J Porous Mater (2013) 20:129–136
DOI 10.1007/s10934-012-9581-2
A new model for water adsorption in porous ceramics
Dinh-Hieu Vu • Kuen-Sheng Wang •
Jung-Hsing Chen • Bui Xuan Nam •
Bui Hoang Bac • Do Van Binh
Published online: 3 April 2012
Ó Springer Science+Business Media, LLC 2012
Abstract This research proposes a new isotherm model
that is derived for adsorption of clustering and condensable
vapors on mesoporous ceramics. The adsorption charac-
teristics of water vapor on both experimental data and
isotherm model were investigated over the relative pressure
ranging from 0 to 0.95. The applicability of the model was
evaluated by significance of fitting parameters. For each
adsorption isotherm there are five parameters (m, qf, Kf, qm
and Km). The comparison of modeling fit with experimental
data was used as the methodology for selecting the most
informative and the best-fitting model. The experimental
testing results showed that this model is able to describe all
possible behaviors of the water adsorption isotherm dis-
playing type IV classification. The model is based on the
forming and growth of the water molecule clusters and
capillary condensation mechanism in mesopore. The find-
ings suggest a significant tool for understanding the
behavior of water adsorption in humidity-control porous
ceramics.
D.-H. Vu (&)  B. X. Nam
Faculty of Mining, Hanoi University of Mining and Geology,
Tu Liem, Hanoi, Vietnam
e-mail: vudinhhieu@gmail.com
K.-S. Wang  J.-H. Chen
Graduate Institute of Environmental Engineering, National
Central University, No. 300, Jhongda Rd., Jhongli, Taoyuan
32001, Taiwan
B. H. Bac
Faculty of Geology, Hanoi University of Mining and Geology,
Tu Liem, Hanoi, Vietnam
D. Van Binh
Faculty of Environment, Hanoi University of Mining and
Geology, Tu Liem, Hanoi, Vietnam
Keywords Model  Water adsorption  Mesoporous
ceramic  Cluster  Capillary condensation
1 Introduction
The study of the adsorption isotherm of mesoporous solids
having humidity controlling ability is closely related to the
interpretation of the type IV or V isotherms [1, 2]. Several
theoretical models for these isotherms have been analyzed
using the kinetic frameworks like BET model of Gregg and
Sing [2], capillary condensation theory of Sircar [1], and
adsorption model for type V isotherm of Mahle [3].
Accordingly, the standpoint of these models is closely
bound up in the concept of capillary condensation and its
quantitative expression in the Kelvin equation. However,
these studies are mainly based on surface tension of liquid
in pore, and therefore just explain the absorption phe-
nomenon from physical aspect, and cannot calculate
adsorbed water in micropore.
Recently, Do et al. [4, 5] proposed a model for water
vapor adsorption by activated carbon adsorbents. This
assumes that there are cluster formation having five water
molecules and penetration of clusters into micropore and
mesopore. Then, Neitsch et al. [6] proposed a modification
which assumes cluster size (or numbers of water molecules
in a cluster) is variable and can be exactly used for
adsorption of type IV and V isotherms. Accordingly, the
water molecules are initially chemisorbed on surface
functionalities locating at the entrance of the micropores
(primary sites). Then the clusters are formed from these
water molecules adsorbed via hydrogen bonds with other
water molecules (secondary sites). The clusters situating on
secondary sites increase to reach a given size and enter
micropores as the relative pressure increases [7]. Various
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modifications and applications have been presented by
other authors since the original introduction of Do et al.
and Neitsch et al. models [7–13]. These studies presented
the extension of the original model to describe adsorption
and desorption of water vapor into general porous carbon
materials. They also indicated that the growth of water
clusters at hydrophilic groups locating in mesopores and at
the entrance of micropores [10]. However, these studies did
not mention the influence of pore characteristics such as
surface area, pore size, and pore size distribution. In
