Journal of Crystal Growth 312 (2010) 33613366

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Journal of Crystal Growth

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

Scale-up synthesis of zinc borate from the reaction of zinc oxide and boric
acid in aqueous medium
- akal b, Sertan Yes-il a, Goknur Bayram a, _Inci Eroglu a, Saim Ozkar c,n
Mert Klnc- a, Gaye O. C
a
Middle East Technical University, Chemical Engineering Department, 06531 Ankara, Turkey
b
National Boron Research Institute, BOREN, Dumlupnar Bulvar 166-10, 06520 Ankara, Turkey
c
Middle East Technical University, Department of Chemistry, 06531 Ankara, Turkey

a r t i c l e in fo abstract

Article history: Synthesis of zinc borate was conducted in a laboratory and a pilot scale batch reactor to see the
Received 24 February 2010 inuence of process variables on the reaction parameters and the nal product, 2ZnO  3B2O3  3.5H2O.
Received in revised form Effects of stirring speed, presence of bafes, amount of seed, particle size and purity of zinc oxide, and
28 April 2010
mole ratio of H3BO3:ZnO on the zinc borate formation reaction were examined at a constant
Accepted 4 May 2010
temperature of 85 1C in a laboratory (4 L) and a pilot scale (85 L) reactor. Products obtained from the
Communicated by M. Schieber
Available online 15 September 2010 reaction in both reactors were characterized by chemical analysis, X-ray diffraction, particle size
distribution analysis, thermal gravimetric analysis and scanning electron microscopy. The kinetic data
Keywords: for the zinc borate production reaction was t by using the logistic model. The results revealed that the
A1. Crystallites
specic reaction rate, a model parameter, decreases with increase in particle size of zinc oxide and the
A1. Growth model
presence of bafes, but increases with increase in stirring speed and purity of zinc oxide; however, it is
A2. Growth from solutions
A2. Seed crystals unaffected with the changes in the amount of seed and reactants ratio. The reaction completion time is
B1. Borates unaffected by scaling-up.
B1. Zinc compounds & 2010 Elsevier B.V. All rights reserved.

1. Introduction reproong applications, zinc borate is a better ame retarder

Both the natural and synthetic forms of metal borates are
numerous and nd widespread industrial applications. Many
synthetic metal borates resemble minerals in structure, contain-
ing isolated polyborate anions or complex polyborate rings,
chains, sheets, or networks. Metal borates can be divided into
two categories, hydrated and anhydrous. Well known hydrated
borates, which account for the majority of known boron-contain-
ing minerals and synthetic borates consumed by industry, have
structures containing BOH groups (hydroxyl hydrated borates)
and may also contain hydrated water. There exist at least eight
unique crystalline forms of hydrated zinc borates having a range
of B2O3:ZnO mole ratios from 0.25 to 5.0: 4ZnO  B2O3  H2O [1],
ZnO  B2O3  1.12H2O [2], ZnO  B2O3  2H2O [2], 6ZnO  5B2O3  3H2O
[3], 2ZnO  3B2O3  7H2O [4], 2ZnO  3B2O3  3H2O, 3ZnO  5B2O3
 14H2O [5], and ZnO  5B2O3  4.5H2O [3]. Zinc borate is primarily
used as a polymer additive and as a preservative in wood
composites. As a polymer additive, it serves as a re retardant,
char promoter, anti-drip agent, smoke and afterglow suppressant,
and modier of electrical and optical properties. In many
n
Corresponding author. + Tel.: 00 90 312 210 3212; fax: 00 90 312 210 3200.
E-mail addresses: mert.kilinc@mam.gov.tr (M. Klnc- ), gaye@boren.gov.tr
- akal), syesil@metu.edu.tr (S. Yes-il), gbayram@metu.edu.tr (G. Bayram),
(G.O. C
ieroglu@metu.edu.tr (_I. Eroglu), sozkar@metu.edu.tr (S. Ozkar).
than other borates used. The most commonly used forms of zinc
borate are 3ZnO  2B2O3  3.5H2O, 2ZnO  3B2O3  3H2O, and anhy-
drous 2ZnO  3B2O3. The 3.5 mol hydrated zinc borate has the
unusual property of retaining its water of hydration at tempera-
tures up to 290 1C. This thermal stability makes it attractive as a
re retardant additive for plastics and rubbers that require high
processing temperatures. Zinc borate does not affect the color of
plastics and is only slowly affected by high temperatures. When
heated, zinc borate promotes the formation of char and inhibits
the release of combustible material [6]. The use of zinc borate
together with aluminum trihydrate (ATH) can form a synergistic
mixture, more effective than using the additives separately,
particularly in reducing the res smoke when added to the
polymeric materials. Previous studies have demonstrated that
they are commonly used as ame-retardant ller in polyvinyl
chloride (PVC), polypropylene (PP), polyamides, epoxy resins, etc.
[714].
Various attempts have been made to produce 3.5 hydrated zinc
borate. Nies et al. [15] investigated different methods by using
borax pentahydrate, boric acid, zinc oxide, and sulfuric acid as raw
materials and 2ZnO  3B2O3  9H2O as seed. Dong and Hu [11]
studied the synthesis of nanometer-size (2050 nm) zinc borate
using the ethanol supercritical uid drying technique. Shete et al.
[16], Gurhan et al. [17,18] and Eltepe et al. [19] presented a
comprehensive set of experimental results on zinc borate
production in a batch reactor via the heterogeneous reaction of

