Jurnal Matematika dan Sains Vol. 10 No.

3, September 2005, hal 101-106

In Situ Measurement of the Growth Rate of the (111) Face of Borax Single Crystal
Suharso Jurusan Kimia FMIPA Universitas Lampung Jl. Sumantri Brojonegoro No. 1 Gedung Meneng-Bandarlampung E-mail: Suharso_s@yahoo.com Received May 2005, accepted for publication July 2005
Abstract The quality of borax crystals is determined by grade and specifically shaped crystals of high purity. One of fundamental studies of this quality is an investigation of the growth rate of each face of borax single crystals. This paper studies the growth rates of borax single crystals along the (111) direction at various relative supersaturations using in situ optical microscopy technique to elucidate mechanism of growth and crystal growth rate equation. The result shows that the growth mechanisms of the (111) face of borax crystal at temperature of 20C are spiral growth mechanism below relative supersaturation of 0.49 and a birth and spread mechanism above relative supersaturation of 0.49. Keywords: Growth mechanism, borax. Abstrak Kualitas kristal borak ditentukan oleh derajat kemurnian yang tinggi disertai bentuk kristal yang khas. Penyelidikan tentang laju pertumbuhan pada setiap bidang kristal tunggal borak merupakan studi yang mendasar bagi kualitas kristal borak. Tulisan ini mempelajari laju pertumbuhan kristal borak pada bidang (111) dengan variasi konsentrasi menggunakan metode in situ optical microscopy tehnique untuk mengetahui mekanisme pertumbuhan dan persamaan laju pertumbuhannya. Hasil penelitian menunjukkan bahwa mekanisme pertumbuhan bidang (111) dari kristal borak pada suhu 20C adalah mekanisme pertumbuhan spiral untuk relative supersaturation di bawah 0,49 dan mekanisme pertumbuhan birth and spread untuk relative supersaturation di atas 0,49. Kata kunci: Mekanisme pertumbuhan, borak. 1. Introduction The quality of sodium borate tetrahydrate, Na2B4O710H2O, (borax) is solely determined by grade and specifically shaped crystals of high purity1). The quality of the high-purity product depends both on the concentrations of the impurities and the product appearance, which are mainly determined by the size and morphology of the crystals2). Thus, knowledge about crystallization of borax is of direct relevance to the industrial production of borax. In addition, fundamental studies of borax crystallization will provide results of relevance to the crystallization of other economically important materials. The growth mechanism of borax crystal has been reported via spiral mechanism and the existence of growth spirals on different habit faces suggests that screw dislocations play their role in the development and growth of respective faces in particular and of borax crystals in general3). However, investigations of growth rate of borax crystal still give limited information. None of the research reported has produced sufficient data of growth rates for each face of the crystals, over a wide range of relative supersaturation. Most of the researchers studied from a big crystal (bigger than 1000 m). 101 This paper report the study of the growth rate mechanism of the (111) face of borax crystal by using in situ cell optical microscopy under various relative supersaturations. The in situ cell optical microscopy allowed measuring the growth rates of the (111) face of borax crystals. The morphology of borax crystal can be seen in Figure 1.

111 001

100

110

010

221

111 Figure 1. The morphology of borax crystal7,8,9). The objective of this research is to improve fundamental knowledge about crystallization of borax, including the mechanism of growth and crystal growth rate equation required in the modeling

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and design of industrial crystallizers. This information will be very useful for borax industry. 2. Experimental Procedure 2.1. Solubility of borax in water The driving force for crystallization is usually expressed as a supersaturation ratio, defined as4):

(111)

S=

A A*
(111) Figure 3. Schematic diagram of the (111) face from borax crystal measurement within optical in situ growth cell. 2.3. Seed Preparation The seed solution was prepared from 30 gram of Univar AR grade sodium tetraborate dissolved in 100 mL of Milli-Q water by heating up until 60C and filtering through filter paper. The solution was quickly cooled down into petri dish that covered by a transparent plastic, producing 40-200 m well formed single crystals. Only single seed crystals between 40-120 m in size were used to investigate the growth rate. 2.4. Preparation of Growth Solutions The growth solution was dissolved in 200 mL of Milli-Q water by heating up until 60C and filtering through a 0.45 m filter membrane. The filtered solutions were placed into waterbath at temperature of 20C with covered plastic bottle for 3 hours before used. To place solutions into sample compartment, the growth solution was pumped by peristaltic pump via rubber tubing. The experiments were performed at temperature of 20C and relative supersaturations (s-1) from 0.18 to 1. 3. Results and Discussions To determine the growth rate of a crystal face, the length of the crystal as a function of time was plotted, and the slope of the line gives the growth rate of the crystal. A typical sequence of images of a crystal grown in the in situ cell is shown in Figure 4. Figure 5 shows a plot of crystal length of (111) faces of borax crystals versus time at temperature of 20C and relative supersaturation of 0.28. For this plot, the correlation coefficients are higher than 99% in all data obtained. From these experiments, it can be concluded that crystal faces show constant growth rate with time.

