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Journal of Membrane Science, 86 (1994) 95-102


Elsevier Science B.V., Amsterdam

A microporous zirconia membrane prepared by the solgel process from zirconyl oxalate
J. Etienne, A. Larbot*, A. Julbe, C. Guizard and L. Cot
Luboratoire de Physicochimie des Materiaux (U.R.A. C.N.R.5 1312), Ecole Nationale Superieure de Chimie de Montpellier, 8 rue de LEcob Norma& 34053 Montpellier Ckder 01 (France)

(Received February 1,1993; accepted in revised form August 6,1993)

Abstract We have prepared a zirconia membrane by the sol-gel process, that is potentially active in the lowultrafiltration or high-nanofiltration range. The precursor is a dried gel available as a powder, which leads to a sol when added to water. Coatinge of tubular ceramic supports by slip-casting have been successfully performed. Characterization was made by scanning electron microscopy, nitrogen adsorptiondesorption and filtration of dextran. This zirconia membrane has pores of -4 nm diameter and also retention properties for dextran molecules of molecular weight higher than 10,000 daltons.
Key words: membrane; dextran; zirconia, alumina; oxalate; filtration; sol-gel

Introduction The interest in ceramic materials as membranes for filtration is now well-established [ 11. As the knowledge of parameters influencing the performance and the behaviour of such membranes (rejection, flux, fouling, etc. ) increases, new materials for new applications, low-cost and safe processes are still needed. The preparation of inorganic membranes by the sol-gel process, either colloidal or polymeric, has been widely investigated [ 2-51. Zirconia membranes can be prepared from colloidal sols, after precipitation and peptization of hydrated zirconia [5]. The polymeric way involves controlled polymerization of hydroxylated species from alkoxide metal solution. In both ways, a

To whom correspondence should be adressed.

sol has to be prepared in carefully controlled conditions before coating. We present in this work the preparation of a zirconia membrane by the sol-gel process, involving neither complicated treatments, nor highly toxic and expensive materials. The preparation and characterization of the zircony1 oxalate gel is described elsewhere [6]. That was the first stage of the search for new precursors of small and homogeneous zirconia particles, prepared by the sol-gel process and available as powder to be added to water. The second stage has been the preparation of a zirconia membrane from this precursor. One of the major results we report in this paper is that a zirconyl oxalate sol is suitable for ZrOz membrane preparation by the sol-gel process. To this end, we chose a support easily available, having a smooth surface free of heterogeneities, and small pores in order to reduce

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J. Etienne et al. /J. Membrane Sci. 86 (1994) 95-102

any infiltration of the sol when coating. y-Alumina appeared to be a good candidate despite its poor pH resistance. Additionally, we improved the performance of the y-alumina membrane infiltration, by depositing a thin zirconia layer on its top. Experimental Precursor preparation Zirconyl oxalate sol was prepared from ZrOC12*8Hz0 (Fluka) and H2C204*2Hz0 (Normapur) in aqueous solution. A volume V of 0.25 M H&,0, was added to a volume V/2 of 0.5 M ZrOC& at room temperature. After gentle stirring, a white sol was obtained. Particles in this sol are hydrated zirconyl oxalate (ZrO&O,) peptized by HCl (released as ZrOC12*8H20dissolves in water) [6]. This sol was heated gently at 30-40 C without stirring until a dry gel was obtained. During the drying treatment, the white sol evolved to an opaque sol in N 30 min. Gelation slowly occurred as we kept on evaporating the sol. The dried gel was finally ground to a powder, which lead to a sol when water was added. The cycle can be performed several times as long as the drying temperature is kept below 60C. If the drying is performed above 6OC, removal of extra HCl occurs and the dried gel loses the property of reverting instantaneously to a sol by adding water. Results are summarized in Scheme 1.
dried eel \ water I I\ f?mmskm \