0022-0248/$ - see front matter & 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2010.05.048
3362 M. Klnc- et al. / Journal of Crystal Growth 312 (2010) 33613366
boric acid and zinc oxide (Eq. (1)):
6B(OH)3(aq)+ 2ZnO(s)-2ZnO  3B2O3  3.5H2O(s)+ 5.5H2O
Almost all works published in the literature deal with
synthesis of 3.5 hydrated zinc borate and characterization of the
nal product. Practically no work has been reported describing
the effect of important reaction parameters on scale-up. Herein,
we report the results of a comprehensive study on the effect of
reaction parameters on zinc borate production in a batch reactor
both on laboratory and pilot scale and the characterization of the
nal product, 2ZnO  3B2O3  3.5H2O. Thus, the effects of stirring
speed and presence of bafe in the reactor, seed amount used in
the reaction, zinc oxide particle size, zinc oxide purity, H3BO3:ZnO
mole ratio on the reaction and nal product were determined at
different reactor capacities. The reaction model adapted to the
production of the 3.5 mole hydrated zinc borate in the previous
study [17] was also applied by scaling up to pilot scale production.
2. Experimental
Boric acid (H3BO3, with a purity of 99.9% by weight), zinc oxide
(ZnO, with a minimum purity 96%), 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,
Kutahya, Turkey. Zinc oxide of four different particle sizes, 20 mm
(96% purity), 25 mm (4 98% purity), o1 mm (99.9% purity) and
5070 nm (99.9% purity), was purchased from Atlas Oksit Limited
(Ankara, Turkey), Kartal Oksit Limited (Ankara, Turkey) and
Aldrich, respectively. Zinc borate with the simplest formula of
2ZnO  3B2O3  3.5H2O in two different sizes of 9 and 3 mm was
purchased from U.S. Borax.
The experimental set-up consists of a stainless steel reactor
having a mechanical stirrer, a heating jacket, a thermocouple, a
temperature control unit, and a vacuum pump. The laboratory
scale reactor having a volume of 4 L is equipped with four bafes
placed like a crosshair, whereas the pilot scale having a volume of
85 L is not equipped with bafes. The reactors were manufactured
by Mismak Limited, Ankara, Turkey.
Experimental procedure, the analysis of boric acid and zinc oxide
amounts in the solid samples, and the particle size distribution by
dry dispersion method were given elsewhere [17]. All laboratory
and pilot scale reactor experiments were performed at 85 1C;
stirring speeds varied in the range of 320580 and 96271 rpm. The
initial reactant, had a H3BO3/ZnO, mole ratio of 5:1 in all runs
except in Run 12, in which the ratio was 3.5:1. Initially zinc borate
crystals were added as seed at an amount of 1.5 wt% of the boric
acid used, except in Run 2 in which the seed amount was 0.75%.
TG/DTA analyses of the nal products were performed by
Perkin Elmer Pyris 1. The measurements were performed under a
N2 ow of 100 ml/min. Uniform heating rate of 10 1C/min was
applied during the measurements. To study the crystal structure
of the produced zinc borate Powder X-Ray Diffraction analysis
was carried out. XRD patterns were recorded from 101 o2y o801
by using the Rigaku X-Ray Diffractometer/ RINT 2100 PC equipped
with CuKa1 radiation. Images of the nal products were obtained
by a scanning electron microscope using a Carl Zeiss Supra 55 VP
SEM instrument.
3. Results and discussion
The reaction of zinc oxide and boric acid was performed in
laboratory and pilot scale batch reactors by scaling up the reactor
described in the previous study [17]. In scaling-up, the stirring
speed is adjusted by using the following relationship [20]:
