Microporous and Mesoporous Materials 142 (2011) 389397

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Microporou s and Mesoporou s Materials

journalhomepag e: www.elsevier.com/locate/micromeso

Chemically controlled particulate properties of zeolites: Towards the face-less

particles of zeolite A. 2. Inuence of aluminosilicate batch concentration
and alkalinity of the reaction mixture (hydrogel) on the size and shape
of zeolite A crystals

- dica Brlek, Boris Subotic

, ur

Sanja Bosnar, Josip Bronic

Ru -der Bokovic
Institute, Division of Materials Chemistry, Laboratory for the Synthesis of New Materials,
Bijenic ka 54, 10000 Zagreb, Croatia

article info

abstract

Article history:
Received 6 October 2010
Received in revised form 20 December 2010
Accepted 21 December 2010
Available online 28 December 2010

Inuence of the simultaneou s change of batch alkalinity

A =( [Na2O/H2O] b) and total batch silica concentration (tsc= [SiO2 /H2 O]b ) o f the reaction mixture,at two characteristic batch molar ratios, y [SiO2/
Al2O 3] b (1.3 and 2.0), on the duration of crystallizatio n, reaction yield and the particulate properties (size
and shape) of the crystalline end product (zeolite A) was investigated. Sharp decrease of the duration of
crystallization proce ss with simultaneous increaseAofand tscis caused by simultaneous increase of the
number of nuclei formed in gel matrix, rate of their release from the gel matrix and their growth with the
increase of the alkalinity of the reaction mixture. Although the reaction yield,
YR, is proportional to the
total batch silica concentration,
tsc, the ratioYR/tscslightly decreases with increasing alkalinity as a consequence of the increasing solubility of zeolite A with the increase of the alkalinity. Specic number of
crystals (number of crystals per unit mass of the crystalline end products),
Ns increases with simultaneous increase ofA and tsc as a consequence of the increase of the number of nuclei formed in the gel
matrix with increase of alkalinity of the reaction mixture. On the other hand, a complex dependence
of the crystal size distribution onA, tsc and y, i s a consequence of inuence of the mentioned chemical
factors not only on the number of nuclei, but also on their distribution in the gel matrix. Four different
morphological forms of zeolite A, namely, (i) regular cubic crystals with sharp edges and apexes, (ii)
cubic crys talswith truncated edges, (iii) cubic crystals with roundededges and apexes and (iv)
pseudo-spherical, face-less particles are obtained during hydrother mal treatment of investigated hydrogels. Inuence of the chemical factors on the formation of particular morphological forms of zeolite A are
discussed and the possible mechanisms of their formation are consider ed.
2010 Elsevier Inc. All rights reserved.

Keywords:
Aluminosilicate hydrogels
Crystallization
Zeolite A
Crystal morphology
Crystal size

1. Introduction

A crystals. Since the mentioned investigatio ns were conducte d under very different and incomparableconditions,and mostly foAmong more than 200 different types of zeolites, zeolite Na-A, cused to only one property of system, the conclusions arising
also known as zeolite 4A is the most important for industrial
from the analysis of the obtained results are more general, e.g., that
applications D
. ue to applicati onsof zeolite A as absorbents[1]
alkalinity of reaction mixture has the most expressive effect on the
ion-exchanger s [2] and especiall y detergent builders [3] , many crystal
atsize [8,9,11] and that crystal habit of zeolite A can be modtempts were focused on the investigatio ns of various factors which
ied by the aluminum content in the reaction mixture [6,8] .
control the crystallization pathway and particulate properties of
Thus, although the results of numerous investiga tions gave very
the crystalline end product.
quality and worthy data, however, they do not offer a complete
Numerous studies [414] have shown that chemical composi- feature on the inuence of the chemical composition of the reaction of the reaction mixture (hydrogel) is the most important factor
tion mixture on crystallizati on pathway and the propertie s o f the
for controlling the particulate properties of zeolite A. In these studproducts, especially the particulate (crystal size distribution, crysies, special attention was paid to inuence of alkalinity
tal morphology ) ones. From this reason, we conducted systematic
[8,9,11,13,14] and the batch molar ratio Si/Al [68,12 14] , respecinvestiga tion of the inuence of the chemical compositi on of the
tively, of the reaction mixture on both the size and shape of zeolite
reaction mixture (hydrogel), entirely dened by the batch molar
ratios [Na2 O/H2 O]b , [SiO2 /Al2 O3 ]b and [SiO2 /H2 O]b , i n wide ranges,
Corresponding author. Tel.: +385 (0)1 46 80 123; fax: +385 (0)1 46 80 098. even these beyond the standar d chemical conditions of zeolite
A synthesis, on the duration of crystallization (detail kinetic

E-mail address:
subotic@irb.hr (B. Subotic
).
1387-1811/$ - see front matter 2010Elsevier Inc. All rights reserved.
doi: 10.1016/j.micromeso.2010.12.027

