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Colloids and Surfaces A: Physicochem. Eng.

Aspects 245 (2004) 3539

Inuence of the suspension composition on the electric eld and deposition rate during electrophoretic deposition
G. Ann , K. Vanmeensel, J. Vleugels , O. Van der Biest e
Department of Metallurgy and Materials Engineering (MTM), K.U.Leuven, Kasteelpark Arenberg 44, B-3001 Heverlee, Belgium Received 24 March 2004; accepted 7 July 2004 Available online 25 August 2004

Abstract Current and suspension conductivity measurements during electrophoretic deposition (EPD) of Al2 O3 powder from different organic suspensions revealed that the suspension composition determines whether a potential drop is generated at the deposition electrode or not. An electrical resistive layer was formed during electrophoretic deposition of Al2 O3 from ethanol with HNO3 , HCl, poly(ethylene)imine or CH3 COOH addition, whereas no potential drop was observed when depositing from a methylethylketone (MEK) + butylamine suspension. Additionally, a clear relationship was found between the yield of deposition and the magnitude of the potential drop at the deposition. 2004 Elsevier B.V. All rights reserved.
Keywords: Electrophoretic deposition; Non-aqueous suspensions; Conductivity; Al2 O3 ; Potential drop

1. Introduction Electrophoretic deposition consists of two processes, i.e. the movement of charged particles in a suspension in an electric eld between two electrodes (electrophoresis) and particle deposition on one of the electrodes or on a membrane (electro-coagulation). The driving force for this process is the electric eld between the two electrodes and therefore it is important to know the electric eld distribution between the electrodes. To predict the yield of deposition during electrophoretic deposition, the mass balance law of Hamaker [1] can be applied: dY = fcES dt (1)

takes into account that not all powder brought to the electrode is incorporated in the deposit (f = 1 or less). As one can see, the change in the electric eld strength, E, during deposition has to be known, which can be determined by solving an equivalent electrical scheme for the resistivity of the suspension and the deposit [2]. E can also be calculated from the relationship between the electric eld strength E, the current I owing through the cell, the suspension conductivity (S/m) and the electrode area S (m2 ): E= I S (2)

with Y is the yield (g), t the deposition time (s), the electrophoretic mobility (m2 V1 s1 ), E the electric eld strength (V/m), c the solids loading (g/m3 ) of the powder in suspension, S the electrode surface (m2 ), f is a factor which

In an electrochemical cell, it is well known that the applied potential, Va , is consumed in three steps: a potential drop at each electrode and an ohmic potential drop over the suspension. Moreover, during electrophoretic deposition, a deposit forms at one of the electrodes, and in principle, the ohmic drop over the deposit can differ from the ohmic drop over the suspension [3]: Va =
1 el + IRsus (d d1 ) + IRdep d1 + 2 el

(3)

Corresponding author. Tel.: +32 1632 1244; fax: +32 1632 1992. E-mail address: jozef.vleugels@mtm.kuleuven.ac.be (J. Vleugels).

i with el is the potential drop at electrode i (V), I the current owing through the cell (A), Rsus the specic resistance of the

0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.colsurfa.2004.07.001

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G. Ann et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 245 (2004) 3539 e