 x
N1 D2
(1) 2
N2 D1
where N is the stirring speed (rpm) and D is the diameter of the
stirrer. The exponent x was taken to be 0.667 with the assumption
of homogeneous suspension of solids [21]. The reaction tempera-
ture was kept constant at 85 1C by varying the experimental
conditions to investigate the effects of scale-up and other
parameters on specications of the nal product zinc borate,
including particle size, reaction time, and conversion of zinc oxide
to zinc borate. The kinetic model developed for the reaction in a
small scale reactor [17] was also adapted for scale-up production
using the data collected during the experiments.
3.1. Parameters affecting the product specication
A total of thirteen runs of the reaction between zinc oxide and
boric acid were performed under different experimental condi-
tions in either laboratory scale or pilot scale reactor. The product
obtained from the reaction in both reactors was analyzed for its
ZnO and B2O3 contents, dehydration temperature, and particle
size. The results are listed together in Table 1.
Comparison of the powder XRD patterns of the zinc borate
products obtained from the experiments in the laboratory and
pilot scale reactors with that of commercial 2ZnO  3B2O3  3.5H2O
shows that the product is pure 2ZnO  3B2O3  3.5H2O [21], similar
to the previous study [17]. Thus, scaling up the reactor to either
4 or 85 L does not change the 3.5 hydrated zinc borate products.
As an illustrative example, the changes in XRD patterns of solid
samples taken during the reaction between zinc oxide and boric
acid in the laboratory scale experiment of Run 6 are depicted in
Fig. 1 along with that of commercial 2ZnO  3B2O3  3.5H2O for
comparison. It is clear that zinc borate does not form till 140th
minute of the reaction. The formation of zinc borate was complete
in 140180 min. These results were conrmed by SEM images
of the same samples given in Fig. 2. No zinc borate crystal was
observed in the SEM images of the samples taken within the rst
120 min given in Fig. 2ad. In the early stage of the reaction, the
SEM images show only nanopowders (o1 mm) of ZnO. The
reaction of zinc borate production proceeds on the surface of
the ZnO particles, as proposed in the previous study [17]. The SEM
image of the sample taken at 120th minute of the reaction
(Fig. 2d) shows particles of both zinc oxide and zinc borate,
indicating that the reaction is incomplete. At 160th minute, the
reaction is complete as the SEM image (Fig. 2e) shows only zinc
borate crystals in the form of nanoplates.
TGA results showed that the zinc borate product, 2ZnO 
3B2O3  3.5H2O, obtained from the experiments under different
conditions has usually a dehydration temperature higher than
that of the commercial one (Table 1). The dehydration starts at
330 1C with the exception of the products obtained from the
experiments of Runs 9 and 12, which have an initial dehydration
temperature of 225 1C. The initial weight loss during the
dehydration corresponds to the removal of 3.5 mol of H2O per
formula of zinc borate product as expected [22].
3.2. Parameters affecting the conversion of zinc oxide and mean
particle size of product
The formation of zinc borate is a heterogeneous reaction taking
place in aqueous medium as the zinc oxide is insoluble in water
and boric acid is soluble in water at the reaction temperature
(Eq. (1)). Zinc borate formation involves (i) the diffusion of borate
ions formed from the ionization of boric acid in aqueous solution
 M. Klnc- et al. / Journal of Crystal Growth 312 (2010) 33613366 3363

