J. of Supercritical Fluids 27 (2003) 187 /193 www.elsevier.

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Formation of zinc oxide nanoparticles in supercritical water

Raghu Viswanathan, Ram B. Gupta *
Department of Chemical Engineering, Auburn University, Auburn, AL 36849-5127, USA Received 29 July 2002; received in revised form 24 October 2002; accepted 11 November 2002

Abstract Supercritical water provides an excellent reaction medium for hydrothermal synthesis of metal oxide nanoparticles. In this work, zinc oxide nanoparticles are produced by oxidation of zinc acetate in supercritical water in a continuous tubular reactor. Less than 1 min is enough for the reaction to occur, and the temperatures are much lower than in the flame combustion or zinc evaporation processes. Effect of flow rates and feed concentrations are studied. Based on transmission electron microscopy and dynamic light scattering analyses, spherical zinc oxide particles are obtained in the range 39 /320 nm. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Supercritical water; Hydrothermal synthesis; Nanoparticles; Zinc oxide

1. Introduction Zinc oxide particles are used for many applications including as an activator of accelerator in the vulcanization process, as a form control in lattices, as a reinforcement filler in white stocks, as an additive in lubricating oil and in catalysts. Ultrafine ZnO particles show a high degree of transparency, making them useful in sunscreens, paints, varnishes, plastics and cosmetics, specially for broad UV-A and UV-B blocking [1].

* Corresponding author. Tel.: '/1-334-844-2013; fax: '/1334-844-2063. E-mail address: gupta@auburn.edu (R.B. Gupta).

Commercially, zinc oxide has been produced by two main methods: (a) the French process, and (b) the American process [2]. In the French process, zinc metal is vaporized in large containers by external heating, and in an adjoining off take pipe or combustion chamber, the vapor is burned off in air to form fine zinc oxide powder. Suyama et al. [3] synthesized ultra-fine zinc oxide particles by the vapor phase oxidation of zinc metal. In the American process, oxidized ores of roasted sulfide concentrates are mixed with anthracite coal and smelted in a flat belt furnace. Vapors of metallic zinc are produced, which are burned under controlled conditions and led to the bag house where the oxide particles are collected. The disadvantages with both the processes are the remaining of unreacted Zn metal, which is a highly undesirable

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impurity, and the need for high temperature (/ 1000 8C) operations. Apart from these commercial processes, recently various newer methods have been developed for the synthesis of zinc oxide particles: (1) Laundon [1] devised a process for making zinc oxide by spraying an aqueous solution of a zinc salt (e.g., zinc acetate, formate, carboxylates, nitrate, chloride or sulphate) directly into a flame in a combustion chamber. The aqueous zinc salt decomposes to zinc oxide, giving particles of B/80 nm. (2) Haile et al. [4] synthesized zinc oxide by reacting zinc hydroxy precursor with NH4OH evaporating it to zinc oxide. (3) Zhong and Matijevic [5] synthesized colloidal zinc oxide by the hydrolysis of zinc nitrate with triethanolamine solution by feeding the two into a reactor containing water at 90 8C. (4) Homogeneous precipitation of zinc oxide [6] from low concentration aqueous solution of zinc nitrate and zinc chloride solution with hexamethylenetetramine yields needles, globules, and rods shaped zinc oxide particles. (5) Zinc ethanoate has been hydrolyzed to produce zinc oxide [7]. (6) Precipitation of basic carbonates from zinc sulfate or zinc chloride and then calcination yields fine zinc oxide particles [8]. (7) Atomization of zinc acetate solution into very fine droplets in a low temperature electric furnace produces ultra-fine zinc oxide particles [9]. (8) Nishizawa et al. [10] synthesized needle like crystals of zinc oxide by the hydrothermal decomposition of Na2Zn */EDTA at 350 8C and 10 MPa. All these processes require a high residence time. In this work, we study the production of zinc oxide nanoparticles using supercritical water as a reaction medium. Lower residence time and operation temperature can occur with the use of supercritical water, as compared to current industrial processes. Supercritical water has been successfully used for the formation of other metal oxide particles such as AlOOH, a-Fe2O3, Fe3O4, NiO, TiO2, ZrO2 [11,12]. Particle size and morphology can be controlled to some extent by varying temperature, pressure, or the reaction atmosphere. Recently, this process has been applied for the production of barium hexaferrite nanoparticles [13], ceria nanoparticles [14] and

La2CuO4 nanoparticles in the size range 70 /120 nm with a high surface area and enhanced O2 mobility [15].

