A NMR Technique for the Analysis of Pore Structure: Numerical Inversion

of Relaxation Measurements

KEVIN MUNN AND D O U G L A S M. S M I T H

UNM Powders and Granular Materials Laboratory, Department of Chemical and Nuclear Engineering,
University of New Mexico, Albuquerque, New Mexico 87131
Received June 23, 1986; accepted November 10, 1986

NMR spin-lattice relaxation measurements of fluids contained in porous solids could be a powerful
tool for pore size/structure analysis. It does not suffer from many of the inherent disadvantages of
mercury porosimetry/nitrogen condensation such as the necessity of a pore shape assumption, measuring
only the smallest constriction in a pore, sample compression (porosimetry), and limited pore size range
(condensation). However, the successful extraction of the desired pore volume distribution from exper-
imental spin-lattice relaxation measurements requires the solution of an "ill-posed" problem. A recently
developed nonnegatively constrained least-squares (NNLS) algorithm was used to approach this problem.
Two methods were used including matching relaxation data in real time using the NNLS algorithm and
transforming both the data and the governing equations into the frequency time domain and subsequent
matching with NNLS. Numerical experiments were conducted using artificial pore size distribution data
generated for a variety of distribution types. The two methods were used to analyze both the exact
generated data and the generated data containing 5% random error. Direct analysis of the data was more
accurate in reproducing the artificial pore structures than the Fourier transform analysis except in the
limit of high experimental noise. Deconvolution of the artificial pore structure from exact data gave
nearly exact results. Analysis of data after introducing 5% random error to the data yielded less accurate,
yet stable results. Small oscillations in the calculated distributions were noted but these are on the same
order of or smaller than those normally encountered in porosimetry/condensation experiments. ©1987
Academic Press, Inc.

INTRODUCTION
Investigators in the field o f nuclear m a g n e t i c
r e s o n a n c e logging for p e t r o l e u m f o r m a t i o n s
have observed t h a t fluids in the vicinity o f a
surface will u n d e r g o s p i n - l a t t i c e r e l a x a t i o n at
a faster rate t h a n fluids far r e m o v e d f r o m the
surface (1). This suggests t h a t i f one c o n d u c t s
a s p i n - l a t t i c e r e l a x a t i o n e x p e r i m e n t o n fluids
c o n t a i n e d in a p o r o u s solid, one should be able
to ascertain p o r e structure i n f o r m a t i o n a b o u t
the solid. N M R p o r e structure analysis c o u l d
be a p o w e r f u l new tool since it does n o t suffer
f r o m m a n y o f the p r o b l e m s i n h e r e n t to m e r -
cury porosimetry and adsorption/condensa-
t i o n analysis. T h e s e p r o b l e m s i n c l u d e the ne-
cessity o f a p o r e shape a s s u m p t i o n , m e a s u r i n g
the smallest c o n s t r i c t i o n in a p o r e r a t h e r t h a n
the average size, l i m i t e d s a m p l e size, s a m p l e
c o m p r e s s i o n (porosimetry), a n d n a r r o w p o r e
size range ( a d s o r p t i o n / c o n d e n s a t i o n ) . D e s p i t e
the p o t e n t i a l a d v a n t a g e s o f N M R s p i n - l a t t i c e
r e l a x a t i o n m e a s u r e m e n t s as a p o r e structure
analysis tool, the m e t h o d has n o t b e e n pre-
viously d e m o n s t r a t e d as a viable tool. T h e
m y r i a d o f p o r e d i a m e t e r s typically f o u n d in
p o r o u s m a t e r i a l s requires the s o l u t i o n o f an
unstable, " i l l - p o s e d " p r o b l e m to extract the
desired p o r e size d i s t r i b u t i o n f r o m the ob-
served r e l a x a t i o n data.
In this paper, we investigate the p r o p e r t i e s
o f the F r e d h o l m integral e q u a t i o n w h i c h m u s t
be successfully i n v e r t e d to extract the desired
p o r e size d i s t r i b u t i o n f r o m the o b s e r v e d re-
laxation decay. Several n u m e r i c a l schemes are
investigated a n d their sensitivity to r a n d o m
e x p e r i m e n t a l m e a s u r e m e n t errors is deter-
m i n e d . In a following p a p e r (2), we illustrate