suspension ( /m), Rdep the specic resistance of the deposit ( /m), d1 the deposit thickness (m), d the distance between the electrodes (m). The resistivity of the deposit, which is formed on the electrode during EPD, and the potential drop at the electrodes has to be known. For electrodeposited polymer coatings, it is clear that the resistivity of the deposit on the electrode depends on the porosity of the deposit [4]. With inorganic deposits made by EPD, an open pore structure and a green density below 60% is almost always obtained [57]. According to Sarkar [8], the deposition yield of Al2 O3 from an ethanol + HCl solvent decreases during EPD due to the increase in deposit resistivity, whereas the resistivity of the deposit is only marginally higher when depositing from an ethanol + CH3 COOH system. Van der Biest and Vandeperre [3] found that depletion of charge carriers in a suspension of SiC in acetone with n-butylamine increases the resistance of the whole deposition cell, slowing down the EPD process. Koura et al. [9] contribute the fast decrease in current during the rst step of EPD of a suspensions of YBaCuO particles in acetone with I2 during a constant voltage experiment to the diffusion controlled electrode reaction. Put et al. [2,10] measured the resistance of wet Al2 O3 and ZrO2 deposits in acetone/n-butylamine suspensions proving that Al2 O3 and ZrO2 deposits have a similar specic resistivity as their corresponding suspensions. In this work, the inuence of the formation of an electrical resistive deposited layer on the deposition behaviour was investigated during electrophoretic deposition of Al2 O3 powder from different organic suspensions.

2. Experimental procedure The starting powder is commercially available -Al2 O3 powder (Baikowski grade SM8) with an average crystal and particle size of 0.6 m. The as-received powders were ball milled in ethanol with Y-TZP milling balls (Tosoh grade TZ3Y) in a multidirectional mixer (type Turbula) for 24 h to break up the hard agglomerates. After mixing, the ethanol is evaporated by means of a rotating evaporator and the powder is dried at 90 C for 24 h. Methylethylketone (MEK) (99%, Acros), n-butylamine (99.5%, Acros), ethanol (technical, Marchem), acetic acid (100% CH3 COOH, Merck), polyethyleneimine (PEI, MW = 10 000, Polysciences Inc.), HCl (37%, Fisher Chemicals) and HNO3 (100%, Acros) were used for suspension preparation. Suspension preparation is carried out by adding a certain amount of powder (100 g/l) to the solvents in a glass container. The suspensions are magnetically stirred for 60 min and subsequently ultrasonicated in an ultrasonic bath (Branson 2510) for 15 min. Afterwards, the suspensions are magnetically stirred again for 15 min. Electrophoretic deposition at constant voltage was performed with freshly prepared suspensions, using a F.U.G. (type MCN 1400-50) power supply. The set-up for the

electrophoretic deposition experiments is schematically presented in Fig. 1. The system is composed of a suspension ow-through deposition cell and a suspension circulation system driven by a peristaltic pump. The distance between the at disc-shaped stainless steel electrodes is 35 mm and the electrodes have a diameter of 37.5 mm. The volume of the deposition cell is 120 ml. The edges of the deposition electrode were shielded by a non-conductive cover, made from acetal. Homogeneous deposits were made by pumping a 180 ml suspension at 2.5 ml/s through the deposition cell for 2000 s. The initial powder load of the suspension was 100 g/l. During deposition, the cell current is automatically recorded [Onron, K3NX] each second, whereas the conductivity of the suspension is measured by a conductivity electrode (WTW, Cond Level 2) in the suspension circulating system outside the deposition cell to avoid interference from the applied electric eld in the cell. In this way, the relationship between the conductivity of the suspension and the current in the deposition cell can be determined. The measurement range of the conductivity electrode varies from 0 to 500 S/cm with an accuracy of 0.5%. After deposition, the deposits were dried, weighted and the green density was determined by the Archimedes method using lacquer (type Renwart Cevema) encapsulation. With the EPD-set-up currentconductivity measurements were performed with the supernatant of the suspensions. To obtain the supernatant, the suspensions were centrifuged (10,000 rpm, 30 min) using a lab centrifuge from Heraeus (Biofuge 17S). The electrophoretic mobility and the zeta potential of the specic suspensions were determined by means of an electroacoustic analyses (ESA 9800, Matec). The operational pH of the ethanol-based suspensions was measured by means of a pH meter (WTW, 315i). The suspension stability of the suspensions listed in Table 1, which were also used for the EPD experiments, was investigated by measuring the weight change of a cone suspended to a balance (Sartorius BP 221S) at a certain depth in an unstirred suspension as a function of time (Fig. 2). The slope of the obtained curves (timeweight change) was

Fig. 1. Schematic view of the EPD set-up.

