Preparation and characterization of activated carbons made up from different woods by

chemical activation with H

3
PO
4
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INSTITUTE OF PHYSICS PUBLISHING SMART MATERIALS AND STRUCTURES
Smart Mater. Struct. 12 (2003) N24N28 PII: S0964-1726(03)69559-5
TECHNICAL NOTE
Preparation and characterization of
activated carbons made up from different
woods by chemical activation with H
3
PO
4
A Macas-Garca
1
, M A Daz-Dez
1
, V G omez-Serrano
2
and
M C Fern andez Gonz alez
2
1

Area de Ciencia de Materiales, Escuela de Ingenieras Industriales, Universidad de
Extremadura, 06071 Badajoz, Spain
2
Departamento de Qumica Inorg anica, Facultad de Ciencias, Universidad de Extremadura,
06071 Badajoz, Spain
E-mail: amacias@materiales.unex.es
Received 13 May 2003, in nal form 9 September 2003
Published 20 November 2003
Online at stacks.iop.org/SMS/12/N24
Abstract
There are many known methods for the preparation of activated carbons.
They are often classied as chemical and physical activation methods, a
division widely used in the scientic literature.
In this paper we study the preparation of activated carbons from different
woods (chestnut, cedarwood, walnut) by chemical activation with different
concentrations of phosphoric acid (36 and 85 wt%). The prepared activated
carbons were characterized by the following techniques: physical adsorption
of gases, mercury porosimetry, chemical analysis and measurement of
density by helium and mercury displacement.
The main conclusion obtained was that chemical activation with 36 wt%
H
3
PO
4
yields activated carbons with better textural properties than those
prepared with 85 wt% H
3
PO
4
. The effects of activation on the textural
properties of the activated carbons improve when the concentration of
phosphoric acid is reduced.
1. Introduction
To prepare activated carbon, different materials such as algae,
olive stones, cherry stones, almond shells, rockroses, woods
of different kinds and waste [111] can be used.
When preparing activated carbons, activating agents can
be used before or after carbonizing the raw materials. Some of
the substances used in the process are boric acid, phosphoric
acid, nitric acidandzinc chloride [12, 13]. After carbonization,
the activating agents most widely used to activate the char
are water vapour, carbon dioxide, air or a combination of
these [6, 14].
The methods for preparing activated carbons are often
classied as chemical and physical activation methods.
Chemical activation methods consist of carbonizing a raw
material after adding substances that restrict tar formation [15].
In this work, chemical activation was done with
phosphoric acid. This technique consists of impregnating
the raw material with the acida strong dehydrating agent
and heating at temperatures around 400500

C to activate
the carbon. Activated carbons made by chemical activation
usually have a porous and very open structure, ideal for the
adsorption of big molecules. The advantages of activation with
phosphoric acid as opposed to physical activation include a
highyieldandlower working temperatures. The disadvantages
are those related to the recovery of the chemical agent, the
cleaning of washing waters and the cost of the washing and
recovery systems.
The raw material (wood) contains mainly water,
holocellulose, lignin and other matter [1618] found in all
woody plants. Holocellulose [17] is made up of cellulose
0964-1726/03/060024+05$30.00 2003 IOP Publishing Ltd Printed in the UK N24
Technical Note
(alpha cellulose) and a mixture of some other polysaccharides,
known as hemicellulose (beta cellulose, gamma cellulose
and some polyuronides) [18]. Cellulose makes the wall of
wood bre cells and is very resistant to chemicals, while
hemicellulose is less resistant to acids and bases.
Lignin is a complex polymer containing a propyl group
bonded to different groups [18]. This substance may degrade
and be dissolved by strong bases at high temperatures and also
by oxidizing agents [17].
The preparation of activated carbon from lignocellulosic
materials by chemical activation is very important from the
industrial point of view. On carbonization many of these
materials (rockrose, olive, etc) produce non-graphitizable,
high-purity chars of appropriate hardness and bulk density,
which are very adequate as precursors for activated carbon of
high quality useful in the adsorption of gases and solutes from
aqueous solution [19].
On the other hand, these materials permit the preparation
of activated carbons with a variety of pore size distributions
by modifying the preparation conditions of the chemical
activation procedure. In chemical activation there is a reaction
of the precursor with the activating agent to develop the
porosity.
The present study evaluates the preparation and porosity
of activated carbons from woods (not studied up to now) using
increasing concentrations of phosphoric acid
2. Material and experimental methods
The woods used in this workchestnut, cedarwood and
walnutwere cut into pieces and dried, as they contain plenty
of water in the vessels and bre. Besides, sap remaining in the
wood could ferment because of the soluble materials in it, and
fungi could also appear, making future changes in non-dried
wood [20].
Once dried and cut into shavings, the woods were used
to prepare two different series of activated carbons. The raw
materials were rst washed with sulfuric acid 10 wt% for 5 h.
Then, they were washed with distilled water until full removal
of the acid was achieved. The dried material was impregnated
with solutions of H
3
PO
4
, heat treated under a ow of nitrogen
and washed with distilled water to extract the phosphoric acid.
For impregnation, 50 g of precursor were added to a
200 ml solution of H
3
PO
4
stirred at 85

