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The rheological behavior and electrophoretic deposition (EPD) very few studies have focused on the colloidal behavior of ZnO
of ZnO nanopowder (nano-ZnO) in aqueous media have been powders,19,20 and much fewer studies have focused on the EPD
described. A cationic polyelectrolyte (polyethylenimine, PEI) processing of ZnO. We are interested in the rheological and EPD
was used to disperse and modify the surfaces of the ZnO properties of nanosized ZnO (nano-ZnO) powder, because the
nanoparticles. The rheological properties of the ZnO aqueous stability of the suspension affects the deposition characteristics.
suspension were investigated by measuring the viscosity versus The rheological properties of the nano-ZnO aqueous suspensions
the pH and amount of dispersant. The EPD processing was that have been prepared under various conditions, and the EPD
conducted via cathodic electrodeposition, using stable suspen- properties from well-dispersed suspensions, are of great interest to
sions with low viscosity, and the depositional behavior was us. ZnO is well-known to be an amphoteric oxide, and it is known
investigated. Bubble-free nano-ZnO deposits with uniform to be easily dissolved in both acids and bases. ZnO is hydrated
microstructures were successfully obtained, which was an to form the Zn2 cation at acidic pHs of 6.3, and it forms
indication of good sintering behavior. hydroxide layers in water at basic pHs, where Zn(OH)2 is in
equilibrium with the Zn2, Zn(OH), Zn(OH) 2
3 , and Zn(OH) 4
species. At pH 12, the latter two zincate ions become the
I. Introduction dominant species in solution.19 In this study, the pH range of 711
has been chosen to prepare the suspension; the ZnO particle is
I NTEREST increasingly has been focused on the processing strat-
egies of inorganic ceramic materials.1 Colloidal processing,
which is one of the recently developed approaches, has been
usually negatively charged in this pH range. To obtain bubble-free
deposits using a palladium cathode,15 the ZnO particles should be
positively charged. In this study, a cationic electrolyte has been
proved to be a very promising method in the processing of used to give the ZnO particles a positive charge potential and good
nanostructured powders, because of its advantages in diminishing dispersion in aqueous media. Dense, bubble-free ceramic deposits
agglomeration and defect populations.2,3 Electrophoretic deposi- with uniform microstructure have been fabricated using nano-ZnO
tion (EPD) is a straightforward method for the assembly of via aqueous EPD processing.
charge-carrying particles on an electrode from stable colloidal
suspensions in a dc electric field.4 6 Compared with convention-
ally slip casting, the thickness and morphologies of materials II. Experimental Procedure
obtained via EPD can be controlled precisely by varying the
electrochemical parameters; moreover, uniform and complex- ZnO nanopowder with an average particle size of 40 nm
shaped deposits with high green densities on the electrode are (Sakai Chemical Industry Co., Ltd., Sakai, Japan) was used.
obtained readily at a high deposit speed. This fact is prominent in A cationic polyelectrolytepolyethylenimine (PEI,
the case of nanopowder suspensions. Nonaqueous suspensions O(CH2OCH2ONHO)n)with an average molecular weight of
often have been chosen to produce bubble-free materials.57 EPD 10000 (Wako Pure Chemical Industry, Ltd., Tokyo, Japan) was
in aqueous media should have an advantage over nonaqueous used to modify the ZnO nanopowder, and 5-vol%-ZnO aqueous
media, because of the benign environment and low cost.8 11 To suspensions were prepared. Reagent-grade hydrochloric acid
suppress the electrolysis of water, which causes bubble contami- (HCl) and ammonium hydroxide (NH4OH) were used for pH
nation, the applied voltage should be maintained at a value that is adjustment. The suspensions were ultrasonicated (Model USP-
less than the electrolysis voltage of water (1.23 V at 25C);12,13 600, Shimadzu, Inc., Kyoto, Japan) at a power of 160 kW for 10
however, this methodology is not practical, because that restriction min, to break the agglomeration,21 and then were stirred for at least
makes the deposition rate too slow. The use of porous molds to 12 h, to ensure the equilibrium of polymer adsorption. The zeta
pass the generated gas through the mold is not considered to be potential () versus pH of the suspensions was measured on a
sufficient.14 Our previous studies have shown that bubble-free zeta-potential analyzer (Model LEZA-600, Otsuka Electronics
deposits can be successfully obtained via deposition onto palla- Co., Ltd., Tokyo, Japan) in a 102M sodium chloride (NaCl)
dium cathodes, because palladium readily absorbs the hydrogen solution with and without PEI addition. The rheological properties
that evolves because of the electrolysis of water.15,16 of the ZnO suspensions were studied by measuring the viscosity
Zinc oxide (ZnO) is well-known as a semiconductor material versus the pH, as well as the amount of dispersant, on an R-type
with a band gap of 3.2 eV; this material has potential application rotational viscometer (Model RC-500, Toki Sangyo Co., Ltd.,
in sensors, solar cells, photo-electronic devices, etc.17,18 However, Tokyo, Japan). Well-dispersed suspensions with low viscosity
were used for the EPD processing. The deposition was performed
using a dc power source (Model Potentiostat/Galvanostat
HA-3001A, Hokuto Denko, Tokyo, Japan) that was operating at a
D. W. Johnson Jr.contributing editor
constant current of 0.375 mA/cm2. A stainless-steel sheet was used
as an anode, and a palladium sheet with a deposition area of 8 cm2
was used as a cathode. They faced each other at a distance of 2 cm.