Membrane preparation Membranes have been prepared by slip-casting [ 71. Tubular porous alumina supports provided by S.C.T. were used. The inner diameter of these tubes is 7 mm. The y-A&O, active layer of the support, exhibiting the smallest pore diameter, is on the inner part of the tube. Successive macroporous a-Al,O, layers on the outer part of the support provide good mechanical properties. The zirconia layer has been deposited onto the inner part of the tube which exhibits pores of N 5 nm diameter. A sol was prepared by adding zirconyl oxalate powder to distilled water. After 1 h stirring, the sol was filtered through a 0.22 pm Millipore membrane to remove dust and large agglomerates; an organic binder was then added, namely, poly (vinyl alcohol) (PVA) (Rhodoviol25/140, 12 wt% in water). After 2 h stirring and 1 h settling, the sol was ready for coating. The inner part of the dry tubular support (thoroughly washed in an ultrasonic bath) was coated by slip-casting with the sol described above. Preliminary tests had shown that the thickness of the zirconia layer obtained by a single coating and after firing treatment must be less than 0.2 pm, in order to obtain membranes: the thicker the membrane, the larger the number of defects per unit area. Therefore, low equivalent Zr02 concentrations in the sol are required. Decreasing the zirconia concentration in the sol by adding higher quantities of organic binder, apdrying 40C


wet gel

dried gel /

\ gelatio;tiLwater

organic binder A
Scheme 1.

J. Etienne et al. /J. Membrane Sci. 86 (1994) 95-102

TABLE 1 Preparation for slip-casting of tubular support Weight % Powder (Zro,) Distilled water PVA, 12 wt% 1.3-1.7 (0.67-0.77) 32-31.6 66.7


peared to be the best solution. Finally, the preparations leading to the best membranes are given in Table 1. The coating process [ 21 was tested on small tubes (3 cm length). One end was plugged and the ceramic tubular support was filled with the sol prepared as described in Table 1. The full tube was left vertically for 10 min (coating time) before emptying. The drying was performed for at least 12 h at room temperature. The layer was then fired at 450 C for 1 h in order to obtain a zirconia membrane. This process has been successfully applied to tubes of 15 cm length. The same characteristics of the zirconia layer were obtained. Characterization of zirconia membranes has been performed mainly by scanning electron microscopy (SEM) and nitrogen adsorptiondesorption. Characterization

monoclinic phase (Fig. 1) . In order to estimate the size of the colloids in the sol, light scattering analysis has been performed on a sol containing 0.7% equivalent ZrO, in water. The results are summarized in Table 2. The average colloid diameter in a 5 h aged sol is m 14 nm. Once calcined, the dried gel leads to a powder made of partially sintered zirconia particles. Voids between elementary particles define the porous properties of the material, which are believed to be relatively close to the membranes structure. The coating process does not greatly influence the morphology. The porous properties displayed by the powder (fired for 1 h at 450 oC ) have been investigated by nitrogen adsorption-desorption. The isotherm shape as well as the hysteresis (Fig. 2) are characteristic of a porous structure created by partially sintered spherical particles [ 81. The pore diameter calculated by the Horwath-Kawazohe analysis from the desorption process is N 4 nm (Fig. 3). The BET surface area equals 132 m/g.

Membrane characterization
Crack-free membranes have been obtainedon the alumina support. By single and double coating (Table 3)) we managed to change the thickness of the zirconia layer much more easily than by varying the coating time (from 5 to 30 min) . Moreover, we previously showed that repeating the firing treatment (necessary if multiple coatings are performed) did not change dramatically the crystalline phase content of the materials (Fig. 1). Photo 1 shows a double coating of the zirconia layer deposited onto a y-alumina membrane, observed by direct and back scattered electron image on SEM texture. A double coating is preferred to facilitate the observation. By high magnification (100,000 x ) we can observe a difference in texture between alumina and zirconia (Photo 2). We could not discriminate by nitrogen adsorption-desorption, because the

Precursor characterization
The dried gel was calcined from 20 to 900 C (heating rate 300 oC/h ) . The weight loss shows 2 decomposition steps at 150 and 350C [6]. The powder (dried gel) contains N 46% equivalent zirconia by weight. At 450 C, the temperature at which the membrane was fired, the weight loss is N 98% of the total loss. X-ray diffraction analysis on powders fired at 450 C for 30 and 160 min proved that the zirconia structure is tetragonal with a tiny amount of a


J. Etienne et al. /J. Membrane Sci. 86 (1994) 95-102











Fig. 1. X-ray diffraction analysis performed on the gel fiid for (a) 30 and (b) 180 min at 450C.

