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Rev.Adv.Mater.Sci.46 14(2007) 46-48 B. Grzmil, B. Kic and K. Lubkowski

STUDIES ON OBTAINING OF ZINC NANOMATERIALS

B. Grzmil, B. Kic and K. Lubkowski

Institute of Chemical and Environment Engineering, Szczecin University of Technology, Pułaskiego 10, 70-322 Szczecin, Poland Received: December 08, 2006

Abstract. Among the phosphate pigments, found the widest application in paints, since it provides excellent resistance and is non-toxic. The two methods of preparation of zinc phosphate with the average crystallite size of 30-40 nm have been developed. Nanocrystalline

zinc phosphate tetrahydrate was formed in the three-stage process: the synthesis of Zn3(PO4)2·4H2O from and zinc nitrate, low-temperature calcination of precipitated phos- phate, and the hydration of the intermediate. Whereas the anhydrous zinc phosphate was ob- tained in the two-stage process of calcination (initially at low temperature, subsequently at higher

temperature) of the gel formed as a result of treatment of aqueous containing Zn(NO3)2,

(NH4)2HPO4, and citric .

1. INTRODUCTION in numerous binders. Zinc phosphate is produced on a commercial scale either from and The primary objective of the application of paint phosphoric acid or zinc and . The and coating products is an effective protection of anticorrosive properties of zinc phosphate depends, the metallic surfaces against an aggressive influ- in a large degree, on the distribution of the particle ence of the environment. The paints are mixtures size. Hence, it is aimed to obtain the pigments with composed of binder, pigment, solvent, and addi- the appropriate size already in the technological tives. Until recently, the most frequently used pig- process or they are subjected to micronization. It ments, possessing very good anticorrosive prop- would be the most advantageous to prepare the erties, included red and zinc chromate. How- single particle with the size which does not exceed ever, both pigments belong to very hazardous and 100 nm, that is being characteristic for the highly toxic substances. With regard to the eco- nanoparticles [1]. logical reasons, these pigments are withdrawn from Several methods of zinc phosphate synthesis the paint composition and they are replaced by the on the base of different raw materials have been environmental friendly pigments. Such pigments developed. However, the products obtained within include, among others, the phosphates, among this approach can hardly be classified as nano- which the zinc phosphate found the widest appli- materials [2-5]. cation. This compound is non-toxic, it possesses excellent anticorrosive properties and can be used

Corresponding author: B. Grzmil, e-mail: [email protected]

@ 2007 Advanced Study Center Co. Ltd. Studies on obtaining of zinc phosphate nanomaterials 47

The objective of these studies was to elaborate calculated taking into account the so-called appa- a new method of preparation of zinc phosphate with ratus broadening. This parameter was determined the crystallite size as small as possible with the on the basis of the sample of coarse crystalline utilization of the inorganic compounds as the pre- . cursors. 3. RESULTS AND DISCUSSION 2. EXPERIMENTAL Several experiments were performed during the The reagents of analytical grades were used in studies on the preparation of nanocrystalline zinc these studies. Zinc phosphate was prepared as a phosphate tetrahydrate (method I), in which the result of the reaction of zinc nitrate with following parameters were changed: the molar ra- 3- diammonium phosphate in an aqueous solution tio of Zn:PO4 (in the range of 1.2-1.5:1), the con- without or in the presence of the complexing agent centrations of the reagents in used (15-

(citric acid). In the first case, the process was con- 50 wt.% of Zn(NO3)2, 7-50 wt.% of (NH4)2HPO4). ducted in three stages: precipitation of Zn3(PO4)2· Depending on the assumed process parameters,

4H2O (hopeite) at temperature from 273 to 363K, the following compounds were identified in the re- low temperature calcination (473-523K) to action products: Zn3(PO4)2·4H2O, Zn3(PO4)2·4H2O,

Zn3(PO4)2 for a time of 1-2 h, and a repeated hy- Zn3(PO4)2·2H2O or Zn3(PO4)2·2H2O, and a small dration to hopeite (temperature 293K, 0.5h, the liq- amount of Zn3(PO4)2·4H2O. As a result of dehydra- uid phase to the phase ratio of 4:1): tion of these products Zn3(PO4)2 or a mixture of Zn (PO ) and Zn (PO ) ·2H O was obtained. A 3Zn(NO ) + 2(NH ) HPO + 4H O = 3 4 2 3 4 2 2 3 2 4 2 4 2 repeated hydration of mentioned phosphates Zn (PO ) ·4H O + 4NH NO + 2HNO , (1) 3 4 2 2 4 3 3 to the preparation of pure hopeite or a mixture of Zn (PO ) ·4H O = Zn (PO ) + 4H O. (2) 3 4 2 2 3 4 2 2 hopeite and Zn3(PO4)2. Whereas in the second case, the reaction mixture It was found that zinc phosphate tetrahydrate containing zinc nitrate, diammonium phosphate, with the average crystallite size of about 180 nm and citric acid was concentrated to achieve a thick can be obtained as a results of a rapid mixing of a foam, that was subjected to a two stage thermal 20 wt.% solution of zinc nitrate with 40 wt.% solu- treatment. The concentration was carried out in an tion of diammonium phosphate at temperature of ultrathermostate (MLW, type U15C) at temperatures 346K. The diffraction pattern of this product was of 348-353K for about 3 h. The first stage of calci- presented in Fig. 1. When the calcination of pre- nation proceeded at temperature 453K for 5– cipitated phosphate was performed at temperature 120 min (spontaneous ignition and swelling of the of 524K for 1h, an anhydrous zinc phosphate was material), and the second one at temperatures of obtained, from which, after the hydration, zinc phos- 873-1023K for a time of 30-120 min (oxidation of phate tetrahydrate was again obtained (Fig. 1). The the organic phase): average crystallite size of the final product amounted to about 30 nm and it was six times 2C6H8O7+3Zn(NO3)2+2(NH4)2HPO4= smaller than Zn3(PO4)2·4H2O obtained after the first Zn (PO ) +12CO +5N +17H O+0.5O (3) 3 4 2 2 2 2 2 stage of process. This effect was achieved as a The calcination was carried out in a muffle fur- result of double recrystallization of the phosphates nace (LINN HIGH THERM GMBH of type LM crystallizing in the various crystallographic systems

