relies on the interaction of nuclei in only a small and
controllable region of the sample by placing the sample in a spatially in-
homogeneous magnetic field whose nuclear resonance frequency is matched to
the r.f. signal in only that region. NMR imaging is involved in obtaining the
spatial distribution of all parameters that NMR can detect. The NMR signals
inherently depend on nuclear relaxation time constants T1 and T2, which in turn
reflect the structural environment of the emitting nucleus. NMR is capable of
providing information about molecular structure and motion; consequently,
NMR imaging can provide a variety of structural factors measured in situ.
There are several ways of spatially encoding the NMR signal [ I ] . One is to
apply a linear magnetic field to the original static field (Figure 6.1). The purpose of
the nonuniform field is to label, or encode, different regions of the sample linearly
with different NMR frequencies. As the magnetic field is varied in a known
manner at specific positions within the sample, the frequency of the NMR signal
indicates the spatial position of the resonating nuclei (Figure 6.1). In one
dimension (D), the position of the sample is related to a frequency by the rela-
tionship
Ao2 = O)2- (O0 = y G2Z9

where the magnetic field gradient G = dBJdz. A tailored r.f. pulse with a narrow
frequency range is used to excite only those nuclei at corresponding positions in
the z dimension. The amplitude of the NMR signal received from the z axis line is
a measure of the number of resonant nuclei on that line, and so the NMR
spectrum represents a graph of spin density versus distance (neglecting relaxation
effects). The field gradient is described by a tensor with nine components but, for
large B, we need only be concerned with the three components Ga = BBJBOL,
where a = x, y, z.
Field Strength

Sample Position

Figure 6.1 Diagram of NMR imaging experiment

 In three dimensions, one operates in a three-dimensional gradient field. The
frequency spectrum (still obtained by Fourier transforming the free induction
decay, or FID) gives the number of resonating spins along a specific direction
of the field gradient. In fact, each plane perpendicular to the direction of the
field gradient has a different resonance frequency, and the signal intensity at
that frequency will be proportional to the number of nuclei contained in that
plane. In other words, the frequency spectrum is just a projection of the spin
density (neglecting relaxation effects for the moment) along the field direc-
tion.

6.1.2 RELAXATION PARAMETERS I N N M R I M A G I N G

The spin densities and the molecular environments of the nuclei are reflected in
the time variation of the amplitude of the measured r.f. signal, and hence are
reflected in the intensity of each voxel in the image. (A voxel is the smallest volume
that the imaging process recognizes and presents.) When the values of T1 and T2
are different in the voxels of a heterogeneous sample, these differences can be
exploited to develop contrast in the NMR images. The pulse sequence that is
usually used to measure the T2 relaxation phenomena in images is called multiple
spin-echo. At a given repetition time TR, the NMR signal is measured at several
different echo times TE. These echoes provide a measure of the T2 relaxation. By
repeating the process at different TR values, the T1 relaxation can also be
measured.
Because differences in relaxation times and spin densities determine image
contrast, data on relaxation times are important in the selection of the optimal r.f.
pulse sequence for imaging a selected sample. Relaxation times can be measured
at any point on an image. The ability accurately to quantify relaxation rates is
important in understanding and optimizing image contrast. Spin density, T1 and
T2 images can be computed from measurements using pulse sequences with
predetermined variations [2]. These fundamental images represent the inherent
data in the system, and can be recombined to reconstitute computed images for
a given pulse sequence.
Contrast in NMRI depends on both material-specific and operator-selected
parameters. The material-specific parameters include the spin density and the
relaxation times T1 and T2. The operator-selected parameters include the pulse
sequence (inversion recovery, spin-echo, etc.) and the pulse delay and repetition
times (timing parameters). For a given imaging system and pulse sequence, it is
the delay and repetition times in conjunction with the intrinsic material par-
ameters which dictate the appearance of the final image. If the correct pulse
sequence is employed and the relaxation times of the two materials are known, it
is possible to calculate the delay and/or repetition times that will produce the
maximum difference in signal intensity between those materials.
Figure 6.2 The timing diagram for a spin-echo imaging pulse sequence using a selective
90° pulse

