Journal of Chemical Engineering of Japan, Vol. 37, No. 5, pp.

669674, 2004 Research Paper

Copyright 2004 The Society of Chemical Engineers, Japan 669
Crystal Growth Behavior of Zeolites Elucidated by Atomic Force
Microscopy
Toru WAKIHARA
1
and Tatsuya OKUBO
1,2
1
Department of Chemical System Engineering,
The University of Tokyo, 3-1, Hongo 7, Bunkyo-ku,
Tokyo 113-8656, Japan
2
PRESTO, JST
Keywords: Atomic Force Microscopy, Zeolite, Precursor, Crystal Growth, Raman Spectroscopy
Seeded growths of faujasite and zeolite A were investigated by atomic force microscopy (AFM). For
seeded growth, clear aluminosilicate solutions (90Na
2
O:xAl
2
O
3
:9SiO
2
:5760H
2
O, where x = 0.11.0), which
are useful for faujasite or zeolite A growth on seeded faujasite or zeolite A, respectively, were prepared at
353 K. Changes at the same position were observed along with growth period, and it was revealed that
crystal growth behaviors of faujasite and zeolite A were different in the same aluminosilicate solution.
Corresponding aluminosilicate solutions were characterized by Raman spectroscopy. By combining the
results of both AFM and Raman spectroscopy, the behavior of aluminosilicate species incorporating into
the solid phase from the liquid one was discussed. Key precursors of crystal growth for faujasite and
zeolite A were proposed to be six-membered and four-membered rings, respectively.
Introduction
Zeol i t es are hydrat ed, cryst al l i ne
tectoaluminosilicates that are constructed from TO
4
tetrahedra (T = tetrahedral atom, e.g. Si or Al) (Barrer,
1982). They contain well-ordered, nanometer-sized
void spaces in their structures. Because of their well-
defined structures and large ion-exchange capabilities,
they have been used as adsorbents, ion-exchangers,
catalysts and molecular-sieving membranes. Synthe-
sis of artificial zeolites started in 1945, and more than
130 kinds of framework structures have been reported.
Most zeolites are synthesized under hydrothermal con-
ditions. After Si and Al sources are mixed, the
hydrogels obtained are heated at prescribed tempera-
tures and crystallized into zeolites. In the synthesis of
zeolites with a high Si/Al ratio, structure-directing
agents (SDAs) are often added. In general, zeolite crys-
tallization is affected by various experimental factors
(e.g. starting composition, pH, temperature, mixing
procedure, agitation and synthesis time). Therefore,
crystallization mechanisms of zeolites have not yet
been well understood, and the elucidation of them still
remains one of the major topics in zeolite science.
Zeolite crystallization consists of two parts; nu-
cleation and subsequent crystal growth. Two routes of
zeolite crystallization have so far been proposed
(Barrer, 1982). One is the direct transformation of
Received on October 20, 2003. Correspondence concerning this
article should be addressed to T. Okubo (E-mail address:
okubo@chemsys.t.u-tokyo.ac.jp).
amorphous intermediates into zeolite structures, and
the other is a mediated route; that is, the dissolution of
amorphous intermediates to soluble species followed
by nucleation and crystal growth of zeolites by the
soluble species. Although experimental results that
support both mechanisms have been proposed, the de-
tails have not yet been well clarified. There are a lot of
publications on the crystallization mechanism of
Silicalite-1, which is pure silica ZSM-5, and its crys-
tallization mechanism is getting clearer (Burkett and
Davis, 1995; de Moor et al., 1999). On the other hand,
the crystallization mechanisms of low Si/Al ratio
zeolites synthesized without SDAs are more compli-
cated, because the interactions among water, alkali
cations and aluminosilicate species are strong and are
themselves interrelated.
In this study, we focus on the crystal growth of
fauj asi t e and zeol i t e A, whi ch are a cl ass of
aluminosilicate zeolites containing three-dimensional
void spaces within their structures, and are widely uti-
lized in industrial fields, for example as adsorbents,
catalysts, and ion-exchangers. Framework structures
of faujasite and zeolite A are shown in Figure 1.
Faujasite consists of sodalite cages connected with
double six membered rings (D6Rs), while zeolite A
consists of sodalite cages connected with double four
membered rings (D4Rs). Note that faujasite with a
Si/Al ratio larger than 1.5 is called zeolite Y, and that
with a ratio smaller than 1.5 is zeolite X.
