Journal

J. Am. Ceram. Soc., 91 [10] 31543159 (2008) DOI: 10.1111/j.1551-2916.2008.02591.x r 2008 The American Ceramic Society

Bubble-Free Aqueous Electrophoretic Deposition (EPD) by PulsePotential Application

Laxmidhar Besra, Tetsuo Uchikoshi,w Tohru S. Suzuki,* Yoshio Sakka*
Nano Ceramics Center, Fine Particle Processing Group (WPI Center Initiative for Materials Nanoarchitechtronics), National Institute for Materials Science (NIMS), Tsukuba, Ibaraki 305-0047, Japan

A novel method based on the application of a square-wave pulse potential of 50% duty cycle has been demonstrated to obtain dense bubble-free deposits of alumina by constant voltage electrophoretic deposition (EPD) from an aqueous suspension. Application of continuous dc voltage invariably resulted in the incorporation of bubbles in the deposits. Bubbles in the deposit decreased progressively with decrease in the size of pulse width during the pulse potential EPD. A unique and narrow band of pulse width exists for each voltage within which a bubble-free deposit is obtained. The band is wider at low applied voltages than at higher voltages. Such bands of pulse width were found to be independent of substrate material and occurred at the same range for stainless steel and nickel substrates, suggesting that the process may be generic and applicable to any conductive substrate. The green density of deposits obtained by pulse EPD has been found to be the same as those obtained by continuous dc voltage EPD. The cathodic pulse EPD produced uniform and homogeneous deposits and was more convenient and amenable to better control than anodic pulse EPD.

result of lower dissociating power, much higher eld strengths can be applied because the problems of electrolytic gas evolution, joule heating, and electrochemical attack of the electrodes are greatly reduced or nonexistent in organic liquids. The preference of organic liquids is also due to their higher density, good chemical stability, and low conductivity. But the use of aqueous systems has important advantages because they need much lower voltage to be applied and the environmental problems associated with organics are avoided.8 Obviously, the use of water also implies advantages such as higher temperature control during the process and faster kinetics, in addition to important health benets, benign environment, and low cost.911 These advantages have promoted interest to develop waterbased EPD to process technical ceramics.1214 The water-based suspension however causes a number of problems in electrophoretic forming.15 First and foremost, the electrolysis of water starts to occur at very low voltage, and gas evolution at the electrodes is inevitable at eld strengths high enough to enable reasonable kinetics of deposition during EPD. Hydrogen and oxygen gases are evolved at the cathode and anode, respectively, in accordance with the following decomposition reactions: Anode : 4OH aq ! O2 g 2H2 Ol 4e Cathode : 4H2 Ol 4e ! 2H2 g 4OH aq The overall cell reaction is 2H2 Ol ! 2H2 g O2 g In the above reactions, the volume of H2 gas produced is twice the volume of O2 gas. The bubbles generated at the electrode surface disturb the electrophoresis of the particles and suppress their deposition. Moreover, the bubbles also get entrapped within the deposit, leading to the formation of a porous deposit. To date, the challenge for aqueous EPD suspension is to inhibit the water electrolysis that interferes with the deposit layer. Several approaches have been investigated in the literature. The simplest method is to conduct EPD experiments at voltages lower than the decomposition voltage of water (1.23 V at 251C), but the deposition rate is negligible and not practical. Ryan and colleagues16,17 investigated the use of porous mold to separate and suppress bubble contamination in the deposit but found it to be ineffective. Clasen18,19 was successful in obtaining bubble-free deposits on a microporous membrane placed in front of the electrode, but the green density of the deposit was comparably low and high shrinkage (up to 30%) occurs during drying and sintering. Other studies have involved anodic deposition of the negatively charged particles on easily oxidizable anodes such as Zn, but the drawback of anodic deposition is the release of metal cations from the anodic material into the suspension, which contaminates the deposit.20,21 Winkle22 suggested a method for eliminating or reducing defects in polymeric lms deposited at the cathode by electrodeposition. The method involves decreasing the evolution of hydrogen gas

I. Introduction
deposition (EPD), a colloidal processing technique, has recently gained considerable interest in traditional ceramics as well as in a wide range of novel applications in advanced ceramic materials and coatings to fabricate thin lms, multilayered composites, functionally graded materials, hybrid materials, micropatterned colloidal assemblies, and nanotechnology.16 In this method, the powder materials dispersed in a liquid medium, on application of certain electrical potential, are attracted and migrate toward the oppositely charged electrode on which they eventually get deposited, forming a relatively dense and homogeneously compact lm. The major advantages and attractiveness of EPD is its simple apparatus, short formation time, little restriction in the shape of substrate, suitability for mass production, and no requirement for binder burnout as the green coating contains few or no organics. Compared with other advanced ceramic processing techniques, the EPD process is very versatile because it can be modied easily for specic applications. In particular, despite being a wet process, EPD offers easy control of the thickness and morphology of a deposited lm through simple adjustment of the applied potential and deposition time. In general, organic liquids are more popularly used as the suspending medium in EPD.7 While the generally low dielectric constants of organic liquids limit the charge on the particles as a
LECTROPHORETIC

