Studies in the synthesis of ZSM-5 zeolites

S. B. Kulkarni, V. P. Shiralkar, A. N. Kotasthane, R. B. Borade

and P. Ratnasamy*
National Chemical Laboratory, Pune 411 008, India
(Received 29 April 1982)

ZSM-5 zeolites have been synthesized using tri-ethyl-n-propylammonium (TEPA) cations as

the source of the organic base. X-ray diffraction, framework i.r. spectroscopy, scanning
electron microscopy, adsorption of n-heptane and cyclohexane and product distribution in
the conversion of methanol to hydrocarbons have been utilized in characterizing the
synthesized zeolite. The rates of both nucleation and growth of ZSM-5 crystals are lower
when TEPA rather than tetrapropylammonium (TPA) cation is used. The amount of cycto-
hexane (but not n-heptane) adsorbed on the ZSM-5 zeolite (prepared by the TEPA route)
decreases at increased SiO2/AI203 ratios. Under certain conditions, the ZSM-5 zeolite (in
both the TPA and TEPA systems) undergoes transformation into s-quartz.

Keywords: Zeolite synthesis; ZSM-5 crystallization; kinetics of crystallization; nucleation

INTRODUCTION yet fully understood, to enhance the siliceous

Most of the early work in the synthesis of zeolites
involved crystallization of the aluminosilicate gel
from solutions containing alkali hydroxide as the
base. Barrer et al. 1, 2 discovered that the presence
of quaternary ammonium ions along with the alkali
led to more open crystal structures. Using the
tetramethylammonium ions (TMA), nitrogenous
zeolites A, X, Y and an ammonium zeolite
belonging to the analcime-type, had been
synthesized. Other zeolites synthesized using TMA
ions include zeolite ZK-43' ~, alpha s, omega6, N 7,
TMAE s, 10 and zeolite Socony Mobil (ZSM) 11.
Similarly, using tetraethylammonium (TEA) ions,
zeolite ~2 and ZSM-813 have been synthesized.
ZSM-5 zeolite, useful as a catalyst for a wide
variety of reactions, has been synthesized from
mixed base systems containing alkali hydroxide
and tetrapropylammonium (TPA) cations ~4.
During the above studies it has been observed
that when a zeolite of a given structural type (A or
faujasite) was synthesized from a single base
(alkali hydroxide) or mixed base (quaternary
ammonium ion-alkali hydroxide) systems, those
obtained in the presence of the alkylamm0nium
ions usually have higher values of Si/A1 ratios,
In the case of zeolites of structure type A for
example, those synthesized from systems con-
taining alkali metal hydroxides alone as the base
have values of Si/A1 around 1, while those obtained
from mixed-base systems, containing TMA ions,
have Si/A1 values as high as 3.5. Apparently,
alkylammonium cations when present in the
synthesis mixture, are able, by a mechanism not
* To whom all correspondence should be addressed
nature of the zeolite.
The present study was undertaken to throw further
light on this problem. The kinetics of nucleation
and growth of ZSM-5 crystals was investigated in
two types of mixed-base systems namely, TAP-
alkali hydroxide and triethyl-n-propylammonium
(TEPA)-alkali hydroxide systems. The change in
the structure of the alkylammonium ion, from
TPA to TEPA, was found to influence not only the
kinetic parameters of the synthesis reaction, but
also the metastability of the zeolite itself towards
further transformation into o~-quartz. It is first
demonstrated that it is feasible to synthesize
ZSM-5 zeolites from TEPA-sodium hydroxide,
mixed-base systems. The various kinetic features
of the synthesis (influence of reaction time and
temperature, SiO2/AI~O3 ratio, alkalinity, etc.)
are next delineated and compared with those
obtained for the TPA-sodium hydroxide system.
The zeolite samples have been characterized by
X-ray diffraction, scanning electron microscopy
(SEM), i.r. spectroscopy, adsorption of n-heptane,
cyclohexane and H20, catalytic activity in the
conversion of methanol into various hydrocarbons.
EXPERIMENTAL
The syntheses were carried out at 433,453 and
473 K in stainless steel autoclaves (75 ml capacity)
at autogenous pressure. The reactant materials
used were sodium silicate (SiO2 = 27.2%, Na20 =
8.4%, H20 = 63.9 wt.%), aluminium sulphate
(Merck), sulphuric acid (Analar grade, BDH), tetra-
alkylammonium compounds TPABr, TEPABr,

0144 -2449/82/020313 -06 $03.00

1982 Butterworth & Co. (Publishers) Ltd. ZEOLITES, 1982, Vol 2, October 313
ZEO 2:4 - F
Studies in ZSM-5 synthesis: S. B. Kulkarni et al.

