Sie sind auf Seite 1von 17

Wood Sci. Technol.

17:241-257 (1983)

Wood Science
and Technology
9 Springer-Verlag 1983

Small Angle X-Ray Scattering Measurement of


Porosity in Wood Following Pyrolysis
M. Kalliat, C. Y. Kwak* and P. W. Schmidt
Department of Physics, University of Missouri, Columbia, Miss. USA
B. E. Cutter and E. A. McGinnes
School of Forestry, Fisheries and Wildlife, University of Missouri, Columbia, Miss. USA

Summary. Changes in the submicroscopic porosity in southern pine latewood resulting from
pyrolysis at temperatures through 600 ~ were measured using small-angle X-ray scattering.
Two types of scattering curves were observed: the first was obtained for wood and for less
intense heat treatment; and the second, for samples heated above 300 ~ This change was
found to be associated with the thermal degradation of crystalline cellulose in the sample.
Specific surfaces and the average dimensions of macropores and micropores were
calculated from the second type of scattering curve. The specific surface was found to increase
from 1.2 to 2.3m2/gm as the temperature and heating time increased. The average
dimensions of the macropores calculated from the scattering curves was about 15 nm. The
first effect of heating sufficiently to decompose the crystalline cellulose was found to be the
production of micropores with average diameters of about 0.7 nm. Micropore volume
increased from 0.06 cm3/gm for the lower heating temperatures to about 0.13 cm3/gm for
samples heated to 600 ~ The average micropore dimension increased as the temperature was
raised and the samples were heated for longer times.
Introduction
When wood is pyrolyzed, the resulting changes in porosity will affect both the
physical properties and the end use of the char. Both the geometric shape and the
size distribution of the pores are altered in the transformation from wood to char
(Blankenhorn etal. 1978; Casteel etal. 1978). Measurement of porosity and
changes therein can be done using several techniques, each of which has unique
advantages and disadvantages. These techniques include light and electron
microscopy (Cousins 1975; McGinnes et al. 1971, 1974, 1976), sorption studies, including both gas adsorption and solution isotherms (Poots et al. 1979; Juhola, Wiig
1949a; Turkdogan et al. 1970), mercury porosimetry (Juhola, Wiig 1949b; Blankenhorn et al. 1978), and small angle scattering of x-rays (v. Bastian et al. 1972;
Casteel et al. 1978; Pringle, Schmidt 1977). The objective of the research presented
in this and other papers (Cutter et al. 1980a, 1981) was to describe the ultrastructural changes in southern pine wood undergoing pyrolysis. In this paper, we
*

Current Adress: Korea Standard Research Institute, Daedeok, Korea

242

M. Kalliat et al.

present the changes in submicroscopic porosity of southern pine latewood charred


to 600~ in flowing N21. Earlier papers by Beall (1977) and Cutter et al. (1980a,
1981) have presented evidence of microscopic changes in anatomy and density of
the southern pine material during this process.

Literature Review

Charcoals tend to be very brittle and difficult to prepare for microscopic


examination. Cousins (1975) found that soaking in 0.5 M NaOH prior to embedding improved infiltration of the embedding medium. Sections as thin as 5 vM were
obtained, thus allowing identification of the parent material. However, only pores
with diameters greater than about 1000 A could be discerned.
The scanning electron microscope (SEM) has proven to be more useful, but
again the limits of the resolution are insufficient to allow examination of the fine
pore structure of the charcoal (Beall et al. 1974; McGinnes et al. 1974; Turkdogan
etal. 1970). McGinnes etal. (1971) used transmission electron microscopy to
examine carbon replicas of commercial oak charcoal. They found that during
pyrolysis, the fibrillar arrangement of the cell walls was destroyed and replaced by
a smooth "amorphous" wall.
Ban and co-workers (1973, 1976 a, b) used high resolution electron microscopy
to study the microstructure of carbonized polymers. Whether or not the quantitative results they obtained are correct has been questioned by Crawford and Marsh
(1977). Regardless of the validity of the actual numbers, the technique has shown
the development of graphite layer planes in both graphitizing and non-graphitizing
carbons. Wood charcoal is a non-graphitizing carbon (Jenkins, Kawamura, 1976).
Brunauer (1976) indicated that the first two methods used to characterize pores
in charcoal were nitrogen adsorption and mercury porosimetry. The volume of
macropores and mesopores (diameters of 20 to 1000 A) can be estimated using Hg
porosimetry, but the micropores (diameter less than 20 A) are too small for
complete penetration by mercury. Juhola and Wiig (1949a, b) found that the
surface area of the macropores in an activated charcoal, prepared by steam treatment of charcoal to increase the porosity, was about 3 m2/g while area of the
mesopores and micropores was about 1500 m2/g.
Blankenhorn et al. (1978) used mercury porosimetry to measure changes in total
porosity, pore size distribution, apparent density and real density in black cherry
chars as functions of carbonization temperatures up to 900~ They found that
distribution of pore sizes changed with carbonization temperature.
Poots et al. (1979) compared mercury porosimetry, N2 adsorption, and solution
isotherms on peat and spruce wood. They found that the specific surface of spruce
ranged from 19 to 27 m2/g using N2 adsorption, 22 to 24.9 m2/g using methylene
blue adsorption, but much less than 1 m2/g using mercury porosimetry. The
authors indicated that the disparity was probably due to the fact that the
immobility of mercury and the large area occupied by the mercury molecule itself
l