117
0021-9797/87 $3.00
Copyright © 1987 by Academic Press, Inc.
Journal of Colloid and Interface Science. Vol. 119, No. 1, September 1987 All fights of reproduction in any form reserved.
118
the application of this method to the charac-
terization of a wide range of actual porous
media.
BACKGROUND
Quantitatively, the return to equilibrium of
the magnetization vector for a fluid following
a 180 ° rotation applied in an external mag-
netic field is given by (3)
M(t) =Mo(1 - 2 exp(--t/Tl)),
where M(t) is the measured magnetization at
time t, M0 is the equilibrium magnetization,
and T1 is the spin-lattice relaxation decay
constant. If bulk fluid or fluid contained in a
single pore size is studied, an exponential de-
cay with a single characteristic time, T~, is
noted.
If diffusion in the pores is much faster than
relaxation, the "two-fraction, fast-exchange"
model may be employed (4, 5). Two distinct
phases are assumed to exist: a phase removed
from the pore surface with spin-lattice relax-
ation properties equal to those of bulk water
and a surface phase with a much smaller decay
time. Therefore, the value of Tl, the observed
decay time, is described by
1/T1 =fa,/Tlb q-fb/Tlsurface,
where T~b is the relaxation time for bulk water,
T~su~a~ is the relaxation time for water affected
by the pore surface, and f~ and fb are the frac-
tions of water in the bulk and surface phases,
respectively. Since the volume of the surface
phase is small except for microporous mate-
rials (6), the pore volume to surface area (i.e.,
the hydraulic radius) is directly related to the
fraction of water in the surface phase, J~.
Multiple masses of water with different
characteristic T~ values contributing to a single
signal form the basis for the inversion problem
which must be solved to extract the desired
pore volume distribution from the M(t) data.
Figure 1 graphically illustrates the effect with
two hypothetical decay curves, one corre-
sponding to a single T~ value decay (T1 = 0.52
s) and one showing the value of the magneti-
Journal of Colloid and Interface Science, VoL 119, No. 1, September 1987
MUNN AND SMITH
7 "~'f ~
O.5-
o . . . . .
-0.5-
I/ SINGLE COMPONENT DECAY.
[1]
o12 o14 0:6 o18
t(s)
FIG. 1. Relaxationcurvesforsingleanddualcomponent
systems.
zation decay if two components (T~'s = 0.16
and 1.68 s) contribute equally to the overall
signal. For water confined within a network
of pores, the total magnetic signal will be the
sum of the individual molecular magnetiza-
tions. These magnetizations relax at different
rates, corresponding to the T~ value charac-
teristic of that pore volume to surface area
(PV/SA) ratio. The measured magnetic signal
is
f Tlraax
M( t) = Mo [1 -
d T lmin
[2]
2 exp(-t/T1)]f(T1)dT,, [3]
wheref(T1) is related via Eq. [2] to the desired
pore size distribution. Equation [3] is a Fred-
holm integral equation of the first kind. With
the presence of multiple decays, each contrib-
uting with different magnitudes, an experi-
mental decay curve that can be described
closely by many T1 value/magnitude combi-
nations results. Small changes in the M(t) data
may result in significant variations in f ( T O
and, hence, the problem is ill-posed.
Traditionally, the problem of inverting Eq.
[3] has been avoided by finding one mean T1
which is an indication of the mean pore radius.
Loren and Robinson (7) related mercury in-
jection pressure to a single T1 obtained from
a semilog plot of M(t) versus t for several por-
celain and sandstone samples. Both water and
 NUMERICAL INVERSION
decane were used and measurements were
made at temperatures of311 and 339 K. Rea-
sonable agreement between the two techniques
was noted. In a study of rock wettability by
N M R techniques, Brown and Fatt (8) also
avoided the solution of Eq. [3] by using a single
T~. Loren (9) related the mean T~ of porous
solids to the sample's permeability. Cowgill et
aL (10) assumed that their M(t) data could be
described by the sum of three exponential
components for spin-lattice relaxation in
sandstones in an effort to correlate perme-
ability and spin-lattice relaxation. A least-
squares routine was used to extract the three
Tl'S and the relative fraction of water with each
component.
The simplest approach to solving Eq. [3] in
order to obtain a T~ distribution is to use the
so-called direct approach. The Fredholm in-
tegral equation is approximated as a finite se-
ries of discrete T1 intervals. The domain of
T~minthrough T~maxis divided into I intervals:
N strained), this method will converge to a
M(ti) = Mo ~, K(ti, Tlj)f (Tlj)A Tlj
j=l
i = 1. . . . , L
Equation [4] can be rewritten in matrix form:
M= KAT~f
The elements of K are given by
K(ti, TIj) = M0[1 - 2 exp(-ti/Tlj)]
j = l . . . . . N, i = 1 . . . . . I.
Given that the elements of K a r e smooth func-
tions and I is sufficiently large, Eq. [4] should
approximate Eq. [3] fairly accurately. Equa-
tion [6] may be solved to yield the T1 distri-
bution, f ( T l ) :
f= AT~IK 1M.
In general, this direct approach will be quite
sensitive to noise in the data.