Several studies on the formation of faujasite and
zeolite A have been reported; Alfredsson et al. (1993)
and Anderson et al. (1996) observed steps of ca. 1.43 nm
670 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
high on the top surface of zeolite Y, which correspond
to the height of unit cell repeat along the <111> direc-
tion, by high-resolution electron microscopy (HREM)
and atomic force microscopy (AFM), respectively.
Dutta et al. (1987) and Xiong et al. (2001) investigated
the crystallization of faujasite (zeolite Y and zeolite
X, respectively) by Raman spectroscopy, and reported
that six membered rings (6Rs) connected by four
membered rings (4Rs), or 4Rs connected by 6Rs to
form sodalite cages is the mechanism for nucleation
of zeolite Y or zeolite X, respectively. On the other
hand, Sugiyama et al. (1999) observed the surface of
zeolite A by AFM, and concluded that D4R is the key
building unit for crystal growth of zeolite A. Dutta and
Shieh (1986) also investigated the crystallization of
zeolite A, and concluded that the gel that transforms
to zeolite A contains a well-defined structure consist-
ing predominantly of 4R. Although the aluminosilicate
precursors for both faujasite and zeolite A are becom-
ing clearer from these studies, aluminosilicate precur-
sors in the liquid phase and crystal growth behavior
on the surface have not yet been satisfactorily linked.
In this study, seeded growth of faujasite and zeolite A
are investigated by AFM. Changes at the same posi-
tion are investigated along with the growth period, and
it is shown that the seeded growth of faujasite and zeo-
lite A can proceed in the same aluminosilicate solu-
tion, and that the crystal growth behavior depends on
the composition of the solution. Corresponding
aluminosilicate solutions for the seeded growth are also
characterized by Raman spectroscopy. By combining
the results of both AFM for solid surfaces and Raman
spectroscopy for gel phases, the behavior by which
aluminosilicate species are incorporated into the solid
phase from the liquid phase is shown.
1. Experimental
1.1 Syntheses of seed zeolites
Zeolites are usually synthesized as a powder form
smaller than 1 m. To observe crystal growth by AFM,
the preparation of large single crystals of zeolites (Qiu
et al., 1998; Shiraki et al., 2001), hopefully larger than
10 m, is desirable. In this study, zeolite syntheses
using a nucleation suppressor (TEA:triethanolamine)
were employed. Seeds of faujasite (zeolite X:Si/Al ra-
tio is ca.1.4) were synthesized after Warzywoda et al.
(1999).
In the same way, seeds of zeolite A were prepared
using TEA. The aluminosilicate solution was prepared
by dissolving sodium metasilicate nonahydrate
(Na
2
SiO
3
9H
2
O, Wako Pure Chemical Industries, Ltd.),
sodium aluminate (NaAlO
2
, Al/NaOH is about 0.75,
Wako Pure Chemical Industries, Ltd.), and TEA (pu-
rity 98%, Wako Pure Chemical Industries, Ltd.) in
distilled water. 10.0 g of Na
2
SiO
3
9H
2
O was added
to 70.8 g of distilled water in a polyethylene bottle,
and in another polyethylene bottle, 8.00 g of NaAlO
2
was added to 70.0 g of distilled water, and stirred for
10 min. Both solutions were pretreated by 0.2 m mem-
brane filter before addition of 10 ml of TEA to each.
Then, the latter solution was poured into the former
solution that had been stirred for 5 min. All the proce-
dures were performed at 333 K. Finally, the solution
was placed in an oven at 353 K, and heated for two
weeks without stirring. The products were filtered,
washed with distilled water, and dried at 353 K for
24 h. The seeds obtained were characterized by field-
emission electron microscopy (FE-SEM, S-900,
Hitachi, Ltd.).
1.2 Seeded growth
For seeded growth, clear aluminosilicate solutions
(90Na
2
O:xAl
2
O
3
:9SiO
2
:5760H
2
O where x = 0.11.0)
(Kumakiri et al., 1999), which are useful for faujasite
or zeolite A growth on seeded faujasite or zeolite A,
respectively, were prepared at 353 K. The solutions
were prepared by dissolving sodium silicate (Na
2
SiO
3
,
SiO
2
5161%, Na
2
O 1723%, Wako Pure Chemical
Industries, Ltd.), aluminum hydroxide (Al(OH)
3
, pu-
rity >95%, Wako Pure Chemical Industries, Ltd.), and
sodium hydroxide (NaOH; purity 96%; Wako Pure
Chemical Industries Ltd.) in distilled water. 0.617 g of
Na
2
SiO
3
was added to 30.0 g of distilled water in a
polyethylene bottle, and the bottle was kept in an
oven at 353 K. In another polyethylene bottle, 0.0115 g
(x = 0.1) to 0.115 g (x = 1.0) of Al(OH)
3
and 4.15 g of
NaOH were added to 30.0 g of distilled water and
stirred for 30 min at 353 K. After the aluminate solu-
tion became clear, the latter solution was poured into
the former solution, and stirred for 15 min at 353 K.
