synthesis of high-silica aluminosilicate zeolites

Studies
in
Surface
Science
and
Catalysis
33
SYNTHESIS OF
HIGH-SILICA
ALUMINOSILICATE
ZEOLITES
This page intentionally left blank
Studies
in
Surface
Science
and
Catalysis
Advisory
Editors:
B. Delman and J.T. Yates
Vol. 33
SYNTHESIS OF HIGH-SILICA
ALUMINOSILICATE
ZEOLITES
Peter
A.
Jacobs
and
Johan

A.
Martens
Leboretorium
voor
Oppervlektecnemie, Katholieke Universiteit Leuven,
B-3030
Leuven, Belgium
with
technical assistance from M. Geelen, L. l.eplat. J. Pierre, M.J. Struyven
and M. Tielen
ELSEVIER
Amsterdam
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Oxford
-
New
York
-
Tokyo
1987
ELSEVIER
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(Vol. 33)
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Printed in The Netherlands
v
CONTENTS
Studies in Surface Science and Catalysis (other
volumes
in the
series)
Scope
of the
work
Acknowledgements
PART
I :
SELECTED
RECIPES
FOR
THE
SYNTHESIS
OF
HIGH-SILICA
ZEOLITES

x
xv
XVI
* Introduction 3
* General procedure used for the synthesis of
high-silica
zeolites
3
* Specific recipes 6
1. Synthesis of
ZSM-34
6
2. Synthesis of ferrieritejZSM-35-type materials 8
3. Synthesis of
ZSM-39
10
4. Synthesis of
high-silica
ZSM-6
with
TMA
11
5. Synthesis of
high-silica
mordenite 12
6. Synthesis of
ZSM-12
13
7. Synthesis of
zeolite

PHI
15
8. Synthesis of
zeolite
BETA
16
9. Synthesis of
zeolite
ZSM-25
17
10. Synthesis of
ZSM-5
with
TPA
17
11. Synthesis of
ZSM-ll
20
12. Synthesis of
ZSM-8
21
13. Synthesis of
ZSM-48
22
14. Synthesis of
ZSM-22
24
*
General
comments

25
* References 44
PART
II
HIGH-SILICA
ZEOLITES
WITH
SOLVED
STRUCTURE-TYPE
CHAPTER
I
SYNTHESIS
OF
ZSM-5
ZEOLITES
IN
THE
PRESENCE
OF
TETRAPROPYLAMMONIUM
IONS
* Introduction
45
47
47
VI
*
The
chemistry of aqueous tetrapropylammonium
silicate

solutions 48
*
The
Argauer-Landolt invention 53
*
The
isothermal metastable phase transformation 55
*
The
dominant
factors
influencing the
crystallization
of the
MFI
structure
58
1.
The
Si0
2A1
203
ratio
of the gel 58
2.
The
TPA/Si0
2
ratio
of the gel 61

3.
The
degree of
dilution
or the H
20/Si02
ratio
64
4.
The
M/Si0
2
ratio
65
5.
The
OH/Si0
2
ratio
70
6.
The
nature of the
silica
source 71
*
Morphology
of
ZSM-5
zeolites

72
*
Mechanism
of
ZSM-5
synthesis 80
*
The
repartition
of aluminium throughout the
ZSM-5
crystal
91
* Synthesis of
ZSM-5
from
reactive
mixtures prepared with unusual
reactants
96
*
Forming
of
ZSM-5
crystals
97
*
Use
of seeds
100

*
The
ZSM-5-silicalite dispute
103
* References
107
CHAPTER
II
SYNTHESIS
OF
THE
MFI
TYPE
OF
STRUCTURE
IN
THE
ABSENCE
OF
TPA
113
* Introduction
* Synthesis of
ZSM-5
different
from
TPA
* Synthesis of
ZSM-5
* Synthesis of

ZSM-5
*
The
use of various
* Synthesis of
ZSM-5
* References
in the
presence of quaternary
ammonium
cations
in the presence
of amines
in
the presence of
alcohols
templates in
ZSM-5
synthesis
in the absence of any organic
compound
113
113
119
125
132
134
144
CHAPTER
III

