Microporous and Mesoporous Materials 29 (1999) 329337

Synthesis of AlPO
4
-5 powder by microwave heating:
Inuence of starting gel pH and reaction time
Tetsuya Kodaira a,b,*, Kohji Miyazawa a,1, Takuji Ikeda c, Yoshimichi Kiyozumi b
a National Institute for Advanced Interdisciplinary Research, 1-1-4 Higashi, Tsukuba, Ibaraki 305-8562, Japan
b National Institute of Materials and Chemical Research, 1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
c Institute of Applied Physics, University of Tsukuba, Ten-noudai 1-1, Tsukuba, Ibaraki 305-8573, Japan
Received 10 August 1998; accepted 21 December 1998
Abstract
Extremely pure AlPO
4
-5 powder was synthesized using a microwave heating method. The yield as well as the size
distribution of the AlPO
4
-5 crystals depended on the pH value of the starting gel. On reducing the pH value from 7.0
to 4.0, the average size of the product crystal was found to increase, the size distribution became wider, and the yield
increased. The pH value of the supernatant liquid after the synthesis was always ca. 7.5, independent of the pH values
of the starting gels. During the rst step of crystallization, disk-like crystals are formed, and they grow in the c-axis
direction resulting in the formation of a hexagonal rod-like shape. The channels of the crystals are completely open,
and, therefore, the crystals obtained are suitable for use as a host to stabilize guest materials. 1999 Elsevier Science
B.V. All rights reserved.
Keywords: AlPO
4
-5; Microwave heating; pH; Reaction time; Synthesis
1. Introduction number of crystal nuclei are simultaneously gener-
ated during the rapid increase in the gel temper-
ature. Therefore, it is believed to be a promising A synthetic method using a microwave (MW)
technique for preparing zeolite crystals with a
heating technique [1] has recently been applied to
narrow size distribution.
produce zeolites in a short time compared with a
Recently, it has become possible to induce new
conventional (CV) heating method. The syntheses
properties into materials by incorporating them
of many kinds of zeolites, materials related to
into the nano-space of zeolites; for example, the
zeolites, and mesoporous materials using the MW
non-linear optical property of p-nitroaniline in
heating method have already been reported [2
channel-type zeolites [ 11,12], or the ferromagne-
10]. In this method, it is believed that a large
tism of arrayed potassium clusters in K-type LTA
[ 13]. For the accurate measurements of some of
* Corresponding author.
the physical properties of the guest materials stabi-
1Present address: Toyota Central Research and Development
lized in the zeolites, e.g. heat capacity and magnetic
Laboratories Co. Ltd., 41-1, aza Yokomichi, oaza Nagakute,
Nagakute cho, Aichi gun, Aichi, 480-1131, Japan. susceptibility using a single crystal, a single crystal
1387-1811/99/$ see front matter 1999 Elsevier Science B.V. All rights reserved.
PII: S1387-1811 ( 99 ) 00002- 5
330 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
of millimeter size is required. It is, however, di- paper in comparison with that obtained by the
CV heating. cult to obtain such large crystals by the CV heating
method. On the other hand, although the size of
each crystal is small, the use of powdered zeolites,
with uniform size and without impurities, may be 2. Experimental
more practical for physical measurements.
