Abstracts / Magnetic Resonance Imaging 19 (2001) 569 –589
glass beads of 2 mm in diameter. Experiments were conducted in a variety
of pressure up to 10 MPa in order to investigate feasibility of MR imaging
with gaseous matter in porous media. It is shown that MR imaging pro-
duces methane images with glass beads owing to high proton density at
pressurized fields. On the other hand, some distortion in image was found
on interaction surface between glass beads and methane gas. Adding that,
effect of glass beads on imaging was also investigated by comparing
acquired images with or without glass beads. Furthermore, hydrogen was
used instead of methane to examine influence of gaseous properties on
high-pressure gaseous MR imaging. It is shown that signal intensity on MR
images of hydrogen was much less than that of methane, suggesting that
gas properties considerably affects MR imaging.
References
[1] Albert MS, Cates GD, Driehuys BD, Happer W, Saam B, Springer CS,
Wishnia A. Nature 1994;370:199.
[2] Middleton H, Black RD, Saam B, Cate GD, Cofer GP, Guenther R,
Happer W, Hedlund LW, Johnson A, Juvan K, Swartz J. MRM 1995;
33:271.
[3] Hari P, Chang CTP, Kulkarni R, Lien JR, Watson AT. Magn Resn
Imaging 1998;16:545.
[4] Hirai S, Kuwano K, Ogawa K, Iriguchi N, Okazaki K. Magn Resn
Imaging 2000;18:221.
PII: S0730-725X(01)00359-9
Self-diffusion of fluid in partially saturated porous medium
Uryadov AV, Skirda VD.
Dept. of Molecular Physics, Kazan State University
A number of works [1–3] are devoted to the study of the process of
molecular exchange, occurring at the self-diffusion of liquid in the partially
saturated porous medium. However in the literature there are equations
describing only concentration [2], or only temperature [3] dependence of a
self-diffusion coefficient of the fluid diffusing in the partially saturated
porous medium.
The equation that describes dependence of the self-diffusion coefficient
of fluid, diffusing in the partially saturated porous medium on concentra-
tion and on temperature has been offered in work [4]. The values of the
self-diffusion coefficient calculated from the offered equation, are satis-
factorily agreed with the values of self-diffusion coefficient, measured by
NMR PFG (maximum magnitude of the pulse gradient was 100 T/m) for
such partially saturated by fluid systems as “kaolinite-fluid”, “SiO2-fluid”,
“zeolite-fluid” and “soot-fluid”.
The heats of an adsorption for the investigated systems “porous media-
fluid” have been determine from the analysis of the temperature depen-
dencies of measured self-diffusion coefficient with using of the offered
equation.
This work was supported by INTAS N 96-1177.
References
[1] Karger J, Pfeifer H, Riedel F, Winkler H. J Colloid Interface Sci
1973;44:187.
[2] D’Orazio F, Bhattacharia S, Halperin VP, Gerhardt R. Phys Rev B
1990;42:6503.
[3] Maklakov AI, Dvoyashkin NK. Kolloid zh 1995;57:55.
[4] Uryadov AV, Skirda VC. Izv vyssh uch zav 1999;11:102– 6.
PII: S0730-725X(01)00360-5
1
H MRI applied to low water and/or low mobility systems: solid-
state fermentor and biomats
587
Van As Ha, Nagel F-Jb, Wieland Ac.
a
Laboratory of Molecular Physics and Wageningen NMR Centre,
b
Department of Food Technology and Nutritional Sciences, Food and
Bioprocess Engineering Group, Wageningen University, Wageningen,
The Netherlands, and cMax Planck Institute for Marine Microbiology,
Microsensor Research Group, Bremen, Germany.
The quantitative imaging of low water content and/or low mobility systems
by NMR is a challenge. Due to short relaxation times only part of the water
is visible and has a relatively low (translational) mobility. Examples of
such systems are porous media like solid-state fermentors (SSF) and
biomats. Water and solute relocation processes in these systems are of
eminent importance for optimal operation, but hard to measure. Here we
demonstrate that important data about these processes can be obtained at
good spatial resolution from an incomplete set of information.
1
H MRI was used to characterize water and glucose transport and water
activity on particle level during SSF. Aspergillus oryzae was grown on
wheat flour in a membrane model system. During fungal growth water
consumption needed for biomass synthesis can lead to water-content gra-
dients. In addition, there is a breakdown of starch to glucose by ␣-amylase
excreted by the fungus. Both, water and glucose content have an influence
on the water activity of the solid substrate and consequently on the growth
rate and metabolism of the fungus.
Single parameter images of the amplitude, 1/T 1 and 1/T 2 were ob-
tained at 0.5 T. Although only about 50% of the water signal was visible,
its parameters could be related to moisture content and glucose concentra-
tions through calibration. Water activity profiles could then be estimated
from moisture-content and glucose profiles in the wheat dough. The de-
duced moisture-content profiles correlated well with a water-diffusion
model and the glucose profile was successfully verified with overall glu-
cose measurements [1].
