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MiMeMat100(2007)173

MiMeMat100(2007)173

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Preparation of templated mesoporous silica membraneson macroporous
a
-alumina supports via direct coatingof thixotropic polymeric sols
V. Boffa, J.E. ten Elshof 
*
, D.H.A. Blank
Inorganic Materials Science, MESA
+
Institute for Nanotechnology and Faculty of Science and Technology, University of Twente,P.O. Box 217, 7500 AE Enschede, The Netherlands
Received 19 September 2006; received in revised form 20 October 2006; accepted 24 October 2006Available online 8 December 2006
Abstract
A simple method for depositing mesoporous silica films directly on macroporous
a
-alumina supports is reported. A polymeric silicasol was prepared by hydrolysis of tetraethylorthosilicate in acid propanol in presence of hexadecyltrimethylammonium bromide as tem-plate. The rheology of the sol was changed by a modified urea-based thixotropic agent, which was used in a concentration range between2% and 10% on volume. The dynamic viscosity of the sol was measured as a function of shear rate. The rheology modifier was found toincrease the viscosity of the sol and confer at the same time a thixotropic behavior to it. Long range order in the unmodified and modifiedmaterials was analyzed by XRD on powders after calcination at 500
°
C. It was found that the pore size increased with increasing con-centration of additive, while the degree of order decreased until eventually, at high concentrations, the ordered porous structure collapsedcompletely. The gradual pore size increase at lower concentration is thought to be caused by swelling of the surfactant micelles by therheology modifier.The modified sols were deposited via dip-coating on
a
-alumina disks. The morphology of the silica top layers was characterized bySEM. Pore size distributions and permeances of the prepared membranes were assessed by permporometry and single gas permeationmeasurements, respectively. The membranes had narrow pore size distributions, with an average diameter of about 2 nm. Permeabilitiesof H
2
, He, CH
4
and O
2
were compared. Hydrogen permeances up to 6
·
10
À
7
mol s
À
1
m
À
2
Pa
À
1
were measured at 473 K. The gas fluxacross the membrane follows a Knudsen-type mechanism, as shown by the permselectivities.
Ó
2006 Elsevier Inc. All rights reserved.
Keywords:
Mesoporous silica; Membranes; Thixotropy; Rheology modifier; Sol–gel
1. Introduction
Templated silica is one of the most attractive materialsfor those applications in which a high specific surface areaand a narrow pore size distribution in the mesoporousrange are required[1,2]. Among all the organic moleculesthat can be used to tailor the pore structure of the silicamatrix, surfactants are the most flexible ones. Silicon oxi-des with lamellar, hexagonal or cubic pore structure canbe obtained under different synthetic conditions by usingnon-ionic or cationic surfactants as templates[3,4]. Theinterest in this new class of materials grew when it was dis-covered that glasses with regular porous structure wereformed in the presence of quaternary ammonium surfac-tants (M41S materials)[5–7]. It was directly recognizedthat these materials may be applicable in a large numberof fields beside heterogeneous catalysis; for example asmembranes, sensors and in nano-electronics[8,9]. Thetwo main requirements for a membrane, for instance, arehigh selectivity and high permeate flux[10]. Thus, tem-plated glasses, which have a high porosity and a regularpore structure, are really attractive materials for the prep-aration of selective ceramic membranes[11].
1387-1811/$ - see front matter
Ó
2006 Elsevier Inc. All rights reserved.doi:10.1016/j.micromeso.2006.10.035
*
Corresponding author. Tel.: +31 53 4892695.
E-mail address:
j.e.tenelshof@utwente.nl(J.E. ten Elshof).
www.elsevier.com/locate/micromeso
Microporous and Mesoporous Materials 100 (2007) 173–182
 