Then, seeds fixed on a glass plate with epoxy resin
were placed in the solution for several hours. Si/Al
ratios of the samples were characterized with a trans-
mission electron microscope (TEM, 2010F, JEOL) by
energy dispersive X-ray spectroscopy (EDX); the sam-
ple was processed with a focused ion beam (FIB, JFIB-
2100, Micrion, Co.).
1.3 AFM observation
In this study, AFM observations (Nanoscope IIIa,
Digital Instruments) were carried out at the same posi-
tion both before and after the seeded growth to clarify
their morphological changes (ex situ observation).
Fig. 1 Framework structures of faujasite (left) and zeolite
A (right)
VOL. 37 NO. 5 2004 671
Note that an in situ experiment could hardly be per-
formed, since the tip of the AFM is soluble in an
aluminosilicate solution.
The observation procedure was that the surface
of the seed was initially observed by AFM (designated
as 0 hour), and then the seed was placed in the
aluminosilicate solution for 2 hours that had been
preheated at 353 K for 15 min in advance. The ob-
tained seed was washed with distilled water, dried, and
observed again by AFM (designated as 2 hours) at
the same position as before. Surface creases provided
clues to find the same position. The seed was placed
again for another 6 hours in the aluminosilicate solu-
tion preheated for 2 hours plus 15 min (By this opera-
tion, the effect was that the seed would be in the same
state as if it had been placed in the aluminosilicate so-
lution for 8 hours plus 15 min). Then, the same posi-
tion of the seed was again observed (designated as
8 hours). The observation errors for the xy and z di-
rections were ca. 10 and 0.1 nm, respectively, and the
radius of the tip curvature was 510 nm. AFM images
were recorded under tapping mode in an atmospheric
condi t i on. For t he AFM observat i ons, si l i con
microcantilevers were used with a spring constant
of ca. 29 N m
1
. The resonance frequency was ca.
285 kHz, and the scan rate was 0.52.0 Hz.
1.4 Raman spectroscopy
Prepared aluminosilicate solutions were charac-
terized by Raman spectroscopy (NRS-1000, JASCO,
Co.). When the solutions were observed directly, no
major changes were found in the composition of the
solution species during seeded growth. Also in the char-
acterization of dynamic light scattering, solution spe-
cies associated with crystal growth were not found.
Thi s was due t o t he l ow concent rat i on of
aluminosilicate species to avoid nucleation in the liq-
uid phase. In order to acquire the information of the
liquid phase, the following characterization was ex-
amined. Aluminosilicate gels were precipitated in the
case that Si and Al sources were mixed at room tem-
perature. The gels recovered were characterized by
Raman spectroscopy. The wavelength of the laser was
532 nm and laser power approximately 550 mW.
2. Results and Discussion
2.1 AFM observation at the same position
Figure 2 shows FE-SEM images of the seed crys-
tals. An octahedral faujasite covered with {111} faces,
and a cubical zeolite A covered with {100} faces are
shown. Morphological changes on these faces in di-
lute aluminosilicate solutions (x = 1.0, 0.5, 0.2 and 0.1)
are investigated, and results obtained are summarized
in Table 1. In the case of the seeded growths of x = 1.0
and 0.5, both faujasite and zeolite A were in the growth
mode, while they were in the dissolution mode of
x = 0.1. When the seeded growths were performed at
x = 0.2, different crystal growth behavior was observed.
In this study, results of x = 1.0 and x = 0.2 are focused
on and the detailed investigations are shown in the fol-
lowing section.
Figures 3 and 4 show morphological changes in
the surface structures of faujasite and zeolite A, re-
spectively, at the same position before (0 hour) and
after the seeded growth for 2 and 8 hours. The compo-
sition of the clear aluminosilicate solution employed
is 90Na
2
O:xAl
2
O
3
:9SiO
2
:5760H
2
O, where x = 1.0.
