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Solvent-Solvent Cooling Crystallization: An Effective Method to Control the

Morphology and Size of Ammonium Perchlorate Crystals

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DOI: 10.1002/crat.201900065

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ORIGINAL PAPER
Ammonium Perchlorate www.crt-journal.org

Solvent–Solvent Cooling Crystallization: An Effective

Method to Control the Morphology and Size of Ammonium
Perchlorate Crystals
Wei Liu,* Yong Xie, Qiang Xie, Kexiong Fang, Xuan Zhang, and Houhe Chen*

of solid rocket propellants are highly de-

Controlling ammonium perchlorate crystals with desired properties is still a pendent upon the shape, size, aspect ra-
challenge in industrial crystallization. In this work, two different cooling tio, surface characteristics, and particle
crystallization methods, namely solvent–solvent cooling crystallization and size distribution of AP crystals.[5–8] In ad-
batch cooling crystallization, are compared to prepare ammonium perchlorate dition, the shape and size of AP crystals
can affect the loading density, mechani-
crystals with tunable shapes and sizes. The influences of crystallization cal properties, and safety performance of
parameters such as cooling pattern, cooling rate, stirring rate, feed rate, and AP-based pyrotechnics and propellants.[9]
solution concentration on the morphology and size of ammonium perchlorate Therefore, controlling AP crystals with
particles are studied. The results indicate that solvent–solvent cooling desired morphology and size is cru-
crystallization makes it easier to control the supersaturation of the cial for their applications in energetic
materials.
crystallization system than bath cooling crystallization, resulting in a more
Crystallization is the most critical step
uniform morphology of the ammonium perchlorate crystals prepared by the in the manufacturing operation to obtain
solvent–solvent cooling crystallization. In addition, by adjusting the AP products with controllable morphol-
crystallization conditions, the shape of ammonium perchlorate crystals can be ogy and size. In current industrial pro-
tailored as long rectangle, tabular, spherical, platy, bipyramid, and high-index duction, AP crystals are mainly prepared
faced polyhedron shaped, the mean size of which can be controlled from 43.9 by fractional crystallization.[10] However,
preparing AP crystals with desired prop-
to 191.9 µm. Moreover, the proposed crystallization method provides a erties remains a challenge in industrial
promising strategy for the continuous production of ammonium perchlorate crystallization.[11] In the past few years,
crystals in industry; it is also a reference for the crystallization of other some works have been devoted to explor-
materials in crystal engineering. ing the effect of crystallization parame-
ters on AP crystal characteristics. For ex-
ample, V. M. Lakshmia et al. established
1. Introduction the effect of crystallization parameters such as cooling patterns,
stirring rate, retention of crystals in the mother liquor, and pres-
Ammonium perchlorate (AP) is an important oxidizer and has ence of surfactant on the morphological and physical charac-
been widely used in solid rocket propellants, explosives, and teristics of AP crystals.[12] Moreover, Liu et al. proposed a drop-
pyrotechnics.[1–3] In particular, the content of AP in solid rocket wise cooling crystallization method to crystallize AP in gas–liquid
propellants can reach as much as 60% to 90%.[4] The crystal two-phase suspension systems; the effect of gas-phase medium
quality of AP has a great influence on the performance of AP- flow rate and feed rates on the shape and size of AP crystals
based energetic materials. For example, the combustion behavior were studied.[13] On the basis of previous studies, a solvent–
solvent cooling crystallization method is proposed in this work
Dr. W. Liu, Dr. Q. Xie, Prof. H. Chen
to control the morphology and size of AP crystals. As shown
School of Chemical Engineering in the schematic representation in Figure 1, the concentrated
Nanjing University of Science and Technology AP solution at a high temperature was continuously added to
Nanjing 210094, China its low-temperature saturated solution to create supersaturation
E-mail: 1104054142@st.nuc.edu.cn; chhh42792@sina.cn by adjusting the crystallization parameters such as stirring rate,
Dr. Y. Xie, Dr. K. Fang feed rate, and solution concentration to control the nucleation
Hubei Dongfang Chemical Industry Company Limited, Norinco Group
Xiangyang 441404, China and growth of the AP crystals. Compared with the batch cool-
Dr. X. Zhang ing crystallization, one of the biggest improvement of this study
Gansu Yinguang Chemistry Corporation, Norinco Group lies in the way that supersaturation is created. During solvent–
Baiyin 730900, China solvent cooling crystallization, the temperature of the crystalliza-
tion solution is kept substantially constant. The supersaturation
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/crat.201900065
of the crystallization system is created by the addition of concen-
trated AP solution. However, in batch cooling crystallization, the
DOI: 10.1002/crat.201900065

