The effect factors of potassium dihydrogen phosphate crystallization in aqueous

solution
Cun Zhou, Fei Sun, and Xuzhao Liu

Citation: AIP Conference Proceedings 1794, 020003 (2017); doi: 10.1063/1.4971885

View online: http://dx.doi.org/10.1063/1.4971885
View Table of Contents: http://aip.scitation.org/toc/apc/1794/1
Published by the American Institute of Physics
 The Effect Factors of Potassium Dihydrogen Phosphate
Crystallization in Aqueous Solution
Cun Zhou1, 2, 3, a), Fei Sun1, 2, b) and Xuzhao Liu1, 2, c)
1
School of Tianjin Polytechnic University, Tianjin, 300387, China.
2
Fine-Chemistry Institute, Tianjin Polytechnic University, Tianjin, 300160, China.
3
Tianjin Engineering Research Center of Textile Fiber Interface Treatment Technology, Tianjin, 300270, China.
a)
zhoucun588@126.com
b)
sunfei920921@163.com
c)
mxmlxz@163.com

Abstract. The effects of cooling rate and pH on the potassium dihydrogen phosphate crystallization process were studied
by means of batch crystallization process. The experiment shows that with the increase of cooling rate, the metastable
zone width increase and the induction period decrease. When the pH is 3.0, the metastable zone width and induction
period are both the minimum, while the crystallization rate is the highest. The crystallization products were characterized
by scanning election microscope. Potassium Dihydrogen Phosphate (KDP) is a kind of excellent nonlinear optical
materials, and belongs to tetragonal system, and ideal shape is aggregate of tetragonal prism and tetragonal dipyramid,
the (100) cone is alternating accumulation by double positive ions and double negative ions [1-4]. The crystals of
aqueous solution method to grow have large electro-optical nonlinear coefficient and high loser-damaged threshold, and
it is the only nonlinear optical crystal could be used in inertial confinement fusion (ICF), KDP crystals are the ideal
system to study the native defects of complex oxide insulating material [5-7]. With the development of photovoltaic
technology, KDP crystals growth and performance have become a research focus worldwide [8, 9]. The merits of the
crystallization process directly affect the quality of KDP products, so the study of the effect of crystallization conditions
has an important significance on industrial production. This paper studied the change rule of metastable zone width,
induction period, crystallization rate and particle size distribution in crystal process, and discussed the technical condition
of KDP crystallization.

Key words: Metastable zone width; Induction period; Crystallization rate; Particle size distribution; Crystal form.

EXPERIMENTAL SECTION

The Measurement of the Metastable Zone Width

The saturated solution of KDP of 60 were added to beaker, and putting beaker in cooling tank, made the
solution keep the temperature for 10 min, which is above the saturation temperature 5, and then made the solution
constant speed cooling. Read the temperature of the first batch crystal nucleus appeared, the temperature difference
between the saturation temperature and the nucleation temperature is metastable zone width [10]. By changing
different factors such as cooling rate, pH value can be observed the impact on the metastable stability zone width.

The Determination of KDP Average Particle Size

In 400 ml beaker, preparation the KDP saturated solution of 60 saturated solution, under certain agitation rate,
cooling rate, made the solution cooling crystallization, when the temperature of solution was 30 [10], standing 10

2016 International Conference on Materials Science, Resource and Environmental Engineering

AIP Conf. Proc. 1794, 020003-1020003-7; doi: 10.1063/1.4971885
Published by AIP Publishing. 978-0-7354-1460-0/$30.00

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min then suction filtration, the filter cake washed by anhydrous ethanol, then put in the oven to drying, crystal
particle size determined by the norm sample sieve.
According to the following formula (1) calculate the average particle size of KDP [11].

L LV i i (1)

L
In the formula The average particle size (m), Li-The average particle size of each scale range (m), Vi-The
mass fraction of each scale range (%).

Characterization of KDP Crystals

The surface morphologies and structures of the KDP crystallizations were observed by field emission scanning
electron microscope(FE-SEM,HITACHI S-4800, Japan),with samples fastened on metal holder by twin adhesive
and sputter-coated with thin gold coating before SEM observation, then the crystal form and length-diameter ratio
were observed.

THE RESULTS AND DISCUSSION

The Effect of Cooling Rate on the Crystal Process of KDP

Cooling rate is the important factors that affect KDP crystallization, by the process of cooling speed and the
degree of supersaturation, indirectly affect the crystal growth rate, the different cooling rate will produce different
degree of supersaturation. This experiment explore the solution of the initial temperature of 60 ,the effect of
cooling rate on the process of KDP saturated solution cooling crystallization.