TABLE 2 Colloid diameter versus age of zirconyl oxalate sol

Time (h)

Colloid diameter (nm) Minimal Average 14 17 Maximal 20 25

5 120

10 10

pore diameter the alumina support was found of between 3 and 5 nm, which overlaps the zirconia range. Besides, the membrane thickness and therefore the quantity of zirconia material is negligible compared to the y-AIPOslayer.

Filtration and discussion Cross-flow filtrations (Fig. 4) have been performed on y-A1203 membranes (5 nm pore di-

ameter support) and on 0.15 mm thick ZrO, membranes (deposited by single coating onto y-AIPOssupport previously described) of 11 cm length. After stabilization, the fluxes (measured at 10 bars, 19C with distilled water) were almost identical (29 + 2 1 h-l me2) (Fig. 5). While the Zr02 membrane exhibits pore diameters smaller than Y-A1203, its thickness (0.15 pm) does not greatly influence the solvent permeability of the whole system, ruled by the pore diameter and thickness (3 pm) of the y-A1203 membrane. Nevertheless, differences in performance can be pointed out if filtration of macromolecules is performed. Filtrations of solutions of dextran (provided by Fluka ) of various molecular weight (MW 70,000 and 9,000) have then been performed. These chemicals present heterogeneously dispersed MW, therefore retention measurement for various MW can be done in a single experiment. The true MW range inves-

J. Etienne et al. /J. Membrane Sci. 86 (1994) 95-102








0.6 ,

41.7 (P/Pa)




Fig. 2. Plot of nitrogen adsorption-deeorption isotherm performed on zirconia powder obtained after calcination of the dried gel for 1 h at 450C. (*) Desorption, ( + ) adsorption.

0.6Cl 0.55 0.50 0.45

.._...... T I-1....;........ ....

I: Ij


.. . .. . . .. . . . .

1 ..;




\ I

0.40 cl. 35




Fig. 3. Deeorption pore volume plot of zirconia powder.

tigated was from 100,000 daltons down to 6,000 daltons in the conditions previously described. Their chemical nature (polysaccharide) makes it unlikely that there is adsorption onto the membrane at neutral pH.

Solutions of 0.5 g/l of each dextran have been used. When a mixture of dextran 70,000 and 9,000 is filtered, we observe a drop in flux compared to pure solvent filtration (water). After stabilization, the flux through zirconia on y-al-

100 TABLE 3 Thickness of zirconia layer obtained onto 5 nm diameter support Coating number Thickness (am) 1 0.1-0.3 2 0.4-0.6

J. Etienne et al. /J. Membrane Sci. 86 (1994) 95-102

drainpipe -w



thermostated -tank

Flig. 4. Diagram of the filtration loop; the nitrogen cylinder allows the user to work under a given pressure, the circulation speed inside the tube is set to 2.5 m/s by the pump, the tank containing the feed solution is thermostated at 19C.

Photo 1. Cross section of the ZrO2 layer (double coating) deposited on y-AleO membrane seen by scanning electron microscopy: left-hand side, direct diffusion; right-hand side, back scattered electron image emphasizing the difference in chemical nature.


Photo 2. slight difference in texture can be observed from A y-A&O3 to ZrOx membrane. Magnification, 100,000 X .

umina was 142 1 1 h- mm2 compared to the flux through y-alumina that was 4 2 11 h- mm2 (Fig. 5). Retentions measured by gel permeation chromatography (GPC ) at various times of filtration (Fig. 6) proved that the sieving ef-



60 Time

80 (min)




Fig. 5. Filtrations of distilled water and dextran solutions were performed through y-AlaO membrane [ (*) water, (0) dextran] and ZrOz membrane [(m) water, (+) dextran]; the results are presented as fluxes versus time.

J. Etienne et al. /J. Membrane Sci. 86 (1994) 95-102


4;6 log(Molecular Weight)




Fig. 6. Filtration of a mixture of dextran 9,000 and 70,000 through y-A&O3 and ZrOz membrane; retention were measured by GPC after various times of filtration. y-A&O3 membrane [ (0) 37 min, (m) 64 min], ZrOz membrane [ (+) 35 min, (*) 124 min].