C, maintaining these
conditions for 4 h to ensure the access of the H
3
PO
4
to the
interior of the wood samples. The initial concentrations of the
H
3
PO
4
solutions were 36 and 85 wt%. Next, the samples were
evaporated to dryness.
All impregnated materials were carbonized in a furnace,
under the same experimental conditions: a ow of nitrogen
of 100 ml min
1
, heating rate of 5

C min
1
up to 450

C,
residence time of 4 h. After cooling down to room temperature
under the same ow of nitrogen, the samples were extracted
with distilled water up to pH = 6. The washed product was
dried overnight in an oven at 110

C [13].
The amount of phosphorus retained in the material after
impregnation was determined by subtracting the amount
of phosphorus remaining in the solution from the amount
originally present; for the determination of phosphorus a
gravimetric method based in the precipitation of quinoline
Table 1. The yield of the process and phosphorus content.
Sample Yield (%) X
P
(g g
1
)
Ca-36 46 0.34
Ce-36 45 0.32
No-36 43 0.41
Ca-85 47 0.39
Ce-85 47 0.43
No-85 44 0.52
phosphomolybdate [21] was used. In the selected range of
concentrations (0.11.0 g PO
3
4
/l), the experimental error is
3.2%. The content of phosphorus, X
P
, is expressed as grams
of phosphorus per gram of precursor.
The ultimate analysis was performed using a Perkin
Elmer model 240C analyser. The oxygen content was
calculated by subtraction (see table 1).
The proximate analysis data (moisture, volatile matter,
ash (see table 2)) were obtained thermogravimetrically as
described elsewhere [22]. The xed carbon content was
determined by subtraction.
The treatment of the activated carbon was very likely to
have changed the texture of the carbons as a consequence of the
quantity of H
3
PO
4
introduced on the surface of the material.
This was determined by N
2
(g) adsorption and helium density
measurements. The N
2
(g) adsorption isotherms at 77 K were
determined using a Quantachrome Autosorb 1. The porosity
of the activated carbons was examined by adsorption of N
2
(77K). The volume of mesopores was calculatedbysubtracting
the volume of micropores from the amount adsorbed at a
relative pressure of 0.95. The BET surface area was calculated
from tha adsorption data of N
2
at 77 K. The density was
determined by displacement of helium using a Quantachrome
stereopyknometer.
Samples were classied as follows:
Activated carbons with 36 wt% H
3
PO
4
:
Chestnut Ca-36
Cedarwood Ce-36
Walnut No-36
Activated carbons with 85 wt% H
3
PO
4
:
Chestnut Ca-85
Cedarwood Ce-85
Walnut No-85.
3. Results and discussion
The yield of the process activation and the amount of
phosphorus retained are shown in table 1. The yield oscillates
around 45%and the phosphorus content varies from0.340.41
for 36 wt% H
3
PO
4
to 0.390.52 for 85 wt% H
3
PO
4
.
3.1. Chemical analysis
Table 2 shows that samples treated with 36 wt% H
3
PO
4
have
around 5% of moisture, a higher value than samples treated
with 85 wt% H
3
PO
4
(around 3%). This might mean that
36 wt%H
3
PO
4
develops a greater porosity that allows water to
be retained to a greater extent. The different values of moisture
N25
Technical Note
Table 2. Proximate and elemental analysis of the activated carbons.
Moisture Volatile mat.
a
Ashes
a
Fixed carbon
b
C H N O
b
dif
Sample (%) (%) (%) (%) (%) (%) (%) (%)
Ca-36 5.18 7.60 8.90 84.02 86.20 0.09 0.61 4.20
Ce-36 5.24 7.68 8.94 80.94 85.90 0.10 0.65 4.41
No-36 5.28 7.80 9.20 79.98 84.01 0.13 0.70 5.96
Ca-85 3.00 6.13 10.00 83.89 86.10 0.08 0.60 3.22
Ce-85 3.20 10.26 10.50 80.01 85.80 0.09 0.54 3.07
No-85 3.30 10.80 11.01 79.80 83.20 2.00 0.46 3.33
