ARTICLE IN PRESS

Journal of Crystal Growth 311 (2009) 1545–1552

Contents lists available at ScienceDirect

Journal of Crystal Growth

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

Improved synthesis of fine zinc borate particles using seed crystals

- akal b, İnci Eroğlu a, Saim Özkar c,
Deniz Gürhan a, Gaye Ö. C
a
Department of Chemical Engineering, Middle East Technical University, 06531 Ankara, Turkey
b
National Boron Research Institute, BOREN, Dumlupınar Bulvarı 166-10, 06520 Ankara, Turkey
c
Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey

a r t i c l e in fo abstract

Article history: Zinc borate is a flame retardant additive used in polymers, wood applications and textile products.
Received 16 December 2008 There are different types of zinc borate having different chemical compositions and structures. In this
Accepted 16 January 2009 study, the production of zinc borate having the molecular formula of 2ZnO  3B2O3  3.5H2O was
Communicated by T.F. Kuech
reexamined by studying the effects of reaction parameters on the properties of product as well as the
Available online 25 January 2009
reaction kinetics. Production of zinc borate from the reaction of boric acid and zinc oxide in the presence
PACS: of seed crystals was performed in a continuously stirred, temperature-controlled batch reactor having a
82.80.d volume of 1.5 L. Samples taken in regular time intervals during the experiments were analyzed for the
82.40.g concentration of zinc oxide and boron oxide in the solid as well as for the conversion of zinc oxide to
87.15.A
zinc borate versus time. The zinc borate production reaction was fit to the logistic model. The reaction
rate, reaction completion time, composition and particle size distribution of zinc borate product were
Keywords:
determined by varying the following parameters: the boric acid to zinc oxide ratio (H3BO3:ZnO=3:1,
A1. Crystallites
A1. Growth models 3.5:1, 5:1 and 7:1), the particle size of zinc oxide (10 and 25 mm), stirring rate (275, 400, 800 and
A2. Growth from solutions 1600 rpm), temperature (75, 85 and 95 1C) and the size of seed crystals (10 and 2 mm). The products
A2. Seed crystals were also analyzed for particle size distribution. The experimental results showed that the reaction rate
B1. Borates increases with the increase in H3BO3:ZnO ratio, particle size of zinc oxide, stirring rate and temperature.
B1. Zinc compounds Concomitantly, the reaction completion time is decreased by increasing the H3BO3:ZnO ratio, stirring
rate and temperature. The average particle sizes of the zinc borate products are in the range 4.3–16.6 mm
(wet dispersion analysis).
& 2009 Elsevier B.V. All rights reserved.

1. Introduction (Eq. (1)) [2–5]:

6BðOHÞ3 ðaqÞ þ 2ZnOðsÞ ! 2ZnO  3B2 O3  3:5H2 OðsÞ þ 5:5H2 OðlÞ

Zinc borate is a boron-based inorganic material widely used as
flame retardant, antibacterial and additive to protect wood
products aboveground from insect and fungal attacks [1]. Zinc
borate can be isolated as crystalline material in various forms
having different chemical compositions and structures. One of
them is crystalline zinc borate with the formula of
2ZnO  3B2O3  3.5H2O, which has the unusual property of retaining
its water of hydration at temperatures up to 290 1C. This thermal
stability makes it attractive as a fire retardant additive for plastics
and rubbers that require high processing temperatures [2].
Therefore, it has been widely used for this purpose. This form of
zinc borate has been produced by the reaction of zinc oxide
and boric acid at proper temperature and mixing conditions
Corresponding author. Tel.: +90 312 210 3212; fax: +90 312 210 3200.
E-mail addresses: denizgurhan@hotmail.com (D. Gürhan), gaye@boren.gov.tr
- akal), ieroglu@metu.edu.tr (İ. Eroğlu), sozkar@metu.edu.tr (S. Özkar).
(G. C
(1)
When the zinc borate, 2ZnO  3B2O3  3.5H2O, is used as an
additive, particles of small size are preferred for an effective and
uniform distribution of particles in the matrix [6]. It is our idea to
produce zinc borate in particles as small as possible by optimizing
the experimental conditions. For this purpose, a comprehensive
study was conducted to determine the effects of experimental
parameters (boric acid to zinc oxide ratio, the particle size of zinc
oxide used, stirring rate, temperature and usage of seed crystals)
on the particle size of zinc borate, conversion of zinc oxide and the
compositional change of zinc borate during the production
reaction. Experimental data collected were also used for model-
ing the reaction of zinc borate production. In conducting the
experiments, the following were assumed to enhance the reaction
rate, and thus to decrease the lag time and completion time of the
reaction: (i) increasing the initial concentration of boric acid up to
the saturation value at the respective temperature, (ii) adding
zinc borate crystals as seed (since the solubility of zinc borate
is 0.1 g/100 mL [7] while zinc oxide is insoluble, zinc borate is