W. Leecontributing editor

Manuscript No. 24334. Received February 19, 2008; approved June 2, 2008. *Member, The American Ceramic Society. This study was supported in part by the Grant-in Aid for Scientic Research of the JSPS and by World Premier International Research Center Initiative (WPI) on Materials Nanoarchitechtronics, MEXT, Japan. w Author to whom correspondence should be addressed. e-mail: uchikoshi.tetsuo@ nims.go.jp

3154

October 2008

EPD by Pulse-Potential Application

Ton V

3155

at the cathode by adding a compound to the polymer emulsion solution. This compound is reduced by the hydrogen produced at the cathode during the electrodeposition. The hydrogen reacts with this nongaseous compound rather than becoming hydrogen gas and forms bubbles, which leads to pinhole defects. Wang et al.23 designed an electrochemical apparatus that includes a physical barrier that prevents any trapped gas or gas generated during processing from residing in areas that can cause defects on the substrate. The apparatus contains two adjacent chambers and two separate electrolyte-containing uids separated by a membrane that prevents the gas from being transferred into the opposing chamber. The method is however complicated and expensive. Sakurada et al.24 obtained bubblefree deposits of zirconia on anodic substrates of palladium or stainless steel by adding hydroquinone (HQ) to the alkaline aqueous suspension during EPD. The oxygen produced by electrolysis of water during EPD was believed to be consumed by the chemical oxidation of HQ to quinone at high pH in alkaline solution, enabling a bubble-free deposit on the anode substrate. Our recent studies have shown that the deposition on palladium cathodic substrate can produce bubble-free deposits with high density because palladium readily absorbs the hydrogen gas generated at the cathode by electrolysis of water.11,2527 We present here a novel method based on the application of pulse voltage for obtaining dense and bubble-free deposits by EPD from aqueous suspensions. The application of pulse current (PC) is not new and has been used extensively for electrodeposition of metals from their inorganic salt solutions.2834 It has been recognized that application of PC in a specic pulse condition permits higher current densities than the limiting direct current density, thus enabling deposits of ne-grained microstructure.35,36 But to the best of our knowledge, the use of pulse voltage has not been investigated for EPD of powder in aqueous suspension. Although the basic techniques involved in electrophoretic and electrolytic deposition are similar, the associated mechanisms of deposition are uniquely different. Hence, it is worthwhile to investigate the application of pulse voltage on EPD. With this background, the present study was aimed at demonstrating the applicability of pulse voltage on EPD using an aqueous alumina suspension.

Toff

Fig. 2. Constant voltage pulse of 50% duty cycle.

II. Experimental Procedure

Alumina powder (Sumitomo AKP-50, average particle size of 0.20 mm) was dispersed in ultrapure distilled water by ultrasonication at 160 kW for 10 min to break up the agglomerates. Nitric acid and sodium hydroxide were used for adjusting the pH of the suspension. The z potential of the suspension was measured by a laser electrophoresis z-potential analyzer (LEZA-600, Otsuka Electronics Co., Osaka, Japan). Figure 1 presents the z potential of alumina suspension as a function of pH. The isoelectric point (IEP) of alumina powder is at pH 7.9. The alumina powder surface is positively charged at a pH below 7.9 and is negatively charged at a pH above 7.9.

EPD experiments were carried out on stainless steel (316 L) plates of 2 cm 5 cm 0.4 mm dimension, hung from the electrode holders into the suspension in a glass beaker. A stainless steel plate of the same dimension, hung parallel and facing the deposition electrode at a distance of 2 cm, formed the counterelectrode. Deposition was carried out on an area of 2 cm 2 cm. Pulse EPD was conducted at constant voltage mode by application of a series of pulses of dc voltage of equal amplitude and duration in the same direction, separated by periods of zero voltage, using a system source meter (Model 2611, Keithley Instruments Inc. Cleveland, Ohio). A simple square-wave pulse as shown in Fig. 2 was used. The duty cycle (DC) of the pulse [i.e., DC 5 Ton/(Ton1Toff)] was set constant at a xed value of 50%. The RC charging time (the response time of the circuit when a step voltage or signal is applied) of the source meter is o100 ms. The height of the pulse in Fig. 2 represents the magnitude of the applied potential. Ton (also called the pulse width) represents the portion of the cycle for which the voltage is ON, and Toff is the portion of the cycle for which the voltage is OFF. By changing Ton and Toff we could change the frequency of pulse application at constant voltage and DC. Unless and otherwise mentioned, deposition was carried out for a total pulse voltage ON time (Ton) of 3 min. It must be noted that the actual time of experiment was much more than 3 min and it increased with decrease in pulse width. The obtained deposits were dried overnight in air at room temperature and weighed together with the substrates to determine the deposit weight. After drying, the deposits were peeled off the substrate surface and their thickness was measured with a digital micrometer caliper. The green densities were measured by the Archimedes method using kerosene as the liquid. The deposit quality was examined macroscopically by optical photographs recorded using a stereomicroscope.