The problem of extracting adsorption en-
ergy site distributions from adsorption iso-
therms is similar to that encountered in this
work. A variety of techniques have been era-
OF RELAXATION MEASUREMENTS 1 19
ployed to attack this problem and are reviewed
by House (11). Sacher and Morrison (12) used
four different algorithms for the solution of
Eq. [7] to extract adsorption energy distribu-
tions. The methods tested include Dantzig's
simplex method, systematic overrelaxafion
(SOR) method, Lemke's complementary pivot
algorithm, and a nonnegatively constrained
linear least-squares (NNLS) routine. Of the
four methods, the nonnegafively constrained
least-squares routine developed by Lawson
and Hanson (13) was found to be significantly
faster and more resistant to round-off errors
than the other three methods. This routine is
"numerically stable" which means that the er-
ror in the solution caused by uncertainty in
the data and round-off error accumulated
during the computation can be bounded.
Wesson et al. (14) have stated explicitly that
if the number of distribution values is signif-
icantly less than the number of data points
(i.e., the problem is significantly overcon-
unique solution for the desired adsorption en-
ergy distribution.
Brown and co-workers (15, 16) have used
[4]
Tikhonov's method of "regularization" (17)
in an attempt to extract pore volume distri-
butions from spin-lattice relaxation measure-
[5]
ments. The advantage of this method is that
a continuousf(T~) distribution is obtained in-
stead of discrete values. Butler and co-worker's
(18) modification of this method, which in-
[6] cludes the constraint that only nonnegative
values o f f ( T 0 are physically acceptable, is
used. The disadvantage of this regularization
technique is that the magnitude of the regu-
larizafion parameter, 6, must be specified. The
f(T~) distribution takes on different values for
each value of 6. As 6 is decreased, f(T1) be-
[7] comes more structured and will start oscillat-
ing as 6 approaches zero. The optimum 6 value
is a function of the data noise level and cannot
be explicitly determined. Brown and co-work-
ers created artificial M(t) data with no noise
from assumed unimodal and bimodal T1 dis-
tributions. Agreement between the calculated
and starting distributions was good. Compar-
Journal of Colloid and Interface Science, Vol. 119, No. 1, September 1987
 120
ison between NMR derived and mercury po-
rosimetry pore size distributions is less clear
since the surface effect parameter, TIsurfac~,was
allowed to vary for each sample to minimize
the observed difference between the two
methods.
A significant body of literature exists on the
matching of experimental data to exponential
decay models. In addition to NMR relaxation,
this problem is of importance in a wide range
of fields including chemical kinetics, Laplace
transform inversion, and astrophysics. Tech-
niques for solving the problem range in com-
plexity from direct inversion, as discussed
above, to complex, multiple-step procedures.
These methods have included Fourier analysis
(19-21), Z-transforms (22), and spline ap-
proximations (23). Since the problem consid-
ered here is whether direct inversion of relax-
ation data in the real-time or frequency-time
domains results in reasonable approximations
to the desired pore size distribution, no exten-
sive review of the literature is included. For
NMR pore size analysis to be practical, the
f(Tl) calculation must be relatively straight-
forward and computationally efficient even if
mathematical rigor must be sacrificed.
MATHEMATICAL ANALYSIS
Since the NNLS scheme is numerically sta-
ble, very fast, easy to implement, and proven
to be effective for the similar problem of cal-
culating adsorption energy distributions, it
appears that this scheme may be useful for the
inversion of spin-lattice relaxation data. For
this work, the NNLS routine is used to min-
imize
[IM--KATlfI[. [8]
The NNLS routine iteratively solves the
least-squares problem given above by using a
Householder orthogonal transformation ap-
plied to the upper diagonal matrix QA where
the matrix A represents KAT1 in Eq. [8]. After
each solution step, the coefficients of the so-
lution matrix, f are checked for nonnegativity.
If a coefficient is less than zero, it is set equal
to zero. The process is repeated until Eq. [8]
Journal of Colloid and InterfaceScience, Vol. 119, No. 1, September1987
M U N N AND SMITH
is minimized such that all elements of f a r e
zero or positive. The complete details of the
scheme are given by Lawson and Hanson (13).
First, the kernal in Eq. [4] is modified to a
simple exponential decay (from 1.0 to 0.0 in-
stead of from -M0 to +M0) and the data ma-
trix, 214, is transformed accordingly. With the
kemal defined as such, the Fourier transform
of the M(t) curve is finite and it is easier to
append zero values to the experimental data
for large times when the system has essentially
reached equilibrium. The elements of the
modified kernal matrix for the real time
matching are