0022-0248/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2009.01.111
 ARTICLE IN PRESS
1546 D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552
initially added to the solution in the amount slightly above the
saturation value), (iii) decreasing the particle size of zinc oxide
used in the reaction.
2. Materials and methods
2.1. Materials
Boric acid (H3BO3, with a purity of 99.9% by weight), zinc oxide
(ZnO, with a minimum purity 99%), zinc borate (2ZnO  3B2O3 
3.5H2O) and distilled water were used to produce zinc borate.
Boric acid (H3BO3) was provided from Emet Boric Acid Plant,
Kütahya, Turkey. Zinc oxide of two different particle sizes 10 and
25 mm size was purchased from MKS Limited (Istanbul, Turkey)
and Kartal Oksit Limited (Ankara, Turkey), respectively. Zinc
borate with the simplest formula of 2ZnO  3B2O3  3.5H2O in two
different sizes of 10 and 2 mm was purchased from Great Lakes
(USA) and Borax Morarji Limited (Bombay, India), respectively.
2.2. Experimental set-up
Experimental set-up described elsewhere [8] was also used
in this study. Essentially, it consists of a reactor with a volume
of 1.5 L, a mechanical stirrer, a heating jacket, a pH meter, a
thermocouple, a temperature control unit and a vacuum pump.
The batch reactor was made up of borosilicate glass. Inside
diameter and height of the reactor were 12 and 30 cm,
respectively. The top section of the reactor was covered by an
acrylic glass (plexiglas) plate, having four entrances. At the center,
a mechanical stirrer (Heidolph RZR 2041) was placed. One of the
entrances was for placing the thermocouple, which was con-
nected to the temperature controller. The reaction temperature
was kept constant at a preset value during each experiment by
means of the controller. The third entrance was used for feeding
the reactants in the reactor and placing the pH electrode inside
the reactor. The samples were withdrawn from the last entrance
by means of a 50 mL syringe attached to a glass pipe.
The product, zinc borate, was isolated as solid material by
vacuum filtration. This unit consists of a vacuum pump (KNF
NO22, Germany) connected to a flask and a funnel. Filter paper
(blue band) was placed on the funnel and solid particles were
collected on the filter paper, whereas the solution was collected in
the flask.
2.3. Experimental procedure
First, the boric acid used in the experiment was dissolved in
water. This solution was prepared in such a concentration that
provides the saturation value of boric acid at the temperature
of experiment performed. The mechanical stirrer was started to
operate at the desired stirring rate. The temperature control unit
was adjusted to the reaction temperature. After the boric acid
solution reached the preset temperature in the reactor, zinc oxide
was added slowly into the reactor. Lastly, zinc borate, acting as
seed in the reaction, was added in an amount of about 1.5%
of boric acid present in the solution. The time for adding the seed
was considered as the start of the reaction. The samples were
withdrawn by a syringe attached to a glass pipe. Then, samples
were filtered immediately with a syringe filter attached to the
syringe and washed with hot water to remove the excess boric
acid stacked to the particle surface. The filtrate was analyzed for
boric acid concentration and the solid remnant was analyzed to
determine B2O3 and ZnO contents.
2.4. Analysis
Boric acid amount in the liquid phase and zinc oxide and boric
acid amounts in the solid phase were determined by titration. The
particle size distribution and the X-ray diffraction analysis of the
solid product were performed. The crystal images were obtained
by using a light microscope.
2.4.1. Determination of zinc oxide in solid sample
Zinc oxide was determined in solid samples by following EDTA
titration [9]. The reagents were prepared as described in the
literature [2]. The solid sample (0.2–0.3 g) was dissolved in 37%
hydrochloric acid (1 mL), and ammonia buffer solution (15–20 mL)
was added to hold the pH around 9.5. The final solution was
titrated with EDTA by adding a few drops of Erichrome Black T
indicator. Zinc oxide percentage in the solid phase was calculated
from [9]
PZnO ¼ 0:004069n V EDTA =n (2)
where PZnO, VEDTA and n are the weight percentage of ZnO in the
sample, the volume of EDTA used and the amount of sample,
respectively.
2.4.2. Determination of B2O3 in solid sample
The solid sample (0.2–0.3 g) was dissolved in 37% hydrochloric
acid (1 mL) and EDTA was added in excess amount to remove zinc
ions from the solution. The solution was titrated with 1 N NaOH
until pH reached 7. Then mannitol (10–15 g) was added to the
solution and it was again titrated with 1 N NaOH until the pH of
the solution reached 7. Boric acid percentage in the solid phase
was calculated by noting the volume of NaOH used in the second
titration
PB2 O3 ¼ 0:348101n ðV nNaOH F NaOH Þ=n (3)
where PB2 O3 , VNaOH, FNaOH and n are the weight percentage of B2O3
in the sample, the volume of NaOH solution used, the factor of
NaOH solution and the amount of solid sample, respectively.
2.4.3. Determination of boric acid in solution
Two–three drops of methyl red indicator were added to the
filtrate. Then H2SO4 (1:3 by vol.) was added to the solution until
the color of the solution was pink. The solution was titrated with
6 M NaOH until the color changes from pink to yellow. H2SO4 was
added until the color of the solution turns back to pink. The
solution was titrated with 1 M NaOH until a pH of 4.5 was
obtained. Phenolphthalein indicator and 2–3 g mannitol (obtained
from Merck) were added to the solution. Finally, the solution was
titrated with 1 M NaOH until the pH of the solution became 8.5.
The volume of NaOH solution used in the second titration step
was recorded. Boric acid concentration in the liquid phase was
calculated by using [10]
cBt ¼ V NaOH F NaOH =V sample (4)
where cBt, VNaOH, FNaOH, NNaOH and Vsample are the concentration of
boric acid solution in the sample taken, the volume of the NaOH
solution used, factor of the NaOH solution, normality of NaOH and
the volume of the sample, respectively.
2.4.4. Particle size distribution analysis
The particle size distributions of the solid samples were
determined by a particle size analyzer (Malvern Instruments,
Mastersizer 2000), utilizing the principle of laser ensemble light
scattering. This instrument can detect the particle range
0.02–2000 mm. The analysis was carried out using either wet or
dry dispersion method with a repeatability of 70.5%. Water was
 ARTICLE IN PRESS