2.1.1 Faujasite As the growth period elapses, the
surface is covered with oriented triangle-shaped
faujasite islands. The directions of the sides are the
Faujasite Zeolite A
x = 1. 0 growth growth
x = 0. 5 growth growth
x = 0. 2 no change growth
x = 0. 1 dissolution dissolution
Table 1 Morphological changes on faujasite
and zeolite A surface
Fig. 2 SEM photographs of faujasite (left) and zeolite A
(right), as used in this study
Fig. 3 Morphological changes in surface structures of
faujasite before (0 hour) and after (2 and 8 hours)
the seeded growth. Images taken in a height and an
amplitude mode are shown in upper and lower part,
respect i vel y. The composi t i on of t he cl ear
al umi nosi l i cat e sol ut i on i s 90Na
2
O: xAl
2
O
3
:
9SiO
2
:5760H
2
O, where x = 1.0
672 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
same as the faujasite face as shown in Figure 5. This
result indicates that crystal growth proceeds under the
influence of the seeded crystal, that is, epitaxial growth.
The interface between the seed and the overgrown
faujasite is characterized by TEM-EDX. The Si/Al ra-
tio of the interface is ca. 1.5; there is no major change
in the ratio between the seed and the overgrown
faujasite. The size of the faujasite islands is around
0.51.0 m in 2 hours, and the islands grow to 1.5
2.5 m in 8 hours. Amorphous adhering on the faujasite
surface is not observed in the AFM image in this con-
dition, which indicates that the morphological changes
in the top surface structure do not proceed via amor-
phous adhesion.
2.1.2 Zeolite A Before seeded growth, steps are
observed on the surface of zeolite A. However, steps
are not observed in Figure 4 (2 hours), which indicates
that the surface of zeolite A is covered with amorphous
matter. As labeled in Figure 4 (2 hours), heterogene-
ous nucleation followed by crystal growth is also ob-
served on the surface. The crystals observed in Figure
4 (2 hours) are well facetted as shown in Figure 4
(8 hours). All crystals observed are parts of cubic crys-
tals; and therefore, it is concluded that crystals observed
on the surface are zeolite A, as mentioned in the previ-
ous study (Kumakiri et al., 1999). The Si/Al ratio of
the interface is ca. 1.0; and as with faujasite, there is
no change in the ratio between the seed and the over-
grown zeolite A. Crystals of zeolite A on the surface
are not oriented; therefore, it is speculated that hetero-
geneous nucleation of zeolite A occurs inside the amor-
phous matter adhered since the composition of amor-
phous matter adhered (Si/Al ratio is ca. 1.0) is proper
for zeolite A nucleation. AFM images at low magnifi-
cation indicate that the side of the seeded crystal at 2
and 8 hours is 10% and 29% longer than before the
seeded growth, which indicates that the seed itself is
in a growth mode, as mentioned in the previous study
(Kumakiri et al., 1999).
From AFM observations, it is concluded that
faujasite grows via mediated growth from the solution
phase, while zeolite A grows via amorphous gel adhe-
sion, and that different zeolites grow with different
crystal growth modes in the same solution.
2.2 Correlation of zeolite growth behavior with
aluminosilicate precursors
The concentration of Al source is reduced to 1/5,
and the same experiment was performed. The compo-
si t i on of t he cl ear al umi nosi l i cat e sol ut i on i s
90Na
2
O:xAl
2
O
3
:9SiO
2
:5760H
2
O, where x = 0.2. Fig-
ures 6 and 7 show the morphological changes in the
surface structures of faujasite and zeolite A at the same
position, respectively, before and after seeded growth
for 2 and 8 hours. The characterization of the liquid
phase at x = 1.0 and x = 0.2 is also performed by Ra-
man spectroscopy as shown in Figure 8.
2.2.1 Faujasite AFM images show that faujasite
is unchanged at x = 0.2, whereas the seed crystal grows
epitaxially on the seed crystal at x = 1.0. It is specu-
lated that the concentration of Al source is too low to
form the precursor for faujasite in the liquid phase.
Magnified images show that the top surface is neither
in growth nor in dissolution mode, and is changed into
a well-developed (111) face via the transfer of
aluminosilicate species between the solution and solid
phases (Wakihara et al., 2004).