TPAOH (40% solution from Fluka-Ag). Appropriate RESULTS A N D DISCUSSION

amounts of aluminium sulphate and sulphuric
Synthesis of Na-ZSM-5 zeolite using TEPA cations
acid were added to distilled water to yield solution
A. Quaternary ammonium bromide was added to The X-ray diffraction pattern, scanning electron
sodium silicate solution yielding solution B. The photomicrograph and i.r. spectra for the zeolite
solutions A and B were mixed in the reaction vessel prepared using TEPA cations are illustrated in
with continuous stirring. The resulting gel had the Figures 1-3, respectively. The values of the inter-
composition 4.38 (TPA)20, 27.6 Na20, A1203, planar spacing (d values)and relative intensities
87.7 SIP2, 3262 H20. When the reaction mixture derived from the X-ray pattern (Figure 1 ) are given
attained the required temperature, the time was in Table 1. Both the d values and relative intensities
noted as the zeroth hour. On termination of the are similar to those reported for ZSM-514, a6,17. The
run the reactors were quenched in cold water. crystalline phase is identified as ZSM-5, confirmed
After the synthesis step, the solid products were by the morphology of the crystals as seen in the
filtered, washed with hot water, dried in a static- scanning electron photomicrograph (Figure 2)
air oven at 393 K for 12 h and finally calcined at which is similar to that reported for ZSM-514'16.
823 K for 8 h in a static-air furnace to obtain the The average size of the crystals was about 1.0/am.
Na form. The chemical composition of fully The infrared spectrum of the Na-ZSM-5 prepared
crystalline ZSM-5 sample estimated by wet- using TEPABr is shown in Figure 3. The major
chemical analysis, atomic absorption and flame
p h o t o m e t r y was SiP2 97.10%, A1203 2.08%, Na20
0.78%. The extent of crystallization was evaluated
by X-ray diffraction (Phillips PW 1730, Ni filtered
CuK~). For quantitative phase identification, a
selected reference sample was used and the per
cent crystallization was calculated from the sum
of the areas of the peaks between 20 = 22 and
25 . The extent of crystallization was estimated
by using the formulalS:

Peak area between 2 0 = 2 2 o - 2 5

o f the product
% Crystallization =
Peak area between 20 = 2 2 - 2 5
o f the reference sample

-- 3~4 3~0 216 2'2 l; ,'o

2O
The crystal size and habit of the crystalline phase Figure 1 X-ray diffraction profile o f a sample of Na-ZSM-5 zeolite
were examined using a scanning electron micro- prepared using TEPA cations. See Table I for values o f interplanar
spacing and relative intensity
scope (JEOL, Model JSM-43). The samples were
coated with a Au-Pd evaporated film. The sorption
properties of the samples for various adsorbates
were measured gravimetrically in a conventional,
high-vacuum adsorption system using a McBain
balance. The zeolite,sample was degassed at 673 K
for 4 h at P ~< 1.3 x 10 -s bar. The sample was then
cooled in vacuum to 298 K. The sorbate was then
admitted and the amount adsorbed at equilibrium
was noted. The i.r. spectra of the samples (nujol
mull technique) were recorded with a Perkin-
Elmer 221 Spectrometer. KCN was used as the
internal standard (reference peak at 2200 cm-t).
The catalytic activity of the samples for the
conversion of methanol to hydrocarbons was
evaluated in a fixed bed, downflow, integral
reactor using 2 g (10-22 mesh) of the ealalyst. The
products were analysed on-stream with a gas
chromatograph (HP 5840A, FID detector). Pora-
pak-Q and SE-30 (20%) on chromosorb W columns Figure 2 Scanning electron photomicrograph of Na-ZSM-5 crystals
(2 m) were used for the analysis of the products. prepared using TEPA cations

314 ZEOLITES, 1982, Vo12, October

 Studies in ZSM-5 synthesis: S. B. Kulkarni et al.