The Southern pine samples were prepared by F. C. Beall and D. H. Slocum while at the
University of Toronto

Measurement of Porosity in Pyrolyzed Wood

243

prevented penetration of pores with cross sectional areas smaller than some minimum value, which varied from 14 to 90 A 2.
Turkdogan et al. (1970) evaluated several methods to describe pore size and
distribution in several carbons, including wood charcoal. They found SEM to be a
valuable tool in describing the surface of the wood and the very large structural
pores, but the resolution was not high enough to define the majority of the pores.
Using Hg porosimetry, they found pores with diameters of 22-32 ~tm and 1.2 gin.
These sizes are not unlike those of the wood cells themselves. Turkdogan and his coworkers also measured internal surface area using the BET method of N2
adsorption isotherms at -195 ~ and CO2 adsorption isotherms a t - 7 8 ~ They
found that N2-isotherms indicated an internal surface area of 348 m2/g and COsisotherms gave an area of 350 m2/g for wood charcoal. They concluded that most
of the internal surface area could be attributed to micropores 10-50 A in diameter.
Stamm (1964) indicates that internal surface area for wood is about 250 m~/g based
on BET adsorption isotherms of water vapor.
Measurements of porosity using small angle scattering of x-rays are based
primarily on the methods outlined by Guinier et al. (1955). Von Bastian et al.
(1972) used small angle scattering to characterize the submicroscopic structure of
oak charcoal prepared in a commercial kiln. Their scattering data suggested that
two types of pores were present: large pores similar to those of the original
structure of the wood, and micropores with maximum diameters of 15 A.
Casteel et al. (1978) obtained small angle scattering data from oak and hickory
charcoals prepared in a laboratory furnace. From their analysis of the scattering
measurements, they found that the pore structure consisted of three parts. The first
part or fraction was attributed to pores in the lignin skeleton of the wood and had
widths in the micron range. The second pore fraction consisted of platelet-shaped
pores with thicknesses of 20-30 A. Pringle and Schmidt (1977) found that the
platelet pores had an average thickness of 17-28 A.

Experimental Procedures
Small angle x-ray scattering (SAXS) studies were performed on latewood samples
of southern pine that had been prepared by F. C. Beall and D. H. Slocum at the
University of Toronto by heating the wood at rates of 1~ 10~ and 50 ~
in
flowing N2 to temperatures of 250 ~ 300 ~ 350 ~ 400 ~ or 600 ~ as described by
Beall (1977). The specific gravity and density of these samples has been reported by
Cutter and McGinnes (I981) while Cutter etal. (1980a) have described the
anatomical changes accompanying pyrolysis. Only powdered samples were studied
by small-angle scattering, since v. Bastian et al. (1972) had found that the same
scattering were obtained for solid and powdered charcoal samples. The scattering
patterns were obtained using nickel-filtered C u K a x-rays (2 = 1.54 A) and a Kratky
collimation system (Kratky, Skala 1958) with a slit arrangement similar to that used
in previous studies of wood and charcoal (Casteel et al. 1978; v. Bastian et al. 1972).
A linear amplifier and a pulse-height analyzer were used to select the scattered xrays detected by the proportional counter.

244

M. Kalliat et al.

Each scattering curve was measured several times in order to account for
fluctuations in x-ray intensity. After the results were averaged and corrected for the
day-to-day fluctuations in the incident intensity, the curves were corrected for the
background scattering from the scattering system and the 0.001 inch mylar plastic
windows of the sample cell and the length and width of the collimating slits ([+in
et al. 1974; Kwak 1981; Taylor, Schmidt 1967).
In order to monitor the constancy of the incident x-ray beam, the scattering
from a carbon black sample at 15 milliradians (mr) was recorded before and after
every run. The transmission of the wood or char samples was measured by placing
a carbon black sample in the normal sample position and recording the scattering
with and without the wood or char sample between the carbon black sample and
the x-ray tube. The measured transmission was used to correct for the effects of
photoelectric adsorption in the sample. The corrected data give the scattering that
would be obtained from a non-adsorbing sample Kalliat et al. 1981).

10 8

iiir

I I III

~ ~ q [

Wood
0 250/01

10 7

U)
tt-

106

to.)
t~

oo
.>__

10 8

IT

10 4

10

10-3

,L,L,I

10 .2

'

10-1

'

~LI

10 0

Scattering Angle (Radians)


Fig. 1. Corrected small-angle x-ray scattering curves for southern pine wood (squares) and for
the 250/01 sample (circles)

Measurement of Porosity in Pyrolyzed Wood

245

In order to follow the decomposition of the cellulose during different heat


treatments, large-angle diffraction patterns were obtained with a General Electric
XRD-6 diffractometer and nickel-filtered C u K a x-rays. Some of the characteristic
features of the diffraction pattern from cellulose are a poorly-resolved double peak
at Bragg angles between 7 and 8.5 degrees and a strong, relatively sharp maximum
at a Bragg angle of 11.4 ~ corresponding to a Bragg spacing of 3.89 A (Murphey,
Cutter 1971; Blackwell et al. 1978). (The scattering angle employed to describe the
small-angle scattering curves and plotted in Fig. 6 is twice the Bragg angle.)

