Pergamon

Materials Research Bulletin 35 (2000) 25152523

Cobalt spinel CoAl2O4 via sol-gel process: elaboration and surface properties
S. Chemlala, A. Larbotb,*, M. Persinb, J. Sarrazinb, M. Sghyara, M. Raqa
a

Laboratoire des Materiaux et Protection de lEnvironnement, Universite Sidi Mohamed Ben Abdellah, Faculte des Sciences Dhar Mehraz Fes, Morocco ` b Laboratoire des Materiaux et Procedes Membranaires, UMR 5635, CNRS, ENSCM, UMII, ENSCM, 8 rue de lEcole Normale, 34296 Montpellier Cedex 5, France (Refereed) Received 25 January 2000; accepted 11 April 2000

Abstract In this work the preparation of cobalt spinel CoAl2O4 is described. The technique of colloidal solution destabilization was used as the sol-gel process. The powder obtained from the dried gel was characterized by thermal analysis (thermogravimetric and differential), X-ray diffraction, infrared spectroscopy, and specic surface area measurement. Crystallization of CoAl2O4 spinels occurs at about 400C. The study of surface properties (surface charge and electrophoretic mobility) of the spinel powder red at 600C, in suspension in different electrolyte solutions (10 3 molar ionic strength), shows that the spinel material charge depends on the pH of the solution. The spinel sol was used for the preparation of membrane by the slip-casting method. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: A. Ceramics; A. Inorganic compounds; A. Oxides; B. Sol-gel chemistry; D. Surface properties

1. Introduction Spinel compounds have a general formula MY2O4, in which M is a divalent metal and Y is a trivalent one. Spinels are usually synthesized at high temperature from a mixture at solid state of the two oxide components [1]. Recently, CoAl2O4 has been prepared by other

* Corresponding author. E-mail address: larbot@cit.enscm.fr (A. Larbot).

0025-5408/00/$ see front matter 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 0 2 5 - 5 4 0 8 ( 0 0 ) 0 0 4 4 4 - X

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methods: coprecipitation [2], and sol-gel [3,4]. Cobalt spinel has been used for catalytic applications [2]. In the present work, cobalt spinel was synthesized by the sol-gel process in order to prepare ultraltration ceramic membranes. A membrane can be characterized not only by its pore diameter value, but also by its selectivity. In the case of pore diameters lower than 10 nm (these values correspond to the lowest range of ultraltration and to the range of nanoltration), electrostatic interactions are necessary for the retention of charged species. In order to understand the membrane selectivity, it is important to know the surface charge of the material; consequently, the surface properties of the material were studied. The stability of the sol and the colloid size are two important parameters for obtaining homogeneous membrane useful in ultraltration. In the present paper, we report on the preparation and the characterization of the spinel powder obtained by the colloidal sol-gel route, from a boehmite sol and an aqueous solution of cobalt chloride. The elaboration of ultraltration membrane is briey described.

2. Experimental The sols of CoAl2O4 were synthesized using the colloidal sol-gel process, from an alumina sol (0.5 M) obtained by peptization under magnetic stirring of boehmite (Condea pural SB) by nitric acid (1.5 M) in a water bath at 50C, and an aqueous solution (0.5 M) of cobalt chloride (CoCl2 6 H2O Prolabo). The latter solution was poured into the boehmite sol dropwise under magnetic stirring at room temperature. The sol obtained under these conditions is very stable if it is kept in a closed vessel. Powder was obtained by drying the sol in an oven at 100C. By ring at 600C, well-crystallized spinel was obtained.

3. Results and discussion 3.1. Characterization 3.1.1. Thermal analysis Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were carried out on the gel dried at 100C. The TGA curve (Setaram 1000) is reported in Fig. 1. After the elimination of residual water, the two weight losses at 120 and 160C correspond to the dehydration of CoCl2 2H2O. The last weight loss, which occurred at about 250C, was due to the decomposition of nitrates and cobalt chloride. The DTA curve (Netzsch DTA 404) shows three endothermic peaks at 143.1, 190.6, and 426.8C (Fig. 2). The rst two peaks correspond to the elimination of residual water and the dehydration of cobalt chloride. The latter peak is attributed to the decomposition of nitrate and CoCl2. 3.1.2. X-ray diffraction X-ray diffraction was performed on powders red at different temperatures, using Cu K radiation (INEL CPS-120) (Fig. 3). The diffraction peaks at 100 and 300C correspond to the

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Fig. 1. TGA curve for the dried gel.

cobalt chloride dihydrate (CoCl2 2H2O) (JPDC no. 76-1624). At room temperature, the prepared sol was very stable, and the cobalt chloride (CoCl2 2H2O) crystallized during drying. The crystallization of the spinel was observed at 400C. Indexing corresponds to a CoAl2O4 spinel phase (JCPDS no. 10-458). 3.1.3. Infrared spectroscopy The same powders were characterized by infrared spectroscopy (Nicolet 5 ZDX-FTIR). The powder spectra are presented in Fig. 4. The spectrum for powder red at 500C shows the disappearance of bands situated at 1068 and 1386 cm 1, which corresponds to the nitrato group and the ion NO3 , respectively [5].

Fig. 2. DTA curve for the dried gel.

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Fig. 3. X-ray patterns of CoAl2O4 spinel red at different temperatures.

3.1.4. Specic surface area measurements Specic surface area were measured by nitrogen adsorption desorption BET [6] (Micromeritics ASAP 2010). Table 1 reports the specic surface area values. It can be observed that specic surface area decreases with increasing ring temperature.