addition, when pore size increases to meso size, capillary
condensation will take over as the dominating mechanism.
Hence, there are co-occupations of both water cluster for-
mation and capillarity condensation mechanism on meso-
porous materials having various pore properties. Until now,
there has been no research describing their relationship in
mesoporous materials.
In this paper, based on the original Neitch et al. model
[6], authors developed an equation to describe moisture
adsorption equilibrium in mesoporous materials. The
model is the relationship between the classical theory of
capillarity condensation and water cluster formation. The
mesoporous materials were prepared from mixture of waste
glass and weathered volcanic ash soil with different pore
properties. Authors tested the new model with the experi-
mental data of water vapor adsorption isotherm of the
prepared samples and the description of the isotherms was
found to be satisfactory.
2 Model development
From the original Neitsch et al. model [6] that describes the
adsorption equilibrium of water from water cluster for-
mation in porous solids:
Pðmþ1Þ
Km xmþ1 Kf i¼1 ixi
V0 ¼ q m þ q f Pðmþ1Þ ð1Þ
Km xmþ1 þ x 1 þ Kf i¼1 ixi
where V0 (g g-1) is water vapor loading (or adsorbed
water), m is the number of water molecules in the cluster,
x is the relative pressure, qf (g g-1) is the functional group
concentration, Kf is the equilibrium constant for chemi-
sorptions and hydrogen bonding, qm (g g-1) is the satura-
tion concentration in the micropores, Km is the micropore
equilibrium constant. In the right hand side of Eq. (1), the
first term describes the adsorption of clusters into the mi-
cropores [4–6]. The second term is simply the BET type
equation; it represents a multiple clustering of each func-
tional group with many water molecules and describes the
adsorption into mesopore [4].
Do and Do [4] indicated that the water molecules
chemically bond with functional groups locating in
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J Porous Mater (2013) 20:129–136
mesopores and at the entrance to micropores. The cluster of
water molecules grows to various sizes on the functional
groups, then the capillary condensation mechanism occurs
and will dominates in adsorption process. Therefore, it is
appropriate for Eq. (1) to be extended by adding an addi-
tional term to account for adsorption in mesopores. The
additional term represents the capillary condensation
mechanism of water clusters in mesopores.
Sircar [1] analyzed surface adsorption and capillary
condensation mechanism in mesoporous solids from
Gamma pore size distribution. Let f(r) is mesopore size
distribution such that f(r)dr is the pore volume having
diameter of between r and r ? dr:
azþ1
f ðr Þ ¼ :r z ear ð2Þ
C ð z þ 1Þ
where r is pore radius and can theoretically vary between
zero and infinity C is gamma function, a and z are con-
stants depending on type of adsorption isotherm [1].
With the amount adsorbed by the growth of clusters is:
Pðmþ1Þ
Kf i¼1 ixi
qf Pðmþ1Þ ð3Þ
1 þ Kf i¼1 ixi
Then the statistical thickness of the adsorbed film in
mesopores is:
Pðmþ1Þ
1 Kf i¼1 ixi
tðxÞ ¼ q f P ð4Þ
SM 1 þ Kf ðmþ1Þ xi
i¼1
where, SM is mesoporous surface area of porous ceramic.
Hence, the capillary condensation and water cluster
formation in mesopores are governed by Kelvin equation
for evaporation:
2vM r
r0 ðxÞ ¼ tðxÞ þ ð5Þ
RTlnðxÞ
where, x is the relative pressure of vapor in equilibrium
with a meniscus having a radius of curvature r0, and r and
vM are the surface tension and liquid molar volume of
liquid adsorption, respectively. R is the gas constant and
T is the absolute temperature [2].
At a given pressure, pores having radius less than
r calculated from the above equation are filled with liquid
water while pores having radius greater than r are covered
with water clusters [4]. Combining Eqs. (2), (4) and (5) the
amount of water adsorbed in mesopores is presented by:
2 3
Zr0ðxÞ Z1
6 2f ðrÞ 7
VMS ¼ 4 f ðrÞdr þ tðxÞ dr5 ð6Þ
r
0 r0ðxÞ
Finally the total amount of water adsorbed by porous
ceramics is:
J Porous Mater (2013) 20:129–136 131