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S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

analysis will be published elsewhere), reaction yield, specic num- The aluminosi licatehydrogels, prepared as described above
ber of crystals, crystal size distribution (by both number and vol- were transferred into stainless-steel reaction vessel preheated at
ume) and crystal morphology.
crystallizati on temperature (80
C). The reaction vessel was proIn the rst part of our study [15] it was found that depending on
vided with a thermostated jacket and tted with a water-cooled
the alkalinity of the reaction mixture, the increase of aluminium reux condenser and thermom eter.The reaction mixture was
content in the reaction mixture (decrease of the batch molar ratioheated at crystallizationtemperatureunder stirring with a Tefy = [SiO
lon-coated magnetic bar driven by magnetic stirrer, until the entire
2 /Al
2 O
3 ]b ) causes not only appearanceof {0 1 1}crystal
planes of zeolite A and thus, formation of cubic crystals with trun-amount of the amorphous aluminosi licate (gel) is transformed into
cated edges[6,8] ,but also a gradual loss the individual crystal
zeolite. The end-point of crystallization,
tc =tc(end) (tc is the time
planes and formatio no f pseudo-sph erical,
face-lessparticles of
of crystallization) was determined by microscopic observation
zeolite A (zeolite FLA). Hence it is evident that morphology of zeo-(optical microscope with magnication of 1000is used for this
lite A crystals is not determinedby only the batch molar ratio
purpose) of the samples used from the reaction mixture at various
y = [SiO
A = [Na2 O/H2 O]b ,
times tc during the synthesis.As tc(end) is used the time tc for
2 /Al
2 O
3 ]b , but also by the batch alkalinity
and total batch silica concentratio tsc=
n,
[SiO
which some irregularly-sha pedparticles (gel) are not observed.
2 /H
2 O]
b or better to
say, by the entire chemical composition of the reaction mixture. The absenceof the gel phase in the products was additionally
From this reason, the inuence of chemical composition of the checked by X-ray diffraction.
reaction mixture (hydrogel) on the size (distribution )and morThe reaction yield,YR, (in wt.%, i.e. grams of zeolite obtained
phology of zeolite A crystals, obtained by hydrothermal treatmentfrom 100 g o f the reaction mixture) was determined as follows: So(heating at 80 C) of hydrogels,was investiga ted.The chemical
lid phase (zeolite A) of the reaction mixture tat
c P tc(end) is sepcomposition of hydrogels was varied by wide-range variations of arated from the liquid phase (supernatant) by centrifugation. After
the batch molar ratiosA (from 0.00507 to 0.0762) andtsc (from
removal of the supernatant, the solid phase was redispersed in dis0.00255to 0.03785) for two characteristic valuesy of
(1.3 and 2.0). tilled water and centrifuged repeatedly until the pH value of the liquid phase above the sediment was 910. The wet washed solids
were dried overnight at 105
C, were cooled in desiccato rs with sil2. Experimental
icagel and were weighed. From known amounts,
mR, o f the reaction
mixture and,mz, o f crystallized zeolite, the reaction yield,
YR, can
Aluminosili cate hydrogels having the batch chemical
be
calculated
by
the
simple
relation:
compositions :
System S1: 3.981Na
Al2O3 2SiO2z1H2O; [Na2O/Al2O3]b = con2 O
stant = 3.981; [SiO2/Al2O3]b = constant = 2.0;[Na2O/SiO2 ]b =
constant = 1.990
System S2: 2.588Na2 OAl2O 3 1.3SiO2 z2H2O; [Na2O/Al2O3]b =
constant = 2.588; [SiO
/Al
O/SiO
]
2
2 3Ob ]= constant = 1.3; [Na
2
2 b=
constant = 1.9905

Y R in grams per 100 g o r w

t 100
:%

mz =mR

After determinationof the reaction yield, the solid samples

were characterized /analysed by several methods: X-ray diffraction
(XRD), scanning-el ectron microscop y (SEM) and particle size analysis (PSD).
The X-ray diffraction patterns of the samples are taken by a Philips PW 1820 diffractometer with vertical goniometer and CuaK
were prepared by pipetting 100 ml of sodium silicate solution of radiation with graphite monochromato r in the correspondi ng region of Braggss angles h(2
= 550).
appropriateconcentrationwith respectto Na2O and SiO2 into a
Shape of zeolite particles (crystals) was determined from SEM
plastic beaker contained 100 ml of stirred (by propeller) sodium
photograp hs of appropriate samples. The SEM photographs were
aluminatesolution of appropriateconcentratio nwith respectto
taken by Philips XL 30, scanning-electr on microscope.
Na2O and Al2 O3 . Sodium aluminat e solutions were prepared by disParticles (crystals) size distribution (PSD) curves of the crystalsolution of anhydrou s NaAlO
Oand
2 (Riedl de Haen; 54 wt.% Al
2 3
41 wt.% Na2 O) in sodium hydroxide solutions of appropriate con- line end products were determinedwith a Malvern Mastersizer
centrations, and sodium silicate solutions were prepared by dilu- 2000laser light-scatter ing particle size analyzer.
Using the PSD data, the averagecrystal size, D, and specic
tion of waterglass solution (SigmaAldrich ;10.54wt.% Na2O,
number of crystals,Ns (number of crystalsper one gram of the
26.53wt.%SiO2, 62.93wt.%H2O) in the sodium hydroxide solucrystalline end product) were calculated as [16] ,
tions of appropriate concentrationsThe
. solutions werethermo. X
stated to 25 C prior mixing together.Chemicalcompositionsof
X
D
Ni Di
Ni
2
hydrogels,determinedby the correspond ingvalues of z =[H2O/
.
X
X
Al2O3] b, total silica concentration,tsc= [SiO
3
2 /H
2 O]
b and alkalinity,
Ns
Ni p=6 q
Ni Di
3
A = [Na
2 O/H
2 O]
b , are shown in Table 1 .
Table 1
Chemical composition of hydrogels H1.1.H1.10. in system S1 and H2.1.H2.10 in
system S2, expressed as the corresponding batch oxide molarz1ratios.
=[H2O/Al2O3] b
for system S1,z2 =[H2O/Al2O3] b for system S2. Total silica content,
tsc= [SiO
2 /H
2 O]
b
and alkalinityA = [Na
2 O/H
2 O]
b are common for both systems.
Hydrogel (No.)

z1

z2

tsc

H1.1./H2.1.
H1.2./H2.2.
H1.3./H2.3.
H1.4./H2.4.
H1.5./H2.5.
H1.6./H2.6.
H1.7./H2.7.
H1.8./H2.8.
H1.9./H2.9.
H1.10./H2.10.