Analysis and Discussion of the Scattering Data


Plots of the corrected scattered intensity measured at scattering angles from 0.003
to 0.06 radians are shown in Figs. 1 through 5 for southern pine latewood and

10 8

Ill

+ I I II I

o 300/01
z~ 300/10
o 300/50

10 7

_z,
E:
t--

10 6

E
L.

o
o3
9~
ro

10s

104

103
10-3

,i
10 -2

illll[

10-1

I I,I

10 o

Scattering Angle (Radians)


Fig. 2. Corrected scattering curves for samples heated to 300~ Squares, triangles, and
circles show the curves for the 300/01,300/10, and 300/50 samples, respectively

246

M. Kalliat et al.
10 8

li

ii I

il

o 350/01
o 350/10
350/50

10 7

E
,e-,

E:

10 6

(I...

.2

10s

rr

10 4

103

10-3

,,tlI

10-2

10-1

10 o

Scattering Angle (Radians)


Fig.& Corrected scattering curves for charcoals heated to 350~ Results of the 350/01,
350/10, and 350/50 samples are shown by squares, triangles, and circles, respectively

charcoal samples prepared at different heating rates and maximum temperatures.


The same intensity scale was used for all samples. If all these samples had the same
chemical composition, and thus the same mass absorption coefficient, the curves
would also correspond to the scattering from samples with constant mass per unit
area. However, since the chemical composition changes during pyrolysis, the
scattering curves must be multiplied by the mass absorption coefficients before
intensities scattered by different samples can be compared.
The scattering curves fall into two classes. The first type was observed for wood
and for charcoals heated to temperatures not exceeding 300 ~ (Figs. 1, 2). In this
type of scattering curve, the intensity decreases rather rapidly at the smallest
scattering angles for which data were recorded. At scattering angles between about
0.01 and 0.02 radians, the intensity falls off less rapidly than at smaller angles, and
there is an inflection in the curve. When the scattering angle is greater than 0.02

247

Measurement of Porosity in Pyrolyzed Wood


108

llll

I I If I

T l I I i_

[3 400/01
o 400/10
9

~ 400/50

10 7

100

r
I,-

.~

10s

rr

104

10-3

1 0 .2

1 0 -1

10 0

Scattering Angle (Radians)


Fig. 4. Corrected small-angle scattering curves for the 400/01 (squares), 400/10 (circles), and
400/50 (triangles) charcoals

radians, the intensity again decreases more rapidly. This rapid rate of decrease is
observed in all of the outer part of the first type of small-angle scattering curve.
Some of the charcoals prepared by heating to 350 ~ or above (Figs. 3-5) gave
another, quite different type of scattering curve, in which the intensity in the inner
part of the curve is very nearly proportional to the inverse fourth power of the
scattering angle, while for scattering angles greater than about 0.01 or 0.015
radians, the rate of decrease becomes smaller, and the intensity either approaches a
constant value or decays slowly. The magnitude of the intensity in the outer part of
the second type of scattering curve is appreciably greater than the intensity in the
corresponding region of the first type of scattering pattern.
The transition from the first to the second type of scattering curve depends both
on the maximum temperature and the rate of heating. At lower rates of temperature increase, the transition occurs at lower temperatures than in sample

248

M. Kalliat et al.

prepared by more rapid heating. However, the second type of scattering curve was
found only in samples heated to a maximum temperature of at least 350 ~ For
samples heated to 350 ~ the first type of curve was obtained for sample heated at
rates of 10~ and 50 ~
while the sample in which the temperature increase
was 1 ~
gave the second type of scattering pattern. For a maximum temperature of 400 ~ on the other hand, the first type of curve was found only at the
highest rate of temperature increase, while the two lower rates produced samples
which gave the second type of curve. No curves of the first type were obtained for
samples heated to a maximum temperature of 600 ~
Since these results suggested that the transition from the first to the second type
of scattering curve was associated with heating to temperatures above 300 ~ and
since previous small-angle scattering studies (Casteel etal. 1978; Cutter etal.
1980b) suggested that the change in the type of scattering curve was associated
with the decomposition of crystalline cellulose in the samples, large-angle diffraction patterns were recorded for scattering angles at which diffraction peaks
characteristic of cellulose are observed (Murphey, Cutter 1971). In Fig. 6, cellulose
diffraction maxima are present only in curves for samples which gave the first type
of small-angle scattering curve. The large-angle diffraction patterns thus provide
10 a

I I

II I

r I I Ill

600/01
o 600/10
a 600/50

_.#

107

rr
1,,-

133
.~.,.,.
II)
106
o
03
.>_
(D
n"

10 5

0 4

10 .3

I l

II

10-2

I tilll

10 -1

I I

100

Scattering Angle (Radians)


Fig. 5. Squares, circles, and triangles show the corrected scattering data for the 600/01,
600/10, and 600/50 samples

