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
-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,
99% purity, Aldrich) was added. The molar ratio of the ﬁnal mixture was TEOS/CTAB/1-propanol/H
= 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
-Alumina disks were used as macroporous supports forﬁlm deposition. They were prepared by colloidal ﬁltrationof
-alumina powder (AKP30, Sumitomo, Tokyo, Japan)dispersed in acidic water, as described elsewhere. 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.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.
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
,followed by stepwise decreasing the speed to 1.0 rad s
.Alldataonpowdersandﬁlmsreportedinthispapercon-cern calcined samples. XRD patterns of powders wererecorded using a Philips SR5056 with Cu K
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. The gas ﬂow 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