G. Ann et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 245 (2004) 3539 e Table 1 Properties of the suspensions, with a powder loading of 100 g/l, used for electrophoretic deposition Suspension Ethanol + HCl Ethanol + HNO3 Ethanol + CH3 COOH Ethanol + PEI MEK + n-butylamine
a

37

Additives pHa = 7.0 pH = 7.0 pH = 7.4 0.7 wt.% PEI 10 vol.% BA

(mV) 65.04 63.35 54.10 33.57 15.52

(m2 V1 s1 ) 1.77E8 1.23E8 1.08E8 6.63E9 9.10E9

Conductivity ( S/cm) 11.73 9.03 6.18 3.33 31.2

Stability ratio 219 155 129 15 320

Operational pH, adjusted by the acid addition. Table 2 Deposition yield and green density of deposits Suspension Ethanol + HCl Ethanol + HNO3 Ethanol + PEI Ethanol + CH3 COOH MEK + n-butylamine Yield (g) 3.38 3.28 5.76 6.80 9.87 Green density (%) 53 51 51 54 55

Fig. 2. Weight change of a cone at a certain depth in an unstirred suspension of ethanol and MEK without addition of any charging agent and ethanolbased suspension with addition of HCl, HNO3 , CH3 COOH, and PEI and a MEKBA based suspension.

calculated over the 5000 s range. The slope of the Al2 O3 suspension without charging additives was divided by this slope to determine the stability ratio of the suspension concerned.

3. Results and discussion Al2 O3 suspensions based on ethanol with HCl, HNO3 , CH3 COOH or PEI addition and a MEK + n-butylamine suspension were investigated. The properties of these suspensions are summarised in Table 1. The highest absolute zeta potential values are reached with the ethanol suspensions stabilised with an acid: HCl, HNO3 and CH3 COOH, what is in agreement with the experimentally determined stability ratio of the suspensions. The electrophoretic mobility and stability ratio of the polyelectrolyte stabilised (PEI) ethanol suspension is lower than that of the electrostatic stabilised ethanol-based suspensions. Despite the lower mobility and zeta potential of alumina in the MEK based suspension compared to the polyelectrolyte stabilised ethanol suspension the stability ratio is higher. With the same suspensions, electrophoretic deposition experiments were performed in a ow-through cell, the yield and the relative green density of the obtained deposits are given in Table 2. The experiments were performed during 2000 s and the applied voltage was 175 V (50 V/cm). Anodic EPD was used for the MEK + n-butylamine suspensions, whereas cathodic EPD was used for the ethanol containing suspensions. All obtained deposits had a very smooth surface and did not crack during drying (Fig. 3). The thickness of the deposits

varies from 1.50 mm for the ethanol-based suspensions with HCl an HNO3 to a thickness of 4.17 mm for the MEK, BA based suspension. The relative green density of the deposits was comparable for the investigated suspensions ranging between 51 and 55%, indicating that the structure of the dry deposit is still very open and porous. Despite the higher electrophoretic mobility (Table 1), the yield of the EPD experiments from ethanol-based suspensions with HCl an HNO3 was the lowest of all investigated suspensions. The acetic acid electrostatically stabilised ethanol-based suspension had a higher yield than the PEI polyelectrolyte stabilised suspension. The highest yield however was obtained with the MEK + butylamine based suspension, despite the lowest zeta potential and electrophoretic mobility. The current and conductivity was logged during EPD and is given in Fig. 4(af). To compare the current and the conductivity of the different suspensions, the current and conductivity were re-scaled between 0 and 1. Subsequently, the conductivity was plotted against the current as presented in Fig. 5. For all suspensions, the conductivity decreased almost linearly with the deposition time, indicating that the amount of charge carrying species, involving the charged powder particles and non-adsorbed ions, in the suspension decreases. The evolution of the current as function of the time is dependent on the suspension composition. For the ethanolbased suspensions, the current decreases linearly with t1/2 . In case of the methylethylketone based suspension, however, the current decreases linearly with time. From Fig. 5, which shows the relationship between the current and conductivity during EPD, one can see a linear relationship between current and conductivity for the MEK + n-butylamine suspension. This indicates that the decrease in current is completely caused by the decrease in conductivity of the suspension and not by the creation of an electrical resistive layer at the electrode. Therefore, the electric eld with this suspension will not decrease as function of