Measurement of Porosity in Pyrolyzed Wood

249

22.8 ~

>" ~
~h
C

1~ "5~
15.60

.>

250/01

n.-

350/10

350/01
,

300

20 o

10~

0o

Fig. 6. A plot of the relative intensity of large-angle x-ray scattering for the wood and samples
heated to 250~ 300 ~ and 350 ~ The scattering angle is plotted on the horizontal axis
(This angle is twice the Bragg angle.)

evidence that the transition from the first to the second type of scattering pattern is
associated with the decomposition of the crystalline cellulose in the sample.
We did not make a detailed, quantitative interpretation of the first type of
small-angle scattering pattern, since any analysis of these curves would have to
consider the scattering from both the cellulose and the pores in the wood or
charcoal and thus would probably be too complicated to provide unambiguous
information. In addition, quantitative interpretation would be possible only for
scattering data from block samples at a known orientation, rather than powders,
since wood samples, unlike charcoals, have been shown to give non-isotropic
scattering patterns (Casteel et al. 1978).
We were able to make a more complete analysis of the data from samples which
gave the second type of scattering curve. In this analysis, we considered that the
scattering was produced by pores in the carbon skeleton of the parent material. The
atomic structure of this skeleton has essentially no effect on the small-angle x-ray
scattering, since at these scattering angles the scattering process cannot resolve the
atomic structure (Guinier et al. 1955, pp. 3-4). The sample thus can be considered
to be composed of two phases - the skeleton and the pores. The scattering from the
air in the pores is so weak that it can be neglected. For this model of the scattering
sample, the scattered intensity can be approximated quite well by an equation for
the scattering from a system with two classes of pores. In this model, the two types
of pores, macropores and micropores, have very different average dimensions. The
dimensions of the macropores are at least 30 nm while the micropores are much
smaller, with average dimensions not exceeding about 1 nm. The scattering
equation was obtained with the assumption that the scattering from each class of
pores can be described by the expression developed by Debye et al. (1957). The
scattering from each class of pores is considered to be independent of the scattering
from the other type of pores.

250

M. Kalliat et al.

Under these conditions, an equation for the scattered intensity I (h) can be
obtained by modification of the expression developed by Kalliat et al. (1981) for an
investigation of the small-angle x-ray scattering from coals. For charcoals, however,
only two classes of pores, rather than three, need to be considered. The intensity
therefore can be written
[ S0maa4
Cmi
]
I(h) = Ioo IeA (1 + h 2 a2) 2 +(1 + h 2 b2) 2]

(1)

where
h = 4=2-1 sin (0/2);

(2)

2 is the x-ray wavelength, 0 is the scattering angle;


2~zd2 M
Ioo- ~ - - a

(3)

Ie is the intensity scattered by a single electron; A is the cross-sectional area of the


sample in a direction perpendicular to the incident x-ray beam; M is the mass of
the sample; d is the number of electrons per unit volume in the wood skeleton; T is
the transmission of the sample; S~ is the specific surface (that is, the surface area
per unit mass of charcoal) of the macropores; Cmiis a constant proportional to the
scattered intensity from the micropores; and a and b are lengths proportional to the
average dimensions of the macropores and the micropores respectively.
As we have done previously (Kalliat et al. 1981), we calculated M/A, the mass
per unit area of the wood and charcoal samples, from the measured values of the
sample transmission T by use of the equation (Guinier 1963)
T = Io0 = exp -/~ ~- ;

(4)

where Io is the intensity of the x-rays striking the sample; I is the intensity transmitted through the sample; and ~t is the mass absorption coefficient of the sample
We considered the charcoal samples to be composed entirely of amorphous carbon,
with mass density 1.80 gm/cm 3. We selected this relatively low density because we
felt that a relatively loose structure is to be expected as a result of pyrolysis. The
mass absorption coefficient for carbon is 4.60 cm2/gm (International Tables for XRay Crystallography, 1962). To evaluate the electron density d, we multiplied the
mass density of amorphous carbon by the number of electrons per gram in carbon.
The quantity IeA was evaluated from the measured intensity for a colloidal
silica sample by the technique employed in our investigation of coals (Kalliat et al.
1981).
We made non-linear least-squares fits (Bevington 1969) of Eq. (1) to the corrected scattering curves of the second type. In these fits, the intensities were
assigned weights inversely proportional to the square of the uncertainty in the
value of the intensity. The collimation-correction calculation employs a propagation-of-error technique to estimate the statistical uncertainty in the corrected
scattered intensity, assuming that the statistical uncertainty in the measured

Measurement of Porosity in Pyrolyzed Wood

251

Table 1. Quantities calculated from the least-squares fits ofEq. (1) ~


Sample

S~ (m2/g)

Cmi (crn6/g)

a (nm)

b (nm)

Z~

350/01
400/10
400/01
600/50
600/10
600/01

1.2_+0.1
1.3_+0.1
1.5_+0.1
1.8_+0.1
1.5_+0.1
2.3-t-0.1

2.8_+0.1 x 10 24
2.9_+0.1 10.24
3.8_+0.1 x 10.24
9.6_+0.1 -24
10.6_+0.1X10-24
18.8-+0.1X 10.24