III. Results and Discussion (1) EPD by Continuous dc Voltage Deposition characteristics of the alumina suspension under a continuous dc voltage were determined rst, because they formed the reference against which the subsequent pulse EPD results were compared. Figure 3 presents the deposited weight and density of deposits on stainless steel as a function of pH at a continuous dc voltage of 20 V applied for 3 min to 5 vol% alumina suspension. It must be noted that because the IEP of alumina is at a pH value of 7.9, the deposits were obtained at the cathode below this pH and at the anode at higher pH. It is evident from Fig. 3 that the deposited amount increased as the pH was increased from 3 to 7.5, but with a decrease in adhesiveness to the substrate. Stronger adhesion to substrate was observed at pH values away from the IEP for both cathodic and anodic EPD. At pH values very near the IEP (as shown by the hatched area in Fig. 3), thick deposits formed under the suspension, but their adhesion to the substrate was very weak and fell off when taken out from the suspension. This may be because of spontaneous occulation of the particles near the IEP. It is well known that in the absence of electrostatic repulsive forces near the IEP, the van der Waals attractive forces between the particles are strong. The gravity effect of the aggregate thus formed at the electrode is perhaps higher than the electrophoretic effect because of the

Fig. 1. z potential of alumina as a function of pH.

3156

Journal of the American Ceramic SocietyBesra et al.

Vol. 91, No. 10

Fig. 3. Yield and relative green density of alumina deposited on stainless steel as a function of pH by continuous dc voltage electrophoretic deposition (Suspension: 5 vol%; interelectrode distance: 20 mm; deposition area: 20 mm 20 mm; applied potential: 20 V; deposition time: 3 min).

small magnitude of z potential near the IEP. The green density of the deposit, on the other hand, was found to be high at pH values away from the IEP, which decreases and tends to reach a minimum near the IEP. This is expected because the particles are well dispersed away from the IEP because of electrostatic repulsion on account of high z potential. Hence, they form deposits of well-packed compacts by electrophoresis compared with that near the IEP. It was also observed during the investigation that more bubbles are formed in the deposit away from the IEP. The number of bubbles in the deposits was found to decrease as the pH approached IEP.

(2) EPD by Pulse Voltage Figure 4 presents the deposition characteristics of alumina by cathodic pulse EPD at pH values 4.5 and 6.0. The pulse width of 180 s shown in Fig. 4 is equivalent to continuous dc voltage applied for 3 min. It is evident from Fig. 4 that the amount deposited by continuous dc voltage is highest for each pH investigated. Application of pulse voltage invariably decreases the deposited amount. The deposited amount was found to decrease

Fig. 4. Deposit yield as a function of pulse width on stainless steel substrate (Suspension: 5 vol %, pH 4.5; applied potential: 20 V; interelectrode distance: 20 mm; deposition area: 20 mm 20 mm). A pulse width of 180 s is equivalent to continuous dc voltage application for 3 min.