The spin-echo (SE) technique is the most common pulse sequence applied in
MRI today [I]. Images are constructed by acquiring a multitude of projections
(typically 256 per image) each with an identical setting of a readout gradient
during which the sequence is samples. Each projection is differentiated from the
others by a phase difference, which is produced by advancing the phase encoding
gradient.
As shown in Figure 6.2, the spin-echo method consists of a series of r.f. pulses
which are repeated many times in order to achieve a sufficient signal-to-noise
ratio. Each projection is produced by a 90° pulse, followed by a 180° pulse for
induction of the spin-echo. The 90° r.f. pulse tips the magnetization into the
xy plane, where it begins dephasing. The 180° r.f. pulse is applied after a time
t, and forces the magnetization to refocus at a time It (also known as the echo
time TE) after the 90° r.f. pulse, at which time the data is collected. The frequency
encoding gradient Gx causes the spins to precess at different frequencies de-
pending on their position in the static magnetic field. The phase encoding
gradient Gy is orthogonal to Gx. Varying the intensity of Gy causes the spins
to dephase at different rates, providing the second dimension of a two-dimen-
sional image. The slice selection gradient G2, and the Gaussian-shaped 90°
r.f. pulse determine the position and thickness of the region of interest. The
data is Fourier transformed in two dimensions to produce the image of the
selected slice. The time delay between the observation pulse and the observation
is called the "echo time" (TE). The time between two consecutive pulse sequences
is labelled as the "repetition time" (TR), and usually ranges from 250 to
2500 ms.
Spin-echo techniques have a unique position in NMR applications. The main
problem with NMR imaging is the long data collection time, due mainly to the
spin-lattice relaxation time T1. Each measurement necessitates a time period of
the order of T1 (which is %0.5 s for aqueous systems) for the system to return to
equilibrium magnetization. By using spin-echo repetition, a large number of
spin-echoes can be repeated within a T1 or T2 decay period.

6.1.3 R E S O L U T I O N I N N M R I M A G I N G

Spatial resolution is limited by the smallest amount of sample that can be

detected by NMR. Spatially resolving a given volume in an NMR image is
equivalent to doing NMR spectroscopy on that volume. To resolve two spatially
distinct volume elements requires the application of a magnetic field gradient of
sufficient strength, such that the elements one wishes to resolve are shifted in
resonance frequency from each other by an amount greater than the natural
linewidth. For a given magnetic field gradient strength, the spatial resolution in
NMR imaging is determined by the linewidth [I]:
Ax = (O112ZyGx
where col/2 is the linewidth and G, is the gradient strength. For mobile liquids the
linewidths are very narrow, and high spatial resolution can be achieved. The
highest resolution reached so far is 1Ox 1Ox 100 \im. This corresponds to an
observable volume element (voxel) of 10~ 5 mm 3 . Routine measurements on
liquids in solids typically have 40 x 40 x 100 ^m resolution.
The attainable resolution is limited by spectroscopic and hardware factors.
Spectroscopic factors are the linewidth and the spread of the chemical shift of an
NMR signal, diffusion processes and susceptibility gradients, both within the
object and at its boundaries. Hardware factors may be the magnetic field
inhomogeneity or instability, nonlinearity of the magnetic gradient field and the
achievable signal-to-noise ratio.
The difficulties of solid state imaging arise because the solid state linewidth is
«1000 times its solution counterpart. Increasing the gradient by three or four
orders of magnitude to maintain spatial resolution in solids imaging is a formi-
dable task, and much effort has gone into finding alternatives to such a brute force
approach [3].

6.1.4 U T I L I T Y O F N M R I

NMRI is a means of detecting and imaging previously invisible material imper-

fections in fabricated articles. Its potential applications in the field of polymeric
materials are many and diverse [4]. They include the detection and imaging of
subsurface defects, including interfacial flaws and microcracks, and the detection
and characterization of areas modified through the introduction of foreign
substances such as additives, degradation products, and contaminants.
The potential applications are exciting, including dynamic studies of compos-
ites and other materials. The NMR imaging technique is a noninvasive monitor-
ing tool, so multiple measurements can be made on the same sample under
different conditions. No special sample preparation is required and this makes
possible in situ studies of fabricated articles including the superposition of images
obtained before and after application of stresses and exposure to environmental
factors, including stress, fatigue, temperature and penetrants.

6.1.5 IMAGE PROCESSING

The underlying purpose of NMR imaging is to detect the presence or absence of

inhomogeneities in situ. By using computer enhancement techniques, it is possible
to compare a perfectly fabricated article with a modified piece, and in this manner
to concentrate on just what makes each test piece different from the ideal. Defects
such as voids and inclusions are represented by very small image discontinuities.
Using a technique called edge enhancement, it is possible for the computer to
make a numerical microshift of the image that has been stored in digital memory
and then display the result. This process can convert images to data for automatic
defect recognition. By putting the computer in the loop, we can employ averag-
ing, smoothing and other forms of enhancement to let the computer make the
quality decision after it has eliminated superfluous information. The computer
can perform gray-scale scanning to detect any areas in the article that are imaging
either too lightly or to intensely. Either effect is a sign that bonding is not proper
on the fibers.