Where A and A* are the initial and the equilibrium solute concentrations. The solubility of borax in water used has been reported by previous researchers5,6). 2.2. Experimental Set-up In situ cell optical microscopy method described by some researchers10,11,12,13) was used. Optical microscopy in situ growth experiments were conducted using a set up that consists of a Nixon Optiphot-2 Microscope with automated video image capture, a Grant W14 (Grand Instruments Ltd.) circulating water bath with temperature controller, Pulnix TM-9701 Camera (Progresive Scanning Full Frame Shutter Camera), and a Pentium II Computer. The schematic diagram of the in situ growth cell is given in Figure 2. The in situ growth cell has two compartments; water at desired temperature was circulated through the lower chamber of the cell to keep the temperature constant in the sample solution compartment (volume 5 ml). During the growth experiments, a digital thermometer (HANNA Instruments, HI 8424) monitored temperature of the sample solution compartment. The images of the growing seed crystals were recorded using the video camera and the change in length of the (111) face was measured using the Optimas Software, Version 6.2 (Optimas Corporation, Bothell, Wa, USA.) linked automatically with Microsoft Excel Program, 1997. The schematic of crystal measurement of the (111) face in the in situ growth cell is shown in Figure 3. Following measurement of crystal length, a linear regression was performed on the length data for each crystal. In order to obtain the growth rate of the (111) face, the slope of the plot was divided by two. The final growth rates are reported as m/minute.

Figure 2. Schematic drawing of the in situ cell used in the growth experiments, (1) sample solution compartment, (2) constant temperature water compartment, and (3) thermocouple. (a) Top View and (b) side view.

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103

100 m

d (111)

(111) e f

Figure 4. (a-f) A sequence of in situ crystal growth experiment at relative supersaturation of 0.28, 10 minutes intervals between images.
300 250
R = 0.9993
Crystal size (mm)
2

200 150 100 50 0 0 20 40 60 80 100 120 140 160

Time (minutes)

20C. The calculated mean growth rates of these faces against relative supersaturation at temperature of 20C are given in Figure 6. The mean growth rate of this face increases with increasing relative supersaturation. Tabel 1. Mean growth rates of the (111) faces at 20C (s-1) 0.18 0.28 0.39 0.49 0.59 0.69 0.90 1.00 Total Number of single crystals 21 19 20 21 20 18 13 16 148 Mean Growth Rate (m/min) 0.20 0.07 0.46 0.07 0.87 0.12 1.08 0.21 1.80 0.38 2.32 0.29 3.90 0.41 4.52 0.57

Figure 5. Length versus time of the (111) faces of borax crystals at 20C and relative supersaturation (s1) 0.28 (number of single crystals measured = 19) Table 1 shows the number of single crystal measured, relative supersaturation (s-1), and the calculated mean growth rates of the (111) faces at

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Ea n GR = k o exp (s 1) RT
y = 4.5549x R2 = 0.9967
1.8204

1)

Growth rate (mm/min)

0 0 0.2 0.4 0.6 0.8 1 1.2 Relative supersaturation (s-1)

Figure 6. Mean growth rates of (111) face of borax crystal as a function of relative supersaturation The general
n

where ko is the kinetic coefficient, ( s 1) is the relative supersaturation, n is growth order and Ea is the activation energy. This equation is used to determine the dependence of growth on supersaturation and to determine the activation energy of individual crystal faces. The experimental results obtained for the growth rates of (111) face can be fitted by Equation 1 using non-linear regression tool of SPSS (unweighed analysis). From investigation using the power law model from all data, the power, n , is 1.82, the activation energy is 52.5 kJ/mol and the kinetic coefficient is 9.67 x 109 m/min with a correlation coefficient of 0.99. The growth rate equation in Figure 6 for power law model calculated from all data obtained may be written as

GR = 9.67 x10 9 exp 52500

RT

)(s 1)

1.8

term

of

growth

rate,

GR = k ( s 1) , where the growth rate constant, k , is related to temperature, T , by the Arthenius Ea equation: k = k o exp . Therefore, the RT
growth kinetic model may be written as:

where correlation coefficient (R2) is 0.99. If the quadratic equation (power law model) is only considered to have best fit, this implies that the (111) face grows via a spiral growth mechanism, which is not consistent with what was observed visually (Figure 7).

Figure 7. (a-b) A Sequence of in situ Optical Microscopy Images showing growth on the surface of the (111) face of borax by polynuclear birth and spread mechanism in relative supersaturation approximately 0.75 at room temperature after the following time intervals 4 minutes. Based on two-dimensional nucleation theories, the critical size of nuclei is generally proportional with increasing temperature and relative supersaturation. A two-dimensional nucleation from birth and spread model will be formed at higher relative supersaturation with a smaller number of molecules, which provide new sources of steps and increases the rate of nuclei formation4). In order to determine if growth of the (111) face at high relative supersaturation (above relative supersaturation of 0.49) is occurring via a two-dimensional nucleation from birth and spread mechanism, different equation upon power law model (spiral growth model) from the equation of two-dimensional nucleation for a birth and spread model10) was applied to the growth rate data of the (111) face by plotting the

versus 1 ln GR , the birth and 5 ( s 1) 6 ( s 1)

spread model rate equations can be linearised, but not the growth rate equation for the spiral growth mechanism. Generally, spiral growth mechanism occurs at low relative supersaturation and the birth and spread mechanism occurs at high relative supersaturation4,10).