K(ti, Tlj) = exp(-ti/Tlj). [9]
In addition to matching the experimental
magnetization data in the real-time domain,
both the data and the model may be trans-
formed into the frequency-time domain before
the model parameters are determined. The
application of an integral transform serves to
average high-frequency experimental noise.
This approach has worked quite well in other
parameter-matching problems such as the
chromatographic determination of adsorp-
tion/diffusion parameters (24, 25). The ex-
perimental data and the multiple exponential
decay model equations are transformed via the
application of a Fourier transform (26):
M(~o) = M(t)exp(-iwOdt. [10]
Expressions for the theoretical (i.e., model)
Fourier series coefficients, a,-mod and bn-mod,
are obtained by transforming Eqs. [4] and [9]
and separating M(~0) into real and imaginary
components, an-rood and b n - m ~ a r e
Pf(Tlj)ATlj T~j
an_mo d = -- nTr
j=l p2+n27r2T2J [11]
and
Pf(TIj)ATljT1j
bn-mod = j=l p2+n27r2T2j [12]
The derivation of these expressions is detailed
in Appendix A. The distribution, f (T1), is ob-
 NUMERICAL INVERSION OF RELAXATION
tained by matching the theoretical coefficients
to those obtained from the M(ti) data. The
experimental Fourier coefficients are obtained
from
a,_exp =
;--M(t)cos(wt)dt/{;.
o J
P M(t)dt
[13]
and
bn-exp= i2P M(t)sin(wt)dt/[ p fo2"M(t)dt] .
[14]
We make the arbitrary decision to match
only the real portions of M(~0). Therefore, the
elements of the M matrix in Eq. [8] are defined
by Eq. [13]. The elements of the K matrix are
given by Eq. [11] divided byf(Tlj)ATlj. The
transformation yields the same number of
transformed data points as raw experimental
data points (as n is defined as going from 1 to
/, the number of raw data points). Thus, the
criterion of overdetermination is still satisfied
(14). The difference is that the problem is now
a function of n, P, and TI instead of time and
7"1. In principle, the analysis should be inde-
pendent of the period, P.
We attempt to solve the problem given by
Eq. [8] by matching in both the real- and the
frequency-time domains. To determine which
analysis scheme would yield the best results,
the two were compared in reproducing known
distributions. The two techniques were first
applied to deconvolutions involving only one
or two discrete T1 components. After estab-
lishing the accuracy and stability of the nu-
merical schemes in this manner, the number
of T~ values was expanded to give a more re-
alistic representation of an actual pore size
distribution. The maximum range of antici-
pated experimental error/noise was used in the
comparison of the Fourier transform (FF) and
non-Fourier transform (non-FT) techniques.
A distribution i n f ( T 0 is defined and then
used to generate an "experimental" data ma-
trix, M, as given by Eq. [4]. This data set is
analyzed directly in the non-Fourier transform
MEASUREMENTS 121
case. For FT analysis, M is transformed into
the frequency-time domain using Eq. [13].
Equation [13] is evaluated numerically using
Filon's cosine formula (27). Both schemes
employ the identical NNLS algorithm, the
only differences being the Kand M matrix def-
initions. The analysis is performed using 100
generated M(t) points and 50f(T1) "patches"
equally spaced on a logarithmic axis covering
three cycles of TI (0.001 to 1.0 s). All numer-
ical experiments were conducted using a VAX
11/785 computer with double-precision ac-
curacy. To ascertain the sensitivity of both
schemes to experimental error, varying
amounts of between 0 and 5% random uni-
form error are introduced into the M(t) data.
The comparison is repeated for f(Tl) distri-
butions containing two separate Gaussian
peaks (to simulate a bimodal pore size distri-
bution around two different radii). The differ-
ence between two adjacent peaks is varied to
determine the capability of differentiating be-
tween neighboring pore sizes. For all numer-
ical experiments, the M(t) decay curve was
calculated from f(TO and Eq. [4] and com-
pared to the initial M(t) curve. Typical values
of the L2 norm were on the order of 0.005 for
the non-FT scheme and 0.01 for the FT
scheme. Complete details of these numerical
experiments are reported by Munn (28).
RESULTS
As a first test, the non-FT and FT schemes
were used to deconvolute M(t) data artificially
generated using single or dual delta functions
forf(Tl). These deconvolution results accu-
rately reproduced the delta functions, which
were then replaced by more realistic artificial
representations of actual pore size distribu-
tions. A comparison of the two analysis
schemes for a single Gaussian distribution is
shown in Figs. 2 and 3. Values of the distri-
bution which are calculated to be zero are not
included. For the non-FT analysis, the single
broad peak was fit well although, instead of
the smooth starting function, the calculated
distribution suffered from some small oscil-
lations. The distribution calculated using the
Journal of Colloid and Interface Science, Vol. 119, No. 1, September 1987
 122 M U N N AND SMITH

