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In summary, we have demonstrated two simple methods for g) P. Yang, T. Deng, D. Zhao, P. Feng, D. Pine, B. F. Chmelka, G. M.
fabricating chirped 3D photonic crystals where the stop band
position changes continuously or in well-defined steps with
position. In the first method, electrically neutral polystyrene
beads of various sizes were assembled into a set of ccp regions
and each region exhibits a specific stop band whose position is
mainly determined by the size of the polymer beads. In the
second method, highly charged polystyrene beads were orga-
nized into an fcc structure whose stop band position changes
continuously from ~474 to ~571 nm over a distance of ~6 mm.
We believe these two methods provide a versatile and flexible
approach to the fabrication of 3D photonic crystals that have
desired properties for use over a broad spectral region. Such
photonic crystals are potentially useful as tunable notch fil-
ters.
Experimental
The crystalline array of polystyrene beads was fabricated using a procedure
previously demonstrated by our group [8]. Monodispersed PS beads were ob-
tained from Polysciences (Warrington, PA), Seradyn (Indianapolis, IN), or
Bangs Laboratories (Fishers, IN). The packing cell (Fig. 1A) used to assemble
the PS beads was formed from two precleaned glass slides and an octagonal or
square frame of photoresist (~9 lm thick, Shipley 1075). The glass substrates
were held together with binder clips. After an aqueous dispersion (~0.10 wt.-%)
of monodispersed PS beads was injected into the cell, a slight positive pressure
of nitrogen gas was applied through the glass tube. The dispersion solvent could
flow through the channels etched in the sides of the frame while the PS beads
were retained in the cell and organized into a 3D crystalline array (under con-
tinuous sonication). Aqueous dispersions of highly charged PS beads were
mixed with an anionic/cationic ion-exchange resin (AG 501-X8, Bio-Rad La-
boratories) for a few weeks and diluted with deionized water prior to insertion
into the packing cell. The transmittance spectra were obtained at normal inci-
dence to the glass substrates through an ~1 mm 5 mm optical window using a
UV-vis spectrophotometer (HP 8453). Pictures of the samples were taken with
a DC260 Kodak digital camera. Due to the similar densities between PS and
water (1.05 g/cm3 vs. 1.00 g/cm3), we believe the gravitational field has very lit-
tle effect on the formation of the second type of chirped photonic crystals [14].
Received: February 25, 2000
Final version: June 8, 2000
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Whitesides, G. D. Stucky, Science 1998, 282, 2244. h) A. A. Zakhidov,
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Direct Conversion of Bulk Materials into MFI
Zeolites by a Bulk-Material Dissolution
Technique**
By Shinichi Shimizu* and Hideaki Hamada
Zeolites are crystalline microporous materials that are cur-
rently attracting much attention owing to their applications as
high-performance catalysts, in separation processes, and in op-
tical, magnetic, and electronic devices.[14] Major efforts have
been undertaken to prepare zeolites with appropriate shapes,
because most applications require certain shapes to allow ef-
fective use of the zeolites' micropores and catalytic properties.
[*] S. Shimizu[+]
Joint Research Center for Harmonized Molecular Materials
Japan Chemical Innovation Institute
1-1, Higashi, Tsukuba, Ibaraki 305-8565 (Japan)
E-mail: shinichi@nimc.go.jp
Dr. H. Hamada
National Institute of Materials and Chemical Research
1-1, Higashi, Tsukuba, Ibaraki 305-8565 (Japan)
[+] Present address: Advanced Technology Laboratory, Kubota Corporation,
5-6, Koyodai, Ryugasaki, Ibaraki 301-0852, Japan.
E-mail: si-simiz@kubota.co.jp
[**] This work is supported by NEDO for an AIST project on Technology for
Novel Highly Functional Materials: Harmonized Molecular Materials.
Adv. Mater. 2000, 12, No. 18, September 15
 COMMUNICATIONS
For example, zeolitic membranes were pre-
pared by utilizing precipitation of zeolites
during their hydrothermal crystalliza-
tion.[5,6] MFI transparent films were synthe-
sized on the interface between an aqueous
solution and mercury under hydrothermal
conditions.[7] It was reported that amor-
phous sodium aluminosilicates crystallize to
zeolite films when they are contacted with
vapors of organic materials and water.[810]
MFI disks were also prepared from silicate
compounds containing the tetrapropylam-
monium (TPA) cation as a structure-direct-
ing agent (SDA) by solid-state transforma-
tion.[11,12] A mullite honeycomb composite
with an MFI film was prepared by hydro-
thermal treatment of aluminosilicate glass,
Fig. l. Schematic illustration of the experimental setup for the DBMD crystallization. Autoclaves were
which phase-separated during crystalliza- rotated about a horizontal axis in a convection oven at approximately 10 rpm during the crystallization
tion of mullite from sintered kaolin honey- period.