SYNTHESIS
OF
HIGH-SILICA
ZEOLITES
WITH
THE
MEL
TYPE
OF
STRUCTURE
147
* Introduction
* Quaternary
salts
used as templates in the synthesis of
ZSM-ll
147
147
* Parameters influencing the
crystallization
rate
of
ZSM-11
* Synthesis of the
MEL
structure
type using diamines
* X-ray
invisible
ZSM-11

zeolites
* References
VII
153
157
162
166
CHAPTER
IV
POTENTIAL
MEMBERS
OF
THE
PENTASIL
FAMILY
OF
HIGH-
SILICA
ZEOLITES
167
* Introduction
167
* Crystallographic
structure
of
ZSM-5
and
ZSM-11
167
* Intergrowths in the pentasil family of

zeolites
177
* Experimental discrimination between pure
ZSM-5,
ZSM-11
zeolites
and
their
intergrowths
180
*
Symmetry
changes of
ZSM-5
zeolites
185
*
Overview
of
some
pentasil-type
zeolites
claimed in the
literature
188
1.
ZSM-8
191
2.
ZETA-l

193
3.
ZETA-3
195
4.
NU-4
195
5.
NU-5
197
6. Other
pentasils
198
* References
212
CHAPTER
V :
HIGH-SILICA
ZEOLITES
OF
THE
FERRIERITE
FAMILY
217
*
Structure
217
* Synthesis of
FER-type
materials using inorganic gels

217
* Synthesis of
FER-type
zeolites
in the presence of organics
220
* Differences between various
proprietary
FER-type
materials
226
* References
231
CHAPTER
VI
:
ZEOLITES
WITH
TON
STRUCTURE
TYPE
233
*
Structure
233
* Synthesis of
TON
structure
types
243

* Differences between the
TON-type
proprietary
zeolites
248
* References
249
VIII
CHAPTER
VII:
HIGH-SILICA
ZEOLITES
WITH
MTT
FRAMEWORK
TOPOLOGY
*
MTT
structure
types
* Synthesis of
MTT
and
related
zeolites
* References
CHAPTER
VIII A
FAMILY
OF

ZEOLITES
WITH
DISORDERED
FERRIERITE-TYPE
STRUCTURE
*
Members
of the family
* Structure of
zeolite
ZSM-48
* Synthesis of
ZSM-48
and related materials
1.
General
conditions
2. Influences of
silica:
alumina
ratio
3. Nature of templates
*
Morphology
and sorption capacity
* References
CHAPTER
IX
:
HIGH-SILICA

ZEOLITES
WITH
MTW
FRAMEWORK
TOPOLOGY
* Potential family
members
of
MTW
zeolites
* Structure of
ZSM-12
* Synthesis of
MTW
zeolites
* Retention of organics in
MTW
zeolites
* References
251
251
260
274
275
275
275
281
281
283
284

289
295
297
297
297
303
312
319
CHAPTER
X
SYNTHESIS
OF
ZEOLITES
THAT
DO
NOT
BELONG
TO
THE
HIGH-SILICA
AND/OR
SHAPE-SELECTIVE
CLASS
OF
ZEOLITES
321
* Synthesis of
siliceous
mordenite
* Materials with

MTN
structure
type
* Siliceous Levynite
zeolites
*
Offretite-erionite
zeolites
and
their
intergrowths
* Faujasite-type
siliceous
zeolites
* References
321
330
333
342
343
346
IX
CHAPTER
XI
GENERAL
CONSIDERATIONS
349
PART
III
BRIEF

DESCRIPTION
OF
POTENTIAL
HIGH-SILICA
ZEOLITES
WITH
UNKNOWN
STRUCTURE
355
* Introduction
*
ZSM-43
*
CSZ-l
*
ZSM-18
* Zeolite
PHI
* Zeolites
BETA
and
NU-2
*
ZSM-25
*
EU-7
and
EU-12
*
NU-23

*
NU-6(l)
*
TMA-zeolites
FU-l
and
NU-l
*
ZSM-6
and
ZSM-47
*
ZSM-50
* ISI-6
*
PSH-3
* References
Subject index
357
357
357
358
358
359
359
359
360
360
361
361

361
362
362
382
385
x
STUDIES IN SURFACE SCIENCE
AND
CATALYSIS
Advisory
Editors: B. Delmon, Universite Catholique de Louvain, Louvain-Ia-Neuve, Belgium
J.T. Yates, University of Pittsburgh, Pittsburgh, PA, U.S.A.
Volume 1
Preparation
of
Catalysts
I. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the First International Symposium, Brussels, October
14-17,1975
edited by B.
Delmon,
P.A.
Jacobs
and G.
Poncelet
Volume 2
The
Control
of
the