The relation between the deposit weight and time was investigated
Manuscript No. 187126. Received February 21, 2002; approved June 10, 2002. at different suspension pHs. The obtained deposits were dried in
Author FT would like to acknowledge the support from the Science and air at room temperature and weighed together with the cathodic
Technology Agency of the Japanese Government, through an STA postdoctoral
fellowship. substrates to determine the deposit weight. After drying, the
*Member, American Ceramic Society. deposits were separated from the substrate and sintered at different
2161
2162 Journal of the American Ceramic SocietyTang et al. Vol. 85, No. 9
Fig. 5. Deposit weight of 5 vol% ZnO versus time, for different PEI contents ((a) 1.5 and (b) 2 wt%).
2164 Journal of the American Ceramic SocietyTang et al. Vol. 85, No. 9
Fig. 8. Microstructure of green deposits with 1.5 wt% PEI addition (a) at pH 9 and sintered for 2 h at temperatures of (b) 1200, (c) 1250, and (d) 1350C).
September 2002 Electrophoretic Deposition Behavior of Aqueous Nano-ZnO Suspensions 2165
7
the particle packing; sintering at high temperature can diminish A. M. Affoune, B. L. V. Prasad, H. Sato, and T. Enoki, Electrophoretic
Deposition of Nanosized Diamond Particles, Langmuir, 17 [2] 54751 (2001).
these pores. Figures 8(c) and (d) show a dense and uniform 8
R. Moreno and B. Ferrari, Effect of the Slurry Properties on the Homogeneity of
microstructure. The grain sizes of the compacts sintered at 1250 Alumina Deposits Obtained by Aqueous Electrophoretic Deposition, Mater. Res.
and 1350C are 15 and 25 m, respectively. Further careful Bull., 35, 88797 (2000).
9
control of the sintering procedure can produce sintered bodies with R. C. Bailey, K. J. Stevenson, and J. T. Hupp, Assembly of Micropatterned
Colloidal Cold Thin Films via Microtransfer Molding and Electrophoretic Deposi-
a denser and more homogeneous microstructure. tion, Adv. Mater., 12 [24] 1930 34 (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,
IV. Conclusions Electrophoretic Deposition to Control Artificial Opal Growth, Langmuir, 15 [14]
4701704 (1999).
11
Polyethylenimine (PEI) is an effective surfactant to disperse F. Q. Tang, T. Uchikoshi, K. Ozawa, and Y. Sakka, Electrophoretic Deposition
of Aqueous Nano--Al2O3 Suspensions, Mater. Res. Bull., 37 [4] 653 60 (2002).
zinc oxide nanopowder (nano-ZnO) suspensions and modify the 12
A. T. Kuhn (ed.), Industrial Electrochemical Processes; p. 128. Elsevier,
particles to become positively charged. Well-dispersed ZnO sus- Amsterdam, The Netherlands, 1971.
13
pensions have been obtained in the pH range of 8.510 with the A. Formeto, L. Montanaro, and M. V. Swain, Micromechanical Characterization
addition of 12 wt% PEI; these suspensions are suitable for EPD of Electrophoretic-Deposited Green Films, J. Am. Ceram. Soc., 82 [12] 3521 49
(1999).
processing. Uniform and bubble-free nano-ZnO deposits with 14
W. Ryan, E. Massoud, and C. Perera, Pottery Section-Fabrication by Electro-
good sinterability have been obtained in this experiment. Aqueous phoresis, Trans. Br. Ceram. Soc., 80 [2] 46 47 (1981).
15
EPD processing has been demonstrated to be an easy approach to T. Uchikoshi, K. Ozawa, B. D. Hatton, and Y. Sakka, Dense, Bubble-Free
produce dense, uniform, bubble-free nanosized ceramic deposits Ceramic Deposits from Aqueous Suspensions by Electrophoretic Deposition, J.
Mater. Res., 16 [2] 32123 (2001).
on a palladium cathode; this procedure has significant potential for 16
Y. Sakka, T. Uchikoshi, and B. Hatton, Processing of Zirconia and Alumina
the economic mass production of a wide variety of components. Fine Particles through Electrophoretic Deposition, Stud. Surf. Sci. Catal., 132,
233236 (2001).
17
H. Nanto, T. Minami, and S. J. Takata, Zinc-Oxide Thin-Film Ammonia Gas
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