Fig. 4. Infrared spectra of the spinel powders red at different temperatures.

S. Chemlal et al. / Materials Research Bulletin 35 (2000) 25152523 Table 1 Specic surface area as a function of ring temperature Temperature (C) Specic surface area (m2/g) 400 156 600 86 800 65

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1000 29

3.1.5. Powder morphology The powders were observed by scanning electron microscopy. Fig. 5 shows the micrographs of two examples of granulometry, at 400 and 800C. These gures show that the particle size increases with ring temperature. Increasing particle size leads to the decrease of specic surface area (Table 1). 3.2. Study of surface properties All the characterizations were performed using powder red at 600C for 1 h. 3.2.1. Point zero charge (PZC) determination 3.2.1.1. Surface charge measurements In the presence of deionized water, the hydroxide groups MOH are formed by chemisorption of water molecules on oxide powder surfaces. The hydroxide groups can react as base or acid as a function of pH [7]: MOH MOH H 3O N MOH 2 OH N MO H 2O H 2O

Therefore, the surface of the oxide becomes positively charged in acidic media and negatively charged in base solutions. The study of surface charge density was performed on powders suspended in various electrolyte solutions (NaCl, Na2SO4, CaCl2, and CaSO4) at 10 3 M ionic strength. A

Fig. 5. SEM micrographs of powders red at 400 and 800C.

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Fig. 6. Variation of surface charge density vs. pH.

suspension of powder in the electrolyte solution (0.1 g/100 ml) was titrated using acid (HCl or H2SO4 0.1 N) and base (NaOH 0.1 N) solutions. Titration was followed by potentiometric measurements. The addition rate of the titrant was very low (0.8 ml/h) to ensure that equilibrium between the solid particles and the solution was established. The charge density ( o) is given by the equation q H
0 a

or q OH m S

96500

C/cm 2

in which q(H q(OH q(H q(H q(H )a )a )a )i )f m S q(H )i q(H )f , for acid titration q(OH )i q(OH )f , for base titration amount of H adsorbed by the powder amount of H total amount of H present in the solution, which can be obtained from direct measurement of pH. mass of powder specic surface area of powder

The curves of variation of the charge density vs. the pH for the different electrolyte solutions are given in Fig. 6. The experimental variation of o intercepts the pH axis at the

S. Chemlal et al. / Materials Research Bulletin 35 (2000) 25152523 Table 2 Point of zero charge (PZC) for CoAl2O4 powder in different electrolyte solutions Electrolyte PZC (surface charge) PZC (variation of pH) NaCl 6 6.5 CaCl2 5.6 6.5 Na2SO4 6.6 6.7

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CaSO4 6.5 6.3

point of zero charge (PZC). The PZC values of the spinel powder in suspension in different electrolyte solutions are gathered in Table 2. 3.2.1.2. pH measurements The powders were immersed in a xed pH (pHi) electrolyte solution (10 3 M ionic strength) under stirring. After about 20 h, the pH of equilibrium was measured (pHf). Fig. 7 shows the curves pHf as a function of pHi; the plateau observed on each curve gives the value of PZC (Table 2). The PZC values obtained from the two methods were in good agreement for all electrolytes except CaCl2.

Fig. 7. Evolution of pHf vs. pHi (pHf

pH at equilibrium, pHi

initial pH).

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Fig. 8. Electrophoretic mobility of CoAl2O4 powder vs. pH.

3.2.2. Isoelectric point (IEP) determination The electrophoretic mobility of particles in suspension in several salt solutions was measured at different pH values by means of a Coulter Delsa 440. The current intensity was xed at 0.1 mA, the frequency at 250 Hz, and the working temperature at 25C. The spinel colloids are positively or negatively charged according to the pH (Fig. 8). The pH value of the isoelectric point (IEP) is a function of the type of electrolyte (Table 3). In the presence of SO42 an important shift of the IEP value to the lowest pH values, due to a strong adsorption of sulphate ions, can be observed. A comparison between IEP values obtained in NaCl and CaCl2 indicates an adsorption of calcium ions stronger than that of sodium ions. 3.3. Membrane preparation The membrane was elaborated by the slip-casting method. The sol composed of 70% spinel sol and 30% polyvinyl-alcohol (PVA) (12 g PVA 88 g water) was deposited onto a microltration layer (an alumina tubular support) of pore diameter 200 nm. The deposition time was 30 sec. After drying at room temperature for 48 h, ring of the gel layer at 250C for one h to eliminate the organic binder was followed by ring for one h at 450C. The morphology of the calcined membrane was observed by scanning electron microscopy (Fig. 9). The surface is homogenous without any crack. The thickness was about 3 m.

4. Conclusions The sol-gel process described in this work leads to CoAl2O4 spinel. The study of surface properties shows that the powder is positively or negatively charged according to the pH of
Table 3 Values of isoelectric point of CoAl2A4 powder, red at 600C, in suspension in different electrolyte solutions Electrolyte IEP NaCl 8.4 Na2SO4 2.6 CaCl2 10.4 CaSO4 3.1

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Fig. 9. SEM micrograph of CoAl2O4 membrane red at 450C.

solution. The pH of the ltered solution may give the membrane prepared from it the ability to govern salt rejection. At a pH lower than that of the IEP, the strong interactions between cation and positive surface charge would lead to high rejection of the electrolyte, whereas at a pH closed to the IEP the rejection would decrease. Work is in progress to determine the selectivity of the membrane for the ltration of salt solutions.

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