AlPO
4
-5 and SAPO-5, both with an AFI struc- The synthesis of AFI-type zeolites (AlPO
4
-5 and
SAPO-5) have been reported by many groups [15 ture, are possible candidates as containers in which
one-dimensional guest materials may be isolated 22] using dierent Al sources and organic tem-
plates. In this study, alumina sol (10 wt.%, and stabilized in their channels [12, 14]. AlPO
4
-5
and SAPO-5 crystals are known to be easily synthe- Kawaken Fine Chemical ) and ortho-phosphoric
acid [ H
3
PO
4
] (85 wt.%, Wako) were employed as sized in sizes larger than 100 mm in the c-axis
direction. The anisotropy of the structure can be the Al and P sources, respectively. Triethylamine
[(C
2
H
5
)
3
N: Et
3
N](99+wt.%, Wako) was used as observed in the optical spectra using one single
crystal of the size mentioned above. It is, however, an organic template. The mole fractions of these
starting materials, dissolved in water, were as well known, and also shown later in this paper,
that large crystals of AlPO
4
-5 and SAPO-5 follows:
obtained by the CV heating methods are often
1 Al
2
O
3
: 1.03 P
2
O
5
: 3.56 Et
3
N: 250 H
2
O
accompanied by a wide size distribution, aggrega-
tions, and byproducts. A few years ago, Girnus These materials are mixed following the pro-
cedure of Demuth et al. in three steps [17]. (1) et al. systematically investigated the synthetic con-
ditions of AlPO
4
-5 using the MW heating method Solution A was prepared by dropwise adding the
alumina sol into two-thirds of the total water [2]. They succeeded in synthesizing large crystals
within a short synthetic time using hydrouoric content. (2) Solution B was prepared by dropwise
addition of Et
3
N to ice-cold diluted H
3
PO
4
aq. acid (HF). For obtaining high quality products,
they also used a secondary synthetic procedure, containing one-third the total water content. (3)
Solution B was added dropwise to solution A which is the re-irradiation with the MW of the
supernatant liquid after the removal of the large under vigorous stirring using a mechanical mixer.
In the third step, the viscosity of the mixture AlPO
4
crystals with the byproducts.
In this study, we report the synthesis of high increases resulting in the formation of a gel. We
stirred this gel long enough to make it homogen- quality AlPO
4
-5 powder with small crystal sizes, a
narrow size distribution, and a high yield without eous. The pH value of this gel was ca. 7.6. The
pH value of the starting gel was adjusted by using HF and a secondary synthesis procedure.
The pH value of the starting gel and the total MW titration with sulfuric acid [ H
2
SO
4
](50 wt.%,
Wako). The pH values of the gels prepared are heating time are selected as the parameters of the
synthesis. The quality of the powder obtained was shown in Table 1. The total amount of water was
increased by the titration, e.g. ca. 10% for the gel evaluated based on scanning electron microscopy
(SEM) images and X-ray powder diraction with pH=4.0. This increase of water in the gel,
however, did not inuence the quality of the nal ( XRD) patterns. It was found that the pH value
of the starting gel plays an important role in product. In the other gels, the increase in the
amount of water by the titration was less than this controlling the average crystal size, the size distri-
bution, and the yield. Furthermore, it was clearly value. These starting gels were kept at room tem-
perature for 1 h before the MW heating. observed in the optical microscopy images of
Se-loaded AlPO
4
-5 crystals that the channels of The gel was heated using a microwave oven
(Questron: Q-wave 3000). The frequency and max- the crystals obtained are open throughout the
crystal with very few defects or impurities. The imum power of the microwave radiation were
2.45 GHz and 1 kW, respectively. The gel of ca. characteristics of the crystal growth of AlPO
4
-5
obtained by the MW heating is discussed in this 50 ml was set in a Teon-lined polyimide autoclave
331 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
Table 1
Conditions of the starting gels and the sizes, yields, etc. of the AlPO
4
-5 crystals obtained
Run Starting Reaction Average sizes in Product Yield of products Number of crystals per
no. pH time (min) a- and c-axes (mm) AFI form (g l 1) gel volume ( l1)
#1-1 7.0 60 4, 8 best (rod-like) 6.19 2.91010
#1-2 6.0 60 6, 8 good 15.6 3.21010
#1-3 5.0 60 8, 14 bad 22.0 1.51010
#1-4 4.0 60 15, 30 (7, 17) no edge 25.3 2.2109
#2a 6.0 4 days 50<, 100< good
#3-1 6.0 10 8, 4 disk-like
#3-2 6.0 20 8, 5 cube-like
#3-3 6.0 30 7, 8 rod-like
#3-4 6.0 40 7, 8 rod-like
a Using the conventional heating method.
