Flow Behavior of Milk Chocolate Melt and the Application to Coating Flow

S UKANY A W ICHCHUKIT, MICHAEL J. MC CAR THY, AND KATHR YN L. MC C AR THY UKANYA ARTHY THRYN ARTHY ABSTRACT : The rheological properties of chocolate, especially shear viscosity and yield stress, are important ABSTRACT: control parameters for enrobing processes in confectionery manufacture. The rheological parameters of molten milk chocolate were measured at 42C during steady pipe flow using a magnetic resonance imaging (MRI) viscometric method. The experimental method combines shear rate values obtained from an MR velocity image and shear stress values obtained from an independent pressure drop measurement. The experimental factors were emulsifier type and emulsifier level. The rheogram data were fit by the Casson model to yield the Casson asson yield str ess r anged fr om 1.9 to 15.0 P a; the C asson viscosity r anged yield str ess and plastic viscosity . The C ranged from Pa; Casson ranged stress viscosity. Casson stress from 6.0 to 14.6 Pa s as a function of emulsifier content. The rheological parameters were incorporated into a drainage theory model to predict coating thicknesses in the enrobing process. The model was solved numerically and yielded good approximations to the experimental values that were between 1.1 to 2.7 mm. Keywor ds: chocolate , viscosity , yield str ess , enr obing, magnetic r esonance imaging (MRI) eywords: chocolate, viscosity, stress ess, enrobing, resonance

Introduction
he use of enrobing technology is prevalent in the chocolate manufacturing industry. The molten chocolate or chocolate coating flows in a sheet above a moving belt. The product is coated as it moves through the sheet. For good quality and accurate weight control, the chocolate must have the correct viscosity (Aeschlimann and Beckett 2000). Extensive rheological studies of molten chocolate have been performed using rotational viscometry to describe flow properties. Prior to 2000, the Casson model was recommended as a standard method by the Intl. Office of Cocoa, Chocolate, and Sugar Confectionery (IOCCC) to quantify rheological properties of the fluid chocolate. The Casson parameters are the Casson plastic viscosity and the Casson yield stress; these values range from 1 to 20 Pa s and 10 to 200 Pa, respectively (Chevalley 1975, 1991, 1999). In a multi-laboratory study, Aeschlimann and Beckett (2000) discuss a sequence of tests and recommendations to improve the standard method for measuring chocolate viscosity. These researchers recommend reporting shear stress values at specified shear rates, for example, 2, 5, 10, 20, and 50 s1. In addition, the chocolate must be completely melted prior to viscosity measurements, that is, 40C. The IOCCC standard for the measurement of viscosity of chocolate products continues to recommend rotational viscometry using a concentric cylinder probe (IOCCC 2000). The Deutsches Instite fr Normung (DIN, standard developed by the German Institute for Standardization) bob is recommended to minimize instrument errors. Other instrument errors, such as wall slip, are recognized potential reasons for inconsistent measurements, especially at low shear rates (Beckett 2001; IOCCC 2000). The success of the enrobing process is dependent both on the rheological characterization of the chocolate and the physics of coatMS 20040648. Submitted 9/23/04, Revised 11/8/04, Accepted 11/20/04. Author Wichchukit is with Dept. of Biological and Agricultural Engineering. Authors McCarthy M.J. and McCarthy K.L. are with Dept. of Food Science and Technology and Dept. of Biological and Agricultural EngineeringOne Shields Ave., Univ. of California, Davis, CA 95616. Direct inquiries to author McCarthy (E-mail: klmccarthy@ucdavis.edu).