Table 1
Final product specications and logistic model parameters for the laboratory and pilot scale zinc borate production.

Final product specications Logistic model parameters

Run no ZnO (%) B2O3 (%) Dehydration Avg. part. Specic growth Normalized critical R2
temp. (1C) size (mm) rate k (h  1) initial concentration wo

Seed 1a 37.5 48.0 290 7.5 b

Seed 2c 37.5 48.0 290 3

Lab scale 1 38.3 45.7 340 4.1 0.050 0.0339 0.954

2 39.2 45.3 340 2.8 0.045 0.0255 0.973
3 40.8 45.9 340 2.7 0.045 0.0134 0.987
4 38.5 47.1 340 5.0 0.037 0.0028 0.857
5 37.8 47.3 340 4.6 0.052 0.0014 0.751
6 39.9 45.7 340 3.8 0.054 0.0014 0.898
7 39.4 48.2 340 2.7 0.055 0.0028 0.797

Pilot Scale 8 39.2 45.9 330 8.7 0.034 0.0036 0.939

9 39.1 46.2 225 4.2 0.037 0.0031 0.931
10 38.8 46.3 330 3.8 0.043 0.0052 0.958
11 38.2 48.7 330 3.4 0.044 0.0095 0.983
12 41.6 42.6 225 5.0 0.028 0.0118 0.916
13 40.5 45.2 330 3.8 0.028 0.0335 0.841

a
US Borax Firebrake ZB, http://www.boraxfr.com/productsmain-1.html.
b
Reported as 9 mm.
c
US Borax Firebrake ZBFine, http://www.boraxfr.com/productsmain-1.html.

borate crystals (2ZnO  3B2O3  3.5H2O) are not added to the

Fig. 1. XRD powder patterns of ZnO solid samples taken from the laboratory scale
experiment, Run 6, with respect to time and commercial zinc borate Firebrake ZB.
to the surface of the zinc oxide particles, (ii) the reaction of borate
ions with zinc oxide particles forming zinc borate nucleation at
the particle surface, and (iii) zinc borate crystal growth on the
surface of zinc oxide particles and precipitation when they
achieve a certain size. As the reaction proceeds on the surface of
ZnO particles, the particle size of the zinc borate will depend on
the particle size of the zinc oxide used as reactant and the time
utilized for crystal growth. Representative SEM images to test this
hypothesis are shown in Fig. 3 to see the effect of zinc oxide
particle size on zinc borate. Zinc borates having average particle
diameters of 8.7 and 2.7 mm (Table 1), produced from 25 mm and
5070 nm zinc oxides, are shown in Fig. 3a and b, respectively.
The crystal growth of zinc borate from the reaction of zinc
oxide and boric acid was interpreted by using the logistic model
[17]. Operating conditions such as stirring speed, reactants ratio,
temperature, seed size, and zinc oxide particle size affect the
parameters in the logistic model (Table 1). In what follows, we
discuss the effect of the amount of seed, presence of bafes,
stirring speed, particle size, and purity of zinc oxide and initial
reactants ratio on the specic growth rate obtained at the
laboratory scale (4 L) and pilot scale (85 L) reactors.
solution as seed. Nies et al. [15] have also found it crucial to use
seed during the synthesis. The previous report has showed [17]
that the seed particle size has no effect on the reaction if
the amount of seed added to the solution is equal to the 1.5 wt% of
the total boric acid used. Runs 2 and 3 were performed with
ZnO particles (25 mm), initial H3BO3:ZnO mole ratio of 5:1 at 85 1C
and stirring speed of 580 rpm in a bafed reactor but using
different amounts of seed (0.75% and 1.5% of total boric acid)
having particle size of 7.5 mm. Thus, doubling the amount of
seed does not affect the reaction rate and the average particle
size distribution for the nal zinc borate product (Table 1).
These results imply that using seed is crucial, but its amount
has no effect on the reaction rate in the range given
(0.751.5%).
3.2.2. Effect of bafes
In various reaction systems, bafes are integrated to the
reactors in order to increase the effect of stirring. To determine
the effect of bafes on zinc borate, synthesis was performed with
and without bafes (Runs 1 and 3 in the laboratory scale reactor)
starting with ZnO (particle size 25 mm), an initial H3BO3:ZnO mole
ratio of 5:1 at 85 1C and 580 rpm, using 1.5% of boric acid as seed
having a particle size of 7.5 mm. In Run 1, the reactor was not
equipped with bafes. The variations in the conversion for both
runs are given in Fig. 4. Despite the advantages of using bafes,
such as increase in mixing and dispersion, one drawback of using
bafes is the presence of dead zones that could possibly occur in
the reactor at the connection points of the bafe and the reactor.
When bafes are used, the reaction rate decreases and the
reaction completion time increases (Fig. 4), both logistic model
parameters the specic growth rate, k, and the normalized
critical initial concentration of zinc borate, wo decrease. Bafes
presumably break down the agglomerates of zinc borate crystals;
consequently, the average particle size of the nal product
decreases from 4.1 to 2.7 mm (Table 1).