D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552 1547

used as dispersant during the wet dispersion analysis. During this
analysis a portion of the solid sample was diluted with water until
the obscuration ratio reaches 0.15. In dry dispersion analysis, solid
sample was given directly to the instrument.
2.4.5. TG/DTA analysis
Thermal behaviour of the selected final products was studied
by using a Setaram Lbsys TGA/DTA Simultaneous Thermogravi-
metric Analyzer and a Differential Thermal Analyzer. The
measurements were performed using platinum crucibles in air
atmosphere. A uniform heating rate of 10 1C/min was applied
during the measurements.
2.4.6. XRD analysis
To study the crystal structure of the produced zinc borate
powder, X-ray diffraction analysis was carried out. XRD patterns
were recorded from 101o2yo90 1C by using the Rigaku Miniflex
X-ray Diffractometer/PW 3710 equipped with Cu Ka1 radiation.
2.4.7. Light microscope image analysis
Images of the solid product were obtained by a light
microscope (Prior Laboratory Microscope Model B 3000) con-
nected online to a CCD camera and analyzed using the analytical
imaging software Image Pro Plus 3.0 for Windows.
The powder XRD patterns of the zinc borate products obtained
from the experiments performed were compared with that of
2ZnO  3B2O3  3.5H2O. The XRD data show that the product
obtained from the experiment without seed (Run 1) is not pure
and contains at least two phases (zinc borate and zinc oxide). In
Fig. 1 the powder XRD pattern of the product obtained from the
experiment (Run 6) in the presence of seed is depicted together
with that of 2ZnO  3B2O3  3.5H2O for comparison, showing that
the product is almost purely 2ZnO  3B2O3  3.5H2O. The
comparison of the powder XRD patterns of the products and the
commercial zinc borate showed that 2ZnO  3B2O3  3.5H2O is
usually formed in the experiments performed in the presence of
seed.
TGA results showed that the zinc borate product obtained from
the experiments under different conditions has usually a
dehydration temperature comparable to that of 2ZnO  3B2O3 
3.5H2O (the dehydration starts at 280 1C) with the exception of
the product obtained from the experiment without seed (Run 1 in
Table 2). The TGA also gives an initial weight loss corresponding to
the loss of 3.5 moles of H2O per formula of zinc borate product as
expected [11]. The first conclusion drawn from these results is
that some crystals of 2ZnO  3B2O3  3.5H2O must be added as seed
into the reaction solution for the synthesis of zinc borate.