785.11
376.23
241.27
173.79
133.29
106.09
86.84
72.44
61.32
52.19

509.17
244.72
156.85
112.97
86.56
68.89
56.44
47.04
39.79
33.90

0.00255
0.00532
0.00829
0.01151
0.01500
0.01885
0.02315
0.02761
0.03262
0.03785

0.00507
0.01058
0.01650
0.02291
0.02986
0.03750
0.04585
0.05500
0.06500
0.07620

whereNi is the number frequency of the crystals having the size betweenD and DD, Di =D + DD/2, D is measured equiva lent spherical
3
diamete r andq = 2 g/cm
is the density of zeolite A.
3. Results and discussion
The solid phases (X-ray amorphous aluminosilicate gels) of all
hydrogels (see Table 1 ) were completely transformed into crystalline ones during hydrothermal treatment at C.X-ray
80
diffraction
analysis revealed that all the crystalline end products obtained by
hydrothe rmal treatment of hydrogels H1.1.H1.7. and H2.1.H2. 8.,
are pure, fully crystalline zeolite A (see XRD patterns in Supplements 1 and 2). However, due to the tendencyof spontaneou s
transformat ionof zeolite A into hydrohysodalite(HS) at higher
alkalinities [14,17] , traces of HS were found in the crystalline end

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S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

products obtained from hydrogels H1.8. (A = [Na

tsc, the crystal size distribution s (CSD) by number ( Fig. 3 ) d o not
2 O/H
2 O]
b=
0.05500) and H2.9.A (= 0.06500), while pure HS was the only prod-indicate a straightforwar dchanges (e.g.,decrease o
) fthe crystal
uct obtained from hydrogels H1.9.A (= 0.0650), H1.10. and H2.10. size with the simultaneou schange(e.g.,increase)of A and tsc.
(A = 0.0762).
For example, the CSD curves of the samples s1.1., s1.2., s2.1. and
As expected, the reaction yield,
YR, increases with the increase s2.2. (see Fig. 3 ) show that the crystals formed by hydrothermal
of the batch molar ratio tcs= [SiO
treatment of diluted, low-alkaline hydrogels H1.1., H2.1. (A =
2 /H
2 O]
b (see Tables 1 and 2).
However, due to simultaneou s increase of the total silica concen-0.00507; tcs = 0.00255), H1.2. and H2.2. (A = 0.01058; tcs =
tration, tsc, and alkalinity,A, (A/tsc= constant = 1.99; see Table 1 ) 0.00532) have the size in the range from 0.5lto
m2with the peak
of hydrogels,YR is not a linear function of tsc; the ratio YR/tsc
size of about 0.7l m and average crystal sizeD)( o f about 1.5
lm
slightly decreases with increasing alkalinity as a consequence of (see Table 2 ). This is, however in contradictio n with the observathe increasing solubility of zeolite A with the increase of the alka- tion of relatively large (520 l m) crystals in the SEM images
linity [18,19] . Since the molar ratio2SiO2 /Al
Ozeolite A is 2 [20] ,s1.1. and s1.2. ( Fig. 1 ) as well as s2.1. and s2.2. ( Fig. 2 ). In addition,
3 of
the excessof aluminum (y = [SiO/Al
] = 1.3)in the reaction although the SEM images s1.2. and s1.3. ( Fig. 1 ) as well as s2.2. and
2 O
3 b
mixture cannot directly inuence the reaction yield. However,
s2.3. ( Fig. 2 ) show a drastic decrease of the crystal sizeA when
and
slightly higher values of YR in systemS2 than in the system S1
tscincrease from 0.01058 and 0.00532 (hydrogels H1.2. and H2.2.),
(see Table 2 ) can be readily explained by the higher total aluminorespectively , t o 0.0165 and 0.00829 (hydrogels H1.3. and H2.3.),
silicate concentratio n in the reaction mixtures of system S2 rela- respectively , the size range, peak size and average crystal size of
tive to the correspondi ngreaction mixtures of system S1, and
the zeolite A crystals obtained from hydrogels H1.3., H2.3. increase
thus by decreaseof solubility of the crystallizedzeolite A with
relative to the correspondi ng size values characteristic for zeolite A
increasing supersaturation [21,22] .
crystals obtained from hydrogels H1.2., H2.2. (see CSD curves s1.2.,
Since the rate of crystallization and thus, its duration , depend s2.2., s1.3. and s2.3. in Fig. 3 ) and the correspond ing data in Table
on both the rate of nucleation,dN/dtc and the rate of crystal
2). Finally, while the increase of A and tsc from 0.01650 and
growth, dD/dtc [2326] , the rapid decrease of the duration of crys-0.00829(hydrogels H1.3. and H2.3.), respectively , t o 0.02291 and
tallization with the simultaneous increasetscandA
of
(see Tables 1
0.01151(hydrogels H1.4. and H2.4.), respectively , does not considand 2) can be discussedin the terms of the inuence of these
erably change the size range, peak size and average crystal size (see
parameters on the nucleation and growth processes .Crystal
CSD curves s1.3., s2.3., s1.4. and s2.4. in Fig. 3 and Table 2 ), further
growth of zeolites is governed by the reactions of monomeric
increase ofA (P 0.02986) andtsc(P 0.0150), causes decrease of the
and/or low-molecular weight aluminate, silicate and aluminosili- size range, peak size and average crystal size. Changes of the parcate anions from the liquid phase on the surfaces of growing zeo-ticulate propertie sfor A > 0.055 and tsc> 0.02761will be dislite crystals [4,23,26 28] and thus, its rate,
D/dt
d c, depend on the
cussed separately.
concentratio ns,
CAl, o f aluminum and,CSi, o f silicon in the liquid
An apparent disagreem ent between the size of zeolite crystals
phase, e.g. [23,27] , i.e.,
observed by scanning electron-micros copy (see SEM images s1.1.
and s1.2. in Fig. 1 as well as s2.1. and s2.2. in Fig. 2 ) and those estidD=dtc kg FC kg CAl CAl eq CSi CSieq
4
mated from the correspond ing CSD curves (see CSD curves s1.1.,
where CAl(eq) andCSi(eq) are concentratio ns of aluminum and sili- s2.1., s1.2. and s2.2. in Fig. 3 and the correspondi ng valuesDof
in Table 2 ) is obviously caused by formation of two separate crystal
con in the liquid phase which corresp ond to the solubilit y o f zeolite
A under the synthesis conditions, and
kg is the growth rate constant. populations, as can be clearly shown in the correspondi ng CSDs by
volume (see CSD curves s1.1., s2.1., s1.2. and s2.2. in Fig. 4 ). An
Since with increase of alkalinit ythe solubilit y o f gel increases
analysis of the CSDs of the zeolite A obtained from hydrogel
[19,29] faster than the solubilit y o f zeolite [18,19] , the concen tration factor F(C) and thus, the rate of crystal growth increases and H1.1. (sample s1.1.) has shown that more than 99% (by number)
of crystals have the size lower than 2l m and that less than 1%
conseque ntly, the duration of crystalliza tion process decreases with
of crystals (by number) have the sizes in the range 650 l m.
increasingalkalinit yo fthe reaction mixture [4,23,27 ,30]O. nthe
other hand, the chang es of average crystalD,
size,
and specic num- While, due to a great disproportion between the numbers of crystals of these crystal populations, the bimodal character of crystal
ber,Ns, o f crystals in the crystalline end products with simultan eous
change ofA and tsc(see Tables 1 and 2 ) indicate s that not only thesize distribution cannot be observed in the CSD curves by number
rate of crystal growth, but also the nucleation events inuence the(see CSD curves s1.1., s2.1., s1.2. and s2.2. in Fig. 3 ), both the small
rate of crystalliza tion and thus, the duration of crystalliza tion pro-peaks of the smaller crystals and large peaks of the larger crystals
can be clearly distinguishe d in the CSD curves by volume (see CSD
cess. This will be discussed latter.
Although the SEM images in Figs. 1 and 2 show a general trendcurves s1.1.,s2.1.,s1.2. and s2.2. in Fig. 4). On the other hand,
although the population of smaller crystals represents more than
of the decrease of crystal size with simultaneou s increase
A and
of
Table 2
The end-times,
tc(end) of crystallization process and reaction yields,
Y,Rwhich correspond to crystallization from hydrogels H1.1.H1.10 of system S1 and H2.1.H2.10. of systems
S2 as well as the corresponding average crystal sizes,
D, and specic number of crystals,
Ns, o f the crystalline end products obtained by hydrothermal treatment of hydrogels
H.1.1.H1.10. of system S1 (samples s1.1.s1.10) and H2.1.H2.10. of system S2 (samples s2.1.s2.10.).
Hydrogel (No.)