0.8 GENERATED GENERATED

0.8
O CALCULATED El C A L C U L A T E D

0.6- 0.6

ff
0.4 q~

II
0.2. 0,2

0
o.ool . . . . . . b.'Ol . . . . . . . . 6:1 ........ 0.001 0.01 0.1
T1
T1

FIG. 2. Deconvolution of a single Gaussian distribution FIG. 4. Deconvolution of a dual Gaussian distribution
using the non-FT algorithm. No error case. using the non-FT algorithm. No error case.

FT scheme located the middle of the generated
peak quite well but was considerably narrower
than the starting peak.
Figu?es 4 and 5 include the generated and
calculated T~ distributions for a bimodal dis-
tribution. Two Gaussian peaks with mean T~
differing by approximately one order of mag-
nitude are used to calculate M(t) with no ran-
dom noise. For the non-FT case, Fig. 4, the
generated and calculated T~ distributions are
virtually identical. However, for the FT
scheme, Fig. 5, only the larger of the two peaks
could be reproduced. The smaller calculated
peak varied by a factor of 2 from the starting
peak.
Comparison of the two methods after ad-
dition of 5% uniform random error to the M(t)
data, the maximum expected for actual mea-
surements, is shown in Figs. 6 and 7 for a single
Gaussian distribution. The FT method dem-
onstrates negligible change in the calculated
distribution case indicating that the filtering
inherent to the FT analysis does serve to min-
imize the effects of random noise. The non-
FT method, in identical circumstances, does
lose accuracy, as compared to the exact case,
and splits the single broad generated peak into
two narrower peaks. However, the accuracy
of the non-FT and FT schemes is still on the
same order at this upper error bound.

0.8- GENERATED GENERATED

D CALCULATED CALCULATED

0.6- .6
I-

"~ 0.4-

[I
0I o . . . . . . . ~.~ . . . . . . . . . . . .
0.001 0.01 0,1 0.001 0.01 0.1
T1 T1

FIG. 3. Deconvolution of a single Gaussian distribution FIG. 5. Deconvolution of a dual Gaussian distribution
using the FT algorithm. No error case. using using the FT algorithm. No error case.

Journal of Colloid and Interface Science, Vol. 119, NO. 1, S e p t e m b e r 1987

 N U M E R I C A L INVERSION OF R E L A X A T I O N M E A S U R E M E N T S 123

GENERATED
0.8- GENERATED
D CALCULATED D CALCULATED

0.6- 6-

4-

A ......l
0,2- 2~

0[ 0( . . . . . . . . . . . . .