comb.[13]
Recently, we have developed a novel synthetic method for
zeolites called the bulk-material dissolution (BMD) tech-
nique. With this technique, we successfully synthesized giant
zeolite crystals, ca. 3.2 mm 2.8 mm 2.6 mm, in aqueous
media by controlling the solubility of the raw materials in the
static hydrothermal systems.[14] In this communication, we re-
port on our attempt to apply stirred crystallizing conditions
instead of static conditions for the BMD method. This new
technique, termed dynamic BMD (DBMD) here, was found
to convert the bulk raw materials into zeolites directly. For ex-
ample, when a piece of tubular quartz glass was used as a raw
material we succeeded in obtaining tube-shaped zeolite. Zeo-
litic fibers and fabrics were also prepared by this new tech-
nique.
Preparation of tube-shaped zeolites by DBMD: A piece of
quartz glass tube (ca. 16.5 mm long, 10 mm external diameter,
and 8 mm internal diameter; 17.5 mmol SiO2) was suspended Fig. 2. Appearance of a zeolitic tube produced by the DBMD technique. The
in a polytetrafluoroethylene (PTFE) sleeve (capacity 23 mL), zeolitic tube was obtained from a quartz glass tube (SiO2: 17.5 mmol) with
which was closed by a piece of PTFE rod to make it suitable 50 mg of seed MFI crystals at 200 C for 61 days in a solution of TPAOH, HF,
and water (8.9, 14.0, and 865 mmol, respectively) with 10 rpm rotation. One
for autoclaving. The sleeve was filled with an aqueous block on the grid indicates 1 cm 1 cm.
solution consisting of tetra-n-propylammonium hydroxide
(TPAOH), hydrogen fluoride (HF), and approximately 50 mg
of MFI seed crystals. The experimental setup is illustrated in
Figure 1. After the autoclave was rotated around a horizontal
axis at 10 rpm in a convection oven at 200 C for 61 days, a
tube-shaped MFI zeolite was obtained (Fig. 2); its shape was
very close to that of the source bulk material. The MFI struc-
ture was identified by X-ray diffraction (XRD) measurement
(Fig. 3). Observation of the cross sections of the tubular zeo-
lites crystallized for 28 days and 61 days suggested that the
MFI crystals grow by replacing SiO2 glass, and the tube raw
materials were finally completely converted to MFI (Fig. 4).
The product obtained after the reaction mixture had been
heated at 200 C for 20 days without seed crystals is shown in Fig. 3. XRD reflections from the surface of an MFI tube. The MFI tube was ob-
tained from a quartz glass tube (SiO2: 16.1 mmol) with 50 mg of seed MFI crys-
Figure 5. It is obvious that the crystals do not completely cov- tals at 200 C for 28 days in a solution of TPAOH, HF, and water (8.9, 14.3, and
er the source tube and the crystals are larger and of differing 863 mmol, respectively) with 10 rpm rotation.

Adv. Mater. 2000, 12, No. 18, September 15 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0935-9648/00/1809-1333 $ 17.50+.50/0 1333
COMMUNICATIONS
sizes. It was considered that the seed MFI crystals dissolved
and released numerous SiO2 clusters containing building units
of the MFI framework into the aqueous phase at the begin-
ning of the hydrothermal reaction. The clusters then reached
the raw material and grew as nuclei on the surface, becoming
MFI crystals by consuming the surface. Accordingly, the MFI
crystals formed are uniform in size and the crystal coverage
on the surface is complete. There is an accompanying de-
crease in crystal size, since numerous nuclei are growing si-
multaneously on the surface of the raw material.
Preparation of zeolitic fibers and a fabric by DBMD:
Quartz glass fibers and a fabric were also tried as bulk raw
materials for the DBMD technique. 5.7 mmol SiO2 fibers
Fig. 4. Cross sections of the tubular MFI observed by Leica M420 microscope
with a cross-Nicol optical system. The bright parts of both pictures indicate
MFI crystals. The specimens were sliced with a diamond saw and both sides
were polished with fine sandpaper. The thickness and outer diameter of both
MFI tubes were about 1 and 10 mm, respectively. A) MFI tube prepared from a
quartz glass tube (SiO2: 16.1 mmol) with 50 mg of seed MFI crystals at 200 C
for 28 days in a solution of TPAOH, HF, and water (8.9, 14.3, and 863 mmol, re-
spectively) with 10 rpm rotation. B) MFI tube prepared from a quartz glass
tube (SiO2: 17.5 mmol) with 50 mg of seed MFI crystals at 200 C for 61 days in
a solution of TPAOH, HF, and water (8.9, 14.0, and 865 mmol, respectively)
with 10 rpm rotation.