The nal pH values of the supernatant liquids after the synthesis were 7.50.1 for #1-1#1-4 and 7.5 for #3.3.
through which the microwave radiation can 3. Results
transmit. The temperature of the gel was controlled
using this oven. The gel was heated to 190C in 3.1. Dependence on the pH values of the starting
gels 90 s, and maintained at that temperature. The total
irradiating time for each sample is shown in
Table 1. After the MW heating, the autoclave was The SEM images of samples #1-1#1-4 are given
in Fig. 1(a)(d). The pH values of the starting gels quench-cooled with iced water. The product
obtained was washed with water and dried over- are 7.0 for #1-1, 6.0 for #1-2, 5.0 for #1-3 and 4.0
for #1-4. The irradiation time of the MW was night at 80C.
The products were characterized using a scan- 60 min for all these samples. With a decrease in
the pH value from 7.0 to 4.0, the average sizes of ning electron microscope (Hitachi: S4500), and an
X-ray powder diractometer (MAC Science: MXP the crystals increased, and the size distributions
became wider. In Fig. 1(a), the crystals have a 3TZ) optimized for measurements of materials
with large lattice constants, such as zeolites [23]. hexagonal rod-like shape with well-dened edges
and faces. This shape is one of the characteristic The chemical composition was also determined as
Al
12
P
12
O
48
[(C
2
H
5
)
3
N]
1.3
using the induction-cou- morphologies of AlPO
4
-5 and SAPO-5 crystals
[ 2, 1518]. The direction of the c-axis is parallel to pled plasma technique and C, H and N elementary
analysis. The concentration of the Et
3
N molecule the six-fold axis of this rod-like shape. The ab
plane is perpendicular to the c-axis. The average per unit cell coincides well with that of AlPO
4
-5
obtained by the CV heating method [19]. crystal sizes in length along the c-axis and along
the a-axis were obtained from the SEM images of To utilize the AlPO
4
-5 crystals obtained to stabi-
lize the guest material, the channels have to be these samples as shown in Table 1. In sample #1-4,
two distinct maxima are observed in the size perfectly opened. In order to check this, Se atoms
are loaded into the channels of the calcined distribution.
The XRD patterns of samples #1-2 and #1-4 are AlPO
4
-5 after dehydration; the AlPO
4
-5 powder
was calcined at 700C for 24 h in an atmosphere recorded as shown in Fig. 2, curves (a) and (b),
respectively. Although the pH values of the starting of oxygen, and then Se atoms were introduced
into the channels using the procedure described in gels are dierent, all the reection peaks in both
samples completely correspond to the standard our previous paper [ 14]. In the present study, Se
atoms were adsorbed at 230C for 10 h. pattern of the AFI structure [24]. The SEM images
332 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
(a) (b)
(c) (d)
Fig. 1. SEM images of AlPO
4
-5 crystals in samples #1-1#1-4 obtained from the gels with dierent pH values: (a) #1-1 (pH=7.0);
(b) #1-2 (pH=6.0); (c) #1-3 (pH=5.0); (d) #1-4 (pH=4.0).
and the XRD patterns conrm the fact that the decrease of the pH value. The pH value of the
supernatant liquid after the MW irradiation was obtained products are the AlPO
4
-5 single phase.
For comparison, a sample of AlPO
4
-5 labeled found to be independent of the pH value in the
starting gel, and was 7.50.1. #2 was synthesized using the CV heating method.
The starting gel with the same composition of
sample #1-2 in a metal autoclave was heated in an 3.2. Eect of MW irradiation time
electric oven. The gel was kept at 190C for 4 days.
An example of the SEM image of this AlPO
4
-5 is The duration of MW heating was varied from
10 to 40 min for samples #3-1#3-4 as shown in shown in Fig. 3. Although large hexagonal rod-
like single crystals are present, there is a wide size Table 1. The pH values of the starting gels in these
samples were 6.0. The SEM images of the distribution of AlPO
4
-5 crystals. Aggregates of the
small AlPO
4
-5 crystals and amorphous-like depos- AlPO
4
-5 crystals for samples #3-1#3-4 are shown
in Fig. 4(a)(d), respectively. The average sizes of its on the surface of the AlPO
4
-5 crystals are also
observed. the crystals are shown in Table 1. In sample #3-1,
hexagonal disk-like shaped crystals have already The yields of AlPO
4
-5 powder in weight per
volume of the starting gel, in units of g l1, are formed. With the increase in the MW heating time,
the crystals grow only in the c-axis direction and shown in Table 1. The yield increases with the
333 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
Fig. 2. XRD patterns of the AlPO
4
-5 powders: (a) #1-2; (b) #1-4.
heating. The pH value of the supernatant uid
was 7.5 for sample #3-3.
