Journal of Crystal Growth 198/199 (1999) 1294—1298

Computer modeling of sugar crystallization during drying of thin sugar films
E. Ben-Yoseph, R.W. Hartel*
Department of Food Science, University of Wisconsin, 1605 Linden Driven, Madison, WI 53706, USA

Abstract A computer model was developed to predict drying and crystallization during processing of thin sugar films under the conditions of importance for sugar-coated cereals. The three-dimensional model analyzed simultaneous heat and moisture transfer, accounting for shrinkage, with temperature and moisture-dependent transport properties. Crystal growth was evaluated from crystallization kinetics based on supersaturation and temperature. The influence of growth on the solution concentration and drying were taken into account. Concentration profiles around the growing crystals during drying of the thin films were evaluated. The model predicts a concentration reduction around the growing crystals, and film temperatures that are higher than the drying temperature (as a result of the release of fusion heat). A phenomenon of case hardening was observed for dried films with a high density of seeds on surface. 1999 Elsevier Science B.V. All rights reserved. Keywords: Crystallization; Drying; Sucrose; Sugars; Modeling; Films

1. Introduction Controlling crystallization of sugars in thin films is critical to development of the proper appearance of sugar-coated cereal products. In this process, a thin sugar film is applied to the surface of a cereal piece, and then allowed to dry. By proper control of the crystallization and drying processes, the appropriate appearance, either frosted or glazed, can be developed. However, our understanding of the

* Corresponding author. Fax: #1 608 263 1965; e-mail: hartel@calshp.cals.wisc.edu.

parameters that influence these processes, for developing a specific appearance, is severely lacking. Cereal companies have problems getting consistent results with this process. Usually, the film is frosty at the end of the process, which is the desired appearance. However, sometimes the appearance is glossy, which is undesired. The objective of this work was to develop a computer model for predicting crystallization kinetics during drying of thin sugar films under the conditions of importance for sugar-coated cereals. This includes developing a three-dimensional model that evaluates changes in all dimensions within the film, evaluating the concentration profile around

0022-0248/99/$ — see front matter 1999 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 2 - 0 2 4 8 ( 9 8 ) 0 1 0 1 4 - 8

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the growing crystals, and accounting for crystals growing together. The simulation program determined the crystal size, shape and distribution in the film. Using this information, the final appearance of the film, either frosty or glassy, will be predicted in the next phase of the study.

z are dimensionless depth into the box in the x, y, and z directions, respectively, defined as X ½ Z x" , y" , z" (3) X ½ Z    where X, ½, and Z are the depth into the box in the x, y, and z directions, respectively, and X , ½ , and   Z are the thickness of the box in the x, y, and  z directions, respectively, as a function of time. D , V D and D are the mutual diffusion coefficients in W X water-sucrose system in the x, y, and z directions, respectively. S , S , and S , are the shrinkage magniV W X tude of the box in the x, y, and z directions. The initial conditions describe the temperature and concentration of the solution at the beginning of the process: at t"0 for all i, j, or k: C "1, (4) G H I at t"0: S"1,¹"¹ , (5)  where i, j, and k are subscripts which refer to nodes in the grid point system in the x, y, and z directions. The boundary conditions supply information on external conditions surrounding the solution, which affect the behavior of the surface solution temperature and heat and mass transfer rates during drying. The boundary conditions used were for z"0 and t'0: jC "0 jz for z"1 and t'0: ¼ D jC X "k (P !P ) ! E    (C#C)SZ jz  dS k !  " (P !P )  dt Z     [m c #c Z X ½ ( ! )       (7) (8) (6)