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G. Ann et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 245 (2004) 3539 e

Fig. 3. Green Al2 O3 disk made by EPD in an ethanol + acetic acid suspension.

Fig. 4. Current (I) and conductivity () vs. time for ethanol-based suspensions with HCl (a), HNO3 (b), CH3 COOH (c) and PEI (d), a MEK + BA suspension (e) and the supernatant of the ethanolHNO3 suspension after centrifuging (f).

G. Ann et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 245 (2004) 3539 e

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Fig. 2f). The second assumption is also unlikely because the green density of the deposited layer for the suspensions, where no resistive layer is built up is for all suspensions of the same order of magnitude. The third source of a potential drop, derived by Koura et al. [9], gives a more plausible explanation. Especially if this is seen as a potential drop over the deposit as function of time. The experimental observations on different organic solvent systems also clearly illustrate that the electrophoretic deposition behaviour from one well-dened suspension should not be generalised to other solventadditive systems.
Fig. 5. The re-scaled conductivity (between 0 and 1) in function of the rescaled current (between 0 and 1) of ethanol with HCl, HNO3 , CH3 COOH or PEI and a MEK + n-butylamine suspension.

4. Conclusions During electrophoretic deposition, a potential drop can be created at the depositing electrode or over the deposit. The extend of this potential drop is determined by the solvent and charging agents. No potential drop was observed during anodic EPD of Al2 O3 from a MEK + n-butylamine suspension, whereas a signicant potential drop was present during cathodic deposition from ethanol-based suspensions with HCl, HNO3 , CH3 COOH or PEI addition. Although the electrophoretic mobility of the alumina powder is lower for the methylethylketone when compared to the ethanol-based suspensions, the deposition yield is higher due to the absence of a potential drop at the deposition electrode.

time during EPD (Fig. 6) and explains the high yield during deposition. For the ethanol-based suspensions, however, the current decreases faster than can be explained by the decrease in conductivity (Fig. 5), indicating that a potential drop exists at the depositing electrode (Fig. 6). This potential drop at the electrode slows down the deposition rate and explains the lower yield after 2000 s of EPD. The potential drop differs for the different additives and increases from CH3 COOH over PEI to HNO3 and HCl. This is also reected in the deposition yield, which is higher for the suspension with CH3 COOH than for PEI. The HCl and HNO3 suspensions show a very large potential drop during EPD, compared to the CH3 COOH and PEI suspensions, which explains their much lower deposition yield. These experimental observations allow to conclude that the potential drop at the electrode determines the deposition rate. The extent of the potential drop is determined by the suspension medium and the charging additives. Several sources of this potential drop were investigated: a potential drop due to polarisation of the electrodes as function of time, the deposited layer on the electrode acts as a resistant layer [11] and a diffusion controlled electrode reaction takes place at the electrode [9]. The rst assumption is very unlikely because no polarisation occurs as function of time when a voltage is applied over the supernatant of the ethanolHNO3 suspension (see

Acknowledgments This work was supported by the GROWTH program of the Commission of the European Communities under project contract no. G5RD-CT2000-00354, by the Fund for Scientic Research Flanders under project no. G.0180.02 and the Research Fund K.U.Leuven under project no. GOA/2005/08TBA.

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Fig. 6. The E-eld strength, calculated according to Eq. (2) as function of time for the ethanol with HCl, HNO3 , CH3 COOH or PEI and a MEK + n-butylamine suspensions.