ing flow. A considerable body of literature published in the mid1960s and early 1970s discusses liquid entrained on a flat surface as the surface is withdrawn vertically from a bath of liquid. This type of physical situation is important to coating, cleaning, draining, lubrication, and viscosity measurement. Tallmadge and Gutfinger (1967) cite early applications and present an approach that incorporates viscous, gravitational, and surface tension forces in the different regimes. Representative work includes Van Rossum (1958), Gutfinger and Tallmadge (1965), and Groenveld (1970). Drainage was considered a special case of the withdrawal process. The unsteady state flow process of a flat plate that has been totally withdrawn from a liquid bath is governed by only viscous and gravitational forces. Film thickness as a function of position and time was presented in a straightforward manner for Newtonian fluids by Bird and others (2002) as fluid draining from tank sides. Gutfinger and Tallmadge (1965) presented the draining analysis for non-Newtonian fluids. Specifically, the 3-parameter Ellis model was evaluated. Depending on the values of the parameters, this model reduced to the Newtonian model, the power law model, or the Bingham plastic model. Insightful comments were made regarding the behavior of power law fluids as compared with Newtonian fluids. A change in the power law consistency index, K, has a more pronounced influence on the film thickness than the change of viscosity in the Newtonian case. In addition, the change in film thickness with time and position is more pronounced for a Newtonian fluid than a power law fluid. This difference is primarily due to the power law fluid being more uniform in thickness than the Newtonian one. This effect becomes more pronounced with decreasing values of the flow behavior index, n. This work utilized a magnetic resonance imaging (MRI) technique as an integral part of tube viscometry and extends the technique that has been reported by McCarthy (1994), Powell and others (1994), Arola and others (1997), and Yoon and McCarthy (2002, 2003). The objectives of this study were to evaluate the rheological properties of molten milk chocolate and to incorporate the measured rheological properties into an unsteady state draining analysis to predict and control coating thickness during the enrobing process.

E: Food Engineering & Physical Properties

Flow behavior of milk chocolate melt . . .

Materials and Methods
Test samples
The test material was milk chocolate obtained directly from the manufacturer in 5 gallon containers (Hershey Foods Corp., Hershey, Pa., U.S.A.). Although chemical analysis was not performed for these particular samples, typical composition by percent for this product is cocoa mass 11.8%, whole milk powder 19.1%, sugar 48.7%, added cocoa butter 20%, for a total fat content of 31.5% (Jackson 1999). The milk chocolate was manufactured without added emulsifier. Five chocolate formulations were used: milk chocolate with no added emulsifier (the control), milk chocolate with 0.1% soy lecithin, milk chocolate with 0.3% soy lecithin, milk chocolate with 0.1% synthetic lecithin (YN), and milk chocolate with 0.3% YN. The emulsifiers were added by weight during the melting and mixing process. The density of the milk chocolate melt was 1270 kg/m3.
Table 1Apparatus geometry and MRI experimental parameters Apparatus geometry MRI parameters

Tube radius, R (mm) 4.9 Pulse repetition time, TR (ms) 400 Tube length, L (m) 1.25 Echo time, TE (ms) 63 Reservoir radius (mm) 57.5 Number of phase encoding 32 Reservoir height (mm) 130 Number of frequency encoding 64 Number of averages 16 Field of view (mm) 60 Velocity sweep width (mm/s) 188.9

Magnetic r esonance imaging viscometr y resonance viscometry

The experimental apparatus consisted of a temperature-controlled capillary viscometer connected to a 1818-mL stainless steel sample reservoir (Figure 1). During each experimental run, the test fluid from the reservoir was pressure driven through a straight length of 9.8 mm inner dimater glass tubing (Pyrex, Corning, Inc., Big Flats, N.Y., U.S.A.) by the downward motion of a piston moving at 0.2 mm/s. The cross-sectional area of the piston was 1.04 104 mm2 and spanned the cross-section of the fluid reservoir. The contact area between the piston and the reservoir surface was a lubricated O-ring. The piston was connected to an actuator/control system fabricated to provide a 0.30-m stroke length and rated for 2200 N (Electric Cylinder Model EC2, IDC, Salem, N.H., U.S.A.). A pressure measurement was acquired upstream of the imaging region using a pressure transducer (Model PX771-100WD1, Omega Engineering Inc., Stamford, Conn., U.S.A.). The pressure difference was determined by the difference between measurement and ambient, characterizing the pressure drop over the length, L, of 1.25 m (Figure 1). The chocolate was melted and held at 42C in a chocolate-tempering system (Revolation X3210, ChocoVision, Poughkeepsie, N.Y., U.S.A.) to ensure that fat was in the liquid phase and well mixed with the milk chocolate solids. The sample temperature was maintained at 42C throughout testing by jacketing the reservoir and flow tube; the heating medium was warm air (42C). Although the target temperature was 40C, there was a 2C offset in the temperature control of the experimental system. The offset was consistent; off-line measurements were therefore performed at the same temperature, 42C. For each flow rate and pressure drop measurement, an MR veloc-