2.2.2 Zeolite A Contrary to faujasite, zeolite A is
in growth mode, and is covered with amorphous mat-
ter, as in the case of zeolite A at x = 1.0 (AFM images
at low magnification indicate that the side of the seeded
crystal at 2 and 8 hours is 5% or 6% longer than before
the seeded growth, respectively). No heterogeneous
nucleation is observed on the seed crystal, whereas it
is observed at x = 1.0. It can therefore be speculated
that the concentration of the Al source in the liquid
phase is too low for heterogeneous nucleation.
2.3 Raman spectroscopy
Two bands centered at 440 cm
1
(broad) and at
490 cm
1
are observed. The broad band at 440 cm
1
is
assigned as an aluminosilicate network including six-
membered ri ngs (6R), and t hat at 490 cm
1
as
Fig. 4 Morphological changes in surface structures of zeo-
lite A before (0 hour) and after (2 and 8 hours) the
seeded growth. Images taken in a height and an
amplitude mode are shown in upper and lower part,
respect i vel y. The composi t i on of t he cl ear
aluminosilicate solution is 90Na
2
O:xAl
2
O
3
:9SiO
2
:
5760H
2
O, where x = 1.0
Fig. 5 A schematic of the relationship between the seed
faujasite face and triangle-shaped faujasite islands
VOL. 37 NO. 5 2004 673
aluminosilicate with four-membered rings (4R)
(Sharma et al., 1981).
Figure 8 shows that the ratio of 4R to 6R is higher
at x = 0.2 than at x = 1.0. This indicates that the stabil-
ity of 4R/6R is higher at x = 0.2 than at x = 1.0. The
crystal growth of zeolite A proceeds at x = 0.2, whereas
the crystal growth of faujasite does not proceed. By
combining the solid and the liquid phase information,
it is speculated that 4R is a key precursor for crystal
growth of zeolite A. This result supports previous stud-
ies (Dutta and Shieh, 1986; Sugiyama et al., 1999) that
proposed a precursor for zeolite A. Similarly, 6R is a
key precursor for crystal growth of faujasite, which
also supports previous study (Dutta et al., 1987).
Crystal growth behavior can be explained as fol-
l ows; 6R and 4R, whi ch are formed i n di l ut e
aluminosilicate solutions in an equilibrium with
aluminosilicate monomers, dimers, etc., are incorpo-
rated into different zeolites, that is, faujasite and zeo-
lite A, respectively. The stabilities of 6R and 4R are
Fig. 6 Morphological changes in surface structures of
faujasite before (0 hour) and after (2 and 8 hours)
the seeded growth. Images taken in a height and an
amplitude mode are shown in upper and lower part,
respect i vel y. The composi t i on of t he cl ear
aluminosilicate solution is 90Na
2
O:xAl
2
O
3
:9SiO
2
:
5760H
2
O, where x = 0.2
Fig. 7 Morphological changes in surface structures of zeo-
lite A before (0 hour) and after (2 and 8 hours) the
seeded growth. Images taken in a height and an
amplitude mode are shown in upper and lower part,
respect i vel y. The composi t i on of t he cl ear
aluminosilicate solution is 90Na
2
O:xAl
2
O
3
:9SiO
2
:
5760H
2
O, where x = 0.2
Fig. 8 Raman spectra of gels from the clear aluminosilicate
solution (90Na
2
O:xAl
2
O
3
:9SiO
2
:5760H
2
O, where
x = 0.2 or 1.0). (a) x = 0.2 and (b) x = 1.0. Arrows
indicate bands assigned to aluminosilicate six-
membered rings (440 cm
1
) and four-membered
rings (490 cm
1
)
different between x = 1.0 and x = 0.2.
Conclusions
Seeded growths of faujasite and zeolite A were
investigated by atomic force microscopy (AFM). Clear
aluminosilicate solutions (90Na
2
O:xAl
2
O
3
:9SiO
2
:
5760H
2
O, where x = 0.11.0) for faujasite or zeolite A
growth on seeded faujasite or zeolite A, respectively,
are prepared. Changes in the atomic-scale height at the
same position are investigated by AFM; it is revealed
that faujasite and zeolite A can grow in the same
aluminosilicate solution, but that their crystal growth
behaviors are different. At x = 1.0, epitaxial growth of
faujasite on the seeded faujasite are observed, whereas
heterogeneous nucleation of zeolite A occurs on the
seeded zeolite A. At x = 0.2, the crystal growth of zeo-
lite A proceeds, whereas the crystal growth of faujasite
does not proceed. Corresponding aluminosilicate so-
lutions for seeded growth are characterized by Raman
spectroscopy; showing that the ratio of 4R to 6R is
higher at x = 0.2 than at x = 1.0. By combining the
results of the surface characterization by AFM and the
liquid characterization by Raman spectroscopy, key
precursors of crystal growth are proposed to be 6R for
faujasite and 4R for zeolite A, respectively. To the best
of our knowledge, this is the first report providing ex-
perimental evidence that bridges between precursors
674
in the liquid phase and crystal growth behaviors on
the top surface.