a
Dry base.
b
O
dif
= 100 (C + H + N + ashes, dry base).
found in the products are probably due to the difference in
porosity because of the different concentrations of phosphoric
acid used.
Content of volatile matter followed a similar pattern,
i.e. values of around 7% for samples treated with 36 wt%
H
3
PO
4
versus values of around 10% for those treated with
85 wt%H
3
PO
4
. This could be due to the lowthermal treatment
both series underwent and to the possible COP bonds and
formation of other species which were not removed during the
preparation of samples [23].
The ash content for all samples was higher than expected
for a normal activated carbon. This could be due to a high
content of inorganic matter, which would conrm the presence
of phosphoric acid in the lignocellulose structure [13].
Both series of samples show a high and quite similar
carbon content.
The difference found between carbon and xed carbon
content is easy to explain: carbon content includes all carbon
present in the sample, both xed and removed in the volatile
compounds; that is why carbon content is higher than xed
carbon content.
Data regarding hydrogen and nitrogen content follow the
expected pattern for activated carbons, showing high values of
carbon because of the likely formation of C=C double bonds,
this lowering the hydrogen content. Nitrogen content shows
the presence of stable nitrogenous structures.
3.2. N
2
(g) adsorption isotherms at 77 K
Figure 1 shows N
2
(g) adsorption isotherms at 77 K. They
are intermediate between those of type I and of type IV in
BDDT classication [24], resulting from adsorption by solids
with a relatively high content of micro- and mesopores. The
main variations with respect to the ideal type I form are the
angles and the plateaus of the curves. We can make qualitative
considerations regarding the adsorbent porosity [25, 26]. The
smaller the isotherm angle, i.e. when the horizontal part of
the isotherm is reached at lower values of relative pressure,
the higher the adsorption energy and the higher contribution
of the micropore volume to the total volume adsorped. As
the number of meso- and macropores increases, the angle
gradually increases and the isotherm plateau shows a higher
slope.
Figure 1 also shows that the plateau slope decreases
in the order Ce-36 > Ca-36 > No-36. This means that as
microporosity grows mesoporosity grows as well, either by
widening of the biggest micropores or by breaking the inner
0.0 0.2 0.4 0.6 0. .0
0
200
400
600
800
V
(
c
m
3
/
g
)
P/P
0
Ca-36
Ce-36
No-36
Ca-85
Ce-85
No-85
Figure 1. N
2
(g) adsorption isotherms at 77 K.
walls, thus openingupcommunicationbetween the micropores
and increasing the volume of the biggest pores.
Figure 1 also shows that in the rst part of the isotherm
the microporosity is quite similar in all samples treated with
36 wt%H
3
PO
4
. This behaviour is reected in the development
of the meso- and macroporosity, what might mean that the
treatment with 36 wt% H
3
PO
4
helps the development of
porosity in these woods.
When comparing the isotherms of samples obtained with
36 wt% H
3
PO
4
with those of samples treated with 85 wt%
H
3
PO
4
, we can see that when H
3
PO
4
concentration increases
the adsorped quantity decreases, which means that the number
and/or volume of micropores decreases due to narrowing of
the biggest micropores or by obstruction, probably due to the
excess of phosphoric acid or even to the presence of collateral
reactions (in concentrated solutions phosphate anions interact
by means of hydrogen bonds [23]) that make it difcult for
N
2
(g) to access the pores, thus reducing the pore volume.