In the first report in which a surfactant templated silicalayer was applied in a stacked membrane, it was applied asa spacer[12]between the mesoporous sub-layer and themicroporous top layer of a ceramic gas separation mem-brane. The spacer prevented penetration of the top layerinto the sub-layer during deposition. In later works tem-plated silica has also been used to replace the conventionalmesoporous intermediate layers[13–15]. However, theapplication of templated silica films directly on a macropo-rous support is not trivial. Indeed both sol synthesis andmembrane coating procedure are critical steps.In the first years after the discovery of ordered mesopor-ous oxides the focus was mainly on the preparation of pow-ders and thin films on dense substrates[5,16]. However, therecipes that were developed for these cases are often notsuitable for preparing membranes. Only a stable silicasol, with polymeric particles in the nanometer-size region,can yield a gas-selective membrane. Highly ordered M41Spowders can be prepared easily at basic pH via strongelectrostatic interaction between the cationic ammoniumsalt (S
+
) and the negatively charged silica particles (I
À
)[17,18]. The S
+
I
À
type interaction is commonly used formaking powders. However, in order to synthesize a stablepolymeric sol, a high degree of control over the condensa-tion reaction is required. At basic pH the rapid condensa-tion of silica particles would lead to fast precipitation orgelation. But when the pH is slightly below the silica iso-electric point at pH 2–2.5[19], the condensation rate is ata minimum and it is possible to obtain transparent sols thatare stable for many days even at room temperature. Never-theless, under such conditions the interaction between thecationic surfactant and the slightly positively charged silicaparticles (I
+
) is weaker and it is mediated by the surfactantcounterion (X
À
). Under such conditions, which are gener-ally described as S
+
X
À
I
+
interactions, it is more difficultto obtain an ordered structure[17]. Furthermore, coatingthe sol onto a porous support is far more difficult becauseof the perturbing effect of the substrate on the drying film.Substrate roughness and capillary forces exerted by thesubstrate pores can easily result in film cracking or distor-tion of the ordered mesostructure[20]. The coating of atemplated silica gel on a macroporous substrate such as
a
-alumina differs from the coating of traditional colloidalsols like boemite[21], titania[22]or zirconia[23]. In the lat- ter cases the sol is formed by dense particles that have a sizebetween 20 and 50 nm. Large quantities of binder such aspolyvinyl alcohol (PVA) are added to change the rheolog-ical properties of the sols and the viscoelastic properties of dried uncalcined films. The coating of polymeric silica solsonto
a
-alumina supports is complicated by the fact that thepolymeric silica sol is formed by particles that are far smal-ler (only a few nm[24]) than the pores of the support,which are often larger than 80–100 nm diameter. Further-more, binders can be used only in small concentrations inorder not to affect the supramolecular ordering of the sur-factant micelles. The necessity to work in a restricted rangeof synthetic conditions, the difficulty to coat a polymericsol onto a macroporous support, and the impossibility touse ordinary binders makes the coating of mesoporous sil-ica films on porous substrates a challenge.Templated silica membranes applied directly on
a
-alu-mina substrates were successfully made by Roy Chowdh-ury et al. via dip coating[13,14], and by Huang et al. viacasting[15]. Solvent transport through membranes pre-pared by Roy Chowdhury et al. showed behavior whichis typical for truly mesoporous systems. On the other hand,the XPS depth profiles implied the absence of a real silicalayer after calcination[13]. The concentration of alumin-ium at the surface of the membrane was larger than thatof silicon, which suggests that the membrane was consti-tuted by silica penetrated into the substrate[14,25].In recent years two solutions to this problem have beenproposed. The most common way for preparing templatedsilica membranes is via hydrothermal growth of the mate-rial on top of a substrate. The substrate is immersed in amixture containing surfactant, solvent and an organic orinorganic silica precursor[26,27]. Water and a base arepresent to promote the hydrolysis and condensation reac-tions that lead to the formation of silica. Membranesobtained with this procedure were gas selective and appli-cable in nanofiltration processes[28]. In spite of that, silicagrew both inside and on top of the support, forming aresistive thick layer. An alternative procedure has beenintroduced by Boissiere et al.[29]. A tubular support wasimpregnated by an aqueous solution of NaF. NaF cata-lyzes the condensation reaction of the silica precursor. Inthis way the growth of the selective silica layer wasrestricted to the area on top of the support. In order to
Nomenclature
g
dynamic viscosity [mPa
Æ
s]
s
torque [%]
u
cylinder velocity
R
gas constant [J
Æ
mol
À
1
Æ
K
À
1
]
temperature [K]
r
k
kelvin radius [nm]
t
t-layer thickness [nm]
mol
molar volume [m
3
Æ
mol
À
1
]
c
s
gas-solid interfacial tension [J
Æ
m
À
2
]
U
flux [mol
Æ
s
À
1
Æ
m
À
2
]
h
contact angle of the condensed phase on thepore wall
e
porosity
s
tortuosity
A
tot
total area [m
2
]
molecular mass [g
Æ
mol
À
1
]
174
V. Boffa et al. / Microporous and Mesoporous Materials 100 (2007) 173–182
 