6.2 ADVANCED IMAGING TECHNIQUES

6.2.1 CHEMICAL SHIFT IMAGING
NMRI usually assumes that the spins (usually that of the protons of water)
precess at the same frequency but, owing to chemical shift differences arising from
different chemical types of protons in substances, some of the spins experience
slightly different local fields, and hence precess at different frequencies. The local
field change is written as 0H0, where H0 is the static field and a is the chemical
shift in parts per million (ppm). In imaging, the presence of two different types of
resonating nuclei can lead to overlapping images and artifacts as shown in Figure
6.3. Figure 6.3 [5] shows the results of an image of xylene. Separate images are
due to the aromatic and methyl protons and they are separated by % 4.8 ppm
from each other. Each individual image is centered at its resonant frequency in
the absence of a magnetic field gradient, and therefore the resulting image is
smeared. As the read or frequency encoding gradient spreads out resonance
frequencies according to positions along the gradient direction, the observed
image actually consists of two or more partially overlapping sets of data (one
Figure 63 A cross-sectional chemical shift image of xylene in a vial. Separate images are
due to the aromatic and the methyl protons of xylene and are separated by 4.8 ppm from
each other

corresponding to each type is nucleus). If the resonances are due to different

species, two or more different images will be obtained. If all resonances arise from
the same molecule, they will have identical spatial distributions and images.
The usual imaging schemes apply a linear gradient G to frequency encode the
data. Applying an inverse Fourier transform maps the spin density as a function
of frequency linearly to spatial location. The linear relation between frequency
(o and position x is:
co = yGx
where y is the gyromagnetic ratio for hydrogen. In a gradient free environment,
the precessional frequency of the proton of a molecule a decreases by:
Ao>a = y<7a£0
This leads to a shift in the image position of the molecule a with respect to that of
the protons of water by:
Ax a = AcoJyGr
Consequently, the image of molecule a would overlap water in the region of
interest and cause an artifact in the image, which might be incorrectly interpreted
as actual spatial features. By increasing Gr, the pixel shift due to chemical
differences is reduced. However, much valuable information is contained in the
image if the chemical shifts can be sorted out correctly. It is possible to form an
image from only a selected portion of the total NMR spectrum. This process is
called chemical shift imaging.
A particular resonance peak can be selectively excited by r.f. irradiation to the
exclusion of others in the chemical shift spectrum. A long, low-power, amplitude-
shaped r.f. pulse can be used to excite a narrow range of resonant frequencies
distributed about a particular frequency. Such a "soft" pulse is more frequency-
sensitive than a short, square "hard" pulse.
High resolution NMR spectra displaying chemically shifted resonances pro-
vide information on the chemical species present in the system and their relative
concentrations. The magnetic resonance response can be simultaneously ob-
tained from all regions of a heterogeneous sample by using a four-dimensional
Fourier transform technique, where the high resolution spectrum obtained
during the data acquisition defines one dimension and the other three dimensions
form a Cartesian coordinate system.
The application of various spatially resolved MRI techniques for the observa-
tion of high resolution spectra has been limited. This is largely due to the
mutually exclusive requirements of both the highly homogeneous magnetic
field which is necessary for the observation of chemical shift information, and
the inhomogeneous field which is applied as a linear magnetic field gradient
and is necessary to obtain spatially resolved data. Chemical shift imaging
techniques use pulsed magnetic field gradients, which in the standard configur-
ation of superconducting magnets generate sufficiently large eddy currents upon
gradient removal to temporarily degrade the field homogeneity. This is one of the
reasons why the implementation of high resolution spatial spectroscopy is
difficult.
Currently, there are several approaches to the problem of the chemical shift
effects in NMRI. First of all, one may attempt to construct an image correspond-
ing to a preselected chemical shift of a sample either locally or globally. When
different chemical shifts originate from different chemical species, an image taken
at a specific chemical shift will provide information on the spatial distribution of
the corresponding species while excluding the interference of other species in the
image. A local method assumes knowledge of the chemical shift and usually
produces an image of the chemical species under consideration. The in-phase and
out-of-phase experiments can be used for this purpose [6]. In addition, chemical
shift-selective suppression of an unwanted species or selective excitation of the
species to be imaged [7, 8] and also a method based on chemical shift-specific
slice selection [9] have been proposed as local methods. A global method
produces essentially a chemical shift spectrum for each localized region or
volume element, and thus creates a stack of chemical shift images. A global
deconvolution calculation technique has been proposed [10] utilizing a combi-
nation of the Wiener filter and an anodization function. A method of convolution
has also been suggested in which the image is deconvoluted by the NMR
spectrum of the sample [ H ] . This latter method shifts the image of each
individual resonance such that it is centered about the carrier frequency. No
totally adequate method of suppressing the chemical shift artifacts has yet been
developed, but all of the methods improve the quality of the images when multiple
chemical shifts are present.
On the other hand, chemical shift imaging is highly desirable. Selective
excitation chemical shift imaging is possible only if the spectrum of the sample is
resolvable for the entire imaging volume. It has been suggested that chemical
shift-sensitve NMR images can be obtained using spectral simplification by
tailoring the excitation pulses [12]. Chemical shift images have been reported for
two rubbery polymers, polybutadiene and polydimethylsiloxane [13], and also
for polyether polyol with an isocyanate curing agent [14].