2. Experiment 2.1. Materials All the materials, zinc acetate dihydrate (99% pure, Aldrich Chemical Company), hydrogen peroxide (30 vol.%, Fisher Scientific) and deionized water were used as received. 2.2. Apparatus A schematic diagram of the apparatus is shown in Fig. 1. The reactor is a 10-ml volume SS316, 1/4in i.d., micro reactor obtained from High Pressure Equipment Company (HIP). The reactor has three inlets: (a) aqueous zinc acetate solution (feed stream), (b) hydrogen peroxide (6 vol.% in water) to provide oxygen, and (c) de-ionized water. A double piston metering pump (Eldex AA 100S) is used to pump the streams (b) and (c). Both of these streams are preheated using 1/8-inch stainless steel (SS 316) tubings of about 5.5 m in length. An Acuflow Series II pump is used to pump the feed stream (a) to the reactor without preheating. All three streams are mixed at the entrance of the reactor using a tee-joint. The reactor/preheater assembly is placed in a constant temperature furnace (Thermolyne 30 400). The reactor temperature is measured using omega Ktype thermocouples and controlled within 3 8C of the set value. Three thermocouples are placed inside the furnace and in contact with the reactor, one at the mixing point in the reactor and the other two at the different locations on the reactor after the mixing point. The pressure was measured at two different points within accuracy of 3.5 bars and controlled using a backpressure regulator (GO Regulator, Inc., Corona, CA; Pmax 0/350 bar). The pressure gauges were placed at the feed line and another at the exit line to measure the pressure inside the reactor. Safety rupture disks rated at 340 bars were installed in the inlet streams. An in-line filter (0.5 mm size filter, 1000 bars pressure rating)

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Fig. 1. Schematic of the supercritical water reactor for zinc oxide nanoparticle production.

was placed before the backpressure regulator to filter out larger particles in order to avoid clogging in the backpressure regulator. The hot exit stream from the reactor passes through a heat exchanger to cool down the exit stream temperature to room temperature. After passing through the backpressure regulator, liquid effluent stream is collected and analyzed. 2.3. Procedure All the experiments were carried out in the continuous mode. The first step was to pump water through all the inlet lines and pressurize the system while flowing just water. After reaching a steady pressure, the inlets are switched to aqueous zinc acetate, hydrogen peroxide and water to their respective feed lines based on the experimental requirement. When either of the water or hydrogen peroxide stream is not required, the corre-

sponding line was disconnected from the reactor and a plug was used to block the opening in the reactor. Water and hydrogen peroxide are preheated before they reach the reactor and the feed solution enters directly into the reactor without any preheating. Preheating is important in order to make sure that at the mixing point when the three streams come in contact, the supercritical water condition is maintained. Hydrogen peroxide completely decomposes into O2 and H2O during preheating. Zinc acetate feed stream was not preheated to exploit the formation of fine particles due to antisolvent effect of supercritical water for metal salts [16]. The feed stream comes in contact with the other two streams at the mixing point in the tee of the reactor. At this juncture, the feed stream gets rapidly heated upon mixing with water and oxidant streams and the reaction occurs. This mixing arrangement can play an important role in

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Fig. 2. TEM micrographs of ZnO particles obtained from experiments at different operating conditions. Concentration of zinc acetate is 10 mM. (a) Flow rate of feed is 2.5 cc/min (exp. 1), (b) ow rate of feed is 3.5 cc/min. (exp. 4), (c) shows the agglomerated particles when analyzed 2 days after collecting the sample, and (d) ow rate of feed is 2.5 cc/min and concentration is 2.5 cc/min and concentration is 20 mM. (exp. 13).

nanoparticle formation. After the solution leaves the reactor it is quenched in a heat exchanger. Only fine particles were produced and essentially no particles were collected at the inline filter. Morphology of the obtained particles was observed using transmission electron microscopy

