Journal of Non-Crystalline Solids 354 (2008) 54325434

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/locate/jnoncrysol

A new chemical strategy: Mineralizer-free synthesis of iron zircon ultrane particles by an epoxide assisted solgel route
Hongtao Cui *, Wanzhong Ren
College of Chemistry and Biology, Yantai University, 32 Street Qingquan, Yantai, Shandong 264005, China

a r t i c l e

i n f o

a b s t r a c t
Ultrane iron zircon particles were prepared by a solgel route using propylene oxide as a gelation agent. The unique chemistry of this method produces highly homogeneous gel intermediate, resulting in the substantial lowering of heat treatment temperature to 1000 C without using of mineralizer. This calcination temperature is lower than that in solid-state chemistry and other solgel routes, leading to the minimizing of the particles aggregation and growth. The non-mineralizer synthesis process guarantees the preparation of pure phase and high quality iron zircon with ultrane particle size. This epoxide assisted solgel route shows great potential as a general procedure for the large scale production of ultrane particles of zircon based pigments. 2008 Elsevier B.V. All rights reserved.

Article history: Received 14 December 2007 Received in revised form 22 August 2008 Available online 9 October 2008 PACS: 61.43.Gt 81.16.Be 81.20.Fw Keywords: Ceramics Solgels (xerogels)

1. Introduction Zircon hosted pigments have been widely applied in the ceramic industry for decades owing to their thermal stability and chemical durability in corrosive environment. The doping of different metal ions (iron, vanadium and praseodymium) in zircons lattice produces various clean and bright colorations (red, blue and yellow). These colorations constitute parts of the most important colors for the ceramic glazes [14] due to their excellent chemical, physical performance, and their generation of a wide variety of tones. An interested new application of inorganic pigments in high temperature ink has triggered great attention in the ceramic industry. The inks can be printed at very high temperatures (800 1100 C) on vitreous, metallic or ceramic surfaces for the decoration and marking [57]. Having small particle size is one of the most important requirements for the pigments to be applied in ink applications, because the control of particle size can promote the performances of ink greatly such as thixotopic ability, coloring ability and disperse stability. The traditional preparation of zircon based pigments is through solid-state chemistry route, where SiO2, ZrO2, and the coloring compounds are mixed homogeneously, and then heat treated at temperature of above 1300 C for long time. The high temperature and long reaction time resulted in the serious aggregation and growth of the particles. The obtained particulate product, with
* Corresponding author. E-mail address: htcui@ytu.edu.cn (H. Cui). 0022-3093/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jnoncrysol.2008.08.009

large particle size and very wide size distribution, does not meet the requirement of some applications such as high temperature ink. Usually, mineralizers [8], such as NaF and LiF, are added into the precursor mixture to lower the reaction temperature to around 1000 C. However, mineralizer can induce serious aggregation of the particles, and lead to the formation of impurity through the reaction with reactants. Although mineralizer and impurity can be washed away, the washing procedure usually deteriorates the performance of the pigments. The only way of solving the problem is to promote the homogeneity of the individual ions in the obtained intermediates. This decreases the diffuse distance of the ions required for reaction, which lowers the reaction temperature, thus reducing the aggregation of the particles. The promotion of homogeneity of zircon based pigments precursors can be achieved through wet chemistry route, usually solgel method [912]; 20 200 nm shape controlled particles were prepared by a pyrolysis method [13]. However, disadvantage of this route is its complicated procedure including drying at 250 C, then decomposition at 500 C, nally calcinations at high temperature. The common problem of all the existing procedures for the preparation of zircon is that pure phase of zircon cannot be obtained, even when mineralizers are used, because the homogeneity of the prepared intermediates is not high enough to completely accomplish the phase transformation of zircon during the calcination. In this work, a new chemical strategy, epoxide assisted solgel route, was adopted to synthesize iron zircon (FeZrSiO4) ultrane particles. Simple procedure and cheap precursors were used in this route, showing characteristics for large scale preparation of

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ultrane particles of zircon hosted ceramic pigments. The epoxide acts as an acid scavenger to consume protons from the metal aquo complexes [M(H2O)x]n+, which promotes the hydrolysis and condensation of the complexes resulting in the formation of solgel [1416]. The unique chemistry of this route lead to the lowering of calcination temperature as compared with solid-state chemistry and other solgel methods, avoiding the using of mineralizer and minimizing the aggregation of particles. Another advantage of this route is that pure phase of iron zircon can be obtained at a moderate calcination temperature.

100 200

264 C
90

150

80 70 60

DTA (V)

50

168 C 842 C
50 40 30 20 100 200 300 400 500 600 700 800 900

2. Experimental
-50

64 C

2.1. Materials Iron chloride tetrahydrate (FeCl2 4H2O), zirconium oxychloride octahydrate (ZrOCl2 8H2O), tetraethyl orthosilicate (TEOS), and propylene oxide were obtained from Aldrich. Methanol was from Merck. All the reagents were used as received. 2.2. Preparation of iron zircon ultrane particles FeCl2 4H2O and ZrOCl2 8H2O with a molar ratio of 0.2 were dissolved in methanol. After propylene oxide was added into the solution (the molar ratio of propylene oxide and metal ions is kept at 10), an exothermic reaction occurred and a transparent gel was formed within a few seconds. The gel was aged at ambient temperature for 12 h, subsequently dried at 100 C for 12 h to obtain the xerogels. The resulting xerogels were ground to powder and calcined at different temperatures for some hours. 2.3. Characterization The thermal behavior (TG/DTA) of the samples was studied by a Seiko SSC/5200 (TG/DTA 320 U) in static air atmosphere from ambient temperature to 1000 C at a heating rate of 10 C/min. The XRD patterns of the samples were measured in a Siemens D8 diffractometer using CuKa radiation. The morphology of the particles was observed using a JEOL 2000 transmission electron microscope working at 200 kV.
Temperature (C)

Fig. 1. TG/DTA analysis of a precursor gel carried out in static air.