tc(end) (min)

Sample (No.)

YR (wt.%)

D (l m)

Ns

H1.1./H2.1.
H1.2./H2.2.
H1.3./H2.3.
H1.4./H2.4.
H1.5./H2.5.
H1.6./H2.6.
H1.7./H2.7.
H1.8./H2.8.
H1.9./H2.9.
H1.10./H2.10.

10,000/6980
2640/2050
524/410
360/260
230/210
180/160
145 /130
95/130
90/90
80/60

s1.1./s2.1.
s1.2./s2.2.
s1.3./s2.3.
s1.4./s2.4.
s1.5./s2.5.
s1.6./s2.6.
s1.7./s2.7.
s1.8./s2.8.
s1.9./s2.9.
s1.0./s2.10.

2.482/2.436
5.036/4.872
7.342/7.368
9.587/9.470
12.127/11.907
14.536/14.176
16.593/16.352
19.042/18.483
21.210/20.518
23.334/22.470

1.448/1.404
1.488/1.610
2.069/1.945
2.201/1.935
1.934/1.409
1.086/1.198
1.031/1.104
1.360/1.256
0.476/1.248
0.787/1.634

1.05
1.86
6.25
5.85
1.83
3.85
4.10
1.94
1.71
4.93

/g)
1010/5.25 1010
1010/5.82 1010
1010/6.82 1010
1010/8.59 1010
1011/2.01 1011
1011/3.16 1011
1011/3.40 1011
1011/2.43 1011
1012/2.26 1011
1011/7.57 109

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S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

Fig. SEM
1. images of the crystalline end products (zeolite A) obtained by hydrothermal treatment of hydrogels H1.1. (s1.1.), H1.2. (s1.2.), H1.3. (s1.3.), H1.4. (s1.4.), H1.5.
(s1.5.), H1.6. (s1.6.), H.17. (s1.7.) and H1.8. (s1.8.).