Table 2
3. Results and discussion Specifications of the final products obtained from the experiments performed at
different operating conditions.

The reaction of zinc oxide and boric acid was performed by Run no. ZnO (%) B2O3 (%) Dehydration Avg. part. Sizesize (mm)
varying the experimental conditions to study the effects of temp. (1C)
experimental parameters on specifications of the final product Dry dispersion Wet dispersion
zinc borate, including the particle size, the reaction time and the a
Seed 1 37.4 48.1 280 5 10.2
conversion of zinc oxide to zinc borate. The reaction kinetic was 1 41.8 40.0 202 –
also modeled using the data collected during the experiments. 2 37.1 48.0 – 3.8 7.7
3 37.0 49.2 – 16.1
4 37.8 47.0 326 6.0
3.1. Effect of experimental conditions on product specification
5 36.8 47.0 – 8.8
6 39.0 48.1 – 3.3 8.2
A total of 15 runs of the reaction between zinc oxide and 7 38.3 47.0 – 8.0
boric acid were performed at different experimental conditions 8 40.0 48.2 330 9.5
9 38.8 46.5 270 4.8
(Table 1). The product was analyzed for its ZnO and B2O3 contents,
10 38.0 46.7 300 4.3
dehydration temperature and particle size. The results are listed 11 39.2 46.5 – 12.7
together with the values of the commercial zinc borate in Table 2. 12 39.2 46.3 – 5.7 14.5
First of all, the product obtained from the reaction in the absence 13 39.7 43.8 – 7.4
of seed (Run 1) has a much higher ZnO content and lower B2O3 14 43.3 44.7 – 9.6
15 39.7 45.9 – 2.9 16.6
content, indicating that the reaction is incomplete. In other words,
not all of the zinc oxide added to the reaction solution is a
Great Lakes ZB-467, http://www.e1.greatlakes.com/freb/common/pdf/
converted to zinc borate. ZB-467_ds.pdf.

Table 1
Experimental conditions.

Run no. Stirring rate (rpm) H3BO3/ZnO mol ratio Size of seed (mm) Temp. (1C) Size of ZnO (mm) Initial boric acid conc. (mol/L)

1 800 5:1 – 95 10 –
2 800 5:1 10 95 10 4
3 1000 7:1 10 95 10 5
4 1600 5:1 10 95 25 5
5 1600 7:1 10 95 10 5
6 1600 5:1 10 95 10 4
7 1600 3.5:1 10 95 10 5
8 1600 3.5:1 10 95 25 5
9 1600 5:1 10 75 25 3
10 1600 5:1 10 85 25 4
11 1600 5:1 2 95 25 5
12 400 5:1 10 95 10 5
13 1600 5:1 10 80 25 5
14 1600 3:1 10 95 10 5
15 275 5:1 10 95 10 5
 ARTICLE IN PRESS

1548 D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552

a This equation can be rearranged into the linear form as follows:

   
1 1
ln  1 ¼ kt þ ln 1 (8)
w wo
Either using the curve fitting software, Curve Expert 1.3, the
experimental data were fit to the integrated rate law (Eq. (6)) or
the linear regression of the data with Eq. (8), the values of two
model parameters k and wo were obtained and listed in Table 3. It
is worth mentioning that the normalized concentration is nothing
but the conversion of zinc oxide, since X* is equal to the maximum
concentration of zinc borate at complete conversion. Xo values are
related to the seed concentration, added to the solution at the
0 10 20 30 40 50 60 70 80 90 100 beginning of reaction. Since zinc borate is initially added as seed
to the solution, the initial normalized concentration wo are
2 theta
nonzero in all experiments but smaller than the experimental
b value wo(exp)=0.0213.
In what follows, the specific growth rate, k, will be discussed
depending on the temperature, stirring rate and zinc oxide
particle size.

3.2.1. Effect of stirring rate

In order to investigate the effect of stirring rate on the reaction
rate and particle size of the product, a series of experiments were
performed starting with the initial molar ratio of the reactants
(H3BO3:ZnO) of 5:1 and particle size of zinc oxide 10 mm at 95 1C
and stirring rate 275, 400, 800 and 1600 rpm (Runs 15, 12, 2 and
0 10 20 30 40 50 60 70 80 90 100
6). The conversion of zinc oxide to zinc borate as determined by
2 theta measuring ZnO and B2O3 in the solid phase is plotted versus time
Fig. 1. The X-ray pattern of zinc borate: (a) commercial one used as seed during
at varying stirring rates in Fig. 2. As the stirring rate increases, one
the experiments and (b) final product obtained at 1600 rpm stirring rate, 5:1 mole observes a decrease in the induction time (the initial part of the
ratio, 95 1C temperature, with 10 mm zinc oxide (Run 6). curves). Although the complete conversion of zinc oxide to zinc
borate is achieved within a period of time less than 200 min at all