15.3_+0.4
21.9_+ 1.2
12.1-+0.2
11.3_+0.1
14.9_+0.3
13.6-+0.2

0.13_+0.01
0.14_+0.01
0.01_+0.05
0.13_+0.01
0.17-+0.01
0.19_+0.01

12
131
8.4
7.5
1.95
2.6

2he uncertainties are either the statistical uncertainties calculated in the least-square fit or
are one unit in the last decimal place shown in the table, whichever is larger

intensity is 0.675 N 1/2, where N is the n u m b e r of counts recorded in the measurement of this intensity value. However, when the calculated statistical uncertainty
was less than one per cent, we set the total uncertainty equal to one per cent, since
we have found that in our scattering measurements there can often be systematic
errors of about one per cent. In other words, we took the relative uncertainty to be
the relative statistical uncertainty when the latter uncertainty exceeded one per
cent, and otherwise we assumed the relative uncertainty to be one per cent.
Although, as we have already mentioned, we feel that Eq. (1) should not
be used for quantitative interpretation of scattering curves from the wood samples
and for samples heated only to low m a x i m u m temperatures or for which the temperature increase was most rapid, we used Eq. (8) of Kalliat et al. (1981) to obtain
the curves drawn through the data points for these samples in the plots shown in
Figs. 1-5.
Table 1 lists the quantities S ~ Cmi , a, and b calculated from the least-squares
fits o f Eq. (1) to the corrected scattering curves. The uncertainties given in Table 1
were determined from the fit and thus allow only for statistical errors. These
uncertainties do not include the contributions from systematic errors or from the
fact that the model on which Eq. (1) is based may not correspond exactly to the
pore structure o f the charcoal.
Table 1 also shows the values X2 (Bevington 1969, Chapter 11, pp 237-240) for
each fit. When X2 > 1, the deviation of a data point from the theoretical curve is,
on the average, greater than the uncertainty in this data point. On the other hand,
when Z2 < 1, the average deviation of a data point from the fitted curve is smaller
than the average uncertainty in the data point. This result is usually interpreted to
mean that the estimate of the experimental uncertainty is too conservative. In an
ideal fit, )~2 is expected to be near 1.
Except for the 400/10 sample, the values of X2 obtained in our fits of the
charcoal scattering data range from 2 through 12. Since the structure model on
which Eq. (l) is based is probably too simple to provide a detailed description of
the pore structure in the charcoals, we feel that the fits of Eq. (1) to the data from
these samples can be considered to be reasonably good. As can be seen from
Table 1, X2 is very large for the 400/10 sample. Figure 4 shows that in the outer
part of the scattering curve for this sample there is a large scatter in the data points.
Although we are unable to suggest a cause for these fluctuations, we have found that

252

M. Kalliat et al.

if the experimental curve is smoothed sufficiently, )~2 is reduced to about 0.2. Most
of the contribution to Z2 for this sample thus appears to be due to the random
fluctuations of the corrected data points in the outer part of the scattering curve.
An advantage of the use of Eq. (1) in the analysis of the scattering data is that
this equation permits identification of the contributions of each of the two types of
pores to the scattering.
The specific surfaces S~ of the macropores are shown in Table 1. As the
temperature is raised and the heating time becomes longer, there is a small but
clearly noticeable increase in S~
which grows from 1.2 m2/gm for the 350/01
sample to 2.3 m2/gm for the 600/01 charcoal.
The average dimension a of the macropores in (1) is related to their average
radius of gyration (Guiner et al. 1955, pp. 24-28) ema by the equation (Kalliat et al.
1981, p. 12)
Rma= V6-a.

(5)

The values of a, listed in Table 1, except for the 400/10 sample, fall between
11.3 and 15.3 nm. There seems to be no systematic relation between a and the
heating time or maximum temperature. The scattering curves do not appear to be
especially sensitive to the value of a. Although detailed information about the
dimensions of the macropores and the variation of these dimensions with the
maximum temperature and the time of heating cannot be obtained from the
scattering curves, the values of a from the fits are consistent with the conclusion
suggested by other parts of this investigation that the dimensions of the macropores
are affected relatively little by heating.
The average radius of gyration gmi of the micropores can be calculated from the
quantity b in Table 1 by an equation analogous to Eq. (5). Thus
Rmi = V~ b.

(6)

For the 350/01 and the 400/10 samples, b is approximately 0.135 nm. The
similarity of the micropore dimensions for these samples suggests that the first
effect of heating charcoals about 300 ~ is to produce micropores with average
dimensions b in the interval between 0.13 and 0.14 nm.
For samples heated to a maximum temperature of 600 ~ b increases as the
heating time becomes longer. For the 400/01 sample, on the other hand, b is
essentially zero. This value of b is so much smaller than those for the other samples
that it almost certainly is incorrect - that is, it does not represent the average
Table 2. Specific volumes V~

specific surfaces S~

micropores"

Sample

V~ (cm3/ g)

S~ (ms/ g)