3.3. Crystallinity of the AlPO
4
-5 obtained
Se atoms were loaded into the AlPO
4
-5 channels
of sample #1-2. The transparent crystals of
AlPO
4
-5 changed to orange because of the loading
of Se atoms under saturated conditions, ca. 5
atoms per unit cell. Fig. 5 is a monochromatic
photograph of a polarized optical transmission
micrograph image of Se-loaded AlPO
4
-5 crystals.
The arrow in the gure indicates the direction of
Fig. 3. SEM image of the AlPO
4
-5 crystals obtained by the the electric eld of the polarized light. We can
conventional heating method.
clearly see that the crystals whose c-axes are paral-
lel to the electric eld of the transmission light are
uniformly darkened. As reported in Ref. [14], become close to hexagonal rod-like shape with no
size change in the ab plane. It was also observed anisotropic coloration originates from the forma-
tion of an Se chain in a channel. Fig. 5 indicates that no disk-like or smaller crystal was formed in
samples #3-2#3-4. In the SEM images of samples that Se atoms were homogeneously loaded into
the channel with no blocking by contamination, #3-3 and #3-4, we can hardly see the dierence in
size and shape of the crystals. This means that the etc. This result shows that the synthesized
AlPO
4
-5 crystals using the MW heating method crystal growth stops after ca. 30 min of MW
334 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
(a) (b)
(c) (d)
Fig. 4. SEM images of the AlPO
4
-5 powders obtained using dierent MW heating times: (a) #3-1 (10 min); (b) #3-2 (20 min); (c)
#3-3 (30 min); (d) #3-4 (40 min).
have completely opened channels, namely from
one hexagonal face of a crystal to the opposite
face. They are suitable as the container of guest
materials and allow the detailed analysis of their
physical properties.
4. Discussion
4.1. Comparison with the previous study using the
MW heating method
In a previous study [2], the secondary synthesis
method was proposed for obtaining AlPO
4
-5 crys-
tals with a homogeneous size without byproducts.
We found, however, that this technique is not
Fig. 5. Transmission polarized optical microscope image of
necessarily used for synthesizing AlPO
4
-5 crystals
Se-loaded AlPO
4
-5. The direction of the electric eld of the
incident light is indicated by the arrow. with high quality. The dierence between the pre-
335 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
sent study and the previous one is in the gel crystals per volume of the gel ( l 1), except for
sample #1-4. This means that the density of the preparation procedure, except for the dierences
in the Al source, i.e. alumina sol or aluminum crystals produced is independent of the starting
pH. Only the crystal size of each sample depends isopropoxide, and in the additive acid, i.e. H
2
SO
4
or HF. They rst prepared the slurry including the on the pH value of the starting gel. The anomaly
found for sample #1-4 is probably due to the wide Al and P sources and the template, and next
diluted it with water. We suspect that this starting size distribution.
As already mentioned in Section 3.1, the crystals gel is not homogeneous enough at the microscopic
level but may have some concentration gradients. grow in the gel until the pH value reaches 7.5.
Therefore, the crystal obtained from the gel with Thus, in the rst step, the reaction takes place
primarily in the dense area of the inhomogeneous pH=7.0 could not grow large enough, because its
starting pH is close to 7.5. On the contrary, the gel. Consequently, large AlPO
4
-5 crystals are
obtained with byproducts in the rst step. The crystals from the gel with pH=4.0 can grow large
enough because of the supply of the Al and P until homogeneous thin gel, which can be used in the
secondary synthesis, is left unreacted. We conclude, the pH becomes 7.5. The origin of the two peaks
on the size distribution in sample #1-4 is not well therefore, that not only using the MW heating
method but also the preparation process of the understood.
gels are important for limiting the byproducts. Our
method presented here makes it simple to synthe- 4.3. Termination of the crystal growth at pH=7.5
size high quality crystals.