Table 2 Framework vibration frequencies for Na-ZSM-5. Source

of organic base = TEPABr; SiOJAI203 ---- 86

Wavenumber (cm- ~) Assignment*

450 Si--O bending

540 Distorted double 5 rings
590 E LC 5
620 ELC5
680
720 ITSS
790 ELSS
840 E LSS
1075 ITAS
1220 Si--O asymmetric stretch

* ELC5 = External link complex 5 membered ring

ITSS = Internal tetrahedral symmetric stretch
ELSS = External link symmetric stretch
ITAS = Internal tetrahedral symmetric stretch
I t I I ]
1200 1000 800 600 400
Frequency ( c rn -I )

Figure 3 Infrared spectra of Na-ZSM-5 zeolite. See Table 2 for Table 3 Conversion of methanol to hydrocarbons
values of framework vibration frequencies
Catalyst H-ZSM-5
Feed Pure methanol
WHSV 2.3 g/g h
Temperature (K) 668
Table 1 Lattice spacings, d, and relative intensity (I/I o) values for Conversion of methanol 100%
Na-ZSM-5 synthesized using TEPABr
Hydrocarbon product distribution (wt. %)
d (A) I~o d(A) I~ o Methane 0.7
Ethylene 2.9
11.040 81,1 3.705 52.4
Ethane 0.2
9,927 51.5 3,698 33.2
Propylene 14.2
9,688 22.0 3.477 6,7
Propane 2.2
7.405 4.9 3.458 11.2
6.681 8.1 3.343 8.9 C4 hydrocarbons 27.9
6.320 15.2 3.299 12.5 C s hydrocarbons 9.9
5.964 18.8 3.162 3.1 C 6 hydrocarbons 10.2
5,675 11.2 3.129 4,5 C 7 hydrocarbons 1.2
5.555 14,8 3,041 13.4 C 8 hydrocarbons 0.5
5.316 3,6 2,976 14,3 Benzene 1.3
5.121 2,7 2,939 8.1 Xylenes 14.4
4.941 6.7 2,855 4.0 Toluene 5.9
4.595 6,3 2.777 2.2 C~ aromatics 8.8
4,349 9,8 2.728 6.3
4.238 15.2 2.602 6.3 Note: H-ZSM-5 was prepared from Na-ZSM-5 by ion-exchange with
3.983 7.2 2.506 4.5 5 N NH4NO 3 solution
3.840 100,0 2.479 6.3
3.808 72.2 2.408 4.0
3,744 35,9 2.390 4.5
The catalytic activity of the sample in the con-
version of methanol into hydrocarbons is illus-
trated in T a b l e 3. The product distribution is quite
framework frequencies of absorption with their similar to that reported 19f o r ZSM-5 zeolite. On
assignments are given in T a b l e 2. Chao et al. 15 and the basis of the evidence presented above, it may
Jacobs et al. 18 had studied the framework i.r. be concluded that ZSM-5 crystals can be obtained
spectra of ZSM-5 crystals. Chao et al. is found from TEPA-alkali-hydroxide, mixed-base systems.
absorption bands of external linkages at 4 0 0 , 5 4 5 ,
800 and 1000-1200 cm -1. The Raman spectrum Kinetic studies o f the f o r m a t i o n of ZSM-5 crystals
of ZSM-5 is exhibited the vibration modes of the T h e crystallization curves at 4 3 3 , 4 5 3 and 473 K
skeletal framework at 330, 350, 770 and 1090 using T E P A B r as the source o f the organic cation
cm -1. The band at 540 cm -1 had been assigned by are illustrated in Figure 4a. T h e s e curves exhibit
Jacobs et al. ~8 to highly distorted, double, five- the t y p i c a l sigmoid n a t u r e characteristic o f
membered rings present in the ZSM-5 structure. processes involving t w o distinct stages: (i) an
The absorbance at this frequency had been utilized i n d u c t i o n p e r i o d w h e n nuclei are f o r m e d ; (ii) a
by Jacobs et al. 2o to estimate the i.r. crystallinity crystal g r o w t h p e r i o d w h e n the nuclei grow into
of the material. The d.t.a./t.g, curves for the crystals. T o c h e c k that the z e o l i t e - f o r m a t i o n in our
sample revealed that the temperature of framework case c o n f o r m s to this general picture, the data in
decomposition of the zeolite was above 1273 K, Figure 4a were f i t t e d to the A v r a m i - E r o f e e v
again in accordance with published literature is. e q u a t i o n , In (111 --c~) = [(kt)] m . T h e results are