ity image was acquired at a position 0.50 m downstream from the reservoir, which ensured fully developed flow. The MR velocity images were obtained using a SMIS NMR spectrometer (Surrey Medical Imaging Systems, Surrey, U.K.) connected to a 0.1 Tesla electromagnet, corresponding to 4.2 MHz for 1H resonance frequency. Unshielded gradient coils produced orthogonal gradients with maximum gradient amplitudes of 2 Gauss/cm. A pulsed gradient spin-echo pulse sequence was applied to acquire the velocity profiles (McCarthy 1994; Arola and others 1997). The apparatus geometry and MRI experimental parameters are given in Table 1. For the MR image, 32 phase encoding steps were used to characterize the z component of the velocity and 64 frequency encoding steps along the x direction read out the radial position (r) of the volume elements. The resulting matrix was zero filled to 64 128 and a twodimensional Fourier transformwas performed. The measurement time was on the order of 1 min and reflects multiple data acquisitions. Data analysis of the MR velocity image was performed to characterize flow behavior using MatLab7.0.0 (R14) software (The MathWorks Inc., Natick, Mass., U.S.A.). Fluid velocity at each radial position was determined by the position of the maximum signal intensity in each row of the image matrix. To evaluate shear rate from the velocity profile, the MRI velocity data were fit with an even-order polynomial; the global fitting error for the polynomial was less than 2%. This analytic expression was then differentiated and evaluated at each radial position to yield the local shear rate (1)

E: Food Engineering & Physical Properties

where v(r) is the axial velocity of the molten chocolate during pipe flow (Arola and others 1997). The range of shear rates evaluated was from 1 to 8 s1; this range corresponds to shear rates relevant to the enrobing process (Steffe 1996; Aeschlimann and Beckett 2000). Local shear stress data, to correspond to the shear rate data, were obtained using the force balance (2)

where is the shear stress, and P is the pressure difference across the pipe length, L. The shear rate and shear stress values were plot as a rheogram. The steady shear rheological data for milk chocolate melt was best described by the Casson model based on goodness of fit and the coefficient of determination. The expression for the Casson model is
Figure 1Schematic diagram of the experimental apparatus

(3)

Flow behavior of milk chocolate melt . . .

where, is the shear rate, CA is the Casson viscosity, and ,CA is the Casson yield stress. The yield stress, o, was also determined directly from the MR image with the plug radius, Ro, and is designated as wide by 50.8 mm height, on each side. The mass of chocolate was allowed to solidify and was then scraped and weighed to determine an average film thickness on each side of the plate. Soy lecithin was added to the milk chocolate to a level of 0.1%. The dipping procedure was repeated. The 0.1% lecithin mixture was brought to a level of 0.3%; the dipping procedure was repeated. The sample preparation, dipping, and weighing procedure were followed for the synthetic lecithin YN as well, starting with emulsifier-free milk chocolate.

= P R
2L

(4)

The image analysis procedure was developed and documented by Sadikin (1999) and Choi (2003) and utilized the graphic user interface feature of MatLab. In addition to the MR viscosity measurement, the flow behavior was measured off-line by rotational viscometry (CVO, Bohlin Instruments, Gloucestershire, U.K.) utilizing the concentric cylinder geometry and the vane method. The chocolate melt temperature was controlled at 42C by a circulating water bath (RTE-111, NESLAB Instruments, Inc., Newington, N.H., U.S.A.). A DIN bob with a diameter of 25 mm and a cup with a diameter of 27.5 mm operated under the controlled rate mode over a shear rate range of 1 to 8 s 1. A 4blade vane with a diameter of 25 mm and the same cup were used over a shear rate range of 0.05 to 10 s1 in the controlled rate vane method to measure the yield stress (Steffe 1996).

Results and Discussion

igure 2 illustrates representative magnetic resonance phase encoded velocity images of molten milk chocolate at 42C. Figure 2a represents the MR reference location of fluid at rest (v = 0); Figure 2b illustrates a velocity profile at a volumetric flow rate of 2.4 mL/ s. Figure 3 illustrates velocity profiles of the molten milk chocolate under the experimental conditions. Typical of these velocity profiles, the velocity is maximum at the center of the pipe and decreases toward the pipe wall. The maximum velocity value increased as the amount of the emulsifier increased from 0% to 0.1% to 0.3%. The velocity values are 38 mm/s, 40 mm/s, and 41 mm/s, respectively, and did not differ significantly with type of emulsifier. Wall slip is also observed as the velocity is nonzero at the pipe wall. For comparison purposes, the apparent viscosity values of test fluids were determined using rotational viscometry data and MRI viscometry data. The apparent viscosity () was calculated by (5) Figure 4 illustrates apparent viscosity compared with shear rate of milk chocolate melt for MRI viscometry and rotational viscometry in the shear rate range of 1 to 8 s1. Overall, the apparent viscosity ranged from 7 to 48 Pa s. Shear-thinning behavior is observed as the apparent viscosity decreases with increasing shear rate. For both emulsifiers, the apparent viscosity decreased as the amount of the emulsifier increased. As the emulsifier level increased to 0.3%, the Casson viscosity values decreased by more than a factor of two. Likewise, the Casson yield stress decreased significantly with increasing emulsifier level (Table 2). Wall slip, in part, plays a role in the discrepancy between the Casson parameters determined for the MRI data and the rotational viscometry data (Table 2). Wall slip occurs when a layer of fluid that