In spite of the wide pH value range of the
4.2. The yield and size of the crystals in relation to starting gel, the pH of the supernatant after the
the pHvalue synthesis was always ca. 7.5. Furthermore, the pH
of the supernatant after MW heating for 30 min,
when the growth of AlPO
4
-5 stopped, was also We have found that the crystal size becomes
large and the yield increases owing to the change 7.5. The crystal growth seems to stop at this pH,
even if the Al and P sources and the Et
3
N remain in the pH value from 7.0 to 4.0. The yield (g l1)
divided by the average weight of the AlPO
4
-5 in the supernatant, because AlPO
4
-5 crystals could
be synthesized using this supernatant with the crystal gives the average number of crystals pro-
duced per volume of the starting gel. To give re-adjustment of the pH value below 7.
It has been reported that the pH value of the physical signicance to the average number, the
sample crystals are required to a have narrow size supernatant after the synthesis is 7.48.6 when
synthesizing the AlPO
4
-5 and SAPO-5 crystals distribution without byproduct contamination.
Fortunately, the powders of AlPO
4
-5 crystals using the CV heating method [19,22, 25]. For the
synthesis of SAPO-5 by the CV heating method, obtained in this study have a narrow size distribu-
tion as shown in Fig. 1, except for sample #1-4. both the increase in the pH value and the crystal
growth stopped at almost the same time [22]. The The average volume of the crystal can be obtained
using the average lengths of the crystals shown in pH value of the gel controls the growth of the
AlPO
4
-5 and SAPO-5 crystals in both heatings. Table 1 and assuming the shape to be a hexagonal
rod. The average weight of the crystal can be The reason that the pH value increases during
the synthesis is as follows. With the growth of the derived by the calculation described in
Appendix A. In sample #1-4, two distinct maxima AlPO
4
-5 crystals during the MW heating, the
densities of Al, P and Et
3
N in the gel gradually in the size distribution were observed as already
pointed out. Neglecting the contribution of the decrease. However, the number of P atoms in the
gel decreases faster than that of the Et
3
N mole- small crystals, the average volume of this sample
was evaluated by taking the crystal size to be 30 cules, because the chemical formula of the
AlPO
4
-5 obtained was Al
12
P
12
O
48
[(C
2
H
5
)
3
N]
1.3
. and 15 mm parallel and perpendicular, respectively,
to c-axis direction. The values obtained are nearly The source of P is phosphoric acid. In contrast,
the Et
3
N in the gel behaves as a base. Therefore, the same as shown in Table 1 as Number of
336 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
the pH of the solution increases with the growth MW. The dielectric loss occurs all over the solu-
of the crystals. However, it is quite dicult to tion. In contrast, in the case of the CV heating
explain why the crystal growth stops at pH=ca. method, the solution is warmed in the autoclave
7.5. Aluminum has a tendency to have an octahe-
by the conduction of heat. Therefore, using MW
dral coordination between pH=3 and 9. Jahn
irradiation, the gel is quickly and uniformly heated
et al. pointed out that phosphoric acid and amine
compared with the CV heating method. For the
molecules play an important role during the stabili-
MW heating, the temperature over all the gel
zation of the tetrahedrally coordinated Al species
quickly reaches the condition that starts the reac-
[26]. This, however, gives us no information about
tion. Thus, the process we imagine is as follows.
the termination of the reaction at pH#7.5. The
Many crystal nuclei (precursors) are simulta-
amine molecules in the gel are supposed to form
neously formed all over the gel. Once the nuclei
clusters with AlO
4
and PO
4
, and shield the tetrahe-
are generated with a high density, the residual Al
dral coordination of Al from attack by water [26].
and P sources are used only for the growth of
The form of the cluster may change as a result of
these nuclei that form crystals until the pH of the
the variation in the pH value. The clusters at pH=
gel is 7.5. This explains why the crystals have a
7.5 may not be able to shield the tetrahedra from
tendency to have a homogeneous size compared
the attack by water.
with the CV heating method.
The duration of synthesis of the AlPO
4
-5 crystals
4.4. Morphology of the crystals during the
needed to terminate the crystal growth was ca.
synthesis
30 min in the present work. The synthesis duration
is shorter than that using the CV heating method.