Reactivity
of Solids. A Critical Survey of the Factors that
Influence the Reactivity of Solids,
with
Special Emphasis on the Control of the
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II. Scientific Bases
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September
4-7,
1978
edited by B.
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Grange,
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Jacobs
and

G.
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Applications to Catalysis and the
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32nd
International Meeting of the Societe
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Physique, Villeurbanne, September
24-28,
1979
edited by J.
Bourdon
Volume 5
Catalysis
by
Zeolites.
Proceedings of an International Symposium, Ecully (Lyon),
September
9-11,
1980
edited by B.
Imelik,
C.

Naccache,
Y. Ben
Taarit,
J.C.
Vedrine,
G.
Coudurier
and
H.
Praliaud
Volume 6
Catalyst
Deactivation.
Proceedings of an International Symposium,
Antwerp,
October
13-15,
1980
edited by B.
Delmon
and
G.F.
Froment
Volume 7
New
Horizons
in
Catalysis.
Proceedings of the 7th International Congress on
Catalysis, Tokyo, June

30-July
4,
1980.
Parts A and B
edited by T.
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K.
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Supported
Complexes
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V.A.
Zakharov
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Solid
Surfaces.
Proceedings of a Symposium, Bechyi'ie, September
29-0ctober
3,
1980

edited by
M.
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Adsorption
at
the
Gas-Solid
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Liquid-Solid
Interface.
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1981
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Sing
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1982
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Meriaudeau,
P.
Gallezot,
G.A.
Martin
and
J.C.
Vedrine
Volume 12
Metal
Microstructures
in
Zeolites.
Preparation - Properties - Applications.
Proceedings of a Workshop, Bremen, September
22-24,
1982
edited by P.A.
Jacobs,
N.1.

Jaeger,
P.
Jiru
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XI
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6-9,
1982
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Grange
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Villeurbanne, September

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S.J.
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Structure
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Reactivity
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Proceedings of an Intenational
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9-13,
1984
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Jacobs.
N.!.
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P.
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1984
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IV. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Fourth International Symposium, Louvain-Ia-Neuve,
September
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edited by B.
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P.
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P.A.
Jacobs
and
G.
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Volume 32
Thin

Metal
Films
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Chemisorption
edited by P.
Wissmann
Volume 33
Synthesis
of
High-silica
Aluminosilicate
Zeolites
by P.A.
Jacobs
and
J.A.
Martens
XII
XIII
TO
JAN
B.
UYTTERHOEVEN
Who
we
consider to be the founder of
all
this
It

should be
stressed
that
some
of the data in
this
book, mainly the
zeolite
synthesis
recipes,
might be the
subject
of patent claims.
It
is
not our
intention
to
violate
any patent
rights
and the recipes should not be used for
any other than
strictly
scientific
purposes without checking
that
this
is
not

so. In every case proper reference
is
made
to what
we
consider to be
pertinent
patents.
This page intentionally left blank
xv
SCOPE
OF
THE
WORK
This
work
certainly
does not have the pretension to be a
complement
to
the
famous
books
by Breck
(ref
i l ) and Barrer
(reL2)
and
also
it

was
not
the authors' aim to
write
an exhaustive review of
high-silica
zeolites.
First
of
all,
the
zeolites
denoted as
high-silica
are not well defined, from
either
a
scientific
or a compositional point of view.
Those
using
this
term
tacitly
assume
that
high-silica
zeolites
with
shape-selective

properties
are the
subject
of the discussion.
The
term
shape-selectivity
has to be understood in the context used by those working
on
catalysis
in the petroleum or petrochemical area. Consequently, as in
these areas one deals with
relatively
simple and small hydrocarbons, the
zeolites
concerned should contain ten-membered rings of T-atoms, belonging to
tetrahedra sharing corner
oxygen
atoms.
Zeolites
with highly
distorted
twelve-membered
rings,
exerting the
same
sieve
effects,
are
also