with decrease in pulse width. This is contrary to the observation in pulse plating of metals from their salt solution in which a higher deposit amount has been reported by pulsing compared with continuous dc plating.2931 It has been advocated that the relaxation period in pulse plating enables a larger current to be applied during the transient period. Further, the population of adatoms on the surface during pulse deposition is higher due to the increased nucleation rate, resulting in the deposition of lms with higher thickness. This is possible during deposition of metals or alloys because the nucleation sites are progressively formed during the deposition on the electrically conductive deposit surface. On the other hand, the number of sites for deposition on the substrate surface during EPD of ceramic particles from suspension is xed and diminishes as deposition progresses. Figure 5 shows the surface photographs of deposits obtained by a total pulse voltage ON time (Ton) of 3 min for different pulse widths to 5 vol% alumina suspension maintained at pH 4.5. Deposits obtained by continuous dc voltage EPD showed the presence of a large amount of bubbles on both stainless steel and nickel substrates at all applied voltages. The amount of bubbles on the deposit decreased on application of pulse potential for each of the cases. In general, more bubbles are found on deposits formed at high pulse widths than those formed at low pulse widths. There seems to exist a critical pulse width for each applied potential, below which the deposit is free from any macrobubbles. It should be noted that the present investigation was aimed solely at studying the inuence of pulse voltage application on controlling bubbles during EPD. Because we did not use any additives such as dispersants or binders, the samples exhibited cracks on drying. The inuence of additives on pulse EPD will be reported in subsequent communications. A series of experiments were conducted at different pulse widths at close ranges for each applied voltage to determine the range within which macroscopically bubble-free deposits are obtained. Figure 6 presents a comprehensive plot of such a range of pulse widths for each applied voltage for 5 vol% alumina deposited on steel substrates at pH 4.5. For each applied voltage, it indicates the existence of a window in the plot with a lower limit, below which deposition does not occur. There also exists an upper threshold limit of pulse width, above which deposits invariably contained bubbles. Homogeneous and bubblefree deposits are obtained within this window of pulse width. The lower limit of pulse width for 20 V applied potential is 0.015 s and the upper limit is 0.02 s for both stainless steel and nickel substrate. Such a window of pulse width was found to be broader at low voltages compared with the very narrow pulse width at higher applied voltages. Hence, it is very critical to set the pulse width carefully, especially at high voltages. It is much easier to control bubble suppression at low voltages because of the broader window of pulse width. But because the deposit yield is lower at low voltages, optimization is necessary depending on the application. Experiments were also conducted at pH values higher than the i.e.p of pH 7.9 at which the negatively charged alumina particles deposited on the anode (i.e., anodic pulse EPD). Because the volume of oxygen gas evolved at the anode is half the hydrogen gas evolution at the cathode, a better suppression of bubbles in the deposit was expected by anodic pulse EPD. On the contrary, the quality of deposit in terms of homogeneity and uniformity was apparently found to be better for cathodic pulse EPD than for anodic pulse EPD. The reason for such a phenomenon is not known at present and warrants further investigation. A probable reason for the formation of inhomogeneous deposits with more bubbles for anodic deposition compared with the cathodic ones may be explained on the basis of the differential solubility of hydrogen and oxygen in water. The solubility of hydrogen in water at 251C and 1 bar pressure is about 1617.6 mg/L whereas that of oxygen is only about 43.3 mg/L.37,38 Therefore, the hydrogen gases might be dissolved and/or diffused away more easily from the cathode surface compared with dissolution and diffusion of oxygen from the anode. This could result in a high residence time of oxygen

October 2008
(a)

EPD by Pulse-Potential Application

3157

1 mm

1 mm

1 mm

1 mm

1 mm

1 mm

Continuous DC voltage (b)

Pulse width: 1.0 sec

Pulse width: 0.05 sec

Pulse width: 0.01 sec

Pulse width: 0.008 sec

Pulse width: 0.006 sec

Continuous DC voltage (c)

Pulse width: 1.0 sec

Pulse width: 0.5 sec

Pulse width: 0.1 sec

Pulse width: 0.05 sec

Pulse width: 0.02 sec

Pulse width: 0.015 sec

Continuous DC voltage

Pulse width: 1.0 sec

Pulse width: 0.5 sec

Pulse width: 0.2 sec

Pulse width: 0.1 sec

Pulse width: 0.05 sec

Pulse width: 0.02 sec

Pulse width: 0.015 sec

Fig. 5. Photograph of the top surface of as-deposited alumina obtained by pulse electrophoretic deposition from a 5 vol% suspension at pH 4.5 on (a) stainless steel (316 L) substrate (applied potential 5 40 V), (b) stainless steel (316 L) substrate (applied potential 5 20 V); (c) nickel substrate (applied potential 5 20 V).

Fig. 6. Pulse width versus applied voltage diagram showing regions of bubble-free deposition of AKP-50 alumina suspension on stainless steel (316 L) substrate (powder concentration: 5 vol%, pH 4.5; pulse ON time (Ton): 3 min).