350/01
400/10
600/50
600/10
600/01

0.060_+0.014
0.050_+0.011
0.21 _+0.05
0.10 _+0.02
0.13 +_0.02

4.4_+ 1.1 102


3.4_+ 1.2X 102
15 _+4 Xl02
5.6_+ 1.2X 102
6.5-+ 1.1 102

a The uncertainties were obtained by propagation of the uncertainties in Table 1

Measurement of Porosity in Pyrolyzed Wood

253

dimension b of the micropores in this charcoal Although we are unable to suggest


why the scattering curves give such a small b for the 400/01 charcoal, we feel that
this b value is not meaningful. In Table 2, we therefore have not included any
results for the 400/01 charcoal.
The constant Cmi in Eq. (1) is proportional to the zero-angle scattered intensity
from the micropores. Information about the micropores can be obtained from Cmi
and b by a technique similar to the method which we employed in our study of oak
and hickory charcoals (Casteel et al. 1978). The intensity from a single micropore
with volume Vmi approaches the value Ied 2 (Vmifl as h approaches zero (Guinier
et al. 1955, p. 7 and p. 16). If the micropores are considered to scatter independently,
1 V~162
Cmi= 2g

(7)

where Vm0ithe micropore volume per unit mass, is

V~ = (l/M) ~ (Vmi)j ,
j=l

(8)

and (V2/V), the volume-average volume of a single micropore, is given by


[(Vmn)j]2
-5
V /v( =j=l

j=l

(9)

(Vmi)j

In Eqs. (8) and (9), (Vmi)j is the volume of micropore j, and the summation extends
over all of the micropores in the sample.
If the micropores are considered to be identical spheres with radius Rs~ ,
Rsp=(5/3) I/2 Rmi, [Guinier et al. 1955, p. 25, Eq. (38)], and from (6), Rsp = ~iOb.
When all the micropores are considered to be spheres with the same radius,
V2/V -- (4 ~/3) (i0) 3/z bL

(10)

After V2/V has been evaluated from Eq. (10), Eq. (7) can be used to obtain V~
the micropore volume per unit mass, from Cmi and ~72/~. The values of V~
calculated in this way are listed in Table 2.
For the 350/01 and 400/10 charcoals, VOi is about 0.06 cm3/g. For samples
heated to a maximum temperature of 600 ~ V~ is larger, lying in the interval
between 0.10 and 0.20 cm~/g. The micropore volume V~ calculated for the 600/50
sample possibly is too large. Even if this result is correct, however, the V~
obtained for the three samples heated to 600 ~ are sufficiently similar to suggest
that as the maximum temperature and the time of heating are increased, V~ may
approach a limiting value of about 0.13 cm 3/g.
If the micropore volume per unit mass remains nearly constant while the
average volume of the individual micropores increases with the length of heating
and with the maximum temperature, as we have suggested appears to be the case
for the charcoals heated to 600 ~ the number of micropores must decrease. This
reduction in the number of micropores could come about by coalescence of pores,

254

M. Kalliat et al.

or, alternatively, the micropores with volumes smaller than some critical value may
shrink, while the pores with larger volumes grow. The fraction of the volume of the
charcoal which is occupied by the micropores is equal to the product of Vomi and
the mass density of the charcoal. Since these densities are about 0.5 g/cm 3 (Cutter,
McGinnes 1981) for the charcoals in Table 2, the micropore volume is only 3 to
10% of the volume of the charcoal. As the micropores occupy such a small fraction
of the volume of the charcoal, they do not appear likely to coalesce, and so the
second alternative, in which the larger micropores grow while the smaller ones
shrink, may be a better explanation of the nearly constant values of V~ for the
samples heated to 600 ~
A very rough estimate of the specific surface Somi of the micropores can be
calculated from Eq. (8) if all of the micropores are considered to be spheres with
radius Rsp = V ~ b. With this assumption, Eq. (8) gives
Vm0i= 4~
1 Rsp S~
3Mn (Rsp)3 = -~-

(11)

In Eq.(ll), n is the number of micropores in the sample. The values of S~


calculated from Eq. (11) are included in Table 2.
The specific surface S~ associated with the micropores in the 600/50 charcoal
is much larger than the specific surfaces S~ calculated for the other samples. As
there is no reason to expect that the 600/50 sample should have especially high
values of Vomiand S~ , these values probably are not correct. A possible source of
this error is that the average micropore dimension b obtained from least squares fit
was too small. Since Vomi and Somi are calculated by dividing C~ by b 3 and b 4,
respectively, the micropore volume V~ and the micropore specific surface SOi are
sensitive to small changes in b. An increase of b by 20 to 30% would make V~ and
S~ for the 600/50 charcoal comparable to the corresponding quantities for the
other charcoals heated to 600 ~
The specific surfaces S~ in Table 1 can be called the "x-ray" specific surfaces,
since they are calculated from Eq. (1) and thus represent the surface associated
with pores large enough to give a scattered intensity proportional to h -4 in at least the
outer part of the interval of scattering angles for which data were recorded. These
x-ray specific surfaces, which are the surfaces associated only with the macropores,
are much smaller than the specific surfaces obtained for charcoals by adsorption
(Juhola, Wiig 1949a; Turkdogan etal. 1970). However, the specific surfaces S~
from Table 1 are comparable to those from adsorption data. The fact that the latter
specific surfaces are so much greater than those calculated from Eq. (1) suggests
that in charcoals, the adsorbing gases are able to penetrate the micropores and that
most of the total specific surface in charcoals comes from the contribution of the
micropores.
Equation (1) neglects the "small-angle tail" of the first large-angle diffraction
maximum. While the contribution of this tail is not expected to be large, at small
angles this part of the first large-angle maximum increases with the scattering angle
and thus tends to reduce the value of b calculated from the small-angle scattering
curves. Consequently, if the small-angle tail of the first large-angle diffraction
maximum is appreciable but not taken into consideration, the calculated values of
Vomiand Somiwill be too large.