The XRD patterns of samples calcined at different temperatures are shown in Fig. 2 to study the phase transformation of samples with the increase of calcination temperature. The sample heat treated at 800 C presents a structure of tetragonal zirconia (JCPDS 49-1642). When the temperature is increased to 900 C, a second phase of zircon (JCPDS 71-0991) is produced; however, tetragonal zirconia remains as the main phase. The appearance of zircon phase at 900 C agrees with the result of DTA/TG. A higher calcination temperature at 1000 C produces a pure phase of zircon, which is due to the high homogeneity of the precursor gel. The XRD patterns of samples calcined at 1000 C for different times are shown in Fig. 3. The sample heat treated for 3 h presents the coexistence of tetragonal zirconia and zircon, where zircon is the main phase. When the calcination is prolonged to 6 h, most of the tetragonal zirconia is converted to zircon. Further heating for another 2 h, only zircon can be observed in its XRD pattern. The TEM micrograph of the sample calcined at 1000 C for 8 h is presented in Fig. 4, which shows the morphology of obtained iron zircon particles. It gives the submicron particles about 200300 nm. As shown in higher magnication image (inset in Fig. 4), these particles are composed of smaller nanoparticles about 2050 nm, which are aggregated together resulting from the calcination.

3. Results DTA/TG measurements were carried out in order to study the thermal behavior of the precursor gels, including the decomposition temperature of the organic matter and the weight loss. The thermal curve (Fig. 1) of the iron zircon precursor show a progressive weight loss of about 29% from room temperature to around 130 C, accompanied by an endothermic peak around 64 C, that is attributed to the evaporation of adsorbed water. The exothermic behavior in DTA curve, beginning from around 168 C and peaking at 264 C is due to the burning of organic matter produced from the reaction between propylene oxide and aquo complexes of metal ions. The corresponding weight loss of organic matter is estimated about 32% of the original precursor, much less than that of other solgel route such as citric gel route, which is very important for the large scale production of pigments. Above 400 C, a atter weight loss curve is observed due to the release of water arising from condensation reaction. The total weight loss from room temperature to 1000 C is about 67%. A small exothermic peak is observed around 842 C, assigned to the phase transformation from tetragonal zirconia to zircon, which will be proven in the following XRD spectra.

Zircon

o Zirconia

20 30 40 50

1000C

900 C

60

800 C
70

2
Fig. 2. XRD patterns of samples calcined at different temperatures for 8 h.

TG (%)

100

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Zircon

o Zirconia

8 hours

40

6 hours

50

3 hours

60

70

20

2
Fig. 3. XRD patterns of samples calcined at 1000 C for different times.

releasing water and forming MOM bonds. The PPO acts as a proton scavenger, reacting with the protons which come from the hydrolysis of the aquo complexes. The protonated propylene oxide is then irreversibly ring-opened. [Zr(H2O)6]4+ species owns strong acidity as compared with other aquo metal ions, resulting in the rapid reaction of metal ions and TEOS with PPO and the rapid gelation in seconds. As in experiment, the hydrolysis and condensation of TEOS alone in methanol are slow, usually requiring hours for gelation. However, the observation of the gelation process and the characterization results show that the hydrolysis and condensation of TEOS and Zr4+ ions, which are mixed together in methanol, are completed almost simultaneously within a short time, resulting in the highly homogeneous gel and the lowering of the reaction temperature. This demonstrates that the reaction occurring between Zr4+ ions and PPO promotes and accelerates the hydrolysis and condensation of TEOS in an unclear mechanism. The thermal behavior analysis reveals the crystallization temperature of zircon around 842 C. Pure phase zircon was obtained at the calcination temperature of 1000 C, which is much lower than that of solid-chemistry route. This is due to the high homogeneity of individual ions in the intermediate gel, which greatly decreases the diffuse distance of different ions. Therefore, as shown in TEM micrograph, ultrane particles of 200300 nm can be prepared under mild calcination temperature. 5. Conclusion Iron zircon ultrane ceramic particles were prepared by a mineralizer-free chemical strategy, epoxide assisted solgel route. Cheap precursors and simple procedure were adopted, using the reaction of propylene oxide with metal ions in methanol solution, followed by drying and calcination of intermediate gels. The unique chemistry of this route guarantees the minimization of difference in chemical reactivity between TEOS and metal ions. This results in the synthesis of highly homogeneous gel intermediate, lowering calcination temperature without using of mineralizer as compared with solid-state chemistry and other solgel routes. Therefore, pure phase ultrane particles of iron zircon were prepared, which can be used in small particle size required applications such as high temperature ink. This epoxide assisted solgel route with abovementioned advantages exhibits a promising future for the large scale production of ultrane particles of zircon based pigments.

Fig. 4. TEM micrograph of sample calcined at 1000 C for 8 h.

References
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4. Discussion

H O [M(H2O)6] n+ + A- + C C [M(OH)(H2O)5] n-1 + O+ C C + A-

ring opening OH C H C A

[9] [10] [11] [12] [13] [14] [15] [16]

During the preparation, the aquo complexes [M(H2O)6]n+ (M = Fe2+, Zr4+) react with propylene oxide (PPO) to form MOH bonds as shown in Eq. (1). The hydrolyzed ions will undergo condensation,