Figure 2 shows that micropore volume (V
m
) and S
BET
values are quite similar in the 36 wt% H
3
PO
4
series and
lower and quite different in the 85 wt% H
3
PO
4
series. The
lower surface area in samples treated with 85 wt% H
3
PO
4
could be due to the higher concentration and to the presence
of excess H
3
PO
4
. This could be conrmed by studying the
values corresponding to the volumes of micropores (V
mi
)
and mesopores (V
me
). Incorporation of H
3
PO
4
into the
lignocellulose structure of woods seems to be the reason for
the creation of micropores. From the volumes of micro- and
mesopores, we can see that these solids show an acceptable
N26
Technical Note
Ca-35 Ce-36 No-36 Ca-85 Ce-85 No-85
200
300
400
500
600
700
800
900
S
BET
S
B
E
T
(
m
2
/
g
)
0.0
0.1
0.2
0.3
0.4
0.5
V
mi
V
me
V
(
c
m
3
/
g
)
Figure 2. Representation of S
BET
, V
mi
and V
me
values for the
samples.
microporosity and mesoporosity, higher in samples treated
with 36 wt%H
3
PO
4
than in those treated with 85 wt% H
3
PO
4
.
This could be due to the fact that in 85 wt% H
3
PO
4
not only is
phosphoric acid present, but also a mixture of polyphosphoric
acids. At acid concentrations lower than 50% phosphate
anions interact with water molecules by means of hydrogen
bonds whereas for concentrated solutions such interaction
involves two or more phosphate anions [23]. Thus, H
3
PO
4
,
H
4
P
2
O
7
, H
5
P
3
O
10
and some others in lower concentrations
(e.g. H
n+2
P
n
O
3n+1
) [27], each one with a different molecular
size, are present in the above-mentioned mixture. This
fact could explain the different distributions of micropore
sizes in carbons impregnated with different concentrations
of phosphoric acid. The polyphosphate species have been
described for carbons made from coconut shells activated with
potassium phosphate [28] and for carbons made by activation
of carbons with phosphoric acid [29].
Thus, the acid introduced within the material plays
a double role. Firstly, it produces hydrolysis of the
lignocellulosic material with subsequent partial extraction
of some components, thus weakening the particle which
swells. This effect is mainly developed in samples treated
with 36 wt% H
3
PO
4
(0.34 < X
P
< 0.41), as indicated
above for concentrations lower than 50%, thus favouring the
development of porosity when compared with those samples
treated with 85 wt% H
3
PO
4
(0.39 < X
P
< 0.52) (gure 2).
Secondly, the acid occupies a volume which inhibits the
contraction of the particle during the heat treatment, thus
leaving a porosity when it is extracted by washing after
carbonization [30].
Samples treated with 85 wt% H
3
PO
4
(i.e. higher
concentration and X
P
values) contain polyphosphoric acids
of greater molecular size than that corresponding to
H
3
PO
4
[23, 2729]. Such polyphosphoric acids occupy the
greatest pore size range and consequently are not involved in
the formation of micropores (gure 2).
3.3. Mercury porosimetry
The results of mercury porosimetry (V
ac
, V
ma
, V
me
values,
table 3) clearly show that the accumulated volume of pores
is lower in samples treated with 85 wt% H
3
PO
4
than in those
treated with 36 wt% H
3
PO
4
, due to the lower contribution of
Table 3. Results obtained from mercury porosimetry.
V
ac
V
ma
a
V
me
a
S
ac
a
Sample (cm
3
) (cm
3
g
1
) (cm
3
g
1
) (m
2
g
1
)
Ca-36 1.35 1.14 0.21 110.74
Ce-36 1.06 0.78 0.27 128.24
No-36 1.12 0.92 0.20 101.66
Ca-85 1.30 1.14 0.16 55.31
Ce-85 0.64 0.49 0.15 56.26
No-85 0.49 0.39 0.10 47.49
a
V
ac
= V
ac
(R = 20 ), V
ma
= V
ac
(R = 250 ),
V
me
= V
ac
V
ma
and S
ac
(R = 20 ).
Table 4. Values obtained from densities.