(TEM) analysis. The hydrodynamic radius of the nanoparticles is measured by dynamic light scattering (DLS) technique, using PSS NICOMP 380 instrument. Measurements were made at room temperature using a laser having wavelength of 635 nm and 908 scattering angle. The diffusion

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Table 1 Results of experiments conducted at different process conditions Exp. No. Temp. (8C) Pressure (atm.) Zinc acetate in feed- Flow rate (ml/min) stream (mM) FeedWaterstream stream 10 10 10 10 20 20 40 40 10 10 10 10 20 20 20 30 2.5 2.5 2.5 3.5 2.0 2.0 2.0 2.0 2.5 2.5 3.5 3.5 2.5 1.0 1.0 1.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 5.0 5.0 5.0 DLS H2O2stream 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 5.0 5.0 5.0 Particle size (nm) 94 78 66 251 92 70 168 39 125 117 213 126 199 80 140 89 Standard deviation (nm) 3 9 6 25 14 10 28 15 24 22 32 32 23 21 10 7 % Particles 99 99 99 97 100 98 99 99 99 99 73 86 95 98 96 64 140 180 160 120 320 240 200 240 125 175 200 150 175 / / / 15.3 15.3 15.3 13.03 16.3 16.3 16.3 16.3 15.3 15.3 13.03 13.03 15.3 8.9 8.9 8.9 TEM particle size (nm) Residence time (s)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

400 400 400 400 400 400 400 400 400 400 400 400 400 400 400 400

245 245 245 245 245 245 245 245 245 245 245 245 245 245 245 245

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Fig. 3. Number weighted NICOMP distribution of particles obtained in (a) exp. 1, (b) exp. 15, (c) exp. 4, and (d) exp. 9, from dynamic light scattering analysis.

coefficients were calculated using the auto correlation function and the particle size was calculated using the Stokes-Einsteins equation.

CH3 COOH'2O2 0 2CO2 '2H2 O Additional acetic acid is also expected to convert to CO2 due to pyrolysis. For example, in the study by Meyers et al. [17] for the decomposition of acetic acid, 35% of acetic acid decomposed at 600 8C, 246 bar, and 8 s residence time without use of any oxidant. In order to ensure complete oxidation of the acetates in the stream, excess oxygen was supplied in the form of hydrogen peroxide, in some experiments. The process of complete oxidation can be controlled and ensured by supplying excess oxygen through hydrogen peroxide in the feed stream. Hydrogen peroxide was also preheated before it comes in contact with the feed stream at the mixing point. During preheating, hydrogen peroxide completely decomposes into O2 and H2O [16], supplying the required oxygen for complete oxidation of the acetate.

3. Results and discussion A series of experiments using flow type apparatus were carried out at 400 8C and 245 atm. (Table 1). The experiments were conducted at different flow rates and concentration of the feed. Rapid decomposition of the zinc acetate at the mixing point is responsible for the fine particles production. When the preheated water comes in contact with zinc acetate solution, zinc oxide is formed. Zn(CH3 COO)2 'H2 O 0 ZnO'2CH3 COOH and some acetic acid is oxidized due to dissolved oxygen in the supplied water.

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Zn(CH3 COO)2 '4O2 0 ZnO'4CO2 '3H2 O It can be seen from TEM micrographs, that spherical, smooth zinc oxide particles were obtained (Figs. 2 and 3). The particle size obtained from TEM analyses are listed in Table 1. There is no obvious trend in the size of the particles produced with changes in concentration or flow rate of the feed. However, all the particles are in 120 /320 nm. DLS technique using NICOMP was also used to determine the average size of the particles obtained which shows a size range of 39/ 251 nm. Zinc oxide has a soft and fluffy surface, which is responsible for agglomeration of the particles over time. This can be easily seen in TEM pictures (Fig. 3 c and d). Table 1 also lists the number weighted NICOMP distribution (average size, percentage of particles in that size range and standard deviation). From data in Table 1, we cannot find any substantial trend in the particle size with the change in concentration or flow rate. Almost all the particles produced were of the similar size within the standard deviation. Thus simply varying the concentration or flow rate of the feed did not affect the particle size, for the conditions studied. However, change in temperature or pressure can have an effect on the particle size, as shown by Hirano and Kato [18] for ceria particles.