Cryst. Res. Technol. 2019, 54, 1900065 1900065 (1 of 8) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 1. Schematic representation of the experimental set-up for a) batch
cooling crystallization and b) solvent–solvent cooling crystallization.
supersaturation is created by continuous cooling of crystalliza-
tion solution.
In addition, the other advantage of this study is that the pro-
posed crystallization method provides a strategy for the continu-
ous production of AP crystals. In industry, with the rapid devel-
opment of chemical production, the shortcomings of the current
crystallization production line have become increasingly promi-
nent. For instance, the batch cooling crystallization process is
time-consuming and complex, which results in low productivity.
Therefore, developing a novel crystallization method to achieve
the continuous production of AP will be the trend of industrial
crystallization. In the solvent–solvent cooling crystallization pro-
cess, after the crystallization system is stable, continuous pro-
duction can be achieved by timely filtering the suspension over-
flowed from crystallizer. Therefore, this work provides a practical
strategy to control the morphology and size of AP crystals; it is
also a promising method for the continuous production of AP
crystals in the industry.
2. Experimental Section
2.1. Materials
The AP raw material (98 wt%) was purchased from Shanghai
Macklin Biochemical Co., Ltd. Distilled water was used as a sol-
Cryst. Res. Technol. 2019, 54, 1900065 1900065 (2 of 8)
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Table 1. Experimental data for the solubility of AP in water at different tem-
peratures.
Temperature [°C] 0 10 20 30 40 50 60 70 80 90 100
Solubility [g] 11.7 16.4 21.8 27.9 34.4 42.7 49.8 58.9 69.2 78.3 88.2
vent for all the experiments. In addition, all chemicals were used
as supplied, if not stated otherwise.
2.2. Experimental Devices
Magnetic stirrer (DF-101SZ) was obtained from Shanghai Shen
Shen Instrument Co., Ltd.; ultrasonic cleaner (KH-250SP) was
purchased from Kunshan Hechuang Ultrasound Instrument
Co., Ltd.; temperature recorder (R2100E) was purchased from
Shanghai Yijie Automation Technology Co., Ltd.; Buchner fun-
nel (diameter 90 mm) and Buchner flask (500 mL) were ob-
tained from Nanjing Zhongdong Chemical Glass Instrument
Co., Ltd.; vacuum pump (2XZ-2) was purchased from Zhejiang
Huangyan Tianlong Vacuum Pump Factory; vacuum drying oven
(DZF-6050) was produced by Shanghai Haixiang Instrument and
Equipment Factory.
2.3. Batch Cooling Crystallization Experiment
In this experiment, water was selected as the solvent because
the solubility of AP in water varies significantly with tempera-
ture. The solubility data were measured in the previous work,[13]
as shown in Table 1. The schematic representation of the ex-
perimental setup is shown in Figure 1a; the typical experimen-
tal steps are described below. At first, the mixture containing
30.0 g AP and 50 mL distilled water was heated to 85 °C to form
AP solution with a concentration of 37.5 wt% (Concentration =
Mass (AP)
Mass (AP) + Mass (water)
× 100 %). Then, the batch cooling crystal-
lization experiment was carried out at an average cooling rate of
0.33 K min−1 and a stirring rate of 300 rpm, where the temper-
ature of the solution was monitored by a temperature recorder.
After the temperature of crystallization solution was lowered to
30 °C, the precipitated white AP crystals were quickly separated
from the liquid by vacuum filtration and dried in an air oven for
characterization. In order to ensure the reliability of the experi-
ment, each experiment was independently repeated at least twice.
The experimental process under other conditions was similar
to the above procedure. In single factor experiments of stirring
intensity, three stirring rates, that is, 100, 300, and 500 rpm, were
selected to crystalize AP at the solution concentration and average
cooling rate of 37.5 wt% and 0.33 K min−1 , respectively. When
