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Powder Technology 186 (2008) 263 266

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Synthesis of an industrially important zinc borate, 2ZnO3B2O33H2O,

by a rheological phase reaction method
Xixi Shi, Yong Xiao, Ming Li, Liangjie Yuan , Jutang Sun
College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, People's Republic of China
Received 4 December 2006; received in revised form 13 December 2007; accepted 20 December 2007
Available online 3 January 2008

Abstract

2ZnO3B2O33H2O is an industrially important zinc borate. Herein, 2ZnO3B2O33H2O has been prepared via a rheological phase reaction
method using zinc oxide and boric acid as starting materials. This route is facile and acceptable for green chemical synthesis, producing no
pollution and giving a yield of near 100% of theoretical value. And in this method, the complete conversion of the starting materials can be
achieved in the presence of only 0.04 mL water (one drop of water). The products have been characterized by X-ray powder diffraction (XRD),
thermogravimetry (TG) and differential thermal analysis (DTA), scanning electron microscopy (SEM) and particle size distribution. The effects of
experimental conditions on the products were investigated. The main factors that affect the formation of zinc borate are water volume, sealing
state, reaction time and temperature.
2008 Elsevier B.V. All rights reserved.

Keywords: 2ZnO3B2O33H2O; Rheological phase reaction method; Green chemistry

1. Introduction to develop green chemical synthesis becomes a great challenge for

Zinc borates have been used in industry since the 1940s [1],
and with the discoveries of hydrated zinc borates with different
compositions [24], it has been found that 2ZnO3B2O33H2O [5]
has the most important industrial applications such as flame
retardant [6], smoke-suppressant [7], anticorrosive pigment [8],
ceramic flux and modifier of electrical and optical properties [5].
In order to seek for environmental and health safety fire retardants
with better fire performance, much efforts have been focused on
the inorganic fire retardants, e.g. zinc borates [9,10], magnesium
hydroxide [Mg(OH)2] [11,12] and aluminum trihydrate [Al(OH)3]
[13,14]. There are major advantages in using 2ZnO3B2O33H2O
as flame retardant because of its high thermal stability [6], no
toxicity, low cost [15], and good performance in particular in
halogen-free systems [16].
Green chemistry has received much attention due to increased
concerns about environment and sustainable development. Thus,
Corresponding author. Tel.: +86 27 87218264; Fax: +86 27 68754067.
E-mail address: ljyuan@whu.edu.cn (L. Yuan).
0032-5910/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2007.12.014
materials scientists. Up to now, many approaches [5,6,17] have
been undertaken for the preparation of ZnO3B2O33H2O. The
zinc source materials include zinc oxide, zinc salts, and zinc
hydroxide, and the boron source materials employed can be boric
acid and borax. A characteristic feature of these routes at present is
that the reactions are carried out in aqueous solution. That is, the
reactants are dissolved in water to react, or react in aqueous slurry
formed by boric acid solution which was initially obtained by
heating and other solid-state starting materials. In these methods,
the ratio of reactants and reaction conditions need rigid control and
complete conversion of the reactants cannot be ensured. Although
the mother liquor can be circularly used, it is impossible to up to
complete use of reactants. Inevitably, these methods lead to
pollution and waste more or less. Moreover, these preparations
require multi-step processes such as agitation, filtration, wash and
the like before getting the final product.
In the present study, we introduce a simple rheological phase
reaction method [18,19] that does not contain troublesome
processes. Rheological phase reaction method is a process for
preparing compounds or materials from a solidliquid rheological
264 X. Shi et al. / Powder Technology 186 (2008) 263266

Fig. 1. Process flow chart of rheological phase reaction method.

Fig. 2. XRD patterns of samples obtained in the presence of different amounts of

mixture. The solid reactants were fully mixed in a proper molar
ratio, by adding a proper amount of water or other solvents to form
a solidliquid rheological body in which the solid particles and
liquid substance were uniformly distributed. After reacting under
suitable conditions, the final product was obtained. In this state,
because the solid particles and liquid phase were uniformly
distributed, there exist many advantages: the surface area of solid
particles can be efficiently utilized, the contact between solid
particles and fluid is close and uniform, heat exchange is very
efficient, local overheating can be avoided, and the reaction
temperature can be easily controlled.
In this work, the rheological phase reaction method was
employed to synthesize ZnO3B2O33H2O. Unlike previous
traditional methods, this route is very simple and acceptable for
green chemical synthesis [20], producing no pollution and
giving a yield of near 100% of theoretical value.
distilled water: (a) S1; (b) S2; (c) S3; (d) S4; (e) S5.
duct S1 was obtained directly by drying at 120 C for 6 h in air
without filtering and washing processes. The procedure is sum-
marized in Fig. 1. S2S10 were obtained under different conditions
(see Table 1).
The samples were characterized by the X-ray powder dif-
fraction (XRD) on a Shimadzu XRD-6000 diffractometer (Cu
K1, 40 kV, 30 mA). The thermal analyses were carried out on
Netzsch STA499 simultaneous thermal analyzer from 20 to
1000 C in air at the rate of 20 C/min. The morphologies of the
products were observed by scanning electron microscopy (SEM),
taken on a Hitachi SEM X650 performed at 25 kV. The particle
size distributions of products were estimated with a Malvern
Mastersizer 2000.