References
[1] R.D. Laundon, Zinc Oxide and A Process of Making It, US, 5876688, 1999. [2] A.S. Perl, Zinc oxide, Am. Ceram. Soc. Bull. 72 (6) (1993) 122 /123. [3] Y. Suyama, S. Takemiya, A. Kato, Synthesis of ultra-ne ZnO powders by vapor phase oxidation of Zn vapor, Yogyo-Kyokai-Shi 93 (1985) 105 /107. [4] S.M. Haile, D.W. Johnson, Jr., G.H. Wiseman, H.K. Bowen, Aqueous precipitation of spherical zinc oxide powders for varistor applications, J. Am. Ceram. Soc. 72 (1989) 2004 /2008. [5] Q. Zhong, E. Matijevic, Preparation of uniform zinc oxide colloids by colloidal double jet precipitation, J. Matl. Chem. 6 (1996) 443 /447. [6] K. Fujita, I. Kayama, Synthesis of zinc oxide by the homogeneous precipitation method, Yogyo-Kyokai-shi 88 (10) (1980) 619 /623. [7] E.M. Vogel, N.C. Andreadakis, W.E. Quinn, T.J. Nelson, Materials for display devices based on metallo-organic precursors, Adv. Ceram., 21 (1987) 131 /137. [8] S. Tichy, ZnO for sun protection: transparent ZnO for skin and sun protection, SOFW J. 119 (1993) 1993. [9] T.Q. Liu, O. Sakurai, N. Mizutani, M. Kato, Preparation of spherical ne ZnO particles by the spray pyrolysis method using ultrasonic atomization techniques, J. Mater. Sci. 21 (1986) 3698 /3702. [10] H. Nishizawa, T. Tani, K. Matsuoka, Crystal growth of ZnO by hydrothermal decomposition of Zn-EDTA, J. Am. Ceram. Soc. 87 (1984) c-98 /c-100. [11] T. Adschiri, K. Kanazawa, K. Arai, Rapid and continuous hydrothermal crystallization of metal oxide particles in supercritical water, J. Am. Ceram. Soc. 75 (4) (1992) 1019 / 1022. [12] T. Adschiri, Y. Hakuta, K. Arai, Hydrothermal synthesis of metal oxide ne particles at supercritical conditions, Ind. Eng. Chem. Res. 39 (2000) 4901 /4907. [13] Y. Hakuta, T. Adschiri, T. Suzuki, T. Chida, K. Seino, K. Arai, Flow method for rapidly producing barium hexaferrite particles in supercritical water, J. Am. Ceram. Soc. 81 (9) (1998) 2461 /2464. [14] Y. Hakuta, S. Onai, H. Terayama, T. Adschiri, K. Arai, Production of ultra-ne ceria particles by hydrothermal synthesis under supercritical conditions, J. Matl. Sci. Lett. 17 (1998) 1211 /1213. [15] A.A. Galkin, G.B. Kostyuk, V.V. Lunin, M. Poliakoff, Continuous reactions in supercritical water: a new route to La2CuO4 with a high surface area and enhanced oxygen mobility, Community 39 (15) (2000) 2738 /2740. [16] P. Muthukumaran, R.B. Gupta, Sodium carbonate assisted supercritical water oxidation of chlorinated waste, Ind. Eng. Chem. Res. 39 (12) (2000) 4555 /4563. [17] J.C. Meyer, P.A. Marrone, J.W. Tester, Acetic acid oxidation and hydrolysis in supercritical water, AIChE J. 41 (9) (1995) 2108 /2121.

4. Conclusion Oxidation of zinc acetate in supercritical water can be successfully used to produce zinc oxide nanoparticles with a reaction time of about less than 1 min. Based on TEM analysis, zinc oxide particles are spherical in shape with 120/320 nm in diameter. Zinc oxide particles agglomerate over time due to the soft and fluffy nature. Based on DLS analysis the particles are in the size range 39/ 251 nm and the particle size is not affected by flow rate or feed concentration in the range studied. Mixing appears to be important in determining the size, which was not controlled in this study.