0.001 0.01 0.1 0.001 0.1 0,01

T1 T1

FIG. 6. Deconvolution of a single Gaussian distribution FIG. 8. Deconvolution of a dual Gaussian distribution
using the non-FT algorithm. Five percent error case. using the non-FT algorithm. Five percent error case.

Similar conclusions can be drawn from
comparison of the dual Gaussian distribution
cases with 5% random noise, Figs. 8 and 9.
For the non-FT method, agreement between
the calculated and the generated peaks is ex-
cellent and better than that for the single broad
peak illustrated in Fig. 2. The addition of 5%
noise has little effect on the FT method since
the calculated distribution is virtually the same
as the no noise case, Fig. 3.
The problems with the Fourier transform
approach are small but significant. Theoreti-
cally, the value of the period, P, is of no con-
sequence as long as it is chosen small enough
so that several cycles of the cosine function
are represented. The value chosen for P, how-
ever, is not inconsequential (i.e., different val-
ues of P yield differentf(T1) distributions). It
should be noted that the FT results in this
study are "best-case" results. The value of P
is varied to achieve the best fit to the known
Gaussian distributions. The optimum P value
was not based upon any of the problem pa-
rameters but was arrived at by trial and error.
This approach could not be used for the in-
version of spin-lattice relaxation data in prac-
tice since it implies some prior knowledge of
the usually unknown pore size distribution.
Apparently, this large dependence of the cal-
culated Tl distribution on P arises from the

GENERATED GENERATED
8-
D CALCULATED D CALCULATED

0.6- 6

'~ 0.4- 4-

2.

0[
0.001 0.01 0.1 0.001 0.01 0,1

T1 T1

FIG. 7. Deconvolution of a single Gaussian distribution FIG. 9. Deconvolution of a dual Oaussian distribution
using the FT algorithm. Five percent error case. using the FT algorithm. Five percent error case.
Journal of Colloid and Interface Science, Vol. 119, No. 1, September 1987
 124 MUNN AND SMITH

errors involved in the calculation of an-exp, Eq.

[13], using Filon's formula.
At all levels of error (up to 5% r a n d o m er- 0.8 GENERATED

[] C A L C U L A T E D
ror), the performance of the non-FT analysis
scheme was superior to the Fourier transform 0.6"

method. The FT method is less sensitive to

the level of noise in the data but errors in the <~ 0.4-
numerical integration required to generate
an-exp caused a significant loss in accuracy even
for the exact (i.e., no noise) comparison. 0.2- .~t
However, the FT scheme m a y have utility for
0 . . . . . . . . . . . . . . . . . . . . . . . .......
inverting data with a large degree of uncer- 0.001 0.0 0.1

tainty. T1

As the non-FT analysis was established as FIG. l 1. Deconvolution of two Gaussian peaks in close
the superior scheme, it was desired to test its proximity using the non-FF algorithm. Five percent error
ability to discern separate distributions in close case.
proximity to each other. This was achieved by
moving the two peaks in the dual Gaussian one might expect that the resolution of the
distribution case closer to each other. Any two peaks would become quite difficult. Figure
breakdown in resolution as the two peaks 12 illustrates this comparison for the exact
neared each other could be observed for both case. Excellent agreement is noted between the
exact and error-containing data. Figures 10 generated and the calculated distributions.
through 13 are the results of this resolution When 5% error is introduced, Fig. 13, both
analysis. Figure 10 contains generated and peaks are identified but the relative magni-
calculated plots for two peaks with m e a n T1 tudes are quite different. This last comparison
of 0.015 and 0.026 s and no r a n d o m error. represents a worst-case analysis for N M R pore
The reproduction of the generated peaks is es- structure analysis since the data is assumed to
sentially exact. When 5% error is introduced be so noisy and the two peaks overlap. Con-
into the same comparison, the two calculated ventional pore size analysis techniques such
peaks appear at the correct Tl's but the peak as mercury porosimetry and nitrogen adsorp-
heights are slightly different. When the two tion would also have difficulty differentiating
peaks are even closer to each other (mean TI between the two peaks for this starting distri-
= 0.015 and 0.019 s) such that they overlap, bution.