gases near the anode compared with the residence time of hydrogen near the cathode. The presence of more oxygen gas near the anode will adversely inuence and limit the mass transport of particles to the electrode surface. Further, incorporation of this oxygen gas will result in a more inhomogeneous morphology of deposits during anodic EPD. Considering the distinct difference in the surface morphology of deposits obtained by pulse EPD compared with that by continuous dc voltage application, we anticipated an increase in green density as well. Figure 7 presents the green density estimated by the Archimedes method. The deposit obtained by continuous dc voltage EPD from 5 vol% alumina suspension at pH 4.5 exhibited a relative green density of 62.0%. It decreased to 54.0% when the pH increased to 6.0. This was obviously because of the better dispersion of the suspension at pH 4.5 than at pH 6.0. It is now well established in the literature that the dispersion and stability of colloidal suspensions can be effectively controlled by changing the solution pH, which in turn changes the ionic strength of the suspension.14,39 The electrical-doublelayer thickness of particles in suspension is a sensitive function of the ionic strength of the dispersing medium. At pH values closer to the IEP, the ion conductivity of the solvent is generally lower than that at more acidic pH.13 Therefore, most of the ap-

3158

Journal of the American Ceramic SocietyBesra et al.

Vol. 91, No. 10

Fig. 7. Green density of deposit on stainless steel (316 L) substrate as a function of pulse width (suspension: 5 vol%; applied potential: 20 V; interelectrode distance: 20 mm; deposition area: 20 mm 20 mm). A pulse width of 180 s is equivalent to continuous dc voltage application for 3 min.

plied current is expected to be carried by particles at pH closer to IEP. Hence, comparatively, the deposit yield is higher at pH 6.0 than at pH 4.5 (Fig. 4). But the z potential at pH 6.0 is lower than that at pH 4.5. Under such conditions, the electrostatic forces at pH 6.0 are of insufcient magnitude to overcome the large van der Waals attraction forces for which the particles form bigger agglomerates and loosely packed deposits compared with those at pH 4.5. The deposit formed by the more dispersed suspension at pH 4.5 was more densely packed because of the smaller agglomerate size. It has also been shown by earlier investigators that a pH gradient is established at the cathode surface during EPD because of charge transport by electrochemical reactions; i.e., protons gets transported from bulk to the electrode surface where they get discharged.39,40 If the charge transfer is in equilibrium, the diffusion rate of protons from the bulk will control the process. In this way, concentration overpotential is established. But it has also been shown that a potential drop is present over the deposit and that no signicant polarization is present at the electrode. The deposit formed on the electrode allows only ions and liquid to pass through it, while the powder particles get deposited as porous compact at the growth front. It has been suggested that a complex mechanism involving electrostatic interactions between the charged deposit and the charged solution species (ions) may play a role. The retention of ions in the deposit, which causes a reduction in mass transport through the deposit, is dependent not only on the pore size but also on the surface charge and Debye screening length of the deposited particles forming the pore wall. The ionic strength generally increases and the Debye screening length decreases with increasing acid concentration (low pH). Hence, in the present investigation, the suspension is expected to have higher ion conductivity at pH 4.5, which may result in higher pH gradient and high retention of ions in the deposit compared with that at pH 6.0. This will result in comparatively more reduction in mass transport at pH 4.5 than at pH 6.0, leading to decreased yield (Fig. 4). Figure 7 also shows the green density of deposits obtained by pulse EPD. Contrary to our expectation, the green density remained constant for each of the pulse widths and was the same as the density of continuous dc voltage EPD for the corresponding pH of the suspension. This implies that the green density is determined solely by the state of dispersion of the suspension and is not inuenced by pulse voltage. The better the dispersion, the higher the density of the deposit. Because the density of deposits obtained by the pulse method is the same as those obtained by continuous dc, it might appear that the regions devoid of bubbles are of higher density. However, this is not true, and the density of the bubblefree regions might be the same because the amplitude of the