99% (by number) of all the crystals formed from hydrogel H1.1, its
and decreases the size ranges and the peak sizes of the larger-size
portion in the total mass of the formed crystals is less than 10%; crystal populations (see the CSD curves s1.1., s2.1., s1.2. and s2.2. in
more than 90% of the mass is yielded by less than 1% (by number)
Fig. 3 ) o f zeolite A obtained from low-alkaline hydrogels H2.1. and
of the crystals having the size in the range 650
H2.2.: For example, the size range and the peak size in the largerl m. Thus, it is
obvious that the CSDs by number of these products are determined
size crystal population of zeolite A obtained from hydrogel H1.1.
by the large number of crystals having the size in the range 0.5 (y = 2.0) are 2.756
l m and 18.7l m (see the CSD curve s.1.1. in
2 l m (see the CSD curves s1.1., s2.1., s1.2. and s2.2. in Fig. 3 ) and
Fig. 4 ), and the correspondi ng values of zeolite A obtained from
that the larger crystals (>6l m) dominate si n the SEM images
hydrogel H2.1. y
( = 1.3) are 2.730l m and 8.2l m (see the CSD
(see the SEM images s1.1.and s1.2.
in Fig 1 as well as s2.1. and
curve s.2.1. in Fig. 4 ).
s2.2. in Fig. 2 ).
Now, taking into considerati on that:
While the excess of aluminiumy( = 1.3) does not markedly
inuence the CSDs, either by number (see the CSD curves s1.3.
(i) zeolite nuclei are formed in the gel matrix during its precips1.10. and s2.3.s2. 10. in Fig. 3 ) o r by volume (see the CSD curves itation [3136] ,
s1.3.s1.10. and s2.3.s2.10. in Fig. 4 ), of zeolite A obtained from (ii) number and distribut ion of nuclei in the gel matrix considerhydrogels H1.3.H1.8. and H2.1.H2.8., the excess of aluminium
ably depend on the chemical composition of hydrogel and
considerably increases specic number,
Ns, o f crystals (see Table 2 )
the mode of its preparation [3537,9,38,39 ] ,

S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

393

Fig.
SEM
2.images of the crystalline end products (zeolite A) obtained by hydrothermal treatment of hydrogels H2.1. (s2.1.), H2.2. (s2.2.), H2.3. (s2.3.), H2.4. (s2.4.), H2.5.
(s2.5.), H2.6. (s2.6.), H2.7. (s2.7.) and H2.8. (s2.8.).

(iii) nuclei cannot grow in the gel matrix, but can start to grow [4446] where AlOH4 anions preferent ially react with largest silafter their releasing from the gel dissolved during crystal-icate anions [47] , results in the forma tion (precip itation) of amorphous phase (gel) having the molar ratio [SiO
/Al3 O
]
than
lization, i.e., when they arein full contact with the liquid
2
2
g higher
is the batch molar ratio y = [SiO
phase [4,26,34,37,39, 40] ,
2/Al 2O 3] b [4850] ,i.e., for y = 2.0
] > 2.0. Or in the other words, number of
(iv) specic number of crystals,
Ns, correspond s t o the number of (system S1), [SiO
2 /Al
2 O
3 g
SiOSi bonds in the gel matrix increasesand at the same time
active nuclei from which growth the crystals are formed
number of SiOAl bonds in the gel matrix decreases with increase
[11,34,9] and
of y, and vice versa. Since for zeolite A are immanen t SiOAl and
(v) CSD depends on the number and distribut ion of nuclei in the
not SiOSi bonds (i.e., Si/Al = 1 in zeolite A framewo rk [20] ) zeolite
gel matrix [34,37,39,41,42 ] ,
A nuclei can be rather formed in SiOAl than in SiO Si environthe considerable differe nces of the particulate properti es (specicment. From this reason number of the nuclei formed in the gel matrix is proportio nal to the content of aluminum in the gel and thus,
number,Ns, o f crystals; see Table 2 , CSD by volume; see Fig. 4 )in
determine d b y the value of [SiO
the products obtained from hydroge lsH1.1. (y = 2.0)and H2.1.
2
2/Al
3O
g ] . O n the other hand, since
the value of [SiO2/Al2O3] g decreaseswith decreasingvalue of y
(y = 1.3) can be explained as follows: Reactio no f monomeri c
AlOH4 anions [43,44] from aluminate solution with higher-p oly- [4850] , number of nuclei formed per unit mass of the solid phase
of hydroge ls H2.1. and H2.2.
y =(1.3) are higher than the number of
merized silicate anions present in low alkaline silicat esolution s

394

S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

Fig. 3. Crystal size distributions (CSD) by number of the crystalline end products Fig. 4. Crystal size distributions (CSD) by volume of the crystalline end products
obtained by hydrothermal treatment of hydrogels H1.1. (s1.1.), H2.1 (s2.1.), H1.2.
obtained by hydrothermal treatment of hydrogels H1.1. (s1.1.), H2.1 (s2.1.), H1.2.
(s1.2.), H2.2. (s2.2.), H1.3. (s1.3.), H2.3 (s2.3.), H1.4 (s1.4.), H2.4. (s2.4.), H1.5. (s1.5.),
(s1.2.), H2.2. (s2.2.), H1.3. (s1.3.), H2.3 (s2.3.), H1.4 (s1.4.), H2.4. (s2.4.), H1.5. (s1.5.),
H2.5. (s2.5.), H1.6. (s1.6.), H2.6. (s2.6.), H1.7. (s1.7.), H2.7. (s2.7.), H1.8. (s1.8.),H2.5.
H2.8.(s2.5.), H1.6. (s1.6.), H2.6. (s2.6.), H1.7. (s1.7.), H2.7. (s2.7.), H1.8. (s1.8.), H2.8.
(s2.8.), H1.9. (s1.9.) H2.9. (s2.9.), H1.10 (s1.10.) and H2.10. (s2.10.). The solid curves
(s2.8.), H1.9. (s1.9.) H2.9. (s2.9.), H1.10 (s1.10.) and H2.10. (s2.10.). The solid curves
(s) corresponds to the CSDs of the products crystallized from system
y = 2.0)
S1 ( and
(s) corresponds to the CSDs of the products crystallized from system
y = 2.0)
S1 ( and
the dashedcurves (d) correspond tothe CSDsof the products crystallized from
the dashed curves d)
( correspond tothe CSDsof the products crystallized from
system S2 (y = 1.3).ND is number percentageof crystals having the spherical
system S2 (y = 1.3).VD is volume percentageof crystals having the spherical
equivalent diameter
D.
equivalent diameter
D.