feet of ZrOz acts at a lower MW than for yA1203. Even at high MW, retention did not reach 100% probably because of the linear nature of the dextran molecules [ 91. Indeed, it is possible to calculate a particle diameter for dextran in solution as a function of their MW [lo] but the conformation of the molecules is probably subsequently changed as the conditions (such as pressure) are changed. Furthermore, we observed that retention is highly dependent on time. The drop in flux for ZrO, membrane, observed when a dextran solution is filtered, is believed to be due to concentration polarization and formation of a viscous layer. Indeed, if we replace the dextran solution by distilled water, the solvent flux measured after a few hours filtration returned close to the initial water flux value. The dramatic drop observed in the case of y-A1203 is more likely due to fouling. Indeed, filtration with distilled water is not sufficient to recover the initial water flux and a calcina-

tion is necessary to remove organic substances responsible for fouling. After a thermal treatment at 299 C, initial water flux was measured. This contrast between ZrOz and y-A1203 points to the fact that the zirconia layer is more able to retain macromolecules because of its smaller pore diameter. The y-A1203 is more permeable to dextran so the dextran tends to block the pores of the membrane, increasing the sieving effect with time, but also decreasing the flux and causing fouling. The conclusions of the first part of this work are promising, since a microporous ZrO, membrane was prepared from a zirconyl oxalate sol and also because the separation properties of the y-A1203 membrane were improved after coating with this ZrO, layer. Unfortunately, the better pH resistance of ZrOz is useless if the membrane is deposited onto y-A1203. Besides, the porous properties of both y-Al,O, and ZrOz membranes are much too close. The next step of this work is finding a support suitable for coating, having a good pH resistance and poor separation properties compared to the zirconia layer. To this end, we have coated by slip-casting another tubular porous alumina support (provided by S.C.T.). Again, the inner diameter of these tubes is 7 mm but the cw-Alz03active layer of the support at the inner part of the tube has a pore diameter of - 200 nm. Some success was achieved with viscous sols and multiple coatings. These results will be reported in a future paper. Conclusion A few years ago, a new kind of sol-gel precursor for zirconia was prepared, namely, zircony1 oxalate gel. This precursor has now been successfully used for membrane preparation by the sol-gel process. As long as the thickness of the zirconia membrane does not exceed a few tenth of microns, crack-free coatings are obtained. This membrane exhibits interesting


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Sci. 86 (1994) 95-102

properties and especially low pore diameters, estimated to be -4 nm. The performance in dextran filtration of a y-alumina membrane (of almost identical pore diameter) was improved when a thin zirconia layer was deposited on the y-alumina membrane. Attempts to deposit this new membrane on supports of much larger pore diameter (50 times as large as the zirconia pore diameter) and with a better pH resistance are underway. References
H.P. Hsieh, P.K.T. Liu and T.R. Dillman, Microporous ceramic membranes, Polym. J., 23 (1991) 407. A. Larbot, J-P. Fabre, C. Guizard and L. Cot, Inorganic membranes obtained by sol-gel techniques, J. Membrane Sci., 39 (1988) 203. A. Larbot, A. Julbe, C. Guixard and L. Cot, Silica membranes by the sol-gel process, J. Membrane Sci., 44 (1989) 289.


A. Larbot, A. Julbe, J. Random, C. Guizard and L. Cot, Sol-gel and inorganic membranes, in L. Cot and J. Charpin (Eds.), Inorganic Membranes, ICIM89, Montpellier, 1989, p. 39. A. Larbot, J-P. Fabre, C. Guizard and L. Cot, New inorganic ultrafiltration membranes: titania and zirconia membranes, J. Am. Ceram. Sot., 72 (1989) 357. J. Etienne, A. Larbot, C. Guizard, L. Cot and J-A. Alary, Preparation and characterization of a xirconyl oxalate gel, J. Non-Cryst. Solids, 125 (1990) 224. D.S. Adcock and I.C. McDowall, The mechanism of filter pressing and slip casting, J. Am. Ceram. Sot., 40 (1957) 355. J.H. De Boer, in D.H. Everett (Ed.), The Structure and Properties of Porous Materials, Butterworths, London, 1958, p. 68. R.W. Baker and H. Strathman, Ultrafiltration of macromolecular solutions with high-flux membranes, J. Appl. Polym. Sci., 14 (1970) 1197. M.N. Sarbolouki, A general diagram for estimating pore size of ultrafiltration and reverse osmosis membranes, Sep. Sci. Technol., 17 (1982) 381.