the effect of concentration on crystallization was studied, three
concentrations, that is, 33.3, 37.5, and 41.2 wt%, were chosen,
and the stirring rate and cooling rate were set as 300 rpm and
0.33 K min−1 , respectively. In addition, when the effect of cooling
rate is studied, three additional cooling rates, that is, 0.67, 3.6, and
19.2 K min−1 , were chosen under the concentration and stirring
rate of 37.5 wt% and 300 rpm, respectively.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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2.4. Solvent–Solvent Cooling Crystallization Experiment
The experimental setup is shown schematically in Figure 1b. At
first, a concentrated solution containing 99.6 g AP and 200 mL
deionized water was heated to 80 °C. Then, 14.1 g AP was
added to 100 mL deionized water at 5 °C to form saturated so-
lution, the temperature of which was controlled through an ice-
water bath. After that, concentrated AP solution was added at
a feed rate of 2 mL min−1 to its saturated solution (at 5 °C).
The crystallization experiments were carried out under stirring
or ultrasound mixing conditions. After each experiment, the AP
crystals were immediately filtered and dried in an air oven for
characterization.
The experimental procedures under other conditions were
the same as those described above and each experiment was
independently repeated at least twice. The relevant parameters
such as solution concentration, feed rate, and stirring rate are
listed in Section 3.2. In addition, the experimental procedures
of using ultrasonic mixing technique were similar to those of
using stirring mixing. The difference was that the crystallizer
was placed in an ultrasonic bath. The parameters such as ul-
trasonic power and frequency were set to 70 W and 25 KHz,
respectively.
2.5. Characterization
The phase purity of the as-prepared samples was confirmed by
powder X-ray diffraction (PXRD, Bruker D8 Advance, Germany)
with Cu K𝛼 (𝜆 = 1.5406 Å) used as a radiation source. The mor-
phologies of the samples were observed by microscope (XSP-30).
Figure 2. The morphologies of AP crystals crystallized at a) 100 rpm, b) 300 rpm, and c) 500 rpm. d,e) Optical microscopy images of AP crystallized at
the concentrations of 33.3 and 41.2 wt%. f) The cooling curve for batch cooling crystallization.
Cryst. Res. Technol. 2019, 54, 1900065
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3. Results and Discussion
3.1. Batch Cooling Crystallization
The key step for cooling crystallization is to determine the sat-
uration concentration and metastable limit. The saturation con-
centration also called solubility represents the minimum solute
concentration for which the crystal growth can occur. In order to
confirm the effect of the proposed solvent–solvent cooling crystal-
lization, conventional batch cooling crystallization experiments
were performed for comparison. The effects of cooling rate, stir-
ring rate, and solution concentration on the morphology and size
of AP crystals were investigated. As shown in Figure 2a–c, three
stirring rates, that is, 100, 300, and 500, were selected to crystalize
AP at the solution concentration and average cooling rate of 37.5
wt% and 0.33 K min−1 (Figure 2f), respectively. When the stir-
ring rate is 100 rpm, blocky AP crystals with an average size of
248.7 µm can be obtained. On increasing the stirring rate to 300
and 500 rpm in comparative experiments, as shown in Table 2,
the mean size of AP crystals become 148.8 and 90.7 µm, respec-
tively, indicating that the mean size of AP crystals decreases with
the increase of stirring rate. This may be because the stirring
accelerates collisions between crystals and facilitates secondary
Table 2. The mean size of AP crystals prepared at different stirring rates.
Stirring rate [rpm] Mean size [µm]
100 248.7
300 148.8
500 90.7
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Figure 3. Particle size distribution curves of AP crystals crystallized at a) 100 rpm, b) 300 rpm, and c) 500 rpm.