Table 1 The chemical components of experimental materials, wt%

Materials SiO2 Al2O3 Na2O K2O MgO CaO TiO2 Fe2O3 ZrO2 MnO P2O5 H2O

Waste glass 66.44 1.63 14.29 0.96 0.52 10.71 0.02 0.09 0.07 0.23 0.34 4.7
Weathered volcanic ash 47.01 19.48 1.58 0.77 0.35 2.31 0.19 1.9 0.11 0.11 0.15 25.55

2 3
Zr0ðxÞ Z1
mþ1
Km x 6 2f ðrÞ 7
V ¼ qm þ4 f ðrÞdr þ tðxÞ
Km xmþ1 þ x
0 r0ðxÞ
where: m, qf, Kf, qm and Km should be treated as the best-fit
parameters.
3 Materials and methods
3.1 Materials
The initial materials including waste glass and weathered
volcanic ash soil were collected from material supplier at
Taoyuan Country (Taiwan). The materials were dried at
105 °C for 24 h and then ground using a wet porcelain ball-
mill machine, and then dried again at 105 °C. The powders
were then passed through 0.075 mm sieves and stored in
desiccators for subsequent experiments [14, 15]. The mixed
powders, included G60A40, G70A30 and G80A20 with the
percentage ratio of waste glass to weathered volcanic ash of
60:40, 70:30 and 80:20, respectively, were pressed uniax-
ially at 32 MPa and molded into a green compact of 50 mm
in diameter and 6 mm in height. The green compacts were
dried at 100 °C and then sintered in electric-heated furnace
at 800 °C for 5 min to form final products.
determined using an ASAP 2010 Machine to analyze the
pore size distribution. The surface area was measured using
dr5
r the BET method. The moisture adsorption and equilibrium
moisture content of final products were determined at
ð7Þ 23 °C by using a TEREHY-HRT-80FA Machine and the
ASTM-1498-01 method [16]. Prior to testing the moisture
adsorption, each test specimen was dried to a constant
mass. The relative humidity (RH) values were achieved
either in the climatic chamber and were controlled to
increase from the lowest values (10 % RH) to the highest
values (98 % RH). For each RH value, the constant mass is
reached if in five successive weightings, with 24 h inter-
vals, the change of mass is less than 0.1 % of the specimen
mass, until the equilibrium is reached at each RH. The full
sorption curve is completed when eleven values are
selected. For the desorption process, the fully saturated
specimen in a weighing cup was placed at the highest RH.
The whole procedure as described in the adsorption process
was repeated until the measurement was completed at the
lowest RH. The equilibrium moisture content at each RH
value was calculated from the measured difference
between the constant saturated mass and the dry weight of
the specimen. The calculation of the moisture content,
v (g g-1), using the mean values of the mass of the test
specimens at each RH: v = (m - m0)/m0; where, m is the
mean mass of the specimens at equilibrium, and m0 is the
mean mass of the dry specimens [15].

3.2 Methods

Chemical analysis of the initial materials is done using the

ICP-AES. The result (Table 1) indicates that the main
chemical components are SiO2 (47.01 %) and Al2O3
(19.48 %) in the weathered volcanic ash soil and SiO2
(66.44 %) in the waste glass. This finding suggests the
alumino-silicate compounds in sintering process of a
mixture of weathered volcanic ash and waste glass. It is
believed that the mixture between them would create new
materials that have interesting porous properties. In addi-
tion, there are small amounts of oxides of K, Mg, Ca, Ti,
Fe, and so forth in both the volcanic ash soil and the waste
glass. These results confirm that both weathered volcanic
ash and waste glass contain metallic iron, which can be
used as a source material for producing ceramic.
The characteristics of the final products were determined
by using various techniques. Nitrogen isotherms were Fig. 1 Pore size distribution of samples

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4 Results and discussion
4.1 Fitting of the water adsorption model
to experimental data
The pore size distributions (Fig. 1) and the surface area
values (Table 2) were determined by applying BET model
to nitrogen adsorption. These results confirm that three
porous ceramics have micro- and meso-porous structure
and this structure has the ability to absorb environmental
humidity [2].
The water adsorption isotherm curves analyzed in Figs. 2,
3, 4 can be basically divided into three consecutive zones. In
the first zone (the relative pressure is less than 0.2); water
molecules are adsorbed on hydrophilic functional groups via
chemisorptions and hydrogen-bonding mechanisms. In the

Table 2 The fitting parameters of the adsorption isotherm model

Sintering tem./time Sample SaM (m2/g) m qf (g/g) qm (g/g) Kf Km Ref.