nuclei formed per unit mass of the solid phase of hydrogels H1.2. tween the correspond ingcrystal size distribut ions(see Figs. 3
and H2.2. y
( = 2.0). Thus, the speci c number of crystals,
Ns, i n the
and 4) and (iii) marked changeof particle (crystal) morphology
(see Fig. 5 ).
crystalline end products obtained from low-alkaline hydrogel s
H2.1. and H2.2. (sampless2.1. and s2.2.)are consider ablyhigher
The increase of specic number,
Ns, o f crystals with increase of
than the specic number of crystals in the crystalline end productsalkalinity (simultaneous increase of free+Na
and OH ions) can
obtained from low-alka line hydroge ls H1.1. and H1.2. (samples s1.1.
be readily explained by the action of structure -forming +
Na
ions
and s1.2.; see Table 2 ).
[32,51,52 ] which induces the formation of nuclei in the gel matrix
The formation of two particle (crystal) populations during crys-[4,11,32, 34,36] . In addition, the increase of alkalinity increases the
tallization of zeolite A form low-alkaline hydrogels can be exconcentr ationof lower-polymer izedsilicate anions (monomers,
plained by specic distribut ion of nuclei in the gel matrix; most dimmers) [4446] ;this governs the reactions between silicate
of nuclei are formed in the centers of the gel particles and lower
and aluminate ions to formation of the gels with higher aluminum
part of nuclei are formed at the surface and subsurface regions ofcontent (decrease in the molar ratio, [SiO
O ] , o f gel) [50] and
2
2/Al
3 g
gel particles [37,9,38,39] . Since the nuclei positioned in the surface
thus, additionally facilitates the formation on nuclei in the gel maand subsurface regions of gel are released from the gel matrix and
trix. Finally, forA > 0.01 the excess of aluminum in the reaction
start to grow at the beginning of crystallization process,their
mixture (y > 2 ) has not a considerably inuence on the molar ratio
growth consumes most of aluminosilicate material before the nu- [SiO2/Al2O3] g [49] , so that the vales N
ofs for both the systems (S1
clei positioned in the centers of gel particles are released from and S2) become close for
A P 0.0165(see Tables 1 and 2 ). Almost
the gel matrix.
the same crystal size distribut ions of the crystalline end product
Simultaneous increase ofA and tsc (A/tsc= 1.99 = constant for obtained at given alkalinity (01656 A 6 0.046) for y = 1.3and
both systems) causes at least three effects; (i) increase of specicy = 2 (see Figs. 3 and 4 ) indicate that not only number of nuclei,
number,Ns, o f zeolite A crystals in the product of crystallization but also their distribut ion in the gel matrix does not considerably
(see Table 2 ) and conseque ntly, decrease of crystal size (see Figs.
depend on excess of aluminum in the reaction mixture at higher
14 ),(ii) decreasein the differenc ebetweenspecic number of
alkalinities of the reaction mixture.
crystals in the products obtained by hydrothermaltreatmentof
The great inuence of the excess of aluminum in the reaction
correspondi ng hydrogels of systems S1
y=
( 2.0) and S2 y( = 1.3.;
mixture at low alkalinity A( <0.01) on the specic number of cryssee Table 2 ) and conseque ntly, decrease in the difference the betals (see Table 2 ) and crystal size distribution (see Figs. 3 and 4 )is