3.2.1. Effect of seed 3.2.3. Effect of stirring speed

As discussed in the previous study [17], the reaction of boric In order to investigate the effect of stirring speed on the
acid and zinc oxide does not yield zinc borate product if zinc reaction rate and particle size of the product, a series of
3364 M. Klnc- et al. / Journal of Crystal Growth 312 (2010) 33613366

Fig. 2. SEM micrographs of laboratory scale reactor experiment, Run 6: (a) 20 min, (b) 40 min, (c) 80 min, (d) 120 min, (e) 160 min, and (f) 240 min after reaction initiates
(temperature 85 1C, seed amount 1.5%, initial reactants mole ratio (H3BO3:ZnO ratio of 5:1), stirring speed 580 rpm, and average particle size of zinc oxide particles
o 1 mm)

experiments were performed on the laboratory and pilot scale
reactors. Laboratory scale experiments were performed starting
with the initial molar ratio of the reactants (H3BO3:ZnO) of 5:1
and particle size of zinc oxide of o1 mm at 85 1C and stirring
speeds of 320, 450, and 580 rpm (Runs 4, 5, and 6, respectively).
Experiments in the pilot scale reactor were performed starting
with the initial molar ratio of the reactants (H3BO3:ZnO) of 5:1,
particle size of zinc oxide of 25 mm at 85 1C, and stirring speed of
96, 150, and 271 rpm (Runs 8, 9, and 10, respectively). In
accordance with the previous study [17], one observes a decrease
in the induction time as the stirring speed increases, both in the
laboratory and in the pilot scale experiments. The conversion of
zinc oxide to zinc borate is plotted versus time at varying stirring
speeds in Fig. 5. Conclusively, the stirring speed has a pronounced
effect on the reaction rate, indicating that the reaction is mass
transfer limited.
The effect of stirring speed can be appreciated much better in
terms of model parameters, wo and k. As seen in Table 1, the k
value increases with the increase in stirring speed, both in
laboratory and in pilot scale experiments, while the wo value
decreases in the bafed laboratory reactor, but increases in the
pilot scale reactor.
The particle size of the nal products decreases with the
increase in stirring speed in both scales. The smallest particle size
of zinc borate is found to be 3.8 mm for both laboratory scale
(580 rpm) and pilot scale (271 rpm). Recall that the stirring speed
of 271 rpm in the pilot scale reactor corresponds to the stirring
speed of 580 rpm in the laboratory reactor (Eq. (2)).
 M. Klnc- et al. / Journal of Crystal Growth 312 (2010) 33613366
Fig. 3. SEM micrographs of the nal products of (a) Run 8, pilot scale reactor experiment, (b) Run 7, laboratory scale reactor experiment (temperature 85 1C, seed amount
1.5%, initial reactants ratio (H3BO3:ZnO ratio of 5:1), stirrings speed 96 rpm (Run 8) and 580 rpm (Run 7), average particle size of zinc oxide particles of 25 mm (Run 8), 50
70 nm (Run 7)).
Fig. 4. ZnO conversion vs. time graph of the laboratory scale experiments (Runs 1,
3) to observe the effect of bafes (temperature 85 1C, seed amount 1.5%, initial
reactants ratio (H3BO3:ZnO ratio of 5:1), stirring speed 580 rpm, and average
particle size of zinc oxide particles of 25 mm were constant). Curves denote the
logistic model.
Fig. 5. ZnO conversion vs. time graph of the pilot scale reactor experiments (Runs
9, 10) to observe the effect of stirring speed (temperature 85 1C, seed amount 1.5%,
initial reactants ratio (H3BO3:ZnO ratio of 5:1), ZnO purity 98%, and average
particle size of zinc oxide particles of 25 mm were constant). Curves denote the
logistic model.
3.2.4. Effect of zinc oxide particle size
To observe the effect of zinc oxide particle size series of
experiments were performed on the laboratory and pilot scale