The Effect of Cooling Rate on Metastable Zone Width and Induction Period

The effect of cooling rate on the metastable zone width and induction period shown in figure 1, with the increase
of cooling rate, the metastable zone width increases and the induction period become shorter. This is because the
production of crystal nucleus needs fixed induction period. When a certain degree of supersaturation is formed in
solution, the time of crystal is detected include induction period and the time of crystal growth to the particle size
which can be detected. During this period, the solution is still cool down at a certain speed, the more the cooling rate,
the greater the drop in temperature of detect the crystal nucleus. So the metastable zone width increased.

25 Metastable zone width 25

Induction period
Metastable zone width/(/min)

Induction period/min

20 20

15 15

10 10

5 5
0.3 0.4 0.5 0.6 0.7 0.8

Cooling rate/(/min)
FIGURE 1. The influence of cooling rate on the metastable zone width and induction period

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 The Effect of Cooling Rate on Crystallization Rate

Figure 2 shows the influence of cooling rate on the crystallization rate, with the increase of cooling rate, the
crystallization rate of KDP gradually increase. This is due to the greater the cooling rate, the higher the falling
temperature of unit time, also making the temperature difference increase, the degree of supersaturation increase, the
crystallization rate increase. On the one hand, with the degree of supercooling increase, the crystal growth rate also
increase, on the other hand, the viscosity of the solution improvement, limits the motility of solute molecules,
making growth speed decrease. Therefore, the acceleration of cooling rate has a dual effect on KDP crystallization
rate. With the increasing of cooling rate, the degree of supersaturation of the solution increases, the heat of solution
need to disperse quickly, so that formation rate of crystal nucleus sharp increase, crystallization rate is increase.
Because generate fine granular crystals are more suited to this purpose than coarse granular crystals.

1.2
Crystallization rate/(g/min)

1.0

0.8

0.6

0.4

0.3 0.4 0.5 0.6 0.7 0.8

Cooling rate/(/min)

FIGURE 2. The influence of cooling rate on the crystallization rate

The Effect of Cooling Rate on Particle Size Distribution

The effect of the cooling rate on particle size distribution shows in table 1. With the increase of cooling rate, the
average particle size decrease. At the different cooling rate, crystal particle sizes are mainly distributed in 30-40
mesh. The mass fractions of the main particle gradually decrease with the increase of cooling rate. By the previous
experiment indicated, with the increase of cooling rate, the metastable zone width gradually increase, the degree of
supersaturation and the degree of supersaturation ratio also increase [12]. Form the nucleation rate formula (2), with
the increase of degree of supersaturation, the crystal nucleation rate increased, this means that the increase of the
number of crystal nucleus, making the average particle size were decrease. At the same time, the need of the crystal
heat removal is faster with the increase of cooling rate, so the crystallization process are more likely to produce fine
grained crystals instead of coarse crystals.

16 Esa3 Vm2 N a
B0 Z C exp 2 3 (2)
3vRT lnS2

0 Esa
In the formula: Sthe degree of supersaturation ratio; B nucleation rate, mesh/cm3s;
7 2 Vm Na
Apparent interfacial energy, 10 J / cm ; molar volumes; Avogadro constant; VNumber of
each molecular ions of the solute; Rgas constant.

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 TABLE 1. The influence of cooling rate on the particle size distribution of KDP
Cooling rate/(/min) Main particle/Mesh Mass fraction/% The average particle/m Macro crystal form
0.3 30-40 70.56 525.28 Prismatic form
0.4 30-40 61.47 490.47 Prismatic form
0.5 30-40 57.18 460.35 Prismatic form
0.6 30-40 50.26 428.79 Prismatic form
0.7 30-40 45.28 412.65 Prismatic form
0.8 50-60 40.98 392.76 Prismatic form

The Effect of Cooling Rate on Crystal Form and Length-Diameter Ratio

Figure 3 panels a-c are the representative FE-SEM micrographs of KDP crystallization products obtained at
different cooling rate. Observation of FE-SEM reveals that the crystal form of KDP is an aggregate of tetragonal
prism and tetragonal dipyramid, and the crystal form and length-diameter ratio almost remained unchanged, the
length-diameter ratio is about 1.With the increase of cooling rate, the crystal would gather to form vug.

FIGURE 3. FE-SEM images of KDP in different cooling ratea. 0.3/min, b. 0.5/min, c. 0.7/min

The Effect of Ph Value on the Crystal Process of KDP

pH is also the important factors that affect KDP crystal, this study explores the solution of the initial temperature
of 60 , the mechanical agitation rate was 200 r/min, the cooling rate was 0.3 / min, the effect of the pH value
on the process of KDP saturated solution cooling crystallization. In this experiment, the pH value of the solution
adjusts by potassium hydroxide and phosphoric acid.