S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

395

s1.3. and s2.1.s.2 .3. in Fig. 5 ) with simultaneous increase of alkalinity, A, and total silica concentration,
tsc, indicate that not only
the value ofy, but also the values of
A and tscinuence the growth
rate inh0 1 1i direction relative to the growth rate h
in
0 0 1i direction. Now, keeping the thesis that the decrease of crystal growth in
h0 1 1i direction and thus, developing of {0 1 1 } crystal planes of
zeolite A is caused by distortion of the terminal SiO
4 tetrahedra
in the presence of aluminate ions [15,53] , the above mentioned effects can be readily explained by the fact that, the ratio,
L [Al/Si] ,in
the liquid phase of hydrogel increases with increasing alkalinity
[50] . Since, on the other hand, for given valuesAofand tsc, [Al/
Si]L increases with decrease yof[48,49] the higher edge-to-face aspect ratios of zeolite A obtained from system S2
y=
( 1.3) than of
these obtained from the correspond ingbatches of system S1
(y = 2.0), was expected .
Further simultaneou sincrease of A (A P 0.02291) and tsc
(tscP 0.01151) causes rounding of the crystal edges and apexes
(see SEM images s1.4., s2.4., s1.5 and s1.6. in Fig. 5 ) following by
partial (fory = 2.0,A P 0.0375and tscP 0.01885; see SEM images
s1.5. and s1.6. in Fig. 5 ) o r complete loss of individua l crystal faces
(for y = 1.3,A P 0.02291and tscP 0.01151; see SEM images s2.5
s2.7. in Fig. 5 also see Fig. 6 ). The rounding of the crystal edges
and apexes can be explained by surface nucleation [15] , as postulated by Unemura et al. (see Fig. 2 i n Ref. [54] ), caused by increase
of supersaturation level with simultaneou s increase Aofand tsc
[21,22] . On the other hand, since the loss of individua l crystal faces
is connectedwith the pseudo-sph ericalshape of the particles
(crystals) of zeolite A (see Fig. 6 ) one can assume that, under the
given chemical conditionsA(P 0.02291,tscP 0.01151for y = 1.3
and A P 0.0375, tscP 0.01885 for y = 2.0),the growth rate is
approximat ely the same in all directions. However, since there is
not a theoretical basis or even an experime ntal evidence for such
an assumption, it is more realistic to assume that a gradual rounding of zeolite A crystals and formation of the pseudo-sph erical
particles of zeolite A i s caused by intensive surface nucleation at
high supersaturati on characteristic for the above mentioned condition. On the other hand, the absence of identiable individual crystal planes accompani ed by high roughness of particles surfaces (see
Fig. 6 ) indicates that the intense surface nucleation [54] was probably followed by a rapid growth [15] of the formed surface nuclei.
In this context, the complete disappearingof individual crystal
Fig. 5. SEM images of the crystalline end products obtained by hydrothermal
planes at lower values of
A (0.02291) andtsc(0.01151) fory = 1.3
treatment of hydrogels H1.1. (s1.1.), H2.1 (s2.1.), H1.2. (s1.2.), H2.2. (s2.2.), H1.3.
(s1.3.), H2.3 (s2.3.), H1.4. (s1.4.), H2.4. (s2.4.), H1.5. (s1.5.), H2.5. (s2.5.), H1.6. (see
(s1.6.)SEM image s.2.5 in Fig. 5 ) relative to only partial disappearing
H2.6. (s2.6.), H1.7. (s1.7.), H2.7. (s2.7.), H1.8. (s1.8.), H2.8. (s2.8.), H1.9. (s1.9.), H2.9.
(s2.9.), H1.10 (s1.10.) and H2.10. (s.2.10.).

followed by a considerableinuenceon the crystal morphology

(see the SEM images s1.1. and s2.1. in Fig. 5 ). Based on the previous
investigatio ns of the inuence of
y on the crystal morphology of
zeolite A [6,8,15] , obtaining the regular cubic crystals with sharp
edges andapexes (seethe SEM image s1.1.in Fig. 5 )for y = 2.0
and cubic crystals with truncated edges (see SEM image s2.1. in
Fig 5) for y = 1.3was expected.Developmen to f {0 1 1}crystal
planes at the excess of aluminum in the reaction mixture indicates that, under such condition, the crystal growth in the
h0 1 1i
direction is suppressed. Knowing that the presence of aluminum
atom on a neighboring T atom (Si, Al) site distorts the silicon tetrahedron, i.e. shortens one of the silicon-oxygen bond [53] , it is reasonable to assumethat just the distortion of the terminal SiO4
tetrahedra caused by the presence of aluminate ions retards the
growth rate at the points (regions) of distortions, e.g., crystal edges
and/or apexes [15] . On the other hand, appearance of {0 1 1} crystal planes on zeolite A crystals obtained from hydrogels H1.2. and
H1.3. (y = 2; see SEM images s1.2. and s1.3. in Fig 5 ) as well as inFig.6. Morphological features of the product obtained by hydrothermal treatment
of hydrogel H2.6. (sample s.26.). Magnication: 33,000
; size-bar: 100 nm.
creaseof edge-to-faceaspectratio We/L (see SEM imagess1.1.