Figure 4. The morphologies of AP crystals crystallized at the cooling rates of a) 0.67 K min−1 , b) 3.6 K min−1 , and c) 19.2 K min−1 . d) The corresponding
cooling curves.

nucleation in crystallization process, resulting in the formation of
small crystals.[14–17] Moreover, the particle size distribution curves
obtained by statistical treatments are shown in Figure 3. It can be
found that as the stirring rate increases, the particle size distribu-
tion of the AP crystals becomes narrower. This can be explained
by the fact that the stirring facilitates the mixing of the AP solu-
tion, so that the thickness of the boundary layer around the AP
crystal nucleus is more uniform. Increasing stirring rate is bene-
ficial to a relatively uniform growth rate of AP crystals, resulting
in a narrower particle size distribution. In addition, the shape of
AP crystals is basically not affected by stirring rate.
In order to further investigate the effect of concentration on
the morphology and size of AP crystals, two additional concen-
trations, that is, 33.3 and 41.2 wt%, were chosen. The reason for
choosing these concentrations is from the point of view of indus-
trial production because they are close to the saturated concen-
tration of AP in water at 60 and 80 °C, respectively. As shown in
Figure 2d,e, when the concentration of AP solution is 33.3 wt%,
the average size of obtained crystals is 180.7 µm, which is larger
than that of 37.5 wt% case (148.8 µm). On increasing the concen-
tration of AP solution to 41.2 wt%, the mean size of AP crystals
decreases to 131.9 µm. In general, a higher concentration of AP
solution leads to an increased rate of supersaturation generation,
which results in faster nucleation and slower growth.[18,19] This is
in accordance with our experimental results.
The effect of cooling rate on the morphology and size of AP
crystals was also explored. As shown in Figure 4d, three cool-
ing rates were selected under the solution concentration and stir-
ring rate of 33.3 wt% and 300 rpm, respectively. The results are
shown in Figure 4a–c; a decreasing trend of the average size with

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Figure 5. The morphologies of AP crystals crystallized at different conditions as listed in Table 3.

the cooling rate is observed, but there is no specific trend seen Table 3. The preparation conditions of AP crystals with different
in the shape of crystals. For example, when the cooling rate is morphologies.
0.67 K min−1 , the average size of AP crystals is 150.6 µm, which
is larger than that of 3.6 K min−1 (111.1 µm) and 19.2 K min−1 Number Concentration Temperature Feed rate Stirring rate or
[wt%] [°C] [mL min−1 ] ultrasonic power
(61.7 µm). However, this is not surprising because when the cool-
ing rates is fast, it is in favor of nucleation which creates a lot of a 33.2 80 2.0 None
crystal nucleus, resulting in the formation of small crystals.[20–22] b 33.2 80 2.0 300 rpm
The PXRD was used to examine the phase purity of AP sam- c 33.2 80 2.0 70 W
ples prepared at the concentration and stirring rate of 33.3 wt% d 24.2 80 2.0 300 rpm
and 300 rpm. As reported in the literature, only two crystalline e 35.2 80 2.0 300 rpm
forms of AP have been reported so far. Namely, orthorhombic
f 35.2 80 5.0 300 rpm
form (JCPDS card No. 43–0648, region of existence: temperature
< 240 °C) and cubic form (JCPDS card No. 02–0232, region of
existence: temperature > 240 °C).[23] As seen in Figure S1, Sup-
porting Information, the reflection peaks located at 15.27, 19.34, rate, and concentration. However, the shape of the as-prepared
22.65, 23.86, 24.61, 27.40, 30.05, 30.82, 34.51, 40.62, 49.18, and crystals is irregular and difficult to control. In order to prepare
54.21 are assigned to the 101, 011, 201, 002, 210, 211, 112, 202, AP crystals with tunable morphology, a solvent–solvent cooling
121, 113, 123, and 132 crystal planes of AP crystal, respectively. In crystallization method was adopted here. The concentrated AP
addition, the diffraction patterns of AP raw material (Figure S1a, solution at high temperature is added to its low-temperature sat-
Supporting Information) and as-prepared samples (Figure S1b– urated liquid to create supersaturation, by adjusting crystalliza-
e, Supporting Information) are basically the same, which are well tion conditions such as stirring rate, solution concentration, and
matched with the peaks of JCPDS card No. 43–0648 by judging feed rate to control the nucleation and growth, and then further
positions of all appeared peaks. This indicates that the crystalline control the size and morphology of AP crystals.
forms of as-prepared AP samples are the same and they crystal- As can be seen in Figure 5, six different morphologies of AP
lize in the orthorhombic system. Moreover, no other diffraction crystals are obtained by adjusting the experimental parameters,
peaks were observed from the PXRD pattern, indicating that the where the preparation conditions are listed in Table 3. As shown
as-prepared AP samples are pure. in Table 3a–c, the effects of mixing ways on the morphology and
particle size distribution of AP crystals were investigated. It can
be found from Figure 5a that when AP is crystallized without
any mixing technique, long rectangle crystals with a mean size of
3.2. Solvent–Solvent Cooling Crystallization 162.4 µm can be obtained. However, when stirring mixing with a
rate of 300 rpm is adopted, the result is significantly different. As
The conventional batch cooling crystallization method above can shown in Figure 5b, the habit of AP crystals is tabular and the av-
control the size of AP crystals by adjusting stirring rate, cooling erage size becomes 123.8 µm. In addition, the aspect ratio of AP