2. Theory, modeling and experimental procedure 2.1. Computer simulation of drying process Okazaki et al. [1] presented the mass transfer equation in a one-dimensional, two component system with shrinkage, assuming all moisture movement was by diffusion. This equation was expanded to three dimensions, since crystal growth is a three-dimensional phenomenon, to get j D jC x jS jC jC V V " # jx Xj x S j t jx jt R V 2D 1 jC  V ! C#C SX j x V R y jS jC j D jC W W # # S j t jy jy ½j y R W 2D 1 jC  W ! C#C S½ j y W R j D jC z jS jC X X # # jz Zj z S j t jz R X 2D 1 jC  X ! , (1) C#C SZ j z X R where C is the dimensionless moisture in film and t is time. C, C and ¼ are defined as follows: ¼ !¼ ¼#¼    , C "   , ¼ !¼ ¼ !¼           , ¼" (2) !    where, ¼ is the mass fraction of water, ¼ is    the equilibrium water mass fraction, ¼ is the   initial water mass fraction,  is the density of pure  water,  is the density of pure sucrose. x, y, and  C"

d¹ #c Z X ½ ( !  )#c Z X ½  S ]            dt dS "h X ½ (¹ !¹)#r  Z X ½ ,        dt (9)

where, is the solution density, k is the mass transfer coefficient at the solution surface, P is   the partial pressure of water vapor at film surface,

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P is the partial pressure of water vapor in hot air,  m is the mass of the flake, c is the heat capacity of the flake, c is the heat capacity of sucrose, c is the   heat capacity of water, is the initial density of  solution, is the water density at the initial  solution temperature, r is the latent heat of vapor ization of water, h is the heat transfer coefficient at film surface, ¹ is the solution temperature and ¹ is the drying air temperature. Calculating the temperature only as a function of time, and not as function of location, we assume that the temperature distribution is negligibly small because of the film being very thin and there is no convection flow in the film at this high viscosity of the solution. Furthermore, the thermal diffusivity of sucrose/water system in high concentration of sucrose, as given by Bhowmik and Hayakawa [2] and by Hayakawa and Bakal [3], is 3 fold higher than the mass diffusivity of the system. The resulting system of nonlinear partial differential equations in time and three dimensions were solved numerically by applying the finite difference method. In the classical finite difference application, the distance between the nodes is constant. However, since shrinkage is not negligible during drying (the film shrinks when dried at a rate depending upon the solution concentration and the degree of drying) the physical dimension of the film is changing during drying. Therefore, the variable grid central finite difference method was applied [4,5]. The physical parameters used during calculation were assumed to be functions of local concentration and/or temperature. These parameters were defined explicitly from several literature sources. 2.2. Predicting the state of solution, and crystal growth rate, size, shape and distribution The information about temperature and concentration at any location in the film during the drying process located each point in the film in the phase diagram; either it is an undersaturated, metastable, labile or glassy solution. A region in the film was considered glassy if its temperature reached below the glass transition

temperature, ¹ , during the drying process. Roos and Karel [6] gave a method to calculate ¹ for sucrose by applying the Gordon and Taylor equation: w ¹ #kw ¹  , (10) ¹"   w #kw   where w and w are weight fractions of component   compounds, ¹ and ¹ are the absolute glass   transition temperatures (K) of the component compounds, and k is a constant. In our case, ¹ "138 K (¹ of water), ¹ "335 K (¹ of pure   sucrose), and k for sucrose—water equal to 4.7. For supersaturated, non-glassy solution, the model calculated the supersaturation level as a function of the local concentration and the saturation concentration (which is a function of temperature). The growth rate of sugar crystals as a function of the supersaturation level and temperature was calculated from a sucrose growth model based on data given by Hartel et al. [7]. Regression from this data (R"0.9697), gave the following equation, valid for temperature range of 44—54°C and supersaturation ratio above 1.0576: G"7.0538S!7.46, (11)

where, G is the growth rate for a single crystal ( m/min) and S is the supersaturation ratio (concentrations of grams sucrose per grams of water). 2.3. Evaluation of the crystal growth influence on the film All the following phenomena were taken into account in the simulation program: (1) Reduction in concentration: when a crystal grew, sucrose was removed from the solution and the concentration around the crystal decreased. The change in concentration was calculated from mass balance of sucrose and water. (2) Generation of fusion heat: when a crystal grew, it generated heat that raised the film temperature. An additional term was added to the heat transfer equation, relative to the amount of mass that was built on the crystal [8]. (3) Decrease in diffusivity: the volume of a crystal acted as a barrier for diffusion of sucrose and water. To model this influence, a mass transfer of