1334 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000 0935-9648/00/1809-1334 $ 17.50+.50/0
(thickness: 412 lm), 8.9 mmol TPAOH, 14 mmol HF,
755 mmol H2O, and 50 mg SiO2-MFI seed crystals were
placed in a PTFE sleeve equipped for an autoclave and
heated at 200 C for 8 h with 10 rpm rotation. Even after this
short reaction time, no residual seed crystals were observed.
Major parts of the fibers were covered with MFI crystals, but
some of the fibers had been used only as a source of MFI crys-
tals and had become thin (Fig. 6). The MFI crystals were
about 10 lm long and arranged in a radial orientation with re-
spect to the source fiber. A similar procedure was applied for
a SiO2 fabric. A photograph and a SEM image of the zeolitic
fabric are shown in Figure 7. In the case of the fabric, the MFI
crystal size was uniform, but the distribution depended on the
position and texture in the weave. It is considered that the
crystal growth and nucleation are affected by the flux of the
reaction mixture in the stirring system. The fabric obtained
Fig. 5. Appearance of MFI crystals on a quartz glass tube produced by the
DBMD technique without MFI seed crystals. The MFI crystals were formed on
a quartz glass tube (SiO2: 16.4 mmol) at 200 C for 20 days in a solution of
TPAOH, HF, and water (8.9, 14.4, and 864 mmol, respectively) with 10 rpm ro-
tation. One block on the grid indicates 1 cm 1 cm.
Fig. 6. SEM image of MFI zeolitic fibers produced by the DBMD technique.
The MFI fibers were prepared from quartz glass fibers (SiO2: 5.7 mmol) with
50 mg of seed MFI crystals at 200 C for 8 h in a solution of TPAOH, HF, and
water (8.9, 14.0, and 755 mmol, respectively) with 10 rpm rotation.
Adv. Mater. 2000, 12, No. 18, September 15

Fig. 7. MFI zeolitic fabric produced by the DBMD technique. The MFI fabric
was prepared from quartz glass fabric (SiO2: 12.7 mmol) with 50 mg of seed
MFI crystals at 200 C for 8 h in a solution of TPAOH, HF, and water (14.2,
22.2, and 1203 mmol, respectively) with 10 rpm rotation. A) Photograph of the
MFI fabric. One block on the grid indicates 0.5 cm 0.5 cm. B) SEM image of
MFI fabric.
after a reaction time of 8 h has enough mechanical strength to
be handled carefully. However, when the reaction time was
greater than 24 h and the coverage of MFI crystals on the
thread was almost complete, the product was extremely frag-
ile or even powdery. A procedure without the seed crystals
was also investigated for the fibers and the fabric. The effect
of the seed crystals was found only to accelerate the crystalli-
zation rate, because, without seeding, few crystals were ob-
served on fibers crystallized for 8 h.
It was considered that, in the present experiments, the seed
MFI crystals act not as seeds but as suppliers of building units
of the MFI framework, and the building units act as nuclei for
the structure. Consequently, the crystallization rate was accel-
erated, owing to the presence of numerous nuclei, resulting in
improved coverage and uniformity of the crystals.
In conclusion, with the new DBMD technique we suc-
ceeded in converting glass bulk materials to zeolites by replac-
ing the glassy part by zeolitic crystals, beginning at the surface
Adv. Mater. 2000, 12, No. 18, September 15 WILEY-VCH Verlag GmbH, D-69469 Weinheim, 2000
COMMUNICATIONS
and working toweards the inside. The validity of this tech-
nique was demonstrated by successful preparation of a com-
pletely converted zeolitic tube and partially converted zeolitic
fibers and fabric. The seed crystals used in the DBMD accel-
erated crystallization and improved both coverage and unifor-
mity of the crystals. Since the shape control of zeolitic materi-
als is an important technical issue for industrial use of
zeolites, we believe that the DBMD technique will provide a
practical solution.
Experimental
Preparation of Seed MFI Crystals: 5 g Cataloid Si-30 (Catalysts & Chemicals
Ind. Co., Ltd., Japan, SiO2 approx. 30 %), 8 g TPAOH aqueous solution (Tokyo
Kasei Kogyo Co., Ltd., Japan, TPAOH approx. 2025 %), 0.42 g HF aqueous so-
lution (Wako Pure Chemical Ind. Ltd., Japan, HF approx. 4648 %), and 5.5 g
water were heated at 200 C for 5 days in a PTFE-lined autoclave. The MFI
crystals obtained were washed with water and identified by XRD measurement.
The crystal dimensions were approximately 0.1 mm 0.1 mm 0.5 mm.
XRD Measurements: The specimen powder was obtained by grinding the
crystals in an agate mortar. Powder XRD patterns were measured on a Rigaku
Rint 2500 diffractometer with Cu Ka radiation, h/2h scans, and 1 deg min1 2h
scan rate.
Received: February 29, 2000
Final version: May 16, 2000
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