GENERATED 0,8. GENERATED

D CALCULATED ~CALCULATED

A 0.6-

<~ 0.4. 0.4-

0,2- 0.2.

o . . . . . . . . . . . . . . . . , . . . . . . . . O . . . . . . . . . . . . . . . . . . . . . . . . .
o.ool O.Ol o.1 0.001 0.01 0.1

T1 T1

FIG. 10. Deconvolution of two Gaussian peaks in close FIG. 12. Deconvolution of two overlapping Gaussian
proximity using the non-FT algorithm. No error case. peaks using the non-FT algorithm. No error case.
J o u r n a l o f C o l l o i d a n d I nt er f ac e Science, Vol.119,No. 1,September1987
 NUMERICAL INVERSION OF RELAXATION MEASUREMENTS 125

proximation have even been reported (30).

One would expect that using this approach to
0.8- GENERATED
obtain a smooth pore volume distribution
D CALCULATED
would lead to even larger errors than those in
O.6- the N M R technique. The method of regular-
I-
v ization could be employed to calculate a
<~ 0.4- smooth distribution from the inversion of M(t)
data. However, the uncertain value of 6 and
0.2-
greatly increased computation time would
seem to preclude its use for the determination
of pore size distributions.
o[i . . . . . . . . ,
o.ool O.Ol o'.1 With the NNLS method described, N M R
T1
spin-lattice relaxation measurements can
FIG. 13. Deconvolution of two overlapping Gaussian serve as a powerful new tool for pore size anal-
peaks using the non-Fl" algorithm. Five percent error case. ysis. In subsequent papers, we will detail the
application of this technique to the actual de-
termination of pore size distributions.
Other comparisons have been conducted to
determine the effects of the number of data APPENDIX: NOMENCLATURE
points,/, and T1 intervals, N, on the inversion
of relaxation data. In general, differences be- f(T1) Distribution of T1.
tween the assumed and the calculated distri- f(PV/SA) Pore volume distribution.
butions were the same as I and N were de- fa Fraction of fluid in the bulk
creased. Only when the starting distribution phase.
was nonzero over a wide range of TI were J~ Fraction of fluid in the surface
matching problems noted. This could be cor- phase.
rected by choosing a larger Tlmin-Tlmaxrange I Number of data points.
at the expense of a lower resolution ofthef(T~) M0 Equilibrium magnetization.
curve. M(t) Magnetization at time t.
M(w) Fourier transform of M(t).
CONCLUSIONS N Number of discrete fvalues.
P Fourier transform period.
The application of the NNLS routine de-
PV/SA Pore volume to surface area ratio.
veloped by Lawson and Hanson (13) to the
rp Average pore radius.
direct inversion of simulated spin-lattice re-
t Time.
laxation data allows the fast and accurate cal-
T1 Overall spin-lattice relaxation
culation of T1 distribution. The scheme is rel-
time.
atively insensitive to random experimental
Tlb Bulk liquid spin-lattice relaxation
noise although, if the noise level is very high,
time.
a Fourier transform approach has also been
developed which is relatively insensitive to the Tlsurface Surface spin-lattice relaxation
time.
noise level at the expense of lower accuracy.
6 Regularization parameter.
Although calculated T1 distributions, and,
60 Frequency, mc/P.
hence, pore volume distributions, display
some small oscillations, these oscillations are
APPENDIX A
no larger than what is often calculated in mer-
cury porosimetry and/or nitrogen condensa-
Starting with the Fourier transform (21):
tion experiments (29). Recently, efforts to
smooth porosimetry/condensation pore vol-
M(w) = M(t)exp(-iwOdt. [10]
ume distributions with a spline function ap-
Journal of Colloid and Interface Science, Vol. 119, No. 1, September 1987
 126 MUNN AND SMITH