reactors. Laboratory scale experiments were performed starting
with zinc oxide in a particle size of 25 mm, o1 mm, and 5070 nm
(Runs 3, 6, and 7, respectively), the initial molar ratio of the
reactants (H3BO3:ZnO) of 5:1 at 85 1C and stirring speed of
580 rpm. Experiments in pilot scale reactor were performed
starting with zinc oxide particle sizes of 25 and o1 mm (Runs 10
and 11, respectively), the initial molar ratio of the reactants
3365
Fig. 6. ZnO conversion vs. time graph of the laboratory scale reactor experiments
(Run 3, 6, 7) to observe the effect of average particle size of ZnO (Temperature
85 1C, seed amount 1.5%, initial reactants ratio (H3BO3:ZnO ratio of 5:1) and
stirring speed of 580 rpm were constant). Curves denote the logistic model.
(H3BO3:ZnO) of 5:1 at 85 1C and stirring speed of 271 rpm. Fig. 6
shows the plots of ZnO conversion versus time for different
particle sizes of zinc oxide used. The rate of reaction is higher
when nano-sized zinc oxide is used, which is followed by the
reaction of 25 mm zinc oxide. The slowest reaction is the one
when o1 mm zinc oxide is used. This sequence is thought to
occur due to the presence of bafes. Large surface area of nano-
size zinc oxide led to an increase in the number of nuclei needed
for the growth of zinc borate particles [17]. 25 mm zinc oxide is
thought to break down at this stirring speed due to the presence
of bafes. o1 mm zinc oxide particles are small enough not to be
broken down, so they might deposit near the bafes, which slows
down the reaction. The model parameter k increases and wo
decreases with decrease in particle size of zinc oxide (Table 1).
The nal zinc borate has a mean particle size of 2.7 mm
(Table 1) when nano-sized or 25 mm zinc oxide was used.
The particle size of zinc borate is higher (3.8 mm) when o1 mm
zinc oxide particles are used, which also supports the above
discussion.
Since the pilot reactor is not equipped with bafes in these
syntheses, a slightly higher reaction rate is expectedly obtained
when o1 mm zinc oxide is used. In Fig. 7, the variation in ZnO
conversion with time is given for different particle sizes of zinc
oxide. The reaction completion times are 240 min for the two
experiments. Although the k values are comparable for these two
reactions, wo increases with decrease in particle size of zinc oxide,
as observed in the previous study [17]. The zinc borates produced
in the pilot scale reactor have similar particle sizes with those
produced in the laboratory reactor with o1 mm zinc oxide
(Table 1).
3366 M. Klnc- et al. / Journal of Crystal Growth 312 (2010) 33613366
Fig. 7. ZnO conversion vs. time graph of the pilot scale reactor experiments (Run
10, 11) to observe the effect of average particle size of ZnO (temperature 85 1C,
seed amount 1.5%, initial reactants ratio (H3BO3:ZnO ratio of 5:1), ZnO purity of
98% for 25 mm ZnO and 99.9% for o 1 mm ZnO). Curves denote the logistic model.
3.2.5. Effect of zinc oxide purity
Zinc oxide is the key reactant in 3.5 hydrated zinc borate
syntheses, so its purity is also an important factor affecting the
product. To test this hypothesis, series of experiments were
performed starting with zinc oxide having particle sizes of 25,
o1, and 20 mm (Runs 10, 11, and 13, respectively), purities of 98%,
99.9%, and 96%, respectively, initial molar ratio of the reactants
(H3BO3:ZnO) of 5:1 at 85 1C and stirring speed of 271 rpm. It is
observed that the reaction becomes slower as the impurity
increases. In line with the decreasing reaction rate, the reaction
completion time increases with increasing impurity. The impu-
rities of zinc oxide might form a barrier that resists the diffusion
of borate ions to react with zinc oxide on the particle surface. The