applied potential, which serves as the driving force of the EPD process, in both the cases is maintained constant. At the same time, because the hydrogen gas when generated must escape through the deposit, it is likely that the deposits will contain only open pores and are devoid of any closed pores. The kerosene used for density measurement in the Archimedes method can easily enter the open pores and will not contribute to any difference in the measured density. Density would be different only if closed pores were present in the deposit. The reason why bubbles get suppressed on application of pulse voltage during EPD is not yet understood clearly. It is perceived that when continuous dc voltage is applied, the mass transport of particles due to the electrophoretic effect and their deposition at the electrode is a continuous process in addition to the electrolysis of water. Hence, the hydrogen or oxygen generated at the electrodes by electrolysis continuously gets incorporated into the deposits resulting in porous deposits. It is known that the electrolysis of water molecules into hydrogen and oxygen occurs through a process that involves several steps.41 Initially, the randomly oriented water molecules spin and orient themselves toward positive and negative poles of the voltage elds applied. The positively charged hydrogen atoms are attracted to a negative voltage eld (cathode), while at the same time the negatively charged oxygen atoms are attracted to the positive voltage eld (anode), resulting in the development of a polar charge alignment/distribution within the molecule and elongation of the water molecule. When the applied potential is high enough such that the attraction force from the voltage elds exceeds the force of covalent bonds between the atoms of the water molecule, the hydrogen and oxygen atoms get separated as charged ions in addition to release of electrons in the process. The released electrons either complete the external circuit or are carried by the particles present in the suspension. During continuous dc voltage EPD, electrons are also continuously introduced into the water bath by the circuit; hence, hydrogen ions reaching the cathode become neutralized and liberated from water as gas bubbles. On the other hand, for pulse voltage EPD, the duration of voltage interruption (Toff) is equal to the time during which no current ows between the electrodes and the electrolysis process is interrupted. Hence, by varying the pulse size and amplitude, the amount of gas evolved at the electrodes can be controlled. With this argument, the bubble generation and incorporation in the deposit for the case of continuous dc voltage EPD are expected to be the maximum and have been indeed experimentally found to be true. With decreasing size of pulse width, the amount of bubble incorporation has been found to decrease because of the decrease in electrolysis at lower pulse sizes. Secondly, the hydrogen or oxygen emitted at the electrode interface might be partly diffused away from the substrate in the duration of voltage interruption (Toff) and suppressed from being incorporated in the deposit during pulse EPD.42,43 At the same time, the population of adparticles near the deposition electrode surface during pulse EPD is still high. This is because the mass transport of the particles from bulk suspension toward the electrode surface is likely to continue even during the voltage interruption due to their inertia of mobility caused by the effect of preceding voltage ON duration (Ton). We had perceived that the incorporation of gas bubbles in the deposit could be reduced if the applied current density is decreased on application of pulse voltage. So, we monitored the change in current with time during deposition for each pulse width. For the same applied voltage of 20 V to 5 vol% suspension at pH 4.5, we observed a very marginal decrease in initial current density (which uctuated between 0.0017 A to 0.0013 A) when the mode of voltage application was changed from continuous dc to 0.01 s pulsed voltage. Such a small change in current density is insignicant to cause a practical change in the extent of electrolysis per pulse. Alternatively, we believe that the gas evolution and dissipation in the case of pulse voltage electrolysis is a dynamic process in which the gas generation sites on the electrode surface change after each voltage interruption time (Toff) and may be different from the preceding and succeeding

October 2008

EPD by Pulse-Potential Application

11

3159

ones. Such evolution of gas at different sites for each pulse ON time (Ton) will lead to the production of separate micro- and nanosized bubbles uniformly distributed throughout. Because the coalescence of such small bubbles is energetically unfavorable, their incorporation will not produce any macrobubbles in the deposit.

IV. Conclusions
Based on the above investigation on EPD of aqueous suspension, it can be concluded that application of pulse potential of suitable width enables obtaining smooth, bubble-free deposit. The yield of deposits obtained by pulse EPD is generally less than that obtained by EPD using continuous dc voltage. The deposited weight decreases progressively with decrease in pulse width. Application of continuous dc produced deposits with maximum thickness and incorporated bubbles in the deposit. The lm thickness and bubble incorporation decreased with decrease in pulse width for the same applied voltage. The green density of deposits obtained by pulse voltage EPD was found to be the same as those obtained by continuous dc voltage EPD. There exists a narrow band of pulse width within which bubblefree deposit is possible by pulse EPD. There is no deposition at pulse voltages smaller than the lower limit of pulse width. At larger pulse width, the deposits invariably contained bubbles in them. The band of pulse width for obtaining bubble-free deposit is wider and lies at a higher value of pulse for lower applied potential compared with that for higher applied potential. The upper and lower limits of pulse tend to merge with each other at high applied voltages. This suggests that it is more convenient and practicable for better control of pulse EPD to obtain bubble-free deposit at lower applied potential, but at the expense of deposit throughput. Apparently the cathodic pulse EPD produced better quality deposit and is amenable to better control of process parameters than the anodic pulse EPD.

Acknowledgments
One of the authors (L. B.) is thankful to the National Institute for Materials Science (NIMS) for the postdoctoral fellowship. The authors also wish to thank Ms. Ayako Miki for assistance in z potential measurement.