Hg

He
V
T
V
ma
Sample (cm
3
g
1
) (g cm
3
) (cm
3
g
1
) (cm
3
g
1
)
Ca-36 0.40 0.94 1.56 1.10
Ce-36 0.46 0.99 1.16 0.69
No-36 0.45 0.97 1.26 0.89
Ca-85 0.40 1.02 1.52 1.16
Ce-85 0.64 1.23 0.75 0.50
No-85 0.76 1.32 0.55 0.38
macro-, meso- and micropores in samples treated with 85 wt%
H
3
PO
4
. The remarkable loss of porosity when treating with
85 wt% H
3
PO
4
is never stressed enough.
The accumulated surface area of macro- and mesopores
is relatively high for all samples treated with 36 wt% H
3
PO
4
.
This is inaccordance withthe acceptable volume of mesopores,
as macropores (whose volume is somewhat higher) hardly
contribute to the overall surface area of the solid.
3.4. Densities from helium and mercury displacement
Values fo V
T
obtained for samples treated with 85 wt%H
3
PO
4
(table 4) show that the overall volume of pores is, generally,
lower than that for samples treated with 36 wt% H
3
PO
4
. In
conclusion, regardless of the activating agent, its concentration
greatly inuences the development of porosity in samples.
Values of
Hg
and
He
(table 4) obtained for samples
treated with 36 wt%H
3
PO
4
show that, as expected,
He
>
Hg
for all samples. According to the denitions of both densities,
the difference between the values of densities is based on the
different development of porosity in the materials. This is
reected by the values of V
T
calculated for samples (table 4).
As macroporosity is so important for the porous texture
of activated carbons, we calculated V
ma
values from V
T
values
using the following equation:
V
ma
= V
T
(V
mi
+ V
me
). (1)
Table 3 shows that (a) the volume of macropores is high
for all samples and (b) V
ma
values are fairly similar to those
based on mercury porosimetry data (table 3).
4. Conclusions
The phosphoric acid concentration greatly inuences the
composition of the activated carbons obtained.
N27
Technical Note
Figure 1 shows that the quantity of N
2
(g) adsorped
at 77 K follows the pattern Ce-36 > Ce-85, Ca-36 > Ca-85
and No-36 > No-85. Also, the quantity adsorped is much
greater for samples treated with 36 wt% H
3
PO
4
than for those
treated with 85 wt% H
3
PO
4
. The increase in adsorption when
increasing P/P
0
also follows the above pattern. Therefore,
samples treated with 36 wt% H
3
PO
4
are much better than
samples treated with 85 wt% H
3
PO
4
, having an important
development of micro- and mesoporosity.
Micro- and mesopore volumes showthat these solids have
an acceptable content of both micropores and mesopores. This
happens to a greater extent in samples treated with 36 wt%
H
3
PO
4
than in those treated with 85 wt% H
3
PO
4
. This
could be due to the fact that in 85 wt% H
3
PO
4
there is not
only phosphoric acid, but a mixture of polyphosphoric acids
consisting mainly of H
3
PO
4
, H
4
P
2
O
7
, H
5
P
3
O
10
and some
others in lower concentrations (e.g. H
n+2
P
n
O
3n+1
) [27], each
one with a different molecular size. This distribution of
species could explain the different distribution in micropore
sizes in carbons impregnated with different concentrations of
phosphoric acid.
The total porosity of wood activated with 36 wt% H
3
PO
4
is higher than that of wood activated with 85 wt%H
3
PO
4
. The
effects of activation on micro- and mesoporosity, as well as
on the surface area, are remarkable in chestnut and cedarwood
samples treated with 36 wt% H
3
PO
4
; they are less marked in
walnut samples.
Activation with 36 wt% H
3
PO
4
produces high develop-
ment in the surface area and porosity of carbons.
As an overall conclusion, chemical activation with
36 wt%H
3
PO
4
produces activated carbons with better textural
properties than those obtained using 85 wt% H
3
PO
4
. The
effects of activation on textural properties of activated carbons
improve when reducing the concentration of phosphoric acid.
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