6.3 APPLICATIONSOFNMRITOPOLYMERS
6.3.1 DETECTION OF VOIDS IN COMPOSITES
The void content of pultruded composite rods have been studied using NMRI
[15]. Glass fiber-reinforced nylon rods with fiber contents of 51% by volume
were first mixed with different catalyst contents following the reaction injec-
tion molding (RIM) process, and then pultruded with a pulling speed of 18 inches
per minute. Approximately 4% of the catalyst mixture, containing sodium
hydride and phenyl isocyanate, was used. The diameter of the die in the pultruder
was 0.90 cm. The rods were then soaked in water at 80 0 C for 25 weeks before
imaging. The uptake in water was 3.7%, as measured by the increase in weight
of the composite rods. The images were recorded on a Bruker MSL 300 spectro-
meter using a spine-echo pulse sequence. The slice thickness was 1.0 mm and
the slices were taken transverse to the fiber axis. With the rods standing in
1.5 cm diameter vials containing water, the two images shown in Figure 6.4
are taken 0.5 cm apart through the pultruded rod. The light areas in the image
represent void areas filled with water. The marker in the upper left hand portion
of the image is 1 mm in diameter. Comparison of the sizes of the voids in the
pultruded rod intidcates that some of the voids approach the magnitude of
the marker. A comparison of the corresponding edge-enchanced images show
that some of the voids in the images occur in the same location, which indi-
cates that the voids are connected or tubular in shape. Thus, a channel-like
void region is suggested over a length of 0.5 cm. From the computer conparison
of the two images taken 0.5 cm apart, it is possible to identify a tubular shaped
void running from one image to the other within the nylon rod. Such a void
could be obtained if an air bubble was trapped in the matrix during the pul-
trusion process. It appears that water diffuses by following the fabers in the
composite.
 Image of water in pultruded nylon Contour plot of image showing
rodsreinforcedwith glass fibers presence of tubular void

Figure 6.4 Image of water in pultruded nylon rods reinforced with glass fibers and a contour plot of image showing the presence of
a tubular void
6.3.2 DETECTION OF N O N U N I F O R M DISPERSION
O F FILLER
The improvement in mechanical properties by inorganic fillers is considerably
reduced if there is a nonuniform dispersion of particles in the polymer matrix by
formation of agglomerates. NMRI can produce visual pictures of the spatial
variation of the organic phase distribution. This is accomplished by observing the
proton images of the elastomers as a function of proton density and spin-spin, T2,
relaxation times. These NMR parameters provide a measure of the molecular
mobility, which in turn is related to the spatial variation of the polymer and the
filler in the sample.
Samples of poly(dimethylsiloxane) (PDMS) which were reinforced by in situ
precipitated silica were examined by NMRI [16]. The images were obtained with
a spin-echo technique, with a slice thickness of 500 |im and a digital resolution of
185 urn, and required a time of 25.6 min. A dark rim was observed around the
sample which indicated a reduced mobility of the network chains compared with
the sample core. This difference arises from the high concentration OfSiO2 in this
region.

6.3.3 NMRI O F PHYSICAL AGING

NMRI has been used to study the physical aging of cross-linked cautchouc
(vulcanized natural rubber filled with carbon) [17]. The nondestructive character
of NMRI provides a method to monitor various changes in the materials
properties of a single sample rather than using the usual methods which destroy
the sample during the analysis. A cylinder sample (5 mm diameter) of natural
rubber filled with carbon black was used. The sample was removed after each
measurement and aged for a predetermined period of time in a dry box at 1300 C.
The samples were imaged using a conventional multiecho pulse sequence. The
gradient strength was 250mT/m and the spatial resolution was 80 x 80 nm with
a slice thickness of 1 mm. The images revealed air bubbles resulting from the
molding process. When the sample was aged, inhomogerieities of varying size
were observed as dark spots with bright shadows around them. The shadows
arose from the difference in susceptibility of the inhomogeneities in comparison
with the surrounding rubber. A ring in the aged surface layer was observed at the
interface of the unaged material in the interior of the sample. This ring may have
arisen from the presence of stabilizers such as stearin or paraffin, which diffuse to
the reaction front.
The onset of aging in the natural rubber can be observed by NMRI after only
two hours. The thickness of the aged layer shows the asymptotic behavior
expected for a radial protective film. If the aging reaction is modeled (for purposes
of NMRI) as
U + O2-A
where U is the soft rubber reacting with oxygen at elevated temperature yielding
a hardened, aged rubber, A, in NMR terms the sample has only two possible
internal states, i.e. soft and hard. These two states have two different T2 values,
which are 5.8 ms for the unaged rubber and 0.3 ms for the aged portion. As the
relaxation times are different by a order of magnitude, the first echo results only
from the unaged rubber U and can be used to determine the concentration. The
concentration dependence of the unaged rubber U on the aging time ra can be
expressed as
[U](O = [U 0 ]exp(-/a a )
and then the amplitude of the echo becomes proportional to the concentration of
U, The inverse rate constant k~l is determined to be 8 h ± 30%.