800/5 G60A40 418.88 5 350 0.1 50 3 This study

800/5 G70A30 163.73 8 250 0.05 5 2 This study
800/5 G80A20 76.89 8.4 150 0.05 4.5 1.5 This study
Sepiolite-Ceram. 249 6.5 280 0.07 23 2.3 [17]
Allophane-Ceram. 198 6.8 260 0.06 14 2.1 [17]
Cristobalite-Ceram. 153 7.3 200 0.047 4.8 1.6 [17]
Halloysite-Ceram. 47 8.6 120 0.03 3 1.1 [17]
a
BET specific surface area obtained by N2 adsorption at 77K

Fig. 2 Fitting of the adsorption

isotherm model to the G60A40
sample

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Fig. 3 Fitting of the adsorption
isotherm model to the G70A30
sample
second zone (the relative pressure is between 0.2 and 0.65),
water clusters rise around hydrophilic groups until a critical
size reached to induce the adsorption into mesopores. The
third zone (the relative pressure is greater than 0.65) is the
place where the growth of cluster is filling up the free space
of pores with the mechanism of water capillary condensation
[4, 10, 12]. The saturated adsorption equilibrium in meso-
pore is closely bound up in the concept of capillary con-
densation and its quantitative expression in the Kelvin
equation [2] and water clusters enter into free pores as for
original micropores.
The fits to the experimental data are also presented in
Figs. 2, 3, 4 as continuous lines. The criteria to identify the
most applicable between experimental data and fitted
adsorption model were the fitting parameters such as m, qm,
qf, Km, and Kf. The fitting results indicated that qf parameter
significantly affects all zones of adsorption isotherm, Kf
parameter affects the first and second zones. The effect of
m on the second and third zones is significant. However,
both qm and Km only affect the third zone. The best-fitting
results of all samples summarized in Table 1 also show a
good description of data with this model. This success is
133
partially attributed to the fact that the model does allow for
the various mechanisms occurring in mesoporous material.
In general, based upon the above discussion, modeling
Eq. (7) was found to be successfully fullfill all criteria for a
water adsorption isotherm model to be applicable to the
experimental adsorption isotherm. Furthermore, this equa-
tion is also able to describe an extremely hydrophilic type
IV water isotherm into two fractions: adsorption of water
molecule clusters on functional groups and capillary con-
densation in mesopores.
Figure 5 shows fitting models for 4 porous ceramics
having deference surface area values of Fukumizu et al.
[17]. Figure 5 results put on satisfactory of all variable sets
according to model trend, meaning that this model can be
successfully applied for multiple mesoporous ceramics.
Figure 6 is the fitting of the water adsorption model to
Zimny et al. data [12]. Two activated carbon samples have
mesopore structure, high surface area, and good water
adsorption ability. Figure 6 shows the significant fitting of
the model for activated carbons, meaning that Eq. (7) is a
water adsorption isotherm mechanism for not only meso-
porous ceramics but also mesoporous materials.
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Fig. 4 Fitting of the adsorption

isotherm model to the G80A20
sample

Fig. 5 Fitting of the water

adsorption model to Fukumizu
et al. data for porous ceramics
[17]

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Fig. 6 Fitting of the water

adsorption model to Zimny
et al. data for activated carbon
[12]

4.2 The variations of fitting parameters
of the adsorption isotherm model
The trend and variations in values of fitting parameters are
shown in Fig. 7. The number of water molecules in a
cluster (m), an important variable to fit in equations of
model, affects the critical size of water clusters entering
into pores [7, 9]. The results in Fig. 7a show that m values
range from 5 to 9 and SM decreases as m values slightly
increase confirming that there are many water clusters