References
S. Put, J. Vleugels, G. Anne, and O. Van der Biest, Functionally Graded Ceramic and Ceramic-Metal Composites Shaped by Electrophoretic Deposition, Colloids Surf. A: Physicochem. Eng. Aspects, 222, 22332 (2003). 2 P. Sarkar, S. Datta, and P. S. Nicholson, Functionally Graded Ceramic/Ceramic and Metal/Ceramic Composites by Electrophoretic Deposition, Compos. Part B, 28B, 4954 (1997). 3 L. Besra and M. Liu, A Review on Fundamentals and Applications of Electrophoretic Deposition (EPD), Prog. Mater. Sci., 52, 161 (2007). 4 A. L. Rogach, N. A. Kotov, D. S. Koktysh, J. W. Ostrander, and G. A. Ragoisha, Electrophoretic Deposition of Latexbased 3D Colloidal Photonic Crystals: A Technique for Rapid Production of High Quality Opals, Chem. Mater., 12, 27216 (2000). 5 Q. Zhang, T. Xu, D. Buttereld, M. J. Misner, Y. Ryu Du, and T. Emrick, Controlled Placement of CdSe Nanoparticles in Block Copolymer Templates by Electrophoretic Deposition, Nanoletters, 5 [2] 35761 (2005). 6 I. Corni, M. P. Ryan, and A. R. Boccaccini, Electrophoretic Deposition: From Traditional Ceramics to Nanotechnology, J. Eur. ceram. Soc., 28, 135367 (2008). 7 H. Negishi, K. Yamaji, T. Imura, D. Kitamoto, T. Ikegami, and H. Yanagishita, Electrophoretic Deposition Mechanism of YSZ/n-Propanol Suspension, J. Electrochem. Soc., 152 [2] J1622 (2005). 8 B. Ferrari and R. Moreno, Electrophoretic Deposition of Aqueous Alumina Slip, J. Eur. Ceram. Soc., 17, 54956 (1997). 9 R. C. Bailey, K. J. Stevenson, and J. T. Hupp, Assembly of Micropatterned Colloidal Cold Thin Films via Microtransfer Molding and Electrophoretic Deposition, Adv. Mater., 12 [24] 19304 (2000). 10 M. Holgado, F. Garcia-Santamaria, A. Blanco, M. Ibisate, A. Cintas, H. Miguez, C. J. Serna, C. Molpeceres, J. Requena, A. Mifsud, F. Meseguer, and C. Lopez, Electrophoretic Deposition to Control Articial Opal Growth, Langmuir, 15 [14] 47014 (1999).
1