6.3.4 NMRI STUDIES O F D I F F U S I O N IN POLYMERS

NMR imaging techniques has been used for the study of sorption and diffusion
and of the desorption of multiple chemical substances in polymeric materials
[18-28]. NMR imaging can directly provide the diffusion coefficients as a char-
acteristic quantity of a liquid component in a sample, making it possible to map
molecular migration on a microscopic scale. NMR imaging also provides
additional information on the microdynamic and structural properties of hetero-
geneous systems, such as subregion diameters, exchange times, and phase
boundary resistances [29, 30].
The principal advantage of NMR imaging is the possibility of making spatially
localized diffusion measurements [30]. One can examine by NMR imaging the
concentration and location of a permeating liquid in a solid sample. A true
diffusion parameter image is obtained, where calculated diffusion coefficients are
encoded into an intensity scale.
One of the obvious advantages of NMR imaging for the study of diffusion is the
visual presentation of the data in the form of images. Such a presentation allows
one to view directly the concentration and location of the penetrant and to ignore
extraneous factors influencing the diffusion. Another advantage of NMR imaging
is that it allows the study of samples of virtually any shape, and allows the
detection of initial imperfections in the sample being studied. It is generally
difficult to interpret liquid sorption measurements in solids because the samples
being examined are not perfect, that is, they initially contain cracks and voids
which increase both the diffusion and the uptake of the liquid. Also, the induced
volumetric changes, though small, can cause microcracking or void formation.
The NMR imaging technique also allows the system to be studied dynamically,
as measurements can be made on the solid sample immersed in the penetrant. The
measurements are rapid. Using the FLASH techniques [22], an image can be
obtained in a few minutes. In this fashion, it is possible to study the dynamics of
the diffusion process. Of course, the sample-penetrant system can be studied
under isothermal conditions.
Finally, a primary advantage of NMR imaging is the fact that all of the NMR
parameters of the sample can be measured and used to interpret the diffusion or
sorption process [30]. Images obtained utilizing different pulse sequences and
interrupt times can be used to calculate the spin-lattice T1 and spin-spin T2
relaxation times and the spin density. These additional parameters relate to the
bonding and environment of the penetrant in the polymer system. These types of
measurements have been useful in understanding the morphological changes
which are observed [22].
NMR imaging techniques have been used for the study of sorption, diffusion
and chemical reactions as well as the desorption of chemical substances in
polymeric materials [23]. NMR imaging can directly provide the diffusion
coefficient as a characteristic quantity of the fluidity of a component in a sample,
making it possible to map molecular migration on a microscopic scale.
The diffusion coefficients have been quantitatively evaluated from a series of
images recorded with different gradient field strengths [22]. Analysis involved the
simulation of the effects of diffusion using the dynamic magnetization equations
to calculate the magnetization for each pixel, which ultimately yielded an image
whose intensities represented the spatially resolved diffusion coefficients. Finally,
a true diffusion constant image was obtained in which the calculated diffusion
coefficients were encoded into an intensity scale [22]. In this scale, high intensities
corresponded to fast diffusion. In this manner, the spatial diffusion of a liquid into
a solid material was characterized in a quantitative fashion.
NMR imaging has been used for methanol diffusing into PMMA [22].
Figure 6.5 shows the image from the PMMA in methanol after 48 h. The diffusion
coefficient can be calculated by measuring the thickness of the sorbed layer as
a function of time. With data processing techniques, it is possible to simplify the
measurements by giving the images a three-level gray scale and then drawing
a profile across the sample as shown in Figure 6.6. The results are shown in Figure
6.7, where the thickness of the layer is plotted versus time. The linearity of this
plot with time confirms that case II diffusion is occurring. The nonzero intercept
at time zero is indicative of an initial Fickian diffusion process followed by case II
diffusion. The constant level of methanol in the penetrant front is also reflective of
case II diffusion.
NMR relaxation parameters are useful probes of molecular motions in poly-
mers. Each correlation time represents the average value of the system, with some
distribution around that average. NMR imaging permits the determination of the
spatial distribution of NMR relaxation times. This distribution provides infor-
mation concerning the local motions of the system. In this case, the polymer is
partially swollen with solvent, and the spatial distributions of relaxation times
reveal the interactions between the solvent and the polymer in the diffusion
process.
Figure 6.5 The proton NMR image of a 30 mm PMMA sphere initially submersed in
methanol (left) and the image taken after 48 h of exposure to methanol at 300C. Reprinted
with permission from John Wiley & Sons Inc. Journal of Polymer Science 1989