Cryst. Res. Technol. 2019, 54, 1900065 1900065 (5 of 8) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Figure 6. Particle size distribution curves of AP crystals crystallized at different conditions (cf. Figure 5 and Table 3).
crystals decreases significantly. Considering the obvious change
in morphology and size, the ultrasonic mixing technique is also
tried in this study. As shown in Figure 5c, when the ultrasonic
power is 70 W, the shape of AP crystals become spherical, the
mean size of which decreases to 43.9 µm. This may be due to the
fact that the nucleation rate significantly increases with sonica-
tion, while the growth rate reduces with sonication as compared
to the stirring mixing case, resulting in a smaller mean size un-
der ultrasonic mixing.[24,25] In addition, it can also be found from
Figure 6a–c that AP crystals crystallized under stirring and ultra-
sonic mixing technique exhibits a narrow particle size distribu-
tion. In fact, this is not surprising because crystallization without
stirring and ultrasonic technique can lead to a poor mixing that
can result in temperature and concentration gradients in the crys-
tallizer. However, large concentration gradients can lead to dif-
ferent growth and nucleation rates at the top and bottom of the
crystallizer, resulting in a wide particle size distribution.[16,26,27]
Moreover, stirring and ultrasonic technique facilitate heat and
mass transfer in crystallization. This ensures a relatively uniform
growth rate of AP nucleus, thereby resulting in a relatively nar-
row particle size distribution.[22,28]
Furthermore, many other parameters such as the solution con-
centration and feed rate are also studied on the basis of the above
experiments. As shown in Table 3d, when the concentration of
AP solution is decreased to 24.2 wt% on the basis of Table 3b, the
morphology of AP crystals is platy (Figure 5d) and its average size
is 191.9 µm. On increasing the concentration of the AP solution
to 35.2 wt%, as shown in Figure 5e, high-index faced polyhedron
AP crystals with a mean size of 102.5 µm are obtained. In addi-
tion, bipyramid AP crystals are obtained under the conditions of
a higher feed rate, and their average size is 90.8 µm (Figure 5f).
Moreover, as shown in Figure 6d–f, the prepared AP crystals ex-
hibit a relatively narrow particle size distribution, indicating that
Cryst. Res. Technol. 2019, 54, 1900065 1900065 (6 of 8)
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the samples prepared by solvent–solvent cooling crystallization
are uniform.
Given the different morphologies of the as-prepared samples,
the phase purity of AP crystals is checked by PXRD. During the
test process, the samples were not subjected to additional pro-
cessing operations such as grinding. As shown in Figure S2,
Supporting Information, the diffraction patterns of AP crystals
precipitated at different conditions (Figure S2a–f, Supporting In-
formation) and AP raw material (Figure S2g, Supporting Infor-
mation) are basically the same, which are well matched with the
peaks of JCPDS card No. 43–0648 by judging positions of all ap-
peared peaks. This demonstrates that the crystalline form of AP
samples are the same and they crystallize in the orthorhombic
system. Moreover, no other diffraction peaks are observed from
the PXRD pattern, indicating that AP samples are pure.
3.3. Comparison of Two Cooling Crystallization Methods
AP crystals prepared by the above two cooling crystallization
methods exhibit different morphology and size. In order to
further explain the difference between the two methods, the
formation process of supersaturation is compared here. As
mentioned above, the key step for cooling crystallization is to
determine the saturation concentration and metastable limit.
The saturation concentration also called solubility represents the
minimum solute concentration for which the crystal growth can
occur. When the concentration is lower than the solubility, crys-
tal nucleation and growth cannot occur. The metastable limit in-
dicates the concentration above which undesirable spontaneous
nucleation occur. For batch cooling crystallization, as shown in
Figure 7a, when the crystallization liquid is cooled from the initial
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 7. The schematic diagram of a) batch cooling crystallization and
b) solvent–solvent cooling crystallization.
state in which the concentration and temperature are C3 and T3
to the final state (C0 , T0 ), the crystallization takes place in the pink
area. As the temperature decreases, the supersaturation of the AP
solution increases, and the crystallization process undergoes an
undersaturation state (T2 < T ≤ T3 ), dissolution equilibrium (T
= T2 ), a metastable state (T1 < T < T2 ), and even a labile super-
saturation state (T < T1 ). The necessary condition for batch cool-
ing crystallization is that the supersaturation is created contin-
uously with decreasing the solution temperature. However, the