3.2. Effect of experimental conditions on the conversion of zinc oxide Table 3

Logistic model parameters for the experiments.
The crystal growth of zinc borate from the reaction of zinc
Run no. k (h1) wo=Xo/X* R2
oxide and boric acid can be modeled by adopting the logistic
model, which has been used for growth in biological systems [12]. 2 0.066 0.0185 0.996
In contrast to the biological system, the extent of reaction in 4 0.165 0.0001 0.999
crystallization is limited to the complete conversion of reactant to 5 0.142 0.0001 1.000
6 0.099 0.0010 1.000
the product. Data for the conversion of zinc oxide versus time 7 0.087 0.0023 1.000
were fit to the logistic model. In this model, the rate law is given 9 0.040 0.0196 0.997
by 10 0.081 0.0072 1.000
11 0.133 0.0001 0.999
  12 0.057 0.0136 0.995
dX X
rate ¼ ¼k 1 n X (5) 13 0.042 0.0131 0.999
dt X 14 0.086 0.0062 0.996
15 0.039 0.0118 0.993
where the rate of crystal growth for zinc borate in M/h is equal to
dX/dt in the case of batch reactor, X is the zinc borate
concentration (M) in the slurry reactor, X* is the maximum zinc
borate concentration (M), and k is the specific growth rate (1/h). 1.0
When X is equal to X* the crystal growth rate is zero. The
ZnO Conversion, X/X*

integrated form of the rate law is 0.8

Xn 0.6
X¼   (6)
X
1þ  1 ekt
Xo 0.4 275 rpm
400 rpm
where Xo is the critical initial concentration of zinc borate. Using 0.2 800 rpm
1600 rpm
the normalized concentrations (w=X/X* and wo=Xo/X*) will reduce
the number of parameters to two, k and wo in the integrated form 0.0
of rate equation 0 50 100 150 200 250
Time, min
1
w¼   (7) Fig. 2. ZnO conversion versus time graph to observe the effect of stirring rate
1
1þ  1 ekt (temperature (95 1C), initial reactants ratio (H3BO3:ZnO ratio 5:1) and type of zinc
wo oxide particles (average particle size 10 mm) were constant).
 ARTICLE IN PRESS

D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552 1549

stirring rates, at an early stage up to 100 min one obtains higher
conversion at higher stirring rate. In general, one can conclude
that the stirring rate has a pronounced effect on reaction rate and
reaction completion time. The change of reaction rate with the
stirring rate shows clearly that the reaction is mass transfer
limited.
The effect of stirring rate can be appreciated much better in
terms of model parameters, wo and k. As seen in Table 3, wo
increases slightly from 0.012 (275 rpm) to 0.019 (800 rpm) with
stirring rate; however, it shows an abrupt decrease on passing
from 800 to 1600 rpm.
The specific growth rate, k, increases with the stirring rate. The
relation of the specific rate, k, to the stirring rate, N, can be
expressed by power law in
k ¼ A Na
lnðkÞ ¼ a lnðNÞ þ lnðAÞ
where a is the exponential power, A is the preexponential factor
that mainly depends on the temperature, and the stirring rate, N,
is given in rpm. The plot of the specific growth rate versus the
stirring rate, both in logarithmic scale, shows a straight line
(Fig. 3), the slope of which gives the exponential power a=0.5.
3.2.2. Effect of reactants ratio
The zinc borate production reaction was studied at different
reactants ratio (H3BO3:ZnO, the initial molar ratio of boric acid to
the zinc oxide) of 3.0:1, 3.5:1, 5:1 and 7:1 at 95 1C, 1600 rpm and
zinc oxide particle size of 10 mm (Runs 14, 7, 6, 5). The results are
given in Fig. 4. The zinc borate 2ZnO  3B2O3  3.5H2O is not formed
when the reactants ratio of H3BO3:ZnO is smaller than 3.5:1. In
experiment 14 (a ratio of 3:1 was used) most of the boric acid
added into the reaction solution was found in solution after the
-3.4
-3.2
-3
-2.8
ln k
reaction. One can conclude that (i) the conversion of zinc oxide
increases with the increasing concentration of boric acid and (ii)
boric acid needs to be used in excess to convert all zinc oxide to
zinc borate. This is in accord with the results reported previously
by Shete et al. [2].
As seen from Table 3 (Runs 5, 6, 7 and 14), the higher the
reactants molar ratio, the larger the specific growth rate (k) and
the smaller the critical initial concentration of zinc borate (wo).
3.2.3. Effect of temperature
The zinc borate production reaction was performed starting
with the initial H3BO3:ZnO mole ratio of 5:1, ZnO particle size of
25 mm at 1600 rpm and at different temperatures 75, 80, 85 or
95 1C (Runs 9, 13, 10 and 4). Fig. 5 shows the conversion of zinc
oxide to zinc borate as determined by measuring the ZnO and
B2O3 contents of solid product obtained at different temperatures.
(9)
As expected, the rate of reaction increases and, thus, the
completion time decreases with increase in temperature.
Comparison of the values of the two model parameters, wo and
k, given in Table 3 at different temperatures indicates that wo
decreases with increase in temperature. This leads to the
conclusion that at higher temperatures a lower seed concentra-
tion is enough as the saturation concentration of zinc borate is
achieved in shorter time at higher temperatures.
The temperature dependence of the specific rate constant is
given by the Arrhenius plot in Fig. 6. The plot of ln(k) versus 1/T
shows a straight line, the slope of which gives the Arrhenius
activation energy Ea=81 kJ/mol for the zinc borate production
reaction. The previously reported activation energy for the same
reaction was 61 kJ/mol [2]; however, in that study no seed has
been used, and compared to the conditions in the present study,
the experiments have been performed at a much lower stirring
rate (350 rpm) and a much lower initial H3BO3:ZnO mole
ratio (3:1).
3.2.4. Effect of seed
As given before, the reaction of boric acid and zinc oxide does
not yield zinc borate product when zinc borate 2ZnO  3B2O3 