Figure 6.6 The intensity profile of the image on the right side of Figure 6.5. The features
are: (a) bulk methanol; (b) equilibrium methanol volume in PMMA; (c) sharp concentra-
tion front; and (d) glassy PMMA. Reprinted with permission from John Wiley & Sons Inc.
Journal of Polymer Science 1989

Acetone swells PMMA to a greater extent than methanol, and the self-
diffusion coefficients of the system are about two orders of magnitude greater
than those of the methanol/PMMA system. This is apparently due to the
increased volume available to the acetone molecules. The self-diffusion coeffi-
cients decrease by 35% from equilibrium in the outer regions to the region near
the glassy core. The decreasing motions of the polymer chains as the core is
 Diffusion distance (mm)

Time (hours)

Figure 6.7 The plot of diffusion distance measured with NMR imaging vs. exposure time
for the PMMA shere in methanol at 300C. Reprinted with permission from John Wiley
& Sons Inc. Journal of Polymer Science 1989

approached reduce the solvent mobility, as reflected in the self-diffusion coeffi-

cients [22].

6.3.5 DESORPTION OF LIQUIDS FROM POLYMERS

Desorption is one diffusion process that has been given little attention, primarily
because of the lack of adequate analytical techniques. Desorption measurements
above the glass transition temperature of an unswollen polymer are expected to
follow Fickian characteristics. Likewise, a polymer swollen so that the Tg is below
the experimental temperature initially exhibits Fickian desorption. The solvent is
thought to desorb rapidly from the surface of the polymer and raise the Tg of the
surface layer. After the surface T8 is above the experimental temperature,
the desorption process slows, and the process is controlled by the diffusion
through the glassy surface layer. NMR imaging provides the spatial distribution
of solvent in the polymer and also the spatial distribution of the rate of desorption
[23].
The desorption process can be related to Td, which is the inverse of the rate of
net solvent loss for a given pixel through the equation:
M = Moexp(-exp7/7d)
A nonlinear least-squares fit of the experimental data is used to calculate a Td
image on a pixel-by-pixel basis [23].
We have reported some results on the NMR imaging of the desorption process
[23]. Images of the desorption of methanol from swollen rods of PMMA were
obtained [23]. The methanol volume fraction was 0.26. The rods were then
placed in fully deuterated cyclohexane. The first image acquisition began 6min
after initial submersion. Images were collected in Ih increments over a 104 h
period. The signal intensity decreased with time, the maximum intensity of the
Figure 6.8 A Td image calculated from 20 images at 5 h increments over a 100 h interval.
Reprinted with permission from [22]. Copyright 1990 American Chemical Society