solubility of AP is not linear with the temperature; it is difficult to
control the supersaturation to the desired range in batch cooling
crystallization.
While for the solvent–solvent cooling crystallization the tem-
perature of the crystallization system remains essentially con-
stant, the supersaturation is produced by the continuous addi-
tion of highly concentrated AP solution. As shown in Figure 7b,
when the concentrated AP solution (C3 , T3 ) was added to its sat-
urated liquid (C0 , T0 ), as the supersaturation of the crystalliza-
tion system increases, the crystallization liquid changes from a
dissolved equilibrium state to a metastable state. With the fur-
ther increase of supersaturation, crystal nuclei begin to form in
the crystallization solution. However, due to external control, the
temperature of the crystallization system is basically stable near
T0 . Therefore, the whole crystallization process is completed in
Figure 8. The schematic diagram of industrial crystallization of AP: a) batch cooling crystallization; b) solvent–solvent cooling crystallization.
Cryst. Res. Technol. 2019, 54, 1900065 1900065 (7 of 8)
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a narrow area surrounded by a yellow border (Figure 7b). By ad-
justing the concentration and feed rate of the concentrated AP
solution, the supersaturation of the crystallization solution can
be easily controlled, so that the AP crystals with uniform mor-
phology can be prepared. Compared with the batch cooling crys-
tallization, solvent–solvent cooling crystallization makes it easier
to control the supersaturation of the crystallization solution to a
suitable range. As a result, AP crystals with uniform morpholo-
gies can be obtained.
3.4. Industrial Crystallization Outlook
The industrial production process of the solvent–solvent cool-
ing crystallization is prospected and compared with the con-
ventional batch cooling crystallization process. As shown in the
schematic diagram of Figure 8, the batch cooling crystallization
is performed on such a way that the concentrated AP solution
is slowly cooled under the control of circulating water. The pre-
cipitated AP crystals are not separated from solution before the
crystallization is completed. In each crystallization cycle, the de-
crease of the temperature is the key factor in controlling the su-
persaturation of the crystallization solution. In order to obtain
AP crystals with desired morphology and size, the entire cooling
process usually takes a long time, resulting in low production ef-
ficiency. However, as for solvent–solvent cooling crystallization,
the industrial crystallization process is quite different. As shown
in the prospective industrial production line in Figure 8b, AP
and water are mixed and heated in a tank to form a concentrated
AP solution. Then, the concentrated AP solution is continuously
added to a crystallizer by a pump, and crystallization is carried
out by the rapid cooling of the added concentrated AP solution.
After that, the AP crystals overflowing from the crystallizer are
separated from the crystallizing solution by filtration to realize
the continuous production of AP crystallization. In addition, the
nucleation and growth of AP crystals are controlled by adjust-
ing the parameters such as stirring rate, feed rate, and solution
concentration, thereby achieving efficient production. Therefore,
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
compared with the batch cooling crystallization, solvent–solvent
cooling crystallization provides a promising strategy for the con-
tinuous production of AP crystals in the industry.
4. Conclusions
In summary, two different cooling crystallization methods,
namely the batch cooling crystallization method and the solvent–
solvent cooling crystallization method, are compared to prepare
AP crystals with tunable shapes and sizes. By adjusting the pa-
rameters such as cooling pattern, stirring rate, cooling rate, feed
rate, and solution concentration, the shape of AP crystals can
be tailored as long rectangle, tabular, spherical, platy, bipyramid,
and high-index faced polyhedron shaped, the size of which can
be controlled from 43.9 to 191.9 µm. In addition, the mecha-
nism of two different cooling crystallization methods is also ana-
lyzed. Moreover, the proposed solvent–solvent cooling crystalliza-
tion method also provides a promising strategy for the continu-
ous production of AP crystals in industry.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
The authors gratefully acknowledge Dr. Chun-pei Yu (Nanjing University
of Science and Technology) for his tests of the PXRD of the samples.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
ammonium perchlorate, batch cooling crystallization, morphology and
size control, solvent–solvent cooling crystallization
Received: April 22, 2019
Revised: July 25, 2019
Published online: September 2, 2019
Cryst. Res. Technol. 2019, 54, 1900065 1900065 (8 of 8)
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