As described in Section 3.2, the crystals grow
In a previous study using the MW heating method,
almost homogeneously in size for between 10 and
AlPO
4
-5 crystals were obtained in only a few 30 min of MW heating. This means that the crystal
minutes [ 2]. This dierence may originate from nuclei are mostly formed within the MW heating
of 10 min. This is the rst observation of the the dierence in the Al source and the acid. Thus,
simultaneous generation of many nuclei during the HF is believed to accelerate the speed of the crystal
MW heating method. growth, and the use of aluminum isopropylate
The aspect ( length-per-width) ratio of the
may lead to a more uniformly dispersed Al source
AlPO
4
-5 crystal varied during the synthetic reac-
than that of the alumina sol. The particle size of
tion. The crystals grow mainly in the ab plane
the initial alumina sol is 20200 A

. The Al source
during the rst 10 min in which disk-like crystals
may be gradually supplied for the growth of the
are formed. After 10 min, the crystals do not grow
crystals in the present case. Girnus et al. proposed
in the ab plane any more but in the c-axis
a model to explain the signicantly short synthesis
direction. This kind of behavior has been reported
time in MW heating from a microscopic view point
in several kinds of zeolites using the CV heating
[ 2]. Hydrogen bonds between the water molecules
method [ 27]. During the synthesis of AlPO
4
-5
are destroyed by the MW irradiation forming
using the CV heating method, the length in the
active water molecules which accelerate the speed
ab plane is constant with the variation in the gel
of the crystal growth.
density, and a large aspect ratio (needle-like) can
be obtained for the diluted starting gel [15]. In the
present study, the concentration of the solution
5. Conclusions
decreases with the growth of the crystal, and,
consequently, the crystals grow only in the c-axis
Powdered AlPO
4
-5 crystals of high quality can
direction after a certain reaction time.
be synthesized using a MW heating technique. In
the MW heating method, the procedure for the
4.5. Comparison with the CV heating method
preparation of the gel aects the quality of the
nal AlPO
4
-5 product. It is concluded that the Generally, in the MW heating method, the solu-
tion is directly warmed by the dielectric loss of the crystal growth depends on the pH of the starting
337 T. Kodaira et al. / Microporous and Mesoporous Materials 29 (1999) 329337
[2] I. Girnus, K. Jancke, R. Vetter, J. Richter-Mendau, J.
gel. When the pH value of the gel is varied from
Caro, Zeolites 15 (1995) 33.
7.0 to 4.0, the average size becomes large and the
[3] M. Fang, H. Du, W. Xu, X. Meng, W. Pang, Microporous
size distribution widens. The yield of the AlPO
4
-5
Mater. 9 (1997) 59.
increases by decreasing the pH value. The pH
[4] J.G. Carmona, R.R. Clemente, J.G. Morales, Zeolites 18
(1997) 340.
values of the supernatants after the synthesis are
[5] P.M. Slangen, J.C. Jansen, H. van Bekkum, Microporous
always ca. 7.5. During the MW heating, the
Mater. 9 (1997) 259.
AlPO
4
-5 crystals grow mainly in the ab plane
[6] I. Braun, G.S. Ekloff, M. Bockstette, D. Wo hrle, Zeolites
rst, and then in the c-axis direction. It is conrmed
19 (1997) 128.
[7] T.-G. Tsai, K.-J. Chao, X.-J. Guo, S.-L. Sung, C.-N. Wu, that the AlPO
4
-5 powder produced by the method
Y.-L. Wang, H.-C. Shih, Adv. Mater. 9 (1997) 1154.
described in the present study is of sucient quality
[8] C.-G. Wu, T. Bein, Chem. Commun. (1996) 925.
to be used as the container for guest material and
[9] S. Mintova, B.J. Schoeman, V. Valtchev, J. Sterte, S. Mo,
for studying its properties in detail.
T. Bein, Adv. Mater. 9 (1997) 585.
[ 10] M. Park, S. Komarneni, Microporous Mesoporous Mater.
20 (1998) 39.
[ 11] S. Cox, T. Gier, G. Stucky, Chem. Mater. 2 (1990) 609.
Acknowledgements
[ 12] L. Werner, J. Caro, G. Finger, J. Kornatowski, Zeolites
12 (1992) 658.