Combining Eqs. [4] and [9] and applying 4. Brownstein, K. R., and Tarr, C. E., J. Magn. Reson.
Eq. [10]: 26, 17 (1977).
5. Senturia, S. D., and Robinson, J. D., Soc. Pet. Eng.
J. 10, 237 (1970).
M(w) =
f?exp(-i~t) 6. Woessner, D. E., J. Magn. Reson. 39, 297 (1980).
7. Loren, J. D., and Robinson, J. D., Soc. Pet. Eng, J.
N 10, 268 (1970).
× ~f(Tlj)exp(-t/Tlj)LXTlflt. [A.1] 8. Brown, R. J. S., and Fatt, I., Pet. Trans. AIME 207,
j=l 262 (1956).
9. Loren, J. D., J. Pet. Technol. 923, August (1972).
Rearranging terms: 10. Cowgill, D. F., Pitman, J. K., and Seevers, D. O.,
"Proceedings of the 1981 SPE/DOE Low Perme-
ability Symposium, Denver, CO," SPE/DOE
M(o~) = ~ f (rli)2~Tlj
j=l N ff #9875, p. 437. 1981.
1I. House, W. A., "Colloid Science," Vol. 4. Royal Society
×exp[-t(iw+ 1/T~j)]dt. [A.21 of Chemistry, London, 1983.
12. Sacher, R. S., and Morrison, I. D., J. Colloidlnterface
Integrating [A.2]: Sci. 70, 153 (1979).
13. Lawson, C. L., and Hanson, R. J., "Solving Least
N
T l j (1 - iwTlj) Squares Problems." Prentice-Hall, Englewood
M(w) = ~ f ( T I j ) A T l j Cliffs, NJ, 1974.
j=l
( 1 + w2T~j)
14. Wesson, S. P., Vajo, J. J., and Ross, S., J. Colloid
[A.3] Interface Sci. 94, 552 (1983).
15. Brown, J. A., Brown, L. F., Jackson, J. A., Milewski,
Separating [A.3] into real and imaginary com- J. V., and Travis, B. J., "Proc. of the SPE/DOE
ponents: Unconventional Gas Recovery Symp.," p. 201.
1982.
= ;f(TIj)ATljT1j 16. Brown, J. A., Brown, L. F., Jackson, J. A., and Travis,
M(w) j~ (1 + w 2 T ~ j ) B. J., in preparation.
17. Tikhonov, A. N., and Arsenin, V. Y., "Solutions of
f ( T I j ) A T l j T1j Ill-Posed Problems." V. H. Winston & Sons,
rA.41Washington, DC, 1977.
18. Butler, J. P., Reeds, J. A., and Dawson, S. V., SIAM
J. Numer. Anal 18, 381 (1981).
The Fourier transform may also be written as
19. Gardner, D. G.,Ann. N.Y. Acad. Sci. 108, 195 (1976).
M(o~) = P[bn - Jan]. [A.5] 20. Provencher, S. W., Biophys. J. 16, 27 (1976).
21. Clark, A. H., and Lillford, P. J., J. Magn. Reson. 41,
By equating the real and imaginary compo- 42 (1980).
nents of [A.4] and [A.5], defining ~o as mr~P, 22. Szamosi, J., and Schelly, Z. A., or. Phys. Chem. 88,
and rearranging, the Fourier coefficients, 3197 (1984).
an-moa and bn-moa, are obtained: 23. Holt, J. N., and Jupp, D. L. B., J. Inst. Math ltsAppl.
?iT 21, 429 (1978).
P f ( T l j ) A TljT21j 24. Gangwal, S. K., Hudgins, R. R., Bryson, A. W., and
an moo= - m r j=l P2 + n2zr2T2j [11] Silverston, P. L., Canad. J. Chem. Eng. 49, 113
(1971).
and 25. Smith, D. M., and Williams, F. L., Fuel 63, 256
(1984).
; Pf(T1j)ATlj Tlj
bn-mo = [121 26. Bracewell, R. N., "The Fourier Transform and Its
j=l Applications," 2nd ed. McGraw-Hill, New York,
1978.
REFERENCES 27. Hildebrand, F. B., "Introduction to Numerical Anal-
1. Brown, R. J. S., Bull. Amer. Phys. Soc. Ser. H 1,216 ysis," 2nd ed. McGraw-Hill, New York, 1974.
(1956). 28. Munn, K., M.S. thesis, University of New Mexico,
2. Gallegos, D. P., Munn, K., Smith, D. M., and Stermer, 1986.
D. L., J. Colloid lnterface Sci. 119, 127 (1987). 29. Lowell, S., "Introduction to Powder Surface Area."
3. Fukushima, E., and Roeder, S. B. W., "Pulse NMR, Wiley-Interscience, New York, 1979.
A Nuts and Bolts Approach." Addison-Wesley, 30. Marcilla-Gomis, A., Molina-Sabio, M., and Rodri-
Reading, MA, 1981. guez-Reinoso, F., J. Catal. 99, 226 (1986).
Journal of Colloid and Interface Science, Vol. 119, No. 1, September 1987