F. Q. Tang, T. Uchikoshi, K. Ozawa, and Y. Sakka, Electrophoretic Deposition of Aqueous Nano-g-Al2O3 Suspensions, Mater. Res. Bull., 37 [4] 65360 (2002). 12 P. Garcia, B. Ferrari, R. Moreno, A. J. Sanchez-Herencia, and M. T. Colomer, YSZ/Ni-YSZ Semi-Cells Shaped by Electrophoretic Deposition, J. Eur. ceram. Soc., 27 [1315] 42414 (2007). 13 J. Zhao, X. Wang, and L. Li, Electrophoretic Deposition of BaTiO3 Films from Aqueous Suspensions, Mater. Chem. Phys., 99 [23] 3503 (2006). 14 T. Uchikoshi and Y. Sakka, Electrophoretic Deposition Characteristics of Alumina Particles in Aqueous Media, J. Ceram. Soc. Jpn., 112 [5] S636 (2004). 15 R. Moreno and B. Ferrari, Effect of the Slurry Properties on the Homogeneity of Alumina Deposits Obtained by Aqueous Electrophoretic Deposition, Mater. Res. Bull., 35, 88797 (2000). 16 W. Ryan and E. Massoud, Electrophoretic Deposition Could Speed up Ceramic Casting, Interceram, 2, 1179 (1979). 17 W. Ryan, E. Massoud, and C. T. S. B. Perera, Fabrication by Electrophoresis, Trans. Br. Ceram. Soc., 80, 467 (1981). 18 R. Clasen, Science Technology and Applications of Colloidal Suspensions; pp. 16984 Edited by J. H. Adair, J. A. Casey, C. A. Randall, and S. Venigalla. American Ceramic Society, Westerville, OH, 1995. 19 J. Tabellion and R. Clasen, Electrophoretic Deposition from Aqueous Suspension for Near-Shape Manufacturing of Advanced Ceramics and GlassesApplications, J. Mater. Sci., 39, 80311 (2004). 20 B. Ferrari, J. C. Farinas, and R. Moreno, Determination and Control of Metallic Impurities in Alumina Deposits Obtained by Aqueous Electrophoretic Deposition, J. Am. Ceram. Soc., 84 [4] 7339 (2001). 21 F. Q. Tang, Y. Sakka, and T. Uchikoshi, Electrophoretic Deposition of Aqueous Nano-Sized Zinc Oxide Suspensions on a Zinc Electrode, Mater. Res. Bull., 38 [2] 20712 (2003). 22 M. R. Winkle, Elimination of Film Defects Due to Hydrogen Evolution During Cathodic Electrodeposition; U.S. Patent No. 5,066,374, 1991. 23 Y. Wang, F. Q. Liu, A. Duboust, S. S. Neo, L.-Y. Chen, and Y. Hu, Hydrogen Bubble Reduction on the Cathode Using Double Cell Design; U.S. Patent No. 7,229,535 B2, 2007. 24 D. Sakurada, K. Suzuki, T. Miura, and M. Hashiba, Bubble-Free Electrophoretic Deposition of Aqueous Zirconia Suspensions with Hydroquinone, J. Mater. Sci., 39, 18457 (2004). 25 T. Uchikoshi, K. Ozawa, B. D. Hatton, and Y. Sakka, Dense, Bubble-Free, Ceramic Deposits from Aqueous Suspensions by Electrophoretic Deposition, J. Mater. Res., 16 [2] 3214 (2001). 26 T. Uchikoshi, T. Hisashige, and Y. Sakka, Stabilisation of Yttria Aqueous Suspension with Polyethyleneimine and Electrophoretic Deposition, J. Ceram. Soc. Jpn., 110, 8403 (2002). 27 F. Q. Tang, T. Uchikoshi, and Y. Sakka, Electrophoretic Deposition Behavior of Aqueous Nanosized Zinc Oxide Suspensions, J. Am. Ceram. Soc., 85 [9] 21615 (2002). 28 M. W. Sing and F. Y. Sing, Pulse Electroplating Process; U.S. Patent No. 4, 789,437, 1988. 29 S. K. Ghosh, A. K. Grover, G. K. Dey, and M. K. Totlani, Nanocrystalline Ni-Cu Alloy Plating by Pulse Electrolysis, Surf. Coat. Technol., 126, 4863 (2000). 30 T. Mahalingam, J. S. P. Chitra, G. Ravi, J. P. Chu, and P. J. Sebastian, Characterisation of Pulse Plated Cu2O Thin Films, Surf. Coat. Technol., 168, 1114 (2003). 31 F. Lallemand, L. Ricq, E. Deschaseaux, L. De Vettor, and P. Bercot, Electrodeposition of Cobalt-Iron Alloys in Pulsed Current From Electrolytes Containing Organic Additives, Surf. Coat.Technol., 197, 1017 (2005). 32 K. C. Chan, N. S. Qu, and D. Zhu, Quantitative Texture Analysis in Pulse Reverse Current Electroforming of Nickel, Surf. Coat. Technol., 99, 6973 (1998). 33 E. A. Pavlatou, M. Raptakis, and N. Spyrellis, Synergistic Effect of 2-Butyne-1, 4-Diol and Pulse Plating on the Structure and Properties of Nickel Nanocrystalline Deposits, Surf. Coat. Technol., 201, 45717 (2007). 34 M. D. Obradovic, G. Z. Bosnjakov, R. M. Stevanovic, M. D. Maksimovic, and A. R. Despic, Pulse and Direct Current Plating of Ni-W Alloys From AmmoniumCitrate Electrolyte, Surf. Coat. Technol., 200, 42017 (2006). 35 C. Kollia, N. Spyrellis, J. Amblard, M. Froment, and G. Maurin, Nickel Plating by Pulse Electrolysis: Textural and Microstructural Modications Due to Adsorption/Desorption Phenomena, J. Appl. Electrochem., 20 [6] 102532 (1990). 36 A. M. El-Sherik, U. Erb, and J. Page, Microstructural Evolution in Pulse Plated Nickel Electrophoresis, Surf. Coat. Technol., 88, 708 (1996). 37 http://www.answers.com/topic/hydrogen?cat=technology 38 http://www.engineeringtoolbox.com/gases-solubility-water-d_1148.html 39 G. Anne, B. Neirinck, K. Vanmeensel, O. va der Biest, and J. Vleugels, Origin of the Potential Drop Over the Deposit During Electrophoretic Deposition, J. Am. Ceram. Soc., 89 [3] 8238 (2006). 40 D. De and P. S. Nicholson, Role of Ionic Depletion in Deposition During Electrophoretic Deposition, J. Am. Ceram. Soc., 82, 30316 (1999). 41 S. A. Meyer, Method for the Production of a Fuel Gas; U.S. Patent No. 4,936,961, 1990. 42 Y. Sakura, I. Tsuchiya, and K. Mano, Metal Plating Method; U.S. Patent No. 6, 641,710 B2, 2003. 43 K. Arlt, K. Eckert, M. Stockbrink, R. Schulte, H. Berlin, and G. Nienhaus, Pulse-Modulated DC Electrochemical Coating Process and Apparatus; U.S. Patent No. 6,197,179 B1, 2001. &