last image being only 50% of that of the initial image. The diameter of the rod
decreases by 816 ±68 mm over the 10Oh period as measured from the images.
A Td image calculated from 20 images taken at 5 h intervals over 100 h is shown
in Figure 6.8. In this image, the light portion represents the largest Td and dark
represents the smallest T6, which corresponds to the slowest and the fastest
intensity decreases, respectively. This image shows that the faster intensity
decreases are near the surface of the rod and the slower intensity decreases are
near the glassy PMMA core. The Td at the surface is 58 h and that at the glassy core
is 450 h, as determined from this image. This agrees with the Fickian characteris-
tics, and indicates that imbibed solvent near the surface desorbs quickly, with the
desorption rate decreasing toward the sample core. However, for this system
there is no evidence of a glassy skin developing on the polymer surface [23].
6.3.6 MULTICOMPONENT DIFFUSION AS STUDIED
BY NMRI
It is possible to use NMRI to study multicomponent diffusion in a number of
different ways, utilizing differences in chemical shifts, relaxation times or by
isotopic labeling. We have chosen the last method [26]. We studied the simulta-
neous diffusion of acetone and methanol into polycarbonate by completely
deuterating one of the components and recording the images of the other
component in the PC. Using perdeuterated methanol (MeOH-J4) and acetone
(AC), the FLASH images show the movement of the acetone diffusion front
within the PC rod. These images show that the 75:25 ACrMeOH-J4 mixture
diffuses more rapidly than the 50:50 AC:MeOH-J4.
Perdeuterated acetone :hydroxy-deuterated methanol (AC-J6: MeOD) mix-
tures of 75:25,65:35 and 50:50 volume ratios AC-J6: MeOD were also studied.
From these images we can monitor the solvent front movement of acetone and
methanol into the PC rods. The movement of the solvent front of acetone into PC
versus the square root of time is shown in Figure 6.9(a) for the 75:25,65:35 and
50:50 AC .MeOH-J4 mixtures. The diffusion into PC increases as the acetone
content of the mixture increases. In addition, there is a linear dependence between
the solvent front movement and the square root of time. This indicates that the
diffusion of AC: MeOH-J4 into PC is Fickian [26]. This result was anticipated, as
the diffusion of both pure methanol' and pure acetone has previously been
determined to be Fickian [33]. (Note, however, that the diffusion of pure acetone
was found to be Fickian after an initial period in which the diffusion was reported
to be anomalous [33]). This may seem contrary to what is usually found for the
diffusion of solvent into a glassy polymer which is below its glass transition
temperature Tr Instead, either case II or anomalous diffusion is most often
encountered in this temperature region. This is because, below the Tg, the polymer
chains are in the glassy state, and are therefore not mobile enough to accommo-
date the solvent. In contrast, Fickian diffusion is prevalent above the 7^ because
the polymer chains are in the rubbery state and can therefore accommodate the
solvent more readily. Although the T% of dry PC is 149 0 C, acetone and methanol
diffuse into PC in a Fickian manner because the 7^ is reduced to « —9 0 C by the
solvent ingress [31]. In this way, PC is able to relax and accommodate the solvent
almost immediately, allowing the solvent movement not to be inhibited by the
rate of polymer relaxation.
The solvent front was also monitored for the AC-J6: MeOD mixtures. For
the mixtures of 75:25,65:35 and 50:50 AC-J6: MeOD into PC, similar behavior
was also seen in Figure 6.9(b), where the methyl resonance of methanol was
monitored. There is an increase in the rate of the front movement as the ace-
tone content increases, and also a linear dependence of the front movement
with the square root of time. This linear dependence indicates Fickian dif-
fusion.
 Millimeters

Square root time (h1/2)

Millimeters

Square root time (h1/2)

Figure 6.9 Solvent front movement of (a) acetone into PC for the 75:25,65:35, and 50:50
v/o AC/MeOH-^ mixtures and (b) methanol into PC for the 75:25,65:35, and 50:50 v/o
AC-</6\MeOD mixtures versus the square root of time. Reprinted with permission from
[26]. Copyright 1992 American Chemical Society

We were interested in determining whether the two solvent fronts move at the
same rates for a particular acetone to methanol ratio. Comparison of the rates of
the solvent front movements of the 65:35 AC:MeOH-^4 and the 65:35 AC-
d6:MeOD mixtures revealed that they were equal within experimental error.
There is an overlapping of the front movement when plotted as a function of
square root of time. This indicates that acetone and methanol are diffusing jointly
through the PC rod in a Fickian manner and do not appear to separate. Similar
behavior is also found when comparing the 50:50 AC:MeOH-^4 and the 50:50
AC-d 6 :MeOD mixtures.
It may be proposed that this joint diffusion through PC is the result of the
formation of a weak "complex", possibly a weak hydrogen bonding interaction
[22] between acetone and methanol. The 65:35 v/o AC:MeOH mixture has
approximately a 1:1 molar ratio, and thereby all the acetone may be complexed
with methanol. This would account for the overlap of the front movement plots
within error. In the 50:50 v/o AC:MeOH mixture, the molar ratio is « 35:65
AC: MeOH. If all the acetone complexes with methanol, that leaves approximate-
ly equal amounts of ACMeOH complex and free methanol which would diffuse
together. As shown by the 65:35 v/o AC:MeOH mixture diffusing at a greater
rate than the 50:50 v/o AC:MeOH mixture, the "complex" may have a greater
interaction with PC than the free methanol would in the 50:50 v/o mixture. The
complex may be able to reduce the T% further than the free methanol, allowing an
increased rate of penetration of slovent.