Diffusion is the predominant mode of solute mass transfer between
bacteria and their surroundings, e.g. in microbial mats. Knowledge about
the spatially resolved diffusive properties is a key information for the
interpretation of O2 concentration profiles in terms of rate and depth of O2
consumption/production zones. Diffusive properties of microbial mats
sampled from Solar Lake (Egypt) were obtained by PFG-MSE NMR
imaging. By combining the data of the relative diffusion coefficient (rang-
ing from 0.4 to 0.9) and porosity (based on water content images) apparent
water diffusivity images were calculated, which compared well to apparent
O2 diffusivities measured with a diffusivity microsensor [2]. The high
variability of these parameters correlated well with the laminated distribu-
tion of microbial cells and exopolymers within the mat.
References
[1] Nagel F-J, Van As H, Tramper J, Rinzema A. Biotechnol Bioeng
(submitted).
[2] Wieland A, van Dusschoten D, Damgaard LR, de Beer D, Kuhl M,
Van As H. Limnol Oceanography 2001;46:248 –259.
PII: S0730-725X(01)00361-7
Monte Carlo simulation and NMR measurement of fluid flow and
holdup dispersion in porous media
Vergeldt FJ, Tallarek U, Van As H.
Laboratory of Molecular Physics and Wageningen NMR Centre,
Department of Biomolecular Sciences, Wageningen University,
Dreijenlaan 3, 6703 HA Wageningen, The Netherlands.
NMR displacement imaging can provide a significant insight into steady-
state and transient parameters of transport phenomena associated with fluid
flow through porous media [1]. For example, this approach may contribute
to the characterisation and optimisation of materials and operational pro-
cedures that are used in analytical or preparative liquid chromatography
588 Abstracts / Magnetic Resonance Imaging 19 (2001) 569 –589

[2]. The adequate numerical simulation of these processes is either impos-

Pore diameter [Cu2⫹] Amount of pores
sible or very time-consuming. In this contribution we describe a compar-
(␮m) (ion/cm3) Sc(A2) per cm2
atively simple approach using Monte Carlo techniques. Our goal is the
incorporation and characterization of the purely-diffusive mass transfer 0.04 1.1 ⫻ 1018 285 5 ⫻ 109
resistance in porous media which may cause a considerable holdup dis- 0.07 2 ⫻ 1018 275 5 ⫻ 109
persion. Examples of relevant systems include chromatography columns or 0.08 2.3 ⫻ 1018 273 5 ⫻ 109
catalytic reactors packed with porous adsorbent particles (where only 0.09 2 ⫻ 1018 353 5 ⫻ 109
molecular diffusion occurs in the intraparticle pore space) or consolidated 0.2 7 ⫻ 1017 34 1.5 ⫻ 108
rocks and clays. The results of these simulations are compared to experi- As shown in the Table, the value Sc not strongly depend on the pore diameters but
mental propagators and to the temporal domain of stagnant mobile phase may be determined by the irradiation flow density.
mass transfer resistance obtained from NMR measurements on fixed beds
of highly porous particulate media. The simulations are then extended to an
electroosmotic flow through these media. Its dispersion characterisitics is The charge properties of PETF track etched membrane pore
contrasted to viscous flow behaviour. surface on the Cu2ⴙ ESR data
Hong Y-Sa, Cho C-Ha, Mitrofanova NVb, Nechaev AN,b, Volkov VI,b,
Mchedlishvili BV,b, Lee C-Ha.
a
Center for Advanced Food Science and Technology, Graduate School
References of Biotechnology, Korea University, Seoul, Korea
b
Shubnikov Institute of Crystallography, Russian Academy of Science,
[1] Tallarek U, Vergeldt FJ, Van As H. J Phys Chem B 1999;103:7654. Moscow, Russia
[2] Tallarek U, Bayer E, van Dusschoten D, Scheenen T, Van As H, (This investigation was supported by RFBR, grant N00-03-32099.)
Guiochon G, Neue UD. AIChE J 1998;44:1962.
