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1998;8 :108-11 7
Experimental
Sample Preparation
Four different samples of HCPs with w / c ratios of 0.30,
0.40,0.60, and 1.0 were prepared for 13C-N MR measurements of the amoun t of exchange and diffusion of
ethanol. The sam p les, which were prepar ed w ith d istilled water, we re betwe en 2 and 3 years old at the tim e
of analysis and are refe rred to as S03, S04, 506, and S10,
res.pectively. Two sa mples, Sl and 52, we re prep ar ed
for l H-N MR measurements. These were made from tw o
3-mo nth-old HCPs w ith w / c rati o of 0.40. Sample 52
differed from 51 in being hydrated u sing 0 20 instead of
H 20. To reduce influence of paramagnetic constituents,
w/c
nt S S D
1111o S$
(%)
m et
Fm a x
0.30
0.40
0.60
1.0
1.206
1.056
1.032
0.797
0.163
0.194
0.286
0.343
13.5
18.4
27.7
43.0
0.0715
0.106
0.196
0.254
56.2
69.5
87.7
94.2
NMR Measurements
The experimen ts w ere performed on two different
NMR spectrometers. Samples S03, S04, S06, and 510
were tested on a Bruker Avance DMX 200 NMR spectrometer, operating at 200-MHz proton resonance frequency using a 10-mm J3C-NMR broadband probeh ead
without proton decoupling. The bandwidth wa s set to
100 kHz u sing an acquisition time of 0.041 s. The
applied 90 pulse length w as 8.0 us. The dead time was
7.14 u s. The total number of transients (radiofrequency
[RF] pulses) was first set to 1024 for samples 504, 506,
and 510 and 3072 for samp le 503 to compensate for the
lower content of ethanol. (Probably due to the application of prolonged high power pulsing and the fact that
the reference samples were sliced, reference sample R03
showe d a tendency to lose weight during the early
experiments. The number of transients for this particular sample was in the end red uced to 1024, resulting in
an inevitable reduction in signal-to-noise ratio.) The
spin-lattice rela xation time , T I , wa s measured in each
sample using a simple inversion recovery (180-.-90)
pulse seque nce. The longer T] of 189 ms wa s measured
in sam p le 510, which con tained the larger pore volume.
The repetition time between RF pulses was set to 1 s,
which is more tha n five times the spin-lattice relaxation
time, and assures quantitative sampling of the spectrum.
Sam ples S1 and 52 were tested on a Varian VXR 3005
NMR spectro meter, operating at 300-MHz proton reso nance frequency using an HR 5-mm probehead. Both
IH and 13C-NMR experiments were carried out. Th e l3C
experiments were performed using a bandwidth of 20
, 2 -
,.
oe
z-
"iii
.e
06
E
0<
02
I
C
0
005
01
0 15
02
025
03
111
between NMR DC intensities and gra vim etrically d etermined contents of ethanol shows a significant deviation fro m a straight line, sugges ting that fast exchange
condition is not satisfied . H owever, since in thi s work
only saturated sa m ples are investiga ted, Figure 1 shows
that the fast exchange condition is sa tisfied .
A lin ear least squares fit to the data is sh own as a
dotted line in Figure 1. The slop e was determined to
3.91 (~0. 19) relat ive NMR peak ar ea units / g (the relative 13C-NMR peak area un it of reference sa mple wi th
w i c = 1.0 chosen as unity).
Amount of Exchange
Calculation of th e amount of ethanol, m el' that ha s
entered the pore system at any tim e during the exchange p rocess is ba sed on th e empirical linear corre lation in Figure 1 be tw ee n lII et and th e intensit y, IeI' (eq
1):
(1)
let cor resp onds to th e su m of the int egrated ar eas of th e
methylen e and methyl peak s in the l3C sp ectra. Th e
am ount of excha nge in percent, F(%), is calculated by
com p ar ing met to the mean volume of water released,
VI" for th e referen ce samples by drying at 105C and
corrected for density difference bet ween water and
etha no l. F(%) is represented by eq 2:
100
,
Pc/V/,
lIl et '
F(% )= -
(2)
112
100
90
eo
70
{:
~
.0
'0
.v o
40
... .
..
30
o
0
10
0 "
.'