3.5H2O is not added to the solution as seed. The question to be

-2.6 addressed now is whether the particle size of the seed crystals has
y = 0.4807x -5.8731
-2.4 R2 = 0.9462 an effect on the reaction product. To answer this question, pairs of
-2.2 experiments were performed starting with the addition of seed
-2 crystals of 2ZnO  3B2O3  3.5H2O in two different sizes under
5.5 6.0 6.5 7.0 7.5 otherwise the same conditions (Table 1). For example, two
ln N experiments Run 4 and 11 were both performed starting with
ZnO having a particle size of 10 mm, an initial H3BO3:ZnO mole
Fig. 3. The plot of Eq. (9), the change of specific growth, k, with stirring rate, N.
ratio of 5:1 at 95 1C and 1600 rpm, but using crystals of

1.0 1.0
ZnO Conversion, X/X*
ZnO Conversion, X/X*

0.8 0.8

0.6 0.6

3:1 75 C
0.4 0.4
3.5:1 80 C
5:1 85 C
0.2 0.2 95 C
7:1

0.0 0.0
0 50 100 150 200 250 0 50 100 150 200 250
Time, min Time, min

Fig. 4. ZnO conversion versus time graph to observe the effect of initial reactants Fig. 5. ZnO conversion versus time graph to observe the effect of temperature
(H3BO3:ZnO) ratio (temperature 95 1C, stirring rate (1600 rpm) and type of zinc (initial reactants ratio (H3BO3:ZnO ratio 5:1), stirring rate (1600 rpm) and type of
oxide particles (average particle size of 10 mm) were constant). Curves denote the zinc oxide particles (average particle size of 25 mm) were constant). Curves denote
logistic model. the logistic model.
 ARTICLE IN PRESS

1550 D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552

-3.5

-3.0

ln k
-2.5
y = -9,7479x + 24,657
R2 = 0,946
-2.0

-1.5
2.70 2.72 2.74 2.76 2.78 2.80 2.82 2.84 2.86 2.88 2.90
1/T*103, K-1

Fig. 6. The Arrhenius plot of zinc borate production reaction.

16
275 rpm
14
400 rpm
12
800 rpm

10 1600 rpm
Volume, %

0
0.01 0.1 1 10 100 1000 10000
Particle size, µm

Fig. 7. Particle size distribution (dry analysis) graph to observe the effect of stirring rate (temperature (95 1C), initial reactants ratio (H3BO3:ZnO ratio 5:1) and type of zinc
oxide particles (average particle size 10 mm) were constant). Curves denote the logistic model.