Track-etched membranes are the pore system possessing the regularly
PII: S0730-725X(01)00362-9 oriented pores with very narrow pore size distribution. It was proposed that
polyethylene terephtalate (PETF) track-etched membranes contain the car-
boxylic groups. The carboxylic groups behaviours was investigated by the
Cu2ⴙ ESR investigation in acrylonitrile sulfocation exchange Cu2⫹ ESR, where Cu2⫹ ions were included in membrane as paramagnetic
membranes probes. The EPR spectra consist of anisotropic lines at 293 K as well as at
Hong Y-Sa, Cho C-Ha, Dejardin Pb, Thomas Mb, Volkov VIc, 77 K, which is typical for the Cu2⫹ complexes possess the axial symmetry
Mchedlishvili BVc, Lee C-Ha. in disordered solid state. It was obtained two types of complexes charac-
a
Center for Advanced Food Science and Technology, Graduate School terized by the spin Hamiltonian parameters g储 ⫽ 2.32, A储 ⫽ 170 G, g⬜ ⫽
of Biotechnology, Korea University, Seoul, Korea 2.05, A⬜ ⫽ 25 G (complex A) and g储 ⫽ 2.27, A储 ⫽ 180 G, g⬜ ⫽ 2.06
b
University Montpellier II, Montpellier, France (complex B), respectively, where g储, A储-g-factor and hyperfine coupling
c
Shubnikov Institute of Crystallography, Russian Academy of Science, constant in parallel orientation; g⬜, A⬜-g-factor and hyperfine constant in
perpendicular orientation. It is possible to propose that complex A contains
Moscow, Russia
two carboxylic groups and two water molecules, Cu(R-COO)2(H2O)2, but
Using the ESR technique, we have investigated the behaviour of Cu2⫹ ions complex B contains four carboxylic groups and two water molecules,
sorbed by sulfocation exchange films and fibres, AN 69 type, which are the Cu(R-COO)4(H2O)2.
copolymer of acrylonitrile and methallyl natrium sulfonate. The ESR Keeping in mind the cylindrical shapes of pores, the area of pore walls
per one carboxylic group, Sc, was calculated from maximum Cu2⫹ mem-
spectra were recorded at 77 K and 293 K. At the room temperature the ESR
brane concentration [Cu2⫹].
spectra of membranes with maximum water content consist of two lines:
anisotropic line as at the 77 K and isotropic symmetric line belongs to the PII: S0730-725X(01)00364-2
fast rotating copper complexes. For the air dry samples, the spectrum is
anisotropic broadened line, the shape of this line doesn’t depend on the
temperature. This spectrum belongs to the unmobile Cu2⫹ complexes The self-diffusion of water and membrane structure in the new type
which are close to each other in order Cu2⫹ unpaired electrons interact by of cation-exchange polyamide-acid membranes
Sokolova SAa, Djakonova OV,a Kotov VVa, Hong Y-Sb, Cho C-Hb,
means electronic dipole-dipole interaction. The spin-Hamiltonian parame-
Volkov VIc, Lee C-Hb.
ters for anisotropic and isotropic lines are g ⫽ 储 2.409; A储 ⫽ 130 G; g⬜ ⫽ a
Department of Chemistry, Voronez State Agricultural University,
2.08; go ⫽ 2.19; gav ⫽ 2.19 where g储, A 储 is hyperfine coupling constant in
Voronez, Russia
parallel orientation, g ⬜-g-factor in perpendicular orientation, go-isotropic b
Center for Advanced Food Science and Technology, Graduate School
g-factor, gav-the average g-factor calculated as (2 g⬜ ⫹ g储)/3. The Cu2⫹ of Biotechnology, Korea University, Seoul, Korea
ions exist in the sulfocation exchange membranes as aquacomplexes c
Shubnikov Institute of Crystallography, Russian Academy of Science,
[Cu(H2O)6]2⫹ even in the dry samples. The Cu2⫹ ions interact to the SO3⫺ Moscow, Russia
groups by means of electrostatic interaction. For this reason the main part
of aqua complexes is rotating very fast in the membrane with the maximum It was supposed that high selectivity of polyamide acid membranes is
water content. The value of the complex rotation frequency is about 1011 determined by specific of water and ionic diffusion channels structure.
Hz. Some Cu2⫹ complex as (about 10%) are undergone to the geometrical Using IR-spectroscopy the particularities of water binding were under-
restriction and its rotation frequency less than 108 Hz. In the air dried stood. The self-diffusion processes were investigated by pulsed field gra-
membranes, the [Cu(H2O)6]2⫹ complex motion is restricted for all com- dient NMR. ESR Cu2⫹ was used in order to investigate the carboxylic
plexes and its spectrum consist of the anisotropic line even at room groups distribution.
temperature. For the maximum water content the sulfogroups are far from Thin membranes (30 –50 ␮m) were made after thermal treatment of
each other and Cu2⫹ ions spectrum shows the isolated behavior. During the line copolymer of 1,2,4,5-tetracarbonic acid with 4,4⬘-diaminediphenylox-
ide in the interval 383– 448 K.
drying the distance between the SO3⫺ groups become less because of
From the IR spectroscopy data the water sorbed in membranes was
magnetic dipole-dipole interaction between Cu2⫹ ions.
divided into four parts; (1) water with the normal hydrogen bond network
PII: S0730-725X(01)00363-0 (3420 cm⫺1); (2) water with damaged hydrogen bond network (3627, 3567