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Figure 8 is a plot of ln GR

( s 1)

5/6

versus

( s 1)

from growth rate of birth and spread

equation, showing linear relationship above a relative supersaturation of 0.49. These indicate that above these levels of relative supersaturations, growth occurs by a birth and spread mechanisms. This mechanism is in agreement with visual observation showed in Figure 7. Below relative supersaturation of 0.49, from the curve of the plot, the spiral growth models suggest the growth mechanisms. Although spiral growth was not obtained in the (111) face of borax crystal, the existence of these cannot be dismissed because the resolution of the optical

microscope may have been insufficient to distinguish them. These results are comparable to the growth rates of gibbsite single crystals determined using in situ optical microscopy10). It can be concluded that the growth rate of the (111) face of borax single crystal at temperature of 20C is a spiral mechanism below relative supersaturation of 0.49 and a birth and spread mechanism above relative supersaturation of 0.49. Based on power law model, the growth rate equation of this face under these conditions for all the data obtained may be written as GR = 9.67 x 109 exp(52500 J /RT)(s-1)1.8 with correlation coefficient of 0.99.

1,8 1,6 1,4 1,2 Ln(GR/(s-1) )

5/6

(s-1)=0,49

1 0,8 0,6 0,4 0,2 0 -0,2 -0,4 0 2 1/(s-1) 4 6 y = -0,7932x + 2,3189 R = 0,9905
2

y = -0,987Ln(x) + 1,5162
Birth and spread mechanism

R = 0,9889
Spiral mechanism

Figure 8. Plot of ln GR

( s 1)

5/6

versus 1 ( s 1) showing regions of different growth mechanism on the (111)

of Technology, Perth, Western Australia for the valuable guidance and support that. Financial support from LPIU-DUE Project University of Lampung and A.J. Parker Cooperative Research Hydrometallurgy, Western Australia are greatly appreciated. References 1. Garret, D.E., & Rosenbaum, G.P., Crystallization of borax, American potash & chemical corp., Trona, Calif. 50, 1681-1684 (1958). 2. Teodossiev, N., & Kirkova, E., On The preparation of high-purity boric acid by crystallization, Industrial Crystallisation, NorthHolland Publishing Company (1982).

face 4. Conclusions The growth rate equation of the (111) face of borax crystal at temperature of 20C can be written as GR = 9.67 x 109 exp(-52500 J /RT)(s-1)1.8 with correlation coefficient of 0.99. The growth mechanism of the (111) face of borax crystal at temperature of 20C is a spiral mechanism below relative supersaturation of 0.49 and a birth and spread mechanism above relative supersaturation of 0.49. Acknowledgements The author is grateful to Prof. Gordon Parkinson and Associate Prof. Mark Ogden from Nanochemistry Research Institute, Curtin University

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3. Takoo, R.K., Growth of borax crystals by spiral mechanism, Crys. Res.Technol. 20:7, 903-906 (1985). 4. Mullin, J.W., Crystallization, third edition, Butterworth-Heinemann Ltd., Oxford, (1993). 5. Nies, N.P., & Hulbert, R.W., Solubility isotherm in the system sodium oxide-boric oxide-water, J. Chem. Eng. Data, 12:3, 303-313 (1967). 6. Sprague, R.W., In Mellors comprehensive treatise on inorganic and theoritical chemistry, Vol. 5, 254, London and New York, Longman, (1980). 7. Betekhtin, A., A course of mineralogy', Agol, V. and Gurevich, A. (ed), Peace Publishers, Moscow, (1964). 8. Dana, E.S., Minerals and how to study them, Third edition, John Wiley & sons, Inc., New York, London and Sydney, (1949). 9. Dana, E.S., A textbook of mineralogy with an extended treatise on crystallography and physical mineralogy, Fourth edition, John Wiley and

Sons, Inc., New York, Chapman and Hall, London, (1954). 10. Lee, M., & Parkinson, G. M., Growth rates of gibbsite single crystals determined using in situ optical microscopy, Journal of Crystal Growth 198:199, 270-274 (1999). 11. Lowe, J., Ogden, M., Mc Kinon, A., & Parkinson, G., Crystal growth of sodium oxalate from aqueous solution, Journal of Crystal Growth 238 (2002). 12. Suharso. Growth of the (010) face of borax crystals, Jurnal Penelitian Sains dan Teknologi, 9:2, 45-50 (2003). 13. Suharso, Parkinson, G.M., & Ogden, M., Growth rate dispersion (GRD) of the (010) face of borax crystals in flowing solution, Indonesian Journal of Chemistry 4:3, 145-148 (2004). 14. Veesler, S., & Boistelle, R., Growth kinetics of hydrargillite aluminium hydroxide from caustic soda solutions, Journal of Crystal Growth 142, 177-183 (1994).