2. Experimental 3. Results and discussions

In order to make complete use of reactants and avoid importing
any impurity, stoichiometric ratio of zinc oxide (ZnO) and boric
acid (H3BO3) of analytical grade were used as starting materials. In
a typical reaction, a uniform rheological phase was made by mixing
zinc oxide 1.62 g (0.02 mol) and boric acid 3.71 g (0.06 mol)
manually with 3 mL distilled water. Then the rheological phase
reaction took place in a closed container at 95 C for 8 h. The two
starting materials reacted completely according to the equation:
2ZnO + 6H3BO3 = 1[2ZnO3B2O33H2O] +6H2O. The white pro-
3.1. Determination of the composition of the product
The XRD pattern for S1 is given in Fig. 2a. All diffraction
peaks of the XRD pattern of S1 can be indexed to 2ZnO3B2
O33H2O (JCPDS files No. 32-1464). No impurity phases were
detected by X-ray diffraction, which indicated that S1 obtained via
our current method was a pure phase 2ZnO3B2O33H2O.
Additionally, the yield of product is near 100% of theoretical
value because no reactants were lost in the reaction process.

Table 1
Summary of the reaction conditions of some representative experiments
Sample Temperature (C) Time (h) Distilled water (mL) Reaction environment 2ZnO3B2O33H2O obtained?
S1 95 8 3.00 Sealed autoclave Yes
S2 95 8 0 No
S3 95 8 0.04 Yes
S4 95 8 4.00 Yes
S5 95 8 18.70 No
S6 85 10 3.00 Yes
S7 80 24 3.00 No
S8 95 7 3.00 Yes
S9 95 6 3.00 No
S10 95 8 3.00 An open vessel No
 X. Shi et al. / Powder Technology 186 (2008) 263266 265

Fig. 3. TG-DTA curves of S1.

3.2. Thermal analysis

Fig. 4. XRD patterns of samples prepared at different temperatures, time and in
TG-DTA curves for S1 are shown in Fig. 3. On the TG curve, a different reaction environments: (f) S6; (g) S7; (h) S8; (i) S9; (j) S10.
sharp weight loss (12.98%) begins to happen when the tempe-
rature is around 290 C. This process is corresponding to loss when the temperature was above 85 C could the aimed product
of water of crystallization through condensation of BOH be obtained. When reaction temperature was raised, shorter
groups, giving birth to the substantially amorphous composition reaction time was required. The rate of reaction increased with a
of 2ZnO3B2O3. At the temperature between 640 and 700 C, temperature rise. The formation of aimed products also de-
there is an exothermic behavior owing to crystallization of two pended on the reaction time. XRD patterns of S1, S8 and S9
anhydrous zinc borate phases, 3ZnO2B2O3 and 4ZnO3B2O3. (Figs. 2a, 4h and i, respectively) obtained from different time at
Along with heating, 3ZnO2B2O3 turns to a liquid and crystalline 95 C revealed that the reaction would not occur completely if
4ZnO3B2O3 completely, which can be observed around 870 C. the reaction time was less than 6 h. 2ZnO3B2O33H2O would
Finally, 4ZnO3B2O3 melts at 960 C [5,21]. not be obtained when a contrast experiment was carried out in an
open environment (S10; Fig. 4j), where the water in the reaction
3.3. Effects of experimental conditions system was vaporized during heating process. This result is
identical with the experiment on S2.
As summarized in Table 1, control experiments were carried out
to investigate the influences of different conditions in the system 3.4. Particle size distribution and morphology of the particles
with the quantity of reactants constant. In order to study the impact
of water volume on the preparation, a range of volume of water The particle size of 2ZnO3B2O33H2O is of great importance
from 0 mL to 18.7 mL were respectively added to the reaction to its industrial applications. Fig. 5 presents the particle size of S1
systems taken at 95 C for 8 h. The XRD patterns are shown in and S3. The average particle size of S1 and S3 is 19.052 m
Fig. 2. No chemical reaction was observed from Fig. 2b (0 mL (D10 = 5.740, D50 = 19.052, and D90 = 46.801 m) and 96.736 m
water in the mixture), the diffraction lines were attributed to two
separate phases, ZnO and H3BO3. The result indicates that the
reaction cannot be conducted without water. It was interesting that
the reaction could completely occur when only 0.04 mL water (one
drop of water) was added, the aimed product was obtained (shown
in Fig. 2c), and no remainders of unreacted reactants in the product.
The reason can be speculated that the 0.04 mL water ensures that
the reactants are in a rheological state within the area of water,
where boric acid dissolve partially first, along with the product of
water in reaction, reactants dissolve continuously and thus ensure
the completion of reaction. Studies also demonstrated that
2ZnO3B2O33H2O could be gotten with the increase of the
amount of water (4 mL) as long as the reaction system remained a
rheological phase (Fig. 2d). When the reaction system was not a
rheological phase any more in the presence of an excessive amount
of water (18.7 mL), 2ZnO3B2O33H2O could not be produced
(shown in Fig. 2e).
Figs. 2a, 4f and g show the XRD patterns of the samples (S1,
S6 and S7) prepared at different temperatures, respectively. Only Fig. 5. Particle size distribution of products: (a) S1 and (b) S3.
266 X. Shi et al. / Powder Technology 186 (2008) 263266

Fig. 6. SEM images of products: (a) S1; (b) S3.

(D10 = 44.489, D50 = 96.736, and D90 = 199.327 m), respectively. ditions on the products were also discussed. Water volume, sealing
Because S1 and S3 were obtained in the presence of different state, reaction time and temperature greatly affect the reaction.
amounts of water when keeping other conditions constant, the
different particle sizes of these two products indicate that the Acknowledgement
quantity of water in the reaction system has an effect on the
particle size of product. The product has smaller particle size if Support of this work by the National Natural Science
more water is added. S1 and S3 were further characterized by Foundation of China is gratefully acknowledged (No.
SEM observations (Fig. 6), which show that the grains consist of 20671074).
layered plates, and the particle size is consistent with the
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