2ZnO  3B2O3  3.5H2O in different particle size, 10 and 2 mm,
respectively. One observes essentially no difference between two
experiments in terms of reaction rate and completion time. This
observation indicates that the particle size of seed crystals has no
effect on the reaction. This might be explained by the assumption
that the zinc borate added to the solution as seed is dissolved and
provides a saturation concentration for zinc borate in solution
during the reaction, so that the zinc borate formed from the
reaction can precipitate on the zinc oxide surface. The formation
of zinc borate on the surface of zinc oxide particles may be
considered as nucleation followed by the autocatalytic growth of
zinc borate crystals. The change in seed particle size affects the
logistic model parameters (Table 3). The result can be summar-
ized as follows: the smaller the seed particle size, the smaller the
specific growth rate, k. The initial concentration of zinc borate, wo,
does not show any significant change.
3.2.5. Effect of zinc oxide particle size
Two experiments were performed starting with zinc oxide in
different particle sizes of 10 and 25 mm, an initial H3BO3:ZnO ratio
of 5:1 at 95 1C, 1600 rpm to observe the effect of zinc oxide particle
size on reaction rate. The reaction with larger size zinc oxide was
found to have a greater value of specific growth rate (k=0.17 h1)
than the one with smaller size zinc oxide (k=0.10 h1). The critical
initial concentration of zinc borate decreases 10 times on
changing the zinc oxide particle size from 10 to 25 mm. By
decreasing the particle size of zinc oxide, the number of zinc oxide
particles and, thus, the surface area of zinc oxide particles
increase. Hence, the growth of zinc borate particles is initiated
at a larger number of nuclei on zinc oxide particles. This indicates
that the use of seed is vital in the production of fine zinc borate
particles.
3.3. Effect of experimental conditions on mean particle size of
product
The particle size distributions of zinc borate 2ZnO  3B2O3 
3.5H2O obtained from the reaction of zinc oxide (average particle
size of 10 mm) and boric acid starting with an initial H3BO3:ZnO
ratio of 5:1 at 95 1C but at different stirring rates are given in Fig. 7.
The volume-weighted mean diameters of the samples are in the
range 2.9–5.7 mm (Table 2). The general observation is that the
particle size of the product does not differ significantly with
the stirring rate.
As seen from Table 2 (Runs 5–7 and 14), changing the initial
H3BO3:ZnO ratio causes practically no change in the particle size
distributions and the mean diameters of zinc borate
2ZnO  3B2O3  3.5H2O. This is in contrast to the previous observa-
tion [2] that the size of zinc borate particles increases with the
increase in quantity of boric acid (please recall that no seed has
been used in that study).
A representative particle size distribution graph showing
difference in wet and dry dispersion at 95 1C (Run 6) is given in
Fig. 8. The volume-weighted mean diameter of the samples was
3.3 and 8.2 mm for dry and wet dispersion analyses (Table 2),
respectively. The increase in particle size on passing from dry to
wet dispersion is due to the agglomeration of zinc borate particles
in water. The agglomeration of particles is also observed from the
 ARTICLE IN PRESS

D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552 1551

light microscope images. The small peak in wet dispersion shows
the actual size of zinc borate particles. A representative image of
Run 4 is given in Fig. 9.
Stirring rate has a pronounced affect on wet dispersion average
particle size, indicating the rupture of the agglomerates with
increasing stirring rate. As seen in Table 2, the wet dispersion
particle size decreases from 16.6 to 7.7 mm by increasing the
stirring rate from 275 rpm (Run 15) to 800 rpm (Run 2). Further
increase in stirring rate up to 1600 rpm (Run 6) does not
significantly change the wet dispersion average particle size.
However, the dry dispersion particle size is obtained within the
2.9–5.7 mm range. This value is in accordance with the seed
crystals, i.e., 5 mm.
The smallest wet dispersion particle size of the final zinc
borate product was obtained as 4.3 mm (Run 10) with 10 mm seed
particles and 25 mm ZnO particles at 1600 rpm, 85 1C for a
reactants ratio of 5:1.
The mean diameters of the final products are quite close
to each other (Table 2) when ZnO in different particle sizes is
used. Wet dispersion average particle size of the final product
decreases from 8.2 mm (Run 6) to 6 mm (Run 4) by increasing ZnO
particle size from 10 to 25 mm. On the contrary, Shete et al. [2]
have concluded that the mean particle size of zinc borate was
higher when the mean initial particle size of zinc oxide was
higher.
The results of the present study show that the operating
conditions are much more affective than the sizes of the initial
ZnO or the seed. Rather than having a skin around the ZnO
particles, the mechanism is based on the nucleation of zinc borate
crystals on the surface of ZnO, followed by the growth around
nuclei and then the rupture of zinc borate crystals from the
surface. This might be the explanation of the production of fine
zinc borate crystals. Therefore, the growth mechanism of zinc
borate crystals is much likely to be explained by a logistic growth

16

14 dry

wet
12

10
Volume, %

0
0.01 0.1 1 10 100 1000 10000
Particle Size, µm

Fig. 8. Particle size distribution graph to observe the change in wet/dry dispersion during the analysis for Run 6; temperature 95 1C, initial reactants ratio (H3BO3:ZnO ratio)
5:1, stirring rate 1600 rpm and zinc oxide particles size 10 mm.