The Effect of Ph Value on Metastable Zone Width and Induction Period

When the pH of the solution was different, the percentage of , , , were

different [13, 14]. The figure 4 shows the influence of pH value on the metastable zone width and induction period.
When the pH value was 3.0,the metastable zone width was minimize, this is because the percentage of is
biggest; In the process of cooling crystallization, the degree of supersaturation and the nucleation temperature are
highest, while the metastable zone width and induction period are minimize. When the pH is less than 3.0, with the
decrease of pH value, the percentage of decrease and the percentage of increase. Part of the
and generate , making the concentration of decrease, in the process of
cooling crystallization , the degree of supersaturation, the nucleation temperature ,the metastable one width and
induction period decrease. When the pH was more than 3.0, with the increase of pH value, the percentage of
decrease, the percentage of increase, the solubility of is bigger than ,the
degree of supersaturation of decrease, the nucleation temperature, the metastable zone width and
induction period decrease.

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 50 50

45 45
Metastable zone width

Metastable zone width/(/min)

Induction period
40 40

Induction period/min
35 35

30 30

25 25

20 20

15 15

10 10
1 2 3 4 5

pH value

FIGURE 4. The influence of pH value on the metastable zone width and induction period

The Effect of Ph Value on Crystallization Rate

By figure 5 can be seen that with the increase of pH value, the crystallization rate firstly increase and then
decrease; when the pH value is 3.0, the crystallization rate was maximum. Because the percentage of is
biggest in this moment, crystal particle density is the largest, the mean free path of adsorption particle is the shortest,
so the number of spread to the crystallization of glass particle more than other pH value in unit time, the
crystallization rate is the largest. When pH value is less than (more than) 3.0, with the decrease (increase) of pH
value, the crystallization rate decreases, the same as the metastable zone width and induction period, this is due to
the degree of supersaturation decrease, making crystallization rate decrease[14].

1.4

1.2
Crystallization rate/(g/min)

1.0

0.8

0.6

0.4
1 2 3 4 5

pH value

FIGURE 5. The influence of pH value on the crystallization rate

The Effect of Ph Value on Particle Size Distribution

The effect of particle size distribution on pH value shown in table 2,when the pH was 1.0, the average particle
size is minimum, and the main particle in 50 to 60 mesh, with the increase of pH value, the average particle size
increases gradually, the quality of the main particle gradually increased.

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 TABLE 2. The influence of pH value on the particle size distribution of KDP
The average
pH value Main particle/Mesh Mass fraction/% Macro crystal form
particle/m
1.0 50-60 42.37 326.79 Prismatic form
2.0 50-60 46.85 361.18 Prismatic form
3.0 40-50 52.93 412.65 Prismatic form
4.0 40-50 55.43 430.57 Prismatic form
5.0 30-40 58.21 455.27 Prismatic form

The Effect of Ph Value on Crystal Form and Length-Diameter Ratio

Figure 6 panels a-c show FE-SEM micrographs of KDP crystallization products obtained at different pH value.
Fig.6a is the representation FE-SEM image of the pH value is 1.0, crystal form is double cone and the length-
diameter ratio less than 1; Fig.6b is the representation FE-SEM image of the pH value is 3.0, the crystal form is a
aggregate of tetragonal prism and tetragonal dipyramid, the length-diameter ratio is about 2, and the crystals have
better dispersity and nearly no vug. Fig.6c is the representation FE-SEM image of the pH value is 5.0, as shown, the
liquidity of crystal particles are not good, it is difficult to disperse, the cluster of particle is obvious.

FIGURE 6. FE-SEM images of KDP in different pH value (a. pH=1.0, b. pH= 3.0, c. pH=5.0)

CONCLUSION
With the increase of cooling rate, the metastable zone width increase, the induction period and average particle
decrease; the change of cooling rate did not change the crystal form and length-diameter ratio of KDP, But with the
increase of cooling rate, Crystals can form vug. When the cooling rate is 0.3/min, the average particle size of
crystal biggest. When the pH is 3, the metastable zone width and induction rate is minimize, the crystallization rate
is maximum. The average particle size is increase with the increase of pH value. PH change has no impact on the
crystal form of KDP, but when the pH value is 3.0, the length-diameter radio is biggest. Comprehensive the above
consideration, in the process of KDP crystallization, control the agitation rate is 200 r/min, the cooling rate is 0.3
/ min, the pH value of the solution is 3.0, the above conditions are meet, making the KDP crystal particles are larger
and can effectively prevent the vug.

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