412.24 with a electronically programmed control- with a different size of the unit cell. Zn3(PO4)2·4H2O ler SE 40LI). The obtained products were exam- crystallizes in the orthorhombic system, whereas ined by X-ray diffraction analysis. The studies were Zn3(PO4)2 in the monoclinic system. The volume of performed on a X’Pert PRO (Philips) diffractometer the unit cell of these compounds amounts, respec- using the X-ray tube with a cobalt anode. The phase tively 0.978 nm3 and 0.668 nm3. composition and the average of crystallite size of In the second series of experiments, the method obtained compounds were determined. The of zinc phosphate preparation was changed. The changes of crystallites average size were deter- process was carried out in the presence of citric mined using Scherrer’s equation [6]. The average acid complexing the zinc ions in the reaction of pre- size of crystallites was calculated from the (460) cipitation of zinc phosphate and causing the for- mation of gel during a stage of the concentration of reflection of Zn3(PO4)2·4H2O (JCPDS 33-1474) and post-reactive mixture. The final stage of the pro- the (611) reflection of Zn3(PO4)2 (JCPDS 29-1390). The width of the peak at half maximum value was cess was a high-temperature crystallization of zinc phosphate. 48 B. Grzmil, B. Kic and K. Lubkowski

Fig. 1. The diffraction pattern of products: (a) – Fig. 2. The diffraction pattern of zinc phosphate. Zn (PO ) ·4H O obtained as a result of the reac- • 3 4 2 2 – Zn3(PO4)2. tion of zinc nitrate with diammonium phosphate;

(b) – Zn3(PO4)2 after the calcination process and ο (c) – Zn3(PO4)2·4H2O after hydration. – • Zn3(PO4)2·4H2O, – Zn3(PO4)2.

In the subsequent studies, the following param- following processes: the synthesis of eters were changed: the molar ratio of the reagents Zn3(PO4)2·4H2O from diammonium phosphate and

(Zn(NO3)2:(NH4)2HPO4:C6H8O7 = (1.5-1.8):l:(0.8- zinc nitrate, a low-temperature calcination of pre- 2.3), calcination time, and temperature of the sec- cipitated phosphate and the hydration of interme- ond stage of calcination. A solid citric acid was diate. Whereas an anhydrous zinc phosphate with added to a solution of zinc nitrate (39-82 wt.%) and the average crystallite size of about 40 nm can be subsequently a solid diammonium phosphate or obtained in the process of a two-stage calcination its solution (30-57 wt.%). (initially at a low temperature, and subsequently at As a result of performed experiments, a pure a higher temperature) of the gel obtained as a re- zinc phosphate or this compound with a small frac- sult of the treatment of aqueous solution contain- tion of zinc was obtained depend- ing Zn(NO3)2, (NH4)2HPO4 and citric acid. ing on the process parameters. The average size of Zn3(PO4)2 crystallites was varied and amounted REFERENCES to 43-130 nm. On the basis of performed studies it was found, [1] Ullmann’s Encyclopedia of Industrial that at the appropriate molar ratio of reagents and Chemistry (Wiley-VCH 2002). the salt concentration in the reaction mixture, the [2] M. Grigoriu, V. Artemie, G. Nastase and calcination of intermediate, initially at temperature I. Ivanovici // Pat RO 110695 (1996). 453K for 5 min, and subsequently at 973K for [3] D. D. Vasovic and D. R.Stojakovic // Mater. 60 min, a pure zinc phosphate with the average Res. Bull. 32 (1997) 779. crystallite size of about 43 nm can be obtained. The [4] Gong Qingjiang and Cui Bo // Ferrous Metals diffraction pattern of this product was presented in and Alloys 32 (1999) 29. Fig. 2. [5] G. Sziklai, I. Szucs and E. Megyeri-Kanya // Hung. J. Ind. Chem. 10 (1982) 215. [6] F.H. Chung and D.K. Smith, Industrial 2. CONCLUSIONS Application of X-Ray Diffraction (Marcel It was found that a nanocrystalline zinc phosphate Dekker, Inc, New York-Basel 2000). tetrahydrate (about 30 nm) can be obtained in the