be reproducible this procedure requires a high degree of control over all the parameters involved in the preparation.In this work, we propose a different approach to deposittemplated mesoporous silica membranes directly on mac-roporous supports. It involves tuning of the rheologicalproperties of the sol to render it a thixotropic behavior,so that it can be coated directly on a macroporous sub-strate. We modified the rheological properties of a poly-meric silica sol by adding BYK-420 (kindly provided byBYK-Chemie, Wesel, Germany), which consists of a mod-ified urea solution. BYK-420 is a commercial additive usedin aqueous coatings to improve anti-sagging properties oras anti-settling agent for pigments. This product is ableto increase the viscosity of a suspension, conferring thixot-ropy at the same time. The thixotropy inhibits penetrationinto the pores of the
a
-alumina substrate during the dryingstage of the silica film. This behavior can simplify the pro-cessing of polymeric sols in the preparation of silicamembranes.
2. Experimental part
 2.1. Sol synthesis
Aqueous nitric acid (0.05 N) was dropped under vigor-ous stirring in a conical flask containing a solution of tetraethylorthosilicate (TEOS, 98% purity, Aldrich), in1-propanol (analytical grade, Acros). After 5 min the tem-plating agent cetyltrimethylammonium bromide (CTAB,
P
99% purity, Aldrich) was added. The molar ratio of the final mixture was TEOS/CTAB/1-propanol/H
2
O/HNO
3
= 1:0.13:15:15.5:0.14. All reagents were mixedunder nitrogen atmosphere in order to avoid the hydrolysisof TEOS before the reaction started.The mixture was heated at boiling temperature for 2 hunder reflux; then it was allowed to cool down. The trans-parent sol was kept at 5
°
C for a few days until it was usedfor sample preparation.
 2.2. Thin film deposition and powder preparation
a
-Alumina disks were used as macroporous supports forfilm deposition. They were prepared by colloidal filtrationof 
a
-alumina powder (AKP30, Sumitomo, Tokyo, Japan)dispersed in acidic water, as described elsewhere[30]. Afterdrying at room temperature, the green supports werecalcined at 1100
°
C (heating/cooling rates of 2
°
C/min).Flat disks of 39 mm diameter and 2.0 mm thickness wereobtained after polishing. The final porosity of these sup-ports was about 30% and the average pore size was inthe range of 80–120 nm[31].Varying amounts of BYK-420 (BYK-Chemie, Wesel,Germany) were added to the aged silica sol and the mixturewas stirred for a few hours. The alumina macroporous sup-ports were then dip-coated in the solution under class-1000clean room conditions. The samples were dried at 40
°
C inair (60% relative humidity) for 3 h. The membranes werethen fired at 500
°
C for 3 h (heating/cooling rates of 0.5
°
C/min). After deposition of the first layer macroporesin the support could still be detected by permporometry inall samples, irrespective of BYK-420 concentration. Inorder to cover these defects a second coating layer wasapplied, followed by calcination.Powders were prepared by drying the same sols as usedfor thin films in plastic Petri-dishes.Table 1lists the differ-ent concentrations of additive used for preparing powdersand thin films. For the sake of simplicity we will refer to thesamples following the designations listed inTable 1.
 2.3. Characterization
The viscosity of the coating sols were measured by aBrookfield DV-II+ Programmable Viscometer (BrookfieldEngineering Laboratories, Middleboro, MA, USA). Theinstrument was calibrated using Brookfield fluid 5 (Brook-field Engineering Laboratories, Middleboro, MA, USA) asstandard. The viscosity of this fluid is 4.8 MPa at 25
°
C.The temperature was kept constant at 30
°
C by a thermo-static water bath. The viscosity was measured using a90 mm long cylinder with a diameter equal to 25 mm anda weight of 78.5 g. The cylinder was stirred in 25 ml of sam-ple contained in a metallic tube. Data were recorded withincreasing angular speed, ranging from 1.0 to 10.5 rad s
À
1
,followed by stepwise decreasing the speed to 1.0 rad s
À
1
.Alldataonpowdersandfilmsreportedinthispapercon-cern calcined samples. XRD patterns of powders wererecorded using a Philips SR5056 with Cu K
a
radiation.Nitrogen sorption measurements were performed at 77 Kon calcined silica, using a porosimeter (Micromeretics,ASAP 2400). Pore size distributions of templated silicamembranes were measured by permporometry using thetype of set-up described by Cao et al.[32,33]. In the perm-porometer the flux of oxygen across the membrane wasmeasured by a Varian 3300 gas chromatograph (Varian,Palo Alto, CA, USA). Scanning Electron Microscopy(SEM) images were taken on a LEO 1550 FEG. Singlegas permeation measurements were carried out in a dead-end mode permeation set-up[34]. The gas ow wasmeasured with a soap film flow meter. Hydrogen, helium,methane and oxygen permeances were measured on differ-ent samples at 200
°
C, with a pressure of 4 bar on the sideof the feed and atmospheric pressure on the retentate side.
Table 1Coating solutions (S) used in this work for the preparation of powders (
)and membranes (
)CoatingsolutionBYK-420volumefractionName of unsupportedsampleNumberof layersName of membraneS00 0.00 P00* *S02 0.02 P02 2 M02S06 0.06 P06 2 M06S10 0.10 P10 2 M10
*
No membranes were obtained without BYK-420.
V. Boffa et al. / Microporous and Mesoporous Materials 100 (2007) 173–182
175

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