considered
to belong to
this
class
of
zeolites.
High-silica
zeolites,
in the authors'
opinion, should be
susceptible
to synthesis over a wide compositional range.
Those
included generally can be synthesized with an Si0
2/A1
203
ratio
varying
over at
least
one order of magnitude and consequently producing materials
for
which
the composition varies over the
same
range.
The
subject
has been
narrowed

still
further,
as only
aluminosilicate
zeolites
are described.
The
potential
substitution
of
half
of Mendeleev's
table
for
aluminium in these
structures
is
still
a matter of debate and
it
is considered
that
an attempt
to
rationalize
the
knowledge
in
this
area

would
be premature.
As
a
consequence of
this
narrowed scope,
materials
have occasionally been included
that
strictly
are not
zeolites,
namely
the
so-called
silica
polymorphs with
structures
identical
with those of
many
high-silica
zeolites.
The
preparation
methods
covered are also confined to
direct
synthesis methods.

The
preparation of
high-silica
zeol
ites
by dealumination
methods
is
not
considered.
Faced with the problem of keeping track of
many
new
zeolites,
or claimed
as such in the
patent
literature,
with the help of
many
students and
technicians a
number
of standard recipes have been
established
in the
"Laboratorium voor Oppervlaktechemi
e",
under guidance of the authors.
We

considered
it
useful to
offer
this
knowledge
to the
scientific
comnunt
ty.
Therefore,
part
of
this
book
contains proven recipes
for
the synthesis of
certain
high-silica
zeol~tes
(and sometimes others) and data on
their
identification
and
characterization.
XVI
Another
objective
was

to
review
critically
many of
the
claimed
materials
and,
based
on
the
available
data,
to
classify
them
into
groups
or
families
of
materials
of
the
same
structural
type,
whether
this
structure

is
known
already
or
remains
to
be
established.
It
will
be
evident
that
this
classification
is
based
on
the
information
available
to
the
best
knowledge of
the
authors
at
the
time

of
writing
and may be
subject
to changes in some
ins
tances
when
pertinent
i nforma t i on on
the
mostly
propri
eta
ry
materi
a1
sis
released.
Many
data,
mainly
published
in
patents,
have been
discussed
but
as none
of

the
authors
is
familiar
with
the
Japanese,
Chinese
or
Russian
languages,
it
might
well
be
that
essential
information
has been
overlooked.
In
principle,
the
literature
has been
covered
up
to
the
end

of
1985.
Particularly
relevant
work which
appeared
in
the
first
half
of 1986 was added
afterwards.
As
mostly
newly
claimed
crystalline
materials
in
this
area
of
science
are
identified
based on
their
X-ray
diffraction
patterns,

the
authors
have
defined
a
specific
layout
of
these
patterns,
containing
all
necessary
data
for
collecting
them in a
personal
1
ibrary
useful
for
the
identification
of
potentially
new
products
synthesized
by

readers.
1.
D.W.
Breck,
Zeolite
Molecular
Sieves,
Wiley,
1974.
2. R.M.
Barrer,
Hydrothermal
Chemistry
of
Zeolites,
Academic
Press,
1982.
ACKNOWLEDGEMENTS
The
authors
particularly
appreciate
the
stimulating
influence
of
Jan
B.
Uytterhoeven

duri
ng
the
past
20
years,
and
consequently
they
deci
ded
to
dedicate
this
book
to
him. The
senior
author
also
acknowledges
continuous
sponsoring
of
his
research
activities
by
the
National

Fund
for
Scientific
Research
(Belgium) and more
recently
to
K.U. Leuven to
allow
him
to
teach
in
this
area
of
science.
The
junior
author
is
also
grateful
to
the
National
Fund
for
Scientific
Research (Belgium)

for
several
research
fellowships.
PART
I:
SELECTED RECIPES FOR THE SYNTHESIS
OF HIGH-SILICA ZEOLITES
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3
I
NTRODUCT
ION
Zeol
ites
in general and
high-sil
ica zeol
ites
more
in
particular
are
often
crystall
ized by nucleation from
inhomogeneous
supersaturated mother
liquids.
Therefore, the

origin,
purity
and exact chemical composition of the
reactants
used for
their
synthesis
may
sometimes be
critical.
The
commercial
origins
and grades of the reagents used in
this
chapter in the recipes for
the synthesis of
high-silica
zeolites
are given in Table
1.1.
They
are not
necessarily
the most advantageous
reactants
for
the synthesis of bulk
amounts
of