Exchange Rates
I
o ~-----+---------+----------<
0001
00 1
0 .1
10
100
~. = k i"
10
(3)
to describe the general solute release behavior of controlled-release polymer devices, where IJIo is the fractional solute release, t is the release time, k is a constant,
and n is the diffusional exponent characteristic of the
release mechanism. Here, we apply eq 3 in an analogous way to describe the fractional amount of solute
diffusing into a porous material. It!10 then describes the
fractional amount of ethanol exchanged with water at
time t. Ritger et al. [12] have shown that in cases of pure
Fickian diffusion, the exponent n has a limiting value of
0.46 for diffusion into a cylinder of infinite length.
Depending on the ratio of length to diameter of the
sample, Fickian diffusion mechanism is described by
0.43 < n < 0.50. The dotted curves displayed in Figure
3 are calculated by fitting eq 3 to the observed 13C-NMR
peak area data from samples 503, 504, 506, and 510 by
a nonlinear least squares technique for ItlIa < 0.6. The
values determined for the exponent n was found to
increase with increasing wi c ratio, i.e., n = 0.442
(::1::0.060), 0.462 (::1::0.072), 0.647 (::1::0.147), and 0.620
(::1::0.240) for samples 503, 504, 506, and 510, respectively, where numbers in brackets represent 90% confidence intervals. The results suggest that the diffusion
can be approximated by Fickian diffusion, which is in
agreement with the results obtained by Feldman [13]
from gravimetric measurements on replacement of water by propan-z-ol and methanol in hydrated cement
pastes. Feldman found a linear behavior between the
amount of water being replaced vs. the square root of
reaction time:
18
16
Sample
14
.
...e
..' .
12
Q.
OB
..
0 ,.
0<
OtP 90
' 00
1.108
0.676
0.336
0.217
0.991
0.998
::'::
::'::
::'::
::'::
::'::
::'::
0.015
0.007
0.004
0.013
0.026
0.023
Dtcm//s)
Correl. Coef.
10 - 8
(r)
59.0::'::
23.4::'::
4.92 ::'::
2.65 ::'::
12.8::'::
43 .8::'::
4.6
1.4
0.22
0.46
0.14
0.57
0.9927
0.9960
0.9967
0.975 1
0.9881
0.9978
N ote: Sa mples S1 a nd S2 a re ta ken from reference 5 and included for com par-
iso n.
"
'0
00
SlO
S06
S04
S03
Sl
S2
.,
.... .'
02
1000
Time lsI
= a,
t)
= Co,
(4b)
t = 0) = 0,
(4c)
(5)
I~
I
.1 - 4
( )
'
) ,
(6)
BODE-O?
fiOOE-O?
4.00E-07
"
200E-07
OOOE+OOL-.~~~~
01
0,2
0.3
0.4
05
0,6
0.7
0.8
0.9
vdc- ratio
Pracuca/Consequences
A knowledge of the time required to reach sufficient
exchange is important when working with liquid replacement techniques. The rather long exchange times
observed for samples 504 and 503 are of less interest in
microscopy where sufficient ethanol exchange is critical
only in a sample thickness of about 100 urn. However,
people working with larger samples, for example, in
MIP, should bear in mind that samples with very fine
pore structure may require several weeks of immersion
in ethanol for sufficient exchange to take place. The
fraction of exchange of ethanol with water at certain
time t will depend on the sample radius, a, according to
eq 6 and implies that an increase of the cylinder radius
from a = 2.75 mm to a = 5 mm will increase the
exchange time in a sample with a pore structure as in
503 from 19.5 to 65 days.
H- and 13C-NMR
+ 6kHf1E
--
[H
T
(7b)
(7c)
The factors 2 and 6 in eq 7b originate from the
number of protons of the water molecule and the
ethanol molecule, respectively.
The D20-saturated cement paste, 52, contains no
observable water protons and makes it possible to
determine the kH Ik c ratio by combining eqs 7b and 7c,
with n H,O = 0:
(7d)
A plot of [~ vs. If is depicted in Figure 5. As already
emphasized, the two intensities are measured at the
same times during the diffusion process. As noticed
from the results presented in Figure 5, eq 7d is valid in
the initial part of the "reaction," but deviates from
linearity at longer exchange times. This behavior can be
rationalized according to the reaction:
115
3.5
9<J
80
70
2
60
'0
40
30
>0
05
'0
o+--,--,--,---+---+---+---+--~--+----<
10
20
40
30
50
60
70
oC
0 .4
0.6
' .2
0 ,8
1.4
16
, 8
m(T)/ldT)
IdT)
FIGURE 6. The plot shows [~ /[~ vs. m r/[~' From the linear
occupied by water, w hich is app roximately 40% (volume by vo lume) at w / c = 0.30 and 0.40 and approximately 10% at w / c = 0.60 and 1.0. These values ar e well
belo w th e water content [7] where d amage can occur to
the pore structure through drying due to internal forces
created by the water liquid meniscus. It thus sh ows that
sufficient exchange (using ethanol) to avoid damage
ma y be achieved in the w / c rati o rang e from 0.30 to 1.0.