Enr obing nrobing

The emulsifier-free milk chocolate, described above, was stored for several days before the experiment to ensure constant temperature and mixed thoroughly before removing 1 kg samples. The 1kg milk chocolate samples were prepared in the tempering bowl of the Revolation X3210, chocolate tempering system (ChocoVision, Poughkeepsie, N.Y., U.S.A.). The chocolate was maintained between 40 0.5C. Flat plastic plates with dimensions of 101.6 mm 101.6 mm (4 4 inch) were prepared for dipping into the chocolate. The plastic plates were paper covered; the adhered paper was removed from the bottom 50.8 mm on each side of the plate using an Exacto knife. Three plates were dipped into the molten milk chocolate for each trial and then gently shook for 20 s over the tempering bowl. The plates were then hung in a controlled environment chamber, which was maintained at 40 1C by two 1500W heaters (Steinel, Model HG3002LCD, Howard Electric Instruments Inc., El Dorado, Kans., U.S.A.). After 30 min, the plates were removed from the chamber and any excess chocolate was scraped from the side and bottom edges of the plate, the protective paper was removed from both sides of the top portion of the plate. The chocolate remaining on the plate had dimensions of 101.6 mm

Figure 2Representative MR image of milk chocolate flow at 42C: (1) at rest and (2) at a volumetric flow rate

E: Food Engineering & Physical Properties

Flow behavior of milk chocolate melt . . .

has lower viscosity than the main fluid forms at the walls of the viscometer and has been observed in many food suspensions and high fat products. The lower apparent viscosity values of the rotational viscometer compared with the MRI technique are consistent with wall slip in the concentric cylinder geometry. In addition, the values of wall slip can be determined directly from the MR image. The values of slip velocity for the lecithin trials ranged from 17.7 to 19.0 mm/s. Similar slip velocities were observed for the synthetic lecithin (YN), though accurate wall slip velocity could not be determined due to lower signal-to-noise ratio at the tube wall. Table 3 shows reasonable agreement between the yield values obtained from the vane method, and the values based on the plug dimension obtained from the MRI viscometry (Eq. 4). However, these yield values are considerably higher that the Casson model yield values and may well represent static yield stress due to the conditions required to initiate shearing flow. It is not unusual that yield stress values obtained by 1 method are different than those obtained by a different method (Steffe 1996). For a milk chocolate with a Casson yield value of 15 Pa, the fluid would ultimately drain to a final coating thickness of 1.2 mm, whereas a Newtonian fluid would theoretically drain to an infinitely thin layer. Equation 6 is most appropriately used for the evaluation of a static film or coat. However, the enrobing process is a transient processing as chocolate drains away from vertical surfaces. The first step of extending the drainage flow analysis to Casson fluids is to evaluate steady state drainage from a vertical surface. The flow of fluid on the vertical surface is controlled by the balance of gravitational and viscous forces (Bird and others 2002). Schematically, the flow is illustrated in Figure 6a, where x is the vertical downward direction and y is the horizontal axis. Mathematically, the problem is formulated as

(7) where the left hand side of the equation is the gravitational forces (g is the gravitational acceleration and is the fluid density) and the right hand side of the equation is the viscous force. For a Newtonian fluid, the relationship between the shear stress and shear rate in terms of the velocity gradient is given by

Application of rheological parameters to the enrobing process

Much of the focus of process rheology is the application of the information to real-time decision-making. For instance, will this particular milk chocolate provide adequate coverage on a wafer during the enrobing process? Figure 5 illustrates a typical enrobing (or coating) process with the chocolate flowing in a sheet from a bin above a moving belt. As the chocolate covers the wafer, excess drains from the vertical sides of a wafer due to the force of gravity. Chocolate is a special case of coating because a phase change occurs during the process. The following analysis is relevant for the time interval immediately following the enrobing of the product when the chocolate is in the molten state prior to solidification of the fat. For fluids with a yield stress, like chocolate, flow ceases when the yield stress is greater than or equal to the shear stress. Therefore the coating thickness, Ho, supported by the yield stress is (Steffe 1996; Lang and Rha 1981)

E: Food Engineering & Physical Properties

(6)

Figure 3Representative velocity profiles of milk chocolate obtained from the MRI viscometry. , 0% soy lecithin; , 0.1% soy lecithin; and , 0.3% soy lecithin.