396

S.Bosnar et al. / Microporous and Mesoporous Materials 142 (2011) 389397

of the individual crystal planes at higher valuesAof(0.0375) and

(mass of zeolite crystallized from 100 g o f the reaction mixture) is
tsc(0.01885) fory = 2.0 (see SEM image s1.6. in Fig. 5 ), can be readproportio nal to total silica batch concentratio
tsc;nhowever,YR/tsc
ily explained by the fact that for given values
A andtsc
of
, supersatslightly decrease s with increasing alkalinity as a consequence of
uration increases with increasing value of
y [21,22] . Formation of the increasing solubility of zeolite A with the increase of the
irregularly- shapedparticles of zeolite A a t A = 0.04585 and
alkalinity.
tsc= 0.02315 (see SEM images s1.7, and s2.7. in Fig. 5 ) i s probablySpecic number,Ns, o f crystals in the crystalline end products
caused by rapid and uncontrolled growth of surface nuclei at in- increases withsimultaneou sincreaseof A and tsc as the conse+
creased supersaturation.
quence of the increase of concentr ation of structure -forming
Na
In addition, for A P 0.055 (which corresponds to P 6.1M
ions, which induces the formation of nuclei in the gel matrix. HowNaOH) and tsc= 0.0276(which correspondsto P 1.53M SiO2),
ever, while the crystalline end products obtained from low alkaline
the rapid and uncontrolledgrowth of surfacenuclei is followed
reaction mixtures (hydrogels H1.1., H2.1., H1.2. and H2.2.;
by aggregation of individual zeolite A crystals and a tendency of 0.005076 A 6 0.01058) are characteri zed by two separate crystal
spontaneou s transformat ion of the formed zeolite A into hydroxypopulations and with a considerable inuenceyofon the specic
sodalite (HS) [14,17] .
number of crystals, CSDs of the crystalline end products obtained
Although the number of nuclei formed in the gel matrixAfor
=
for 0.01656 A 6 0.055are monomodal with no considerable inu0.055is assumed to be higher than the number of nuclei formed inence ofy on either CSD or specic number,
Ns, o f crystals. This was
the gel matrix forA = 0.04585, specic number of particles as cal- explained by specic polyconden sation reactions between alumiculated by Eq. (3) using the correspondi ng CSD data is lower andnate and (poly)silicate anions during precipitatio n o f amorpho us
the average crystal size,
D, is higher for the product obtained at
aluminosi licate precursor (gel) under various alkalinities .
higher alkalinity (A = 0.055) relative to the corresponding values
Morphol ogy of the crystallized zeolite A depends not only on
of the product obtained at lower alkalinity
A =( 0.04585) (see Table the ratioy = [SiO
2 /Al
2 O
3 ]b , as it was assumed on the basis of previ2). This can be readily explained by a tendency of the formation ofous studies, but on the overall chemical compositi on of the reaccrystal aggregates (see the SEM images s1.8. and s2.8 in Fig. 5tion
)at mixture, and especially on its alkalinity, A = [Na
2 O/H
2 O]
b .
high alkalinity (A P 0.055) and high crystal yield (1819 wt.%;
Four different morphologi cal forms of zeolite A, namely (i) regular
see Table 2 ) caused by high
tsc (=0.02761). However, the differ- cubic crystalswith sharpedgesand apexes,(ii) cubic crystals
ences in the particulate propertie s o f the products obtained fromwith truncatededges,(iii) cubic crystals with rounded edges
hydrogels H1.8. and H2.8. (see SEM images s1.8. and s2.8. in
and apexes and (iv) pseudo-s pherical particles with no recognizFig. 5 , CSD curves s1.8. and s2.8. in Figs. 3 and 4 , and the corre-able individual crystal planes are obtainedduring hydrothe rmal
sponding data in Table 2 ) show that the tendency of formatio n otreatment
f
of investigated hydrogels. The formation of cubic cryscrystal aggregat es
is less during the hydrothermaltreatmentof
tals with truncated edges (formation of {0 1 1 } crystal faces) was
hydrogel H2.8. (system S2,
y = 1.3) than during the hydrothe rmal explained by decrease of crystal growth ion the
h0 1 1i direction
treatment of hydrogel H1.8. (system yS1,
= 2.0). This indicates that caused by distortion of terminal SiO
4 tetrahedr ons positioned at
the excess of aluminum retards the aggregation processes .
crystal edges and apexes in the presence of aluminate ions. Since
Finally, as expected, at high alkalinityA( P 0.055) there is a
for given values ofA and tsc, concentratio n o f aluminat e ions intendency of spontaneou s transformat ion of the formed zeolite Acreases, this effect (decrease of crystal growth inhthe
0 1 1i direcinto HS [14,17] . However, while the products obtained by hydro- tion) increases with increasing alkalinity of the reaction mixture.
thermal treatment of hydrogels H1.8. and H2.9. contains only
On the other hand, formatio no f cubic crystals with rounded
traces of HS, the products obtained from hydrogels H1.9. and
edges and apexes and even complete loss of recognizable crystal
H1.10. are pure HS, as revealed by XRD and the SEM images; theplanes and formation of pseudo-spherical particles is caused by insponge-like features in the SEM images s1.9., s1.10. and s2.10. intense surfacenucleationat increasedsupersaturati on
causedby
Fig. 5 , are characterist ic for HS [55] . The absence of HS in the prodrelatively high alkalinity of the reaction mixture at excess of aluuct obtained from hydrogels H2.8. and presence of only traces of minium in the liquid phase.
HS in the product obtained from hydrogel H2.9. indicates that
Because of simultaneou s occurring of several processes , e.g., rathe excess of aluminum prevents not only the aggregation pro-pid and uncontrolled growth of surface nuclei, crystal aggregation
cesses, but also the transformat ion of zeolite A into HS even at high
and transformat ion of the formed zeolite A into hydroxysodal ite
alkalinities. This combination of the tendency of transformat ion of
(HS), the processes of crystallizati on at high alkalinity
A >( 0.055)
zeolite A into HS and protective role of aluminat e ions makes the
is unstable and particulate properties of the crystalline end prodprocesses of crystallization at high alkalinity
A >( 0.055) unstable ucts cannot be predicted.
and particulate propertie so f the crystalline end products are
unpredictab le(see SEM images s1.9.,s2.9.,s1.10. and s2.10. in
Acknowledgement
Fig. 5 and CDS curves s1.9., s2.9., s1.10. and s2.10. in Figs. 3 and 4 ).
The authors gratefully acknowledgefunding from Barchem
Companyand Ministry of Science,Education and Sport of the
4. Conclusions
Republic of Croatia.
The presente d results show how the pathway of crystallization,
Appendix A. Supplementary material
reaction yield and especiall yparticulateproperties (crystal size
distribution ,crystal morphology)of zeolite A can be controlle d
Supplement ary data associated with this article can be found, in
by chemical composition of starting aluminosilicate hydrogel, de- the online version, at doi:10.1016/j .micromeso.2010 .12.027 .
ned by the batch molar ratiosA = [Na
2 O/H
2 O]
b ,tsc= [SiO
2 /H
2 O]
b
and y = [SiO
2 /Al
2 O
3 ]b at the constant ratio A/tsc= 1.99.Duration
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