ZEOLITES, 1982, Vol 2, October 315

Studies in Z S M - 5 synthesis: S. B. K u l k a r n i et al.

rate of crystallization was obtained from the

inflection point in the crystallization curves (when
the crystallization rate is highest). The values of
E n and E e for the formation of ZSM-5 using
TEPABr and TPABr as the source of organic
cations are given in Table 5. It is seen that both the
2
? structure of the quaternary ammonium ion and the
SiO2/A1203 ratio determine the values of E n
4 and E C.
c

When using TPAOH as the organic base, Chao

I 2
et al. is (SIO2/M203 = 70, OH/H20 = 2.2 x 10 -3)
had observed values of 25 and 29 kI tool -1, for E n
and Ec, respectively. Erdem and Sand 16 (TPAOH;
SiO2/A1203 = 28; OH/H~O = 26.7 x 10-3),
b however, obtained values of En and E~ of 107.5 and
3 81.5 kJ tool -1, respectively. Obviously, these
kinetic parameters are complex functions of many
reaction variables and a more detailed investigation
is necessary to get their 'true' (not apparent)

l values.
The crystallinity of the samples obtained at
5o different synthesis times were evaluated b y both
0 a
X-ray diffraction and i.r. spectroscopy (Figure 6).
As mentioned earlier, the absorbance of the
25~/ n skeletal vibration at 540 cm -1 was used to estimate
i.r. crystallinity using a high crystalline (X-ray)
:. ,../Xo sample as the 100% standard. Both the i.r. and
t(h)
Figure4 Influence of temperature on the kinetics of crystalliza-
tion; organic cation -- TEPA; curves 1, 2 and 3, refer to 4 3 3 , 4 5 3 Table 4 Avrami-Erofeev parameters f o r ZSM-5 synthesis using
and 473 K, respectively; (a) crystallization curves; (b) f i t of experi- TPABrandTEPABrln(1/1 c~)=(kt) m
mental data to the Avrami-Erofeev equation (see text)
Source of organic base

TPABr TEPABr
shown in Figure 4b. In the above equation, c~ and Synthesis
temperature (K) 10 2k m 10 2 k m
t are the fractional conversion and time, respec-
tively, and h and m are constants. The values of h 433 9.0 2.4 2.2 4.5
and m at 4 3 3 , 4 5 3 and 473 K are given in Table 4 453 38.3 2.0 3.7 3.2
473 44.9 1.2 14.9 2.4
where they are compared with those obtained
using TPABr instead of TEPABr as the source of
the organic base. The crystallization curves for the
TEPABr system are compared with those of
TPABr in Figure 5. From the good 'fit' of the data
to the equation, it is concluded that the crystalliza- ,P /6 I
tion process can be described, at least mathemati- F P / I
cally, by the Avrami-Erofeev equation involving
the nucleation and growth of the crystalline,
zeolite phase. Assuming that the formation of the
nuclei during the induction period is an energeti-
'11' /' /3
d /
cally activated process and, since nucleation is I r 7 /o
the rate determining step during the induction It /
I
period, the apparent activation energy for nuclea-
tion, En, was calculated from the temperature Ji / / o
dependence of the rate of nucleation. The rate of /
nucleation was assumed to be inversely pro- " 8o J 24 40
portional to the induction period. Similarly, Ec, /(h)
the apparent activation energy for crystal growth,
Figure 5 Influence of organic cation on kinetics of crystallization:
was calculated from the temperature dependence (1) TPABr, 453 K; (2) TPABr, 433 K; (3) TEPABr, 453 K; (4)
of the rate of crystallization. Assuming that the TEPABr, 433 K

316 ZEOLITES, 1982, Vo12, October

 Studies in ZSM-5 synthesis: S, B. Kulkarni et al.