Acknowledgment
We are grateful to Dr. T.Kodaira (AIST) for fruitful sugges-
tions regarding the synthesis of zeolite A. This work was finan-
cially supported by a Grant-in-Aid for Scientific Research (JSPS)
and NEDO.
Literature Cited
Alfredsson, V., T. Ohsuna, O. Terasaki and J. Bovin; Investigation
of the Surface-Structure of the Zeolites FAU and EMT by High-
Resolution Transmission Electron Microscopy, Angew. Chem.
Int. Ed. Engl., 32, 12101213 (1993)
Anderson, M. W., J. R. Agger, J. T. Thornton and N. Forsyth; Crys-
tal Growth in Zeolite Y Revealed by Atomic Force Microscopy,
Angew. Chem. Int. Ed. Engl., 35, 12101213 (1996)
Barrer, R. M.; Hydrothermal Chemistry of Zeolites, Academic Press,
London, UK (1982)
Burkett, S. L. and M. E. Davis; Mechanisms of Structure Direc-
tion in the Synthesis of Pure-Silica Zeolites. 1. Synthesis of
TPA/Si-ZSM-5, Chem. Mater., 7, 920928 (1995)
de Moor, P. P. E. A., T. P. Beelen, B. U. Komanschek, L. W. Beck,
P. Wagner, M. E. Davis and R. A. van Santen; Imaging the
Assembly Process of the Organic-Mediated Synthesis of a Zeo-
lite, Chem. Eur. J., 5, 20832088 (1999)
Dutta, P. K. and D. C. Shieh; Crystallization of Zeolite-A. A
Spectroscopic Study, J. Phys. Chem., 90, 23312334 (1986)
Dutta, P. K., D. C. Shieh and M. Puri; Raman-Spectroscopic Study
of the Synthesis of Zeolite Y, J. Phys. Chem. B, 91, 2332
2336 (1987)
Kumakiri, I., T. Yamaguchi and S. Nakao; Preparation of Zeolite
A and Faujasite Membranes from a Clear Solution, Ind. Eng.
Chem. Res., 38, 46824688 (1999)
Qiu, S., J. Yu, G. Zhu, O. Terasaki, Y. Nozue, W. Pang and R. Xu;
Strategies for the Synthesis of Large Zeolite Single Crystals,
Micropor. Mesopor. Mater., 21, 245251 (1998)
Sharma, S. K., J. F. Mammone and M. F. Nicol; Raman Investiga-
tion of Ring Configuration in Vitreous Silica, Nature, 292,
140141 (1981)
Shiraki, T., T. Wakihara, M. Sadakata, M. Yoshimura and T. Okubo;
Millimeter-Sized Sodalite Single Crystals Grown under High-
Temperature, High-Pressure Hydrothermal Conditions,
Micropor. Mesopor. Mater., 42, 229234 (2001)
Sugiyama, S., S. Yamamoto, O. Matsuoka, H. Nozoye, J. Yu, G. Zhu,
S. Qiu and O. Terasaki; AFM Observation of Double 4-Rings
on Zeolite LTA Crystals Surface, Micropor. Mesopor. Mater.,
28, 17 (1999)
Wakihara, T., A. Sugiyama and T. Okubo; Crystal Growth of
Faujasite Observed by Atomic Force Microscopy, Micropor.
Mesopor. Mater., 70, 713 (2004)
Warzywoda, J., N. Ba and A. J. Sacco, Jr.; Synthesis of Large
Zeolite X Crystals, J. Crystal Growth, 204, 539541 (1999)
Xiong, G., Y. Yu, Z. Feng, Q. Xin, F. Xiao and C. Li; UV Raman
Spectroscopic Study on the Synthesis Mechanism of Zeolite
X, Micropor. Mesopor. Mater., 42, 317323 (2001)