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Fig. 1. Concentration profiles during drying of thin sucrose film without nucleation sites. Drying air was at 50°C, 0% RH and velocity of 3.0 m/s.

zero was used between two points when a crystal was present between them. (4) Decrease in drying rate: crystals that grew on the surface of the film decreased the surface area for water migration from the solution to the air. In order to take this into account, the drying surface area was multiplied by one minus the ratio of crystal cross sectional area to film cross sectional area in the direction of water flux.

3. Results The concentrations at any time and location in the film during drying were determined using the simulation program. The initial conditions of the film, for all the simulations, were: concentration of 70% TS, temperature of 40°C and thickness of 200 m. The drying air velocity was 3.0 m/s and its relative humidity was 0%. The drying air temperature was 50°C. Simulating a dehydration process without crystallization, we observed a concentration increase of sucrose as the drying time increased, at any location in the film (Fig. 1). The rate of change and the final concentration were higher for locations closer to the surface of the film (after 2 min of drying the concentration was 96% in the surface, compared to 87% near the flake). The concentration reached

a plateau very fast near the surface and then the change was mild. At the initial stages of drying the concentration gradient was high, whereas at later stages the concentration gradient flattened. Simulating a drying process that includes crystallization showed the concentration fields around growing crystals (Fig. 2). Here, we placed two spherical seed crystals (diameter of 5 m) in the film, at 24 and 120 m distance from the surface. The seed that was closer to the surface grew much faster than the other. A concentration reduction around the fast growing crystal can be seen, as well as interference for diffusion by both crystals. The film temperature was higher than the drying temperature due to release of fusion heat. After 5 min of drying the film temperature reached 51.4°C. When high density of seed crystals were placed on the surface of the film, the seeds grew very fast during drying and formed a closed crust after approximately one minute. This crust inhibited moisture migration from the film to the drying air (case hardening). In the first 12 s, the sucrose concentration was high at the surface and decrease toward the bottom (Fig. 3). Later (25 and 40 s in the chart), the concentration was high between the growing crystals, but low in the immediate layer below the crystals, because of the concentration reduction during the growth. After 60 s of drying, the film reached equilibrium, with crystalline material on

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Fig. 2. Concentration field around two growing sucrose crystals after 5 min of drying of thin film of sucrose solution. Drying air was at 50°C, 0% RH and velocity of 3.0 m/s.

Fig. 3. Concentration profiles in a thin film of sucrose with high density of seeds on its surface. Drying air was at 50°C, 0% RH and velocity of 3.0 m/s. The values above the curves are the drying times. After one minute the film temperature was 45.2°C, then, the saturation concentration was 71.2% w/w.

the surface, and saturated solution (with uniform concentration) below. References
[1] M. Okazaki, K. Shioda, K. Masuda, R. Toei, J. Chem. Eng. Japan 7 (1974) 99. [2] S.R. Bhowmik, K. Hayakaw, J. Food Sci. 44 (1979) 469.

[3] K.I. Hayakawa, A. Bakal, J. Food Sci. 38 (1973) 623. [4] B.A. Finlayson, Numerical Methods for Problems with Moving Fronts, Ravenna Park, Seattle, WA, 1992. [5] M. Balaban, G. M Pigott, J. Food Sci. 53 (1988) 935. [6] Y. Roos, M. Karel, Food Technol. (December 1991) 66. [7] R.W. Hartel, K.A. Berglund, S.M. Gwynn, P.M. Schierholz, V.G. Murphy, AlChE Symp. Ser. 193 (1980) 65. [8] A. Benard, S.G. Advani, Int. J. Heat Mass Transfer 38 (1995) 819.

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