Measurement of Porosity in Pyrolyzed Wood

255

The uncertainties shown in Table 1 are the statistical uncertainties obtained


from the least-squares fits and include only the effects of the estimated statistical
uncertainties in the corrected scattered intensities. A more realistic evaluation of
the total uncertainty must also consider systematic errors. While systematic errors
are always difficult to evaluate, our experience suggests that the largest systematic
error probably comes from the estimate of IeA in Eq. (1). We estimate that this
uncertainty is about 10 to 25%.
Equation (1) assumes that there are only two types of pores, while in our study
of coal (Kalliat et al. 1981), we considered three pore types - micropores, transitional
pores, and macropores (Dubinin 1955) - and used an equation like Eq. (1) but which
includes contributions from three types of pores (Kalliat et al. 1981, Eq. 8). When
we analyzed the data from Southern pine charcoal with the latter equation, we
obtained essentially the same parameters associated with the micropores (i.e., C~
and b) and also the same x-ray specific surfaces S~ as were obtained from Eq. (1).
However, since there seemed to be no discernable pattern in the effects of the
heating time and maximum temperature on the dimensions of the macropores and
transitional pores, and since the fits with the equation with three types of pores did
not reduce 2 (and, thus, give a better fit) than the Eq. (l), we concluded that the
scattering curves from the charcoals do not contain enough information to justify
an analysis which considers three types of pores.
In our previous investigation of charcoals, in which we considered the contribution of platelet-shaped pores (Casteel et al. 1978), the scattering from ptatelet
pores was most appreciable in charcoals which had been heated to 600~ and
800 ~ In the present work with southern pine charcoals, on the other hand, the
samples were heated to maximum temperatures which did not exceed 600 ~ The
fact that there appears to be no necessity of considering platelet pores in the
analysis of the scattering from charcoals produced from southern pine, even though
the scattering curves from oak and hickory charcoals (Casteel et al. 1978) suggested
that these pores were present, may be a result of the difference in the maximum
temperatures considered in the two investigations.
The values of VOmi and Somilisted in Table 2 were calculated under the assumption that the pores were spherical and that the individual pores scattered
independently. Although the magnitude of the quantities in Table 2 certainly
depends on the assumption of a spherical shape, the relative variation of these
quantities with maximum temperature and with length of heating should be independent of the shape of the pores, as long as the pores scatter independently and
their shape does not change when the charcoals are heated. If these two conditions
are satisfied, V~ and SO i will be proportional to Comi/b3 and C~
4, respectively,
regardless of the shape of the pores. The suggestion that Vomiapproaches a constant
limiting value for charcoals heated to a maximum of 600 ~ thus does not require
the pores to be spherical.

References
Ban, L. L.; Hess, W. M. 1976a: Microstructure and morphology of carbon blacks. In:
Deviney, M. L.; O'Grady, T. M. (Eds) Petroleum Derived Carbons (ACS SympOsium
Series No. 21) pp. 358-377. Washington, D.C.

256

M. Kalliat et al.

Ban, L. L.; Crawford, D.; Marsh, H. 1976b: Lattice-resolution electron microscopy in