Fig. 9. Image of product zinc borate obtained at Run 4 (temperature of 95 1C, stirring rate of 1600 rpm, H3BO3:ZnO ratio 5:1, ZnO size 25 mm).
 ARTICLE IN PRESS
1552 D. Gürhan et al. / Journal of Crystal Growth 311 (2009) 1545–1552
model rather than by shrinking core model that has been
suggested by Shete et al. [2].
4. Conclusions
This study aimed to investigate the effects of reaction
parameters (temperature, stirring rate, reactants ratio, size of
zinc oxide particles and the role of zinc borate as seed) on the zinc
borate production reaction rate and the particle size of the final
zinc borate product. It was observed that
 Excess boric acid and zinc borate as seed should be used in the
fine zinc borate production reaction in order to convert all the
zinc oxide and to get a high reaction rate.
 High stirring rates have beneficial effects on reaction rate and
particle size (high reaction rate and smaller particle size) but
after a limit (800 rpm) increasing stirring rate does not cause
any significant change in the particle size of the final zinc
borate product.
 The specific growth rate increases and the reaction completion
time and the initial critical seed concentration decrease with
increasing temperature.
 The particle size of zinc oxide does not have a considerable
effect on the reaction rate and the final size of zinc borate.
There exist no significant differences at the reaction comple-
tion time when zinc oxide in different particle size is used.
 The size of zinc borate seed has no significant effect on reaction
rate and completion time. The larger the particle size of zinc
borate seed, the smaller the particle size of the final zinc borate
product.
 The zinc borate production reaction fits to the logistic growth
model, having two parameters, the specific growth rate, k, and
the normalized critical initial seed concentration wo.
Considering the lower completion time, higher reaction rate
and lower particle size of the zinc borate product, the suggested
experimental conditions for producing fine zinc borate (3–5 mm)
could be summarized as follows: H3BO3:ZnO ratio of 5:1, ZnO
particle size of 10–25 mm, stirring rate of 800–1600 rpm, tem-
perature of 85–95 1C and zinc borate particle size of 2–10 mm as
seed.
Acknowledgements
We are grateful to the Turkish Academy of Sciences for partial
support, to Eti Maden İs- letmeleri A.S- . for providing boric acid, to
METU for the financial support and to Ankara University, Chemical
Engineering Department and The Central Laboratory, Middle East
Technical University for the analysis. We would like to express
special thanks to Prof. Dr. Zeki Aktas- for the particle size analysis,
to Prof. Dr. Nusret Bulutc- u for valuable discussion and to Ms.
Kerime Güney for her assistance in chemical analysis.
References
[1] The Economics of Boron, tenth ed., Roskill Information Services Ltd., London,
2002.
[2] A.V. Shete, S.B. Sawant, V.G. Pangarkar, J. Chem. Technol. Biotechnol. 79
(2004) 526.
[3] N.P. Nies, L. Beach, R.W. Hulbert, US patent no.: 3,549,316, 1970.
[4] E. Eltepe, D. Balköse, S. Ülkü, Ind. Eng. Chem. Res. 46 (2007) 2367.
[5] J.X. Dong, Z.S. Hu, Tribol. Int. 31 (5) (1998) 219.
[6] S.R. Owen, J.F. Harper, Polym. Degrad. Stab. 64 (1999) 449.
[7] R. Gachter, H. Muller, Plastics Additive Handbook, fourth ed., Hanser, New
York, 1993.
- etin, İ. Eroğlu, S. Özkar, J. Cryst. Growth 231 (2001) 559.
[8] E. C
[9] C.L. Wilson, D.W. Wilson, Comprehensive Analytical Chemistry, Elsevier, New
York, 1992.
- akal, Ph. D Dissertation, Middle East Technical University, Ankara, 2004.
[10] G.Ö. C
[11] D. Gürhan, M.Sc. Dissertation, Middle East Technical University, Ankara, 2005.
[12] H. Koku, I. Eroglu, U. Gündüz, M. Yücel, L. Türker, Int. J. Hydrogen Energy 28
(2003) 381.