zeolites
but
their
prices
are such
that
the average budget of a
university
laboratory will permit the synthesis of kilogram
amounts
of these
materials.
The
recipes advanced here are highly reproducible.
They
were checked
independently by
two
laboratory
technicians.
Each
synthesis
was
carried
out
in
home-made
stainless-steel
autoclaves, which could be equipped with a
PTFE

coating or a glass 1
iner.
A drawing representing the
PTFE-l
ined version of
these autoclaves
is
shown
in Fig.
1.1.
Twenty
of such autocl aves could be
mounted
together
ina
furnace and
heated while they
are
being
rotated
at
50
rpm
(rotations
per minute). In each
autoclave from 10 to 15 g of
zeolite
on a dry calcined basis can generally be
recovered.
GENERAL

PROCEDURE
USED
FOR
THE
SYNTHESIS
OF
HIGH-SILICA
ZEOLITES
For the
synthesis
of
high-silica
zeolites,
in most instances
two
solutions
are prepared. Solution A contains the
organosilicate
and
solution
B
is prepared by dissolving successively in water the inorganic base(s) and the
aluminium
salt.
Solution A is prepared by adding the organic molecule
(or
its
solution)
to the
silicate

solution
for
all
silica
sources except
Aerosil.
In
the
latter
instance,
the
silica
powder
is added with continuous
stirring
to
an aqueous
solution
of the organic
material.
Solution B is added slowly to A
with vigorous st i
rri
ng, and the
pH
iss
ubsequently adj usted by
dropwi
se
addition of a mineral

acid.
The
gel thus obtained
is
then autoclaved; the
autoclaves are
mounted
in the heated furnace and are continuously
rotated
at
50
rpm
during
synthesis.
The
synthesis
efficiency
is
defined as the weight
4
65
~I
o
CO)
,
I"
40
~I
~-:0
50rpm

FIGURE
1.1.
Technical drawing of the PTFE-lined version of autoclaves used
for
the synthesis of
laboratory-scale
amounts
of
high-silica
zeolites.
Dimensions in
millimetres.
5
TABLE
1.1
Origin of
reactants
used in the recipes
for
the synthesis of
high-sil
ica
zeolites
REACTANT
ORIGIN
GRADE
Aeros
il-200
Degussa
Silicic

acid Riedel-De
Haen
Water
glass
Merck
Technical
Ludox
AS30
Du
Pont de
Nemours
Technical
Ludox
AS40
Du
Pont de
Nemours
Technical
TEO-sil
icate
a
Merck
Sodium
aluminate
Al(N0
3)3·
9
H2
0
A12(S04)3·18H20

NaOH
KOH
Hopkin
and Williams
Merck
Merck
Merck
Merck
Technical
Pro analysi
Purum
Pro analysi
Pro analysi
TMA-OH
b
Fluka 25 %aqueous; technical
TEA-OH
c
Fluka 40 %aqueous; technical
TMA-Br
b
Fluka
Purum
TEA-Br
c
Fluka
Purum
TPA-Br
d
Fluka

Purum
Choline
chloride
Aldrich
99 %
Piperidine
Aldrich 98 %
Pyrrol idine
Merck
Technical
Ethylamine
Fluka
70 %aqueous
Propyl
ami
ne
Aldrich
98 %
Octylamine
Fluka
Purum
Ethylenediamine
Merck
Technical
1,8-Diaminooctane Aldrich
98 %
1,6-Diaminohexane Fluka
Purum
a,
tetraethyl

orthosilicate;
b, tetramethylammonium; c, tetraethylammonium; d,
tetrapropylammonium.
6
percentage of Si0
2
+
A1
20
3
that
is recovered
after
the whole operation
compared
with the Si0
2
+
A1
203
in the gel. This operation includes
synthesis,
several washings
(to
neutral pH),
air
drying at
325
K and
air

calcination
at
823
K.
In every
instance,
the recipes are optimized synthesis
methods
which
to
our
knowledge
give
maximum
efficiency.
The
zeolites
thus obtained are phase
pure and also are
free
from
significant
amounts
of residual
amorphous
material.
The
phase
purity
was

checked by comparing the peaks in the X-ray
diffractograms
(XRD)
with those given in the 1
iterature.
Using scanning
electron
microphotographs,
it
was
decided whether residual
amorphous
material
was
present.
SPECIFIC
RECIPES
1. Synthesis of
lSM-34
1.a.
~t~!~~~!~_9f_~~~:~~_~!!~_I~~:Q~_~~_9~9~~!~_~~~~
Solution A 42
ml
TMA-OH
(2.5
M)
+ 27.2 g
silicic
acid
Solution