Table 6 Activation energies for nucleation and crystallization: both the induction period for nucleation and the
OH/H2O = 5.5X 10-3; Na~O/Si% = 0.295
rate of crystallization. Now, during the synthesis
Source of reaction, the amorphous aluminosilicate gel formed
organic base SiOJAIzO 3 En (kJ moF 1) Ec (kJ reel -1) initially dissolves, under the influence of OH ions,
TEPABr 86 270.4 206.8 into smaller hydroxylated A1, Si and alumino-
TEPABr 800 249.5 276.3 silicate species, OH- ions accelerate this process.
TPABr 86 199.5 238.6
In the next stage, these dissolved species, in the
presence of templates, like the quaternary
ammonium ions, condense to form nuclei which
grow into zeolite crystals. OH- ions, when present
a b in excess, inhibit this nucleation and crystal
I00

.~ 75
'e 4

(J
5

jf growth process. An optimum OH- ion concentra-

tion, sufficient to maintain enough dissolved
h y d r o x y species but not in such excess as to
inhibit the subsequent nucleation and crystal
growth, is desirable.
o
50
of Adsorption properties
25
The adsorption properties of ZSM-5 crystals of
varying SiO2/A1203 ratios synthesized using
8 16 24
f (h) ~,n(X-ray-c rystallinity) TEPABr are shown in Table 6. All the samples
Figure 6 (a) Change of crystallinity of Na-ZSM-5 materials with
were highly crystalline (>95%). It may be noted
synthesis time as estimated by i.r. spectroscopy (curve 1 ) and X-ray that the amount of n-heptane adsorbed 1.30 x
diffraction (curve 2). (b) Relationship between the values of 10-3mol/g (SiOe/A1203 = 150), agrees with that
crystallinity evaluated from i,r. spectroscopy and X-ray diffraction
reported by Doelle et al. 17 for a sample of ZSM-5
(1.28 x 10 -3 mol/g, SiO2/A120 ~ -- 130) further
confirming the identity of our samples. While the
decrease in the adsorption of H20 and the constant
n-heptane adsorption correspond to general expec-
IOO tations, the decrease in the adsorption of cyclo-
hexane with increasing SIO2/A1203 ratios is
surprising, it is possible that while adsorption of
y_o~
7s //?~// n-heptane occurs in both the channels and at pore
interactions, cyclohexane, having a larger cross-
sectional area is adsorbed preferentially at pore-
~3 50 intersections, cyclohexane, having a larger cross-
g was observed that the catalytic activity for the
isomerization of xylenes (wherein the locus of
25 activity is mainly at the pore-intersections 2)
correlated with the amount of cyclohexane
adsorbed 21. No such correlation was found for
o . / f8 , / 24
.0_ /4 0 n-heptane adsorption. Further studies are in
t(h) progress to elucidate this point.
Figure7 Influence of alkalinity of the reaction mixture on the
kinetics of crystallization of Na-ZSM-5 zeolite. SiOJAI203 = 86;
433 K; curves 1 - 4 refer to OH/H20 (X103) values of 2.5, 0.83, Metastable phase transformation to c~-quartz
5.5 and 10.0, respectively
During our work involving both TPABr and
TEPABr, we had observed that under certa)n
X-ray crystallinity plots are sigmoid in nature
(Figure 6a), the lower values of crystallinity
Table 6 Influence of SiOJAI203 ratio on adsorption properties:
obtained by X-ray diffraction being due to its Na20/SiO 2 ~- 0.295; (TEPA)zO/SiO 2 = 0.051
inability to 'see' crystals smaller than about
5.0 nm z. The linear correlation between the two Adsorption (mmol g-1 dry zeolite)
values of crystallinity (Figure 6b) is also in accor-
SiOJAI203 OH-/H20 H20 C7H16 06H~2
dance with the above picture.
86 5.5 x 10 -3 5.4 1.32 0.56
T h e influence of alkalinity on the rates of nuclea- 150 4.8 x 10 -3 4.3 1.30 0.39
tion and crystallization of ZSM-5 zeolite is shown 200 4,5 x t 0 -3 3.8 1.32 0.38
300 4.2 x 10 _3 3.2 1.33 0.38
in Figure 7. In the range of concentrations of 800 3.7 x 10 -3 2.5 1.34 0.35
[OH] of interest, an increase in alkalinity increased

Z E O L I T E S , 1982, Vo/ 2, October 317

Studies in ZSM-S synthesis: S. B. Kulkarni et al.