model parameter k decreases with increase in impurity, whereas
wo increases excessively with the decreasing purity of zinc oxide.
The particle size of the products obtained, however, remains
unaffected by the purity of zinc oxide (Table 1).
3.2.6. Effect of H3BO3:ZnO mole ratio
The zinc borate production reaction was studied at different
reactants ratio (H3BO3:ZnO) of 3.5:1 and 5:1 (Runs 12 and 13,
respectively) starting with zinc oxide having a particle size of
20 mm and a purity of 96% at 85 1C and stirring speed of 271 rpm.
Similar to the observation made in the previous study using zinc
oxide with 10 mm particle size and 98% purity [17], it was found
that the reaction rate increases with increase in concentration of
boric acid. The reaction completion time increases to 320 min
when the reactants ratio of 3.5:1 is used. The results are in
accordance with the previous study even though a less pure zinc
oxide was used in this work. The k value remains unaffected while
the wo value increases with increasing reactants ratio. The particle
size of the product is found to be 5 mm (Table 1) when the
reactants ratio of 3.5:1 is used. This is slightly higher than the
value of 3.8 mm obtained using the reactants ratio of 5:1.
4. Conclusions
Successful synthesis of 3.5 hydrated zinc borate at both
laboratory and pilot scale was achieved in this study. The effects
of stirring speed and bafes in the reactor, the amount of seed
used in the reaction, the particle size and purity of zinc oxide, the
H3BO3:ZnO mole ratio on the reaction and nal product were
investigated at different reactor capacities. The ndings were
compared with the small scale reactor experiments in the
previous study [17].
It was observed that scaling up the reactor either to 4 L or to
85 L did not change the essential results obtained in the 1.5 L
laboratory scale batch reactor. The reaction model adapted to the
production of the 3.5 mol hydrated zinc borate in the previous
study [17] can also be applied to bigger capacity reactors. The
results revealed that the model parameter, specic growth rate k,
remains unaffected by changing the amount of seed and reactants
ratio, while it decreases with the presence of bafes, increasing
particle size of zinc oxide, and increases with increasing stirring
speed and zinc oxide purity. More importantly, the reaction
completion time remains unaffected by scaling up the reactor.
By using the logistic model one obtains a better t for the data
in the pilot scale than that obtained for the data in the laboratory
scale. Note that R2 values are much closer to 1 in the case of pilot
scale production. In general, the conversion curves obtained from
the logistic model are in accordance with the experimental
conversion values calculated for the reaction. This indicates a
good t of the experimental data obtained from the zinc borate
synthesis reaction to the logistic model.
All the products of zinc borate give up their hydration water at
temperatures above 330 1C. This property of the product is
boosting up the usage of zinc borate as a ame retardant additive
in plastics. The particle size of zinc borate products obtained
varies in a narrow range of 35 mm, which provides good
dispersion during the processing of plastics.
Acknowledgements
Partial support of this work by National Boron Research
Institute (BOREN) and Turkish Academy of Sciences is gratefully
acknowledged. We are grateful to Eti Maden _Is- letmeleri A.S- . for
the supply of boric acid, Materials Engineering Department of
Anadolu University and Central Laboratory of Middle East
Technical University for the analyses.
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