B 118 g water + 5.5 g sodium hydroxide + 5.2 g
sodium
aluminate
Mixing
was
carried
out in an ice-bath and afterwards concentrated
sulphuric acid
was
added dropwise
until
a
pH
of 11
was
reached.
Synthesis occurred
at
353
K for 7 days with
stirring.
The
gel had the
following molar composition:
The
efficiency
of the synthesis
method
was
about 80

%.
The
Si/A1
Z
ratio
of the
zeolite
was
15. This
method
is
original
and has not been derived,
as
far
as
we
are aware, from eXisting information. Individual elongated
crystals
about 1
~m
long dominate (Photograph
1.1),
and the presence of
a small
number
of
0.2-0.4
~m
crystals

is
indicative
of secondary
nucleation.
PHOTOGRAPH
1.1.
Scanning
electron
micrograph
(SEM)
of
ZSM-34
synthesized with
T~IA
1.b.
?~~!~~~1~_~!_~?~:~~_~1!~_I~~_~~9_1~_e~~~~~~~_~!_~_~1:~9_~l~~l1:~~~~~~
Solution A 33.3 9
Ludox
AS30
+ 3.2 g
TMA-OH
(25
%,
aqueous)
Solution
8:
2.5 9
KOH
+ 7.4 9
NaOH

+ 3.9
NaA10
2
+ 10 9 water
Bo
tf
solutions,
pre-cooled in
ice,
were
mixed
together
at
the
same
temperature and autoclaved
at
463 K
for
2 h with continuous
agitation.
The
gel had the following molar
composition:
The
efficiency
of the
method
was
70

%.
The
Si/A1
2
ratio
of the
zeolite
was
12.
8
I.e.
~~~!~~~~~_~!_~~~:~~_~~!~_~~~l~~~_~~_~~~~~~~_~~l~~~l~
{~~~~~~_!~~~_~~!~_!!_~~~~~l~_!Q2
Solution
A:
45 g Aerosil in
155
g water
Solution B : 17 g
NaA10
2
+ 6 g
NaOH
+ 5.6 g
KOH
+
110
g H
20
This solution

was
stirred
until
it
became
transparent and then 50 g of
choline chloride were added.
Solution A
was
mixed
with B; the final gel
was
then autoclaved
at
423
K
for
8 days with continuous
agitation.
The
gel had the following molar
composition:
in
which
R represents the choline molecule.
The
efficiency
was
80 %and
the

ZSM-34
showed
an
Si/A1
2
ratio
of 10.
The
XRD
of
ZSM-34
looks
like
the one of
offretite
materials and possibly
the material belongs to the
offretite-erionite
family.
2. Synthesis of ferrierite/ZSM-35-type materials
Based
on
their
X-ray diffractograms,
ZSM-35,
-38 and -21 and
ferrierite
are not
easily
distinguishable and therefore belong possibly to the

same
family of
zeolites.
The
distinction
made
in
this
paragraph
between
ferrierite
and
ZSM-35
is
therefore only formal.
The
crystalline
solid
is
denoted according to the notation used in the
initial
publication from
which
the present materials are derived.
2.a.
~~~!~~~~~_~!_~~~:~~_~~_!~~_~~~~~~~~_~!_~!~~l~~~~~~~~~~
{~~~~~~~_!~~~_~~!~_~l_~~~~pl~_§2
Solution A 46.47 g
Ludox
AS30

+ 18.3 g ethylenediamine
(C
2DN)
Solution B : 129 g H
20
+ 0.7 g
NaOH
+ 3.3 g
NaA10
2
Solution A
was
mixed
with B.
Crystallization:
10 days
at
450 Kwith
agitation.
In
this
way,
a gel with the following molar composition
was
transformed into
crystalline
ZSM-35,
with an
efficiency
of 60 %and

giving an
Si/A1
2
ratio
of 13.
The
crystals
were elongated with a length
of about 1
urn
(Photograph
1.2).