Fig. 7 The variations of fitting

parameters of the adsorption
isotherm model

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having similar size in mesopores. In addition, Figs. 2a, 3a
4a indicate that the effects of the number of molecules in a
cluster on the model occur when P/Po is larger than 0.25.
The saturation concentration of water in micropores (qm)
depends on micropore volume including original micro-
pore in samples and free part of mesopore (free micropore).
When P/Po is small, water molecules are adsorbed in ori-
ginal micropores, resulting in no effect of qm values on the
model. When P/Po increases (P/Po [ 0.3), the capillary
condensation mechanism will dominate in mesopores [4],
resulting in the occurrence of free micropore in mesopore.
Therefore, there are effects of qm values on the model and
these effects increase as BET surface area increases
(Fig. 7b). The qm values are low and slightly change in
samples because water in micropores exists as molecule
clusters that are unstable and bond with other cluster to
form capillary condensation in mesopore [7].
The equilibrium constant for water clusters in microp-
ores (Km) depends on chemical bonding and the number of
water molecules bonded to the coalescence of water
aggregation [7]. Hence, its effect on the model occurs when
P/Po increases (Figs. 2c, 3c, 4c). However, Km values
range from 1.5 to 3 and slightly increase as BET surface
area increases (Fig. 7c). Both of qm and Km values are
small and slightly change, indicating that water adsorption
in micropores is an important intermediary part of full
water adsorption isotherm in mesoporous material.
Figures 2d, 3d, and 4d indicate that the effect of qf on
the model is shown in full region of adsorption isotherm. It
is basically the increased amount around the functional
group to fit in the pore [4] and the functional groups can
stabilize the cluster in mesopore [5]. Figure 7d shows that
qf values increase as surface area values increase; it is a
correct trend as expected as the adsorbed water volume
rises up with the increasing adsorption ability of samples.
Trend in values of Kf parameter vs BET surface area of
HCM shown in Fig. 7e. The equilibrium constant (Kf)
determined by the ratio of the equilibrium constant for
water chemisorptions and the equilibrium constant for
water physisorption expresses the thermodynamic stability
of the H2O–H2O bond [7]. Therefore, Kf value affects the
first and second zones of modeling adsorption isotherm
(Fig. 2e, 3e, 4e) where the formations of water clusters
occur. Hence, Kf value is high as the adsorbed water
amount in the primary stage of adsorption is high with
quickly adsorbed rate [4]. The Kf values of G60A40,
G70A30 and G80A20 samples are 50, 5 and 4.5 respec-
tively, indicating that the water adsorption ability of the
G60A40 sample is much higher than those of G70A30 and
G80A20 samples. In addition, the increase of all four
parameters (qf, qm, Kf, and Km) when water adsorption
ability increases proposes the satisfactory of the model for
mesoporous ceramics. Finally, Table 2 fully summered the
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J Porous Mater (2013) 20:129–136
fitting parameters of the adsorption model to experimental
data.
5 Conclusion
This paper has presented a developing model to describe
adsorption isotherm of water vapor into mesoporous
ceramics. The mesoporous ceramics were prepared from
sintering the mixture of volcanic ash and solid waste. For
all samples, water adsorption isotherms displayed type IV
behavior. The Matlab software was used to fit the new
equation with both experimental and literature data, the
descriptions of the adsorption isotherms were found to be
satisfactory. The physical interpretation of the fitting
parameters m, Kf, Km, qf and qm, obtained using the model
developed in this paper, were in agreement with the
structural characterization of mesoporous ceramics.
Finally, the above parametric study shows that the
proposed model for vapor adsorption on mesoporous solids
is very flexible in describing the relationship between water
molecule clusters and capillary condensation mechanism in
an adsorption isotherm. This model can also calculate the
adsorbed amount of water and predict water adsorption
ability of mesoporous ceramics.
Acknowledgments This work was financially supported partly by
Waste Management and Resource Recovery Group, Graduate Insti-
tute of Environmental Engineering, National Central University,
Jhongli, Taoyuan 32001, Taiwan.
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