structural studies of nongraphitizing carbons from poly (vinylidene chloride) (PVDC). J.
Appl. Cryst. 8:415-420
Ban, L. L.; Hess, M. W. 1973: Microstructure of carbonized polymers. Polym. Prep., Am.
Chem. Soc., Div Polym. Chem. 14:410-415
Beall, F. C. 1977: Properties of wood during carbonization under fire conditions. In:
Goldstein, I. (Ed.) Wood Technology: Chemical Aspects (ACS Symposium Series No. 43).
pp. 107-114. Washington, D.C.
Beall, F. C.; Blankenhorn, P. R.; Moore, G. R. 1974: Carbonized wood-physical properties
and use as an SEM preparation. Wood Sci. 6:212-219
Bevington, P. R. 1969: Data Reduction and Error Analysis for the Physical Sciences.
Program CURFIT, pp. 237-240. New York: McGraw-Hill
Blackwell, J.; Kolpak, F. J.; Gardner, K. H. 1978: The structure of celluloses I and II. Tappi
61:71-72
Blankenhorn, P. R.; Barnes, D. P.; Kline, D. E.; Murphey, W. K. 1978: Porosity and pore size
distribution of black cherry carbonized in an inert atmosphere. Wood Sci. 11:23-29
Brunauer, S. 1976: Pore structure of solids. Pure. Appl. Chem. 48:401-405
Casteel, J. L.; Pringle, O. A.; Lin, J. S.; Schmidt, P. W.; Slocum, D. H.; McGinnes, Jr., E. A.;
Beall, F. C. 1978: Small angle x-ray scattering study of the porosity in charcoals. Wood
Fiber 10:6-19
Cousins, W. J. 1975: Optical microscopy of charcoal. J. Micros. 105:15 - 18
Crawford, D.; Marsh, H. 1977: High resolution electron microscopy of carbon structure. J.
Microsc. 109:145-152
Cutter, B. E.; McGinnes, Jr., E. A. 1981: A note on density change patterns in charred wood.
Wood Fiber 13:39-44
Cutter, B. E.; Cumbie, B. G.; McGinnes, Jr., E. A. 1980a: SEM and shrinkage analysis of
southern pine wood following pyrolysis. Wood Sci. Technol. 14:115-130
Cutter, B. E.; Schmidt, P. W.; McGinnes, Jr., E. A. 1980b: X-ray scattering and x-ray
diffraction techniques in studies of gamma-irradiated wood. Wood Fiber 11:228-232
Debye, P.; Anderson, Jr., H. R.; Brumberger, H. 1957: Scattering by an inhomogeneons solid.
II. The correlation function and its application. J. Appl. Phys. 28:679-683
Dubinin, M. M. 1955: A study of the porous structure of active carbons using a variety of
methods. Quart. Revs. (London) 9: 101-114
Guinier, A. 1963: X-ray diffraction in crystals, imperfect crystals, and amorphous bodies,
pp. 3-4. San Francisco: Freeman
Guinier, A.; Fournet, G.; Walker, C. B.; Yudowitch, K. L. 1955: Small angle scattering x-rays.
New York: J. Wiley and Sons
International Tables for X-Ray Crystallography, Vol. III. International Union of Crystallography 1962: Birmingham: Kynoch Press p. 162
Jenkins, G. M.; Kawamura, K. 1976: Polymeric carbons-carbon fibre, glass and char. London:
Cambridge Univ. Press
Juhola, A. A.; Wiig, E. O. 1949a: Pore structure in activated charcoal. I. Determination of
micropore size distribution. J. Am. Chem. Soc. 71:2069-2077
Juhola, A. A.; Wiig, E. O. 1949b: Pore structure in activated charcoal. II. Determination of
macropore size. J. Am. Chem. Soc. 71:2078-2080
Kalliat, M.; Kwak, C. Y.; Schmidt, P. W. 1981: Small-angle x-ray investigation of the porosity
in coals. In: Blaustein, B. D.; Bockrath, B. C.; Freeman, S. (Eds) New approaches in coal
chemistry (ACS Symposium Series No. 169), pp. 3-22. Washington, D.C.
Kratky, O.; Skala, A. 1958: Neues Verfahren zur Herstellung yon Blendenstreuungsfreien
R6ntgenkleinwinkelaufnahmen V. Z. f. Elektrochemie, Ber. Bunsenges. Phys. Chemic
62:73-77
Kwak, C. Y. 1981: Ph.D. Thesis, University of Missouri
Lin, J. S.; v. Bastian, C. R.; Schmidt, P. W. 1974: A modified method for slit-length
collimation corrections in small angle x-ray scattering. J. Appl. Cryst. 7:439-442
McGinnes, Jr., E. A.; Harlow, C. A.; Beall, F. C. 1976: Use of scanning electron microscopy
and image processing in wood charcoal studies. IITRI/SEM 1976. pp. 543-548

Measurement of Porosity in Pyrolyzed Wood

257

McGinnes, Jr., E. A.; Kandeel, S. A.; Szopa, P. S.; Phelps, J. E. 1974: Use of scanning electron
microscopy in studies of wood charcoal formation. IITRI/SEM 1974. pp. 469-476
McGinnes, Jr., E. A.; Kandeel, S. A.; Szopa, P. S. 1971: Some structural changes observed in
the transformation of wood into charcoal. Wood Fiber 3:77-83
Murphey, W. K.; Cutter, B. E. 1971: Calibration procedures for cellulose x-ray difl'raction
diffractograms. Wood Fiber 4:363-366
Poots, V. J. P.; McKay, G. 1979: The specific surfaces of peat and wood. J. Appl. Polym. Sci.
23:1117-1129
Pringle, O. A.; Schmidt, P. W. 1977: Determination of the thickness distribution for randomly
oriented independently-scattering polydisperse systems of platelets. J. Colloid Interface
Sci. 60:252-257
Stature, A. J. 1964: Wood and cellulose science. New York: Ronald Press
Taylor, T. R.; Schmidt, P. W. 1967: A method for correcting small angle x-ray scattering
curves for the effects of the width of the collimating slits. Acta Phys. Austriaca 25:293-296
Turkdogan, E. T.; Olsson, R. G.; Winters, J. V. 1970: Pore characteristics of carbon. Carbon
8:545-564
v. Bastian, C. R.; Schmidt, P. W.; Szopa, P. S.; McGinnes, Jr., E. A. 1972: Small angle x-ray
scattering study of oak charcoals. Wood Fiber 4: 185-192

(Received October 12, 1982)


M. Kalliat
Research Associate in Physics
C. Y. Kwak
Research Assistant in Physics
Paul W. Schmidt
Professor of Physics
Department of Physics, University of Missouri
Columbia, Missouri 65211
B. E. Cutter
Associate Professor of Forestry
E. A. McGinnes Jr.
Professor of Forestry
School of Forestry, Fisheries and Wildlife
University of Missouri
Columbia, Missouri 65211