conditions, (x-quartz is formed in significant CONCLUSION

quantities. The presence of ~-quartz was confirmed
(1) Synthesis of ZSM-5 zeolite using triethyl-n-
mainly by X-ray diffraction. (x-Quartz was also
propylammonium cations has been demonstrated.
identified to be present in the ZSM-5 zeolite
(2) The rate of both nucleation and growth of
sample of Chao et al. is from their published X-ray
ZSM-5 crystals are lower when TEPABr rather
diffraction diagram (Figure i of Ref. 15). The
than TPABr is used as the source of cations.
X-ray diffractogram of a sample containing both
(3) The amount of cyclohexane (but not n-
ZSM-5 and c~-quartz (70 : 30), prepared from a
heptane) adsorbed on the ZSM-5 zeolite (prepared
solution containing TEPABr, is shown in Figure
by the TEPABr route) decreases at increased
8a. The peaks at 20 = 26.6 and 20.9 (I/Io values
SIO2/A1203 ratios.
of 100 and 25, respectively) exactly match those (4) Under certain conditions, the ZSM-5 zeolite
for (x-quartz 22. The rate of formation of ~-quartz
(in both the TPABr and TEPABr systems) under-
from solutions containing TPABr and TEPABr is
goes phase transformation into (x-quartz.
illustrated in Figure 8b. The concentration of
(x-quartz in Figure 8b was estimated from a calibra-
tion graph (a plot of the area of (x-quartz peak at ACN2~OWLEDGEMENT
20 = 20.8 against wt.% (x-quartz) prepared using We thank members of the analytical and S1L
mixtures of (x-quartz and pure ZSM-5. groups of NCL for the help provided during this
study.

RE FERENCES
1 Barrer, R. M. and Denny, P. J. J. Chem. Soc. 1961,971
2 Barrer, R. M,, Denny, P. J. and Flanigen, E. M. US Pat.
3 306 922 (1967)
3 Kerr, G.T.J. Inorg. Chem. 1966,5,1537
4 Kerr, G. T. US Pat. 3 247 195 (1966)
5 Wadlinger, G. T., Rosinski, E. J. and Plank, C. J. US Pat.
3375205 (1968)
c 6 Union Carbide Corp. Br. Pat. 1 178186 (1970)
7 Acara, N. A. US Pat. 3414602 (1968)
8 Aiello, R. andBarrer, R . M . J . Chem. Soc. 1970, A, 1470
9 Rubin, M. K. Ger. Offen. 1 806 154 (1960)
10 Jenkins, E. E. US Pat. 3 578398 (1971)
11 Mobil Oil Corporation, Br. Pat. 1 117568 (1968)
34 30 z6 2'2 i; ~'4 ,b 12 Wadlinger, R. L., Kerr, G. T. and Rosinski, E. J. US Pat.
zo b 3 308069 (1967)
13 Mobil Oil Corporation, Neth. Pat. 7014807 (1971)
/ \ 7s:-s --.:. 14 Argauer, R. J. and Lendolt, G. R. US Pat. 3 702 886 (1972)
15 Chao, K. J., Tasi, T. C., Chen, M. S. and Wang, I.J. Chem.
/ o Soc. Faraday Trans. I 1981,77,547
(~ ~o ~ o 16 Erdem, A. andSand, L.B.J. CataL 1979,60,241
17 Doelle, H. J., Hearing, J., Riekert, L. and Marosi, L. J. Catal.
1981,71, 27
16 32 48 64 80 18 Jacobs, P. A., Bayer, H. K. and Valyon, J. Zeolites 1981,1,
/{h) 161
19 Chang, C. D. andSilvestri, A. J.J. CataL 1977,47, 249
Figure 8 Phasetransformation to e-quartz. (a) X-ray diffraction 20 Jacobs, P. A., Derouane, E. G. and Weitkamp, J. J. Chem. Soc.
of a sample containing Na-ZSM-5 zeolite and c~-quartz synthesized Chem. Comm. 1981, 12, 591
using TEPABr as organic cation. (b) Kinetics of crystallization of 21 Ratnasamy, P. and Kulkarni, S. B. Unpublished results
ZSM-5 zeolite and s-quartz; source of organic cation-TEPABr full 22 Hanawalt, J. D., Rin, H. W. and Frevel, L. K. Ind. Eng. Chem.
line, TPABr dotted line 1938, 10, 457

318 ZEOLITES, 1982, V o 1 2 , O c t o b e r