In the next sectio n an estimate of the mole fraction of
ethanol, X E, from dec on volution of the IH-NMR spectra
will be discussed .
obs erv ed proton and carbon in tens ities vs . diffusion of eth anol int o wa ter satu ra ted cement p astes (see eq 7e)
Calibration Factor
Value
0.2151 :': 0.0015
15.01 :': 0.42
69.80 :': 0.50
r
:M'~~~0~~~
,.
..
.!:
~ 55
Co
43205
.~.~! ~1\
:
10
..
"fi
's
.
4 .5
:E
CH3
3 .5
a1
0.2
0 .3
0.4
0 .5
0 .6
0.7
0.8
0 .9
'0
s:
.....~~
20
r:J
6]
-10
1825
-20
Conclusions
A linear relationship betw een 13CNMR peak intensities
and gravimetrically d etermined amount of ethanol inside the pore system of HCPs is observed for w Ic ratio
from 0.30 to 1.0. Although cement paste s made w ith
d iffer en t wi c ratios exhi bit differ ent relative amounts
of micropores and capillary pores resulting in a va ryi ng
average environm ent expe rience d by the p or e fluid , no
observable effects on 13C-NMR peak intensities resulting fro m such variations we re present in the wi c rati o
range used. Quantitati ve 13C-N MR ma y therefor e be
app lied success fu lly for etha no l w ithin th e pore structure of HCPs.
The d iffusion of etha nol was shown to be described
by Fickian d iffusion, ass u ming one-d im ensiona l d iffusio n under perfect sink bounda ry conditions.
The diffusion coefficients determined for the four
samp les 503, 504, 506 , and 5 10 are significantly di fferent
and vary between 2.65 X 10 - 8 forw/c = 0.30 and 5.9 X
10- 7 for wi c = 1.0.
References
1. Feldman, R.F.; Beaudoin, J.J. Celli. Cancr. Res. 1991, 21,
297- 308.
2. Bager, D.H.; Sellevold , E.J. Cem. Callcr. Res. 1979, 9,
653-654.
3. Gran, H.C Cem. Caner. Res. 1994, 25, 1063-1074.
4. Sandstrom, M. Sw ed ish N ational Testing Institute, Report
SP-AR 1988: 43, 1988, 31; or NORDTEST-Build No. , 677687.
5. Gran, H.C; Hansen , E.W. J. Magn. Reson. Imaging 1996, 14,
903-904.
6. Taylor, H.F.W. Cement Chemistry; Academic Press: New
York, 1990.
7. Pow ers, T.C; Browneyard, T.L. Res. Labs. Portland Cement
Association, Bulletin 22 (Ma rch 1948).
8. Sande rs, J.K.; Hunter, B.K. Modem NMR Spectroscopy: A
Guide for Chemists; Oxford University Press: Ne w York,
1988.
9. Bhatt acharja, S.; Moukawa, M.; D'Orazio, F.; [ehng, J.;
Halp erin, W.P. Adv. Cenl. Based Mater. 1993, 1, 67-76.
10. Winslow, ON.; Diamond, S. ]. Mater. 1970, 5, 564-585.
11. Mikhail, R.S.; Cop eland, L.E.; Brunauer, S. Canad. J. Chern.
1964, 42, 426-437.
12. Ritger, P.L.; et al. ]. Controlled Release 1987, 5, 23- 36.
13. Feldman, R.F. Cenl. Caner. Res. 1987, 17, 602-612.
14. Abramowitz, M.; Stegu n, I.A. Handbook of Mathematical
Functions. Dover Publicat ion s: New York, 1970.
15. Wilson , A.H. Phil. Mag. 1948, 39, 48-58.
16. H un t, C M.; Tom es, L.A.; Blaine, R.L.J. Res. Nat. Bur. Std.
1960, 2, 163--169.
17. Pow ers, T.C; Copeland, L.E.; Hayes, J.C; Mann, H.M.
ACI ]011 mal, 1954, November, 285-298 .
18. Shaw, D. Fourier Transf orm NMR Spectroscopy; Elsevier
Science: New York, 1976.