6.3.7 A B S O R P T I O N - D E S O R P T I O N CYCLING O F LIQUIDS

IN POLYMERS

We have studied the absorption-desorption cycling of water and methanol into

and out of the PMMA rods to determine its effect on the diffusion characteristics.
There is an increase in the rate of weight gain with cycling. The increase in the rate
of weight gain becomes even more evident as the initial water content in PMMA
increases. This may be caused by the increased plasticization of PMMA by the
water for higher water contents followed by higher methanol contents. This may
have created increased porosity within the PMMA as the solvent contents were
increased.
A similar effect can be seen for the cyclic diffusion of methanol into water-
soaked PMMA with water contents of 0.6 and 0.75 wt%. The percentage weight
gain versus time of diffusion is linear with time except for an initial lag time, which
is anomalous. The lag time may be attributed to methanol desorbing a thin layer
of water from the PMMA, which causes the layer to be in tension from the
shrinkage back to the unswollen state. This descreases the mobility of the
polymer in this layer and makes the polymer less accommodating to methanol
diffusion [27].
For polymers which are in the glassy state, the removal of diluents or small
molecules may cause an increase in sorption and mass transport properties of the
polymer [32]. It has been found that the removal of liquids from a polymer below
its Tg can increase the porosity within the polymer [32]. This would therefore
result in an increase in the rate of diffusion of diluents such as water and MeOH
into PMMA. It should be noted that there was no reduction in dry weight with
each successive absorption-desorption cycle of water and MeOH, which would
indicate initially that unreacted monomer and other small molecules were not
leaching out. This would also indicate that the initial drying was sufficient to
remove unreacted monomers and other small molecules from the PMMA rods,
and none were further released by the absorption-desorption of methanol and
water.
In a sense, this conditioning of the PMMA rods allows the uptake of increased
amounts of solvent with each successive cycle [33]. These increased uptakes may
be attributed to reduced packing or lack of reconsolidation when the solvent is
removed from the swollen polymer in the glassy sate [32,33]. It may be suggested
that increases in uptake are due to an increase in free volume [33], although no
increase in dry volume was observed. It is possible that not all the methanol was
removed in the drying process, and there may have been some loss of other low
molecular weight materials, such as unreacted monomer, from the PMMA
sample. It has been well established that it is difficult to remove solvents or
monomers from polymers [34]. The PMMA rods were kept in a vacuum at 60 0 C
until no further weight loss was apparent.
It has been shown in previous experiments [32] that, when PMMA is exposed
to solvents such as MeOH, unreacted monomer present within the material will
leach out. It is expected that, after drying the polymer to remove the solvent that
has diffused into PMMA, the zero weight of the sample should decrease.
However, the zero weight of the samples analyzed in this experiment remained
the same. This indicates that not all of the methanol that diffused into the PMMA
is removed during the drying periods between the absorption cycles.
In addition to using weight gain measurements to describe the effects of cycling
on the diffusion characteristics of water and methanol in PMMA, NMRI was
used to observe the solvent front movements within the PMMA rods [27]. The
proton NMR images were obtained for the diffusion of MeOD into three
different PMMA samples. These three samples had previously been subjected to
no, one and two cycles of the absorption and desorptuon of MeOD. The FLASH
images were obtained, and show the movement of the MeOD diffusion front
within the PMMA rods after 5.92,18.75, 23.70 and 31.2Oh. The images showed
that the diffusion of MeOD increased with an increase in the number of cycles.
This corresponded to our previous weight gain experiments. The rate of MeOD
diffusion increased with cycling. A linear dependence of the solvent front move-
ment with time was seen for the PMMA samples subjected to no and to one cycle.
This indicated that case II diffusion occurred after an initial time period of
anomalous diffusion. However, the MeOD front movement for the second cycle
was not linear with time, but rather was linear with the square root of time. After
an initial lag period of anomalous diffusion, the front movement for the second
cycle behaved in a Fickian manner. This indicates that the diffusion character-
istics of the PMMA are altered with absorption-desorption cycling.
The solvent front velocities were determined for case II diffusion as being 12.6
and 14.5 nm/s, respectively. These values are more than twice the magnitude of
those found by Thomas and Windle [35] and by Weisenberger and Koenig [22,
23] for methanol diffusion in PMMA. This can be explained by the fact that the
water content and the drying treatment of the PMMA were never taken into
account in their experiments. The removal of water and the leaching out of
unreacted monomer were also not considered. The increases in diffusion of
MeOD may be accounted for by the plasticization by water of PMM A, which can
be demonstrated between the samples exposed to zero and one cycle. The
increased plasticization allows for the increased rate of relaxation of the polymer
chains and a greater solvent front velocity.
The translational diffusion coefficient was determined to be 4.0 x 10" Vs. This
compares with a value of 2.4 x 10" Vs for the diffusion of methanol into PMMA
at the elevated temperature of 60 0 C reported by Weisenberger and Koenig [22]
for as-received PMMA rods. This shows that, even at a low concentration, the
cyclic absorption-desorption of water and MeOD has a more significant effect
on the characteristics of the methanol diffusion into PMMA than does the
temperature at which diffusion occurs. The value of 4.0 x 10" Vs for the diffusion
of MeOD after two cycles of absorption-desorption of water and MeOD appears
to be comparable with that of MeOD diffusion in PMMA for a high water
content (.25 wt% of polymer).

6.4 ACKNOWLEDGEMENTS
The author acknowledges the support of ALCOM (Advanced Liquid Crystalline
Optical Materials) DMR 8920147 and the students whose work was responsible
for the citations in this paper.

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