T.K. and Y.K. gratefully thank CREST (Core
[ 13] Y. Nozue, T. Kodaira, S. Ohwashi, T. Goto, O. Terasaki,
Phys. Rev. B 48 (1993) 12253. Research for Evolutional Science and Technology)
[ 14] T. Kodaira, M.S. Ivanova, Y. Kiyozumi, H. Takeo, T.
of the Japan Science and Technology Corporation
Yamamoto, V.V. Poborchii, Trans. Mater. Res. Soc. Jpn.
(JST) for the nancial support to use the micro-
20 (1996) 470.
wave oven. T.K. and Y.K. thank Dr. A. Iwasaki
[ 15] G. Finger, J. Richter-Mendau, M. Bu low, J. Kornatowski,
and Dr. P.K. Nair for their useful comments on Zeolites 11 (1991) 443.
[ 16] S. Qiu, W. Pang, H. Kessler, J.-L. Guth, Zeolites 9
the mechanism of the AlPO
4
-5 crystal growth by
(1989) 440.
MW heating.
[ 17] D. Demuth, G.D. Stucky, K.K. Unger, F. Schu th,
Microporous Mater. 3 (1995) 473.
[ 18] G. Finger, J. Kornatowski, Zeolites 10 (1990) 615.
Appendix A
[ 19] S.T. Wilson, B.M. Lok, C.A. Messina, E.M. Flanigen,
Synthesis of AlPO
4
molecular sieves, in: D. Olson, A. Bisio
The average weight of the crystals can be derived ( Eds.), Proceedings 6th International Zeolite Conference,
Butterworths, London, 1983, p. 97.
as follows.
[ 20] G. Finger, J. Kornatowski, J. Richter-Mendau, K. Jancke,
The average volume of the regular hexagonal-
M. Bulow, M. Rozwadowski, Stud. Surf. Sci. Catal. 65
rod is given as (3/2)x2y where the average lengths
(1991) 501.
of the crystals in the a- and c-axes directions are [ 21] J.A. Martens, M. Mertens, P.J. Grobet, P.A. Jacobs, Stud.
Surf. Sci. Catal. 37 (1988) 97.
represented by x and y in A

, respectively. The
[ 22] H. Weyda, H. Lechert, Zeolites 10 (1990) 251.
weight M of the present AlPO
4
-5, Al
12
P
12
O
48

[ 23] T. Ikeda, F. Izumi, T. Kodaira, T. Kamiyama, Chem.

[(C
2
H
5
)
3
N]
1.3
, is 1.6103 a.u., neglecting the small
Mater. 10 (1998) 3996.
amount of adsorbed water in the channels.
[ 24] M.M.J. Treacy, J.B. Higgins, R. von Ballmoos ( Eds.),
Collection of Simulated XRD Powder Patterns for The volume V of the unit cell, derived from the
Zeolites, Elsevier, New York, 1996, p. 353 [Special issue
lattice constants a=13.7 A

and c=8.4 A

[28], is
on Zeolites, 16 (1996)].
1.4103 A

3. Therefore, the average weight is given

[ 25] B.L. Newalkar, B.V. Kamath, R.V. Jasra, S.G.T. Bhat,
as (3/2)x2yM/NV in grams, where N is
Zeolites 18 (1997) 286.
[ 26] E. Jahn, D. Mu ller, W. Wieker, J. Richter-Mendau, Avogadros constant of 6.021023.
Zeolites 9 (1989) 177.
[ 27] F. Fajula, in: D. Barthomeuf, E.G. Derouane, W.
Holderich (eds.), Guidelines for Mastering the Properties
of Molecular Sieves: Relationship between the
References
Physicochemical Properties of Zeolitic Systems and their
Low Dimensionality, Plenum, New York, 1990, p. 53.
[1] A. Arafat, J.C. Jansen, A.R. Ebaid, H. van Bekkum, [ 28] J.M. Bennet, J.P. Cohen, E.M. Flanigen, J.J. Pluth, J.V.
Smith, ACS Symp. Ser. 218 (1983) 109. Zeolites 13 (1993) 162.