Figure 4Apparent viscosity of milk chocolate melt for the 2 emulsifiers: (a) soy lecithin and (b) synthetic lecithin. In each figure, circles represent 0% emulsifier, squares, 0.1% emulsifier, and triangles, 0.3% emulsifier. The filled marks are MRI data; the open marks are CVO concentric cylinder data.

Flow behavior of milk chocolate melt . . .

Table 2Casson parameters from the MRI-based viscometry and rotational viscometry, T = 42 C Sample MRI-based viscometry Casson viscosity (Pa s) 0% 0.1% lecithin 0.3% lecithin 0.1% YN 0.3% YN 14.6 12.5 6.0 12.7 6.6 Casson yield stress (Pa) 15.0 3.1 2.6 3.9 1.9 R2 Rotational viscometry Casson viscosity (Pa s) 6.7 4.2 2.1 4.3 2.6 Casson yield stress (Pa) 16.4 12.7 10.4 12.1 9.6 R2

0.995 0.996 0.977 0.980 0.978

0.986 0.994 0.999 0.994 0.998

(8)

(12) This approach assumes that the average velocity at a given vertical position can be approximated by Eq. 10, with the fluid thickness H replaced by h(x,t) (for example, a typical lubrication approximation). Equation 12 is useful because the average fluid thickness (<h>) at a time t is determined by integrating the expression over the height of the region draining for

where u is the downward velocity of the fluid and is the Newtonian viscosity. This expression is substituted into Eq. 7. Equation 7 is integrated to yield the fluid velocity as a function of position (ydirection) and the steady-state fluid thickness (H).

(9)

(13) As an example, if the height of coverage is L = 5 cm, the average fluid thickness at 20 s is 2 mm for a Newtonian fluid with a viscosity of 60 Pa s and density of 1270 kg/m3. In concept, this approach was used by Cisneros-Zevallos and Krochta (2003) to evaluate coating thickness applied to fruits and vegetables. The limitation of this approach is that the solution is valid only for Newtonian fluids and for finite values of x/t. In contrast to Newtonian fluids, the unsteady state mass balance (Eq. 11) cannot be solved analytically for Casson fluids (Eq. 2). However, Eq. 11 can be numerically evaluated using the analytical expression for the average velocity of the Casson fluid. The Casson model, with the shear rate expressed in terms of velocity gradient, was substituted into Eq. 7. Equation 7 was integrated to yield the fluid velocity as a function of position

By integrating over the velocity profile with respect to y, the average velocity (<u>) under steady state conditions is

(10)

This expression is useful because it gives the relationship between the drainage velocity and fluid properties, the more dense the chocolate, the greater the drainage velocity; the higher the viscosity, the lower the drainage velocity. The next step is to consider the unsteady state nature of the chocolate enrobing process. An unsteady state mass balance over a volume of fluid between x and x + x yields

(11)

(14)

which is written in terms of the local fluid thickness, h, as a function of time (t) and vertical position (x) (Figure 6b). This approach is based on the draining of a viscous fluid down a tank wall (Bird and others 2002). The solution to Eq. 11 for fluid thickness of a Newtonian fluid is

Figure 5Schematic of the enrobing process

Figure 6Downward flow of fluid from a vertical surface: (a) steady state and (b) unsteady state

E: Food Engineering & Physical Properties

Flow behavior of milk chocolate melt . . .

Table 3Yield stress values of milk chocolate using MRIbased viscometry and the vane method, T = 42C MRI Sample with emulsifier 0% 0.1% soy lecithin 0.1% synthetic lecithin 0.3% soy lecithin 0.3% synthetic lecithin Yield radius (Ro) (mm) 0.98 0.98 0.98 1.00 0.75 Vane Table 4Average film thickness measured experimentally and estimated theoretically based on the MRI-based Casson parameters given in Table 2 Experimental Theoretical film thickness film thickness SD (mm) (mm) Soy lecithin 0% 0.1% 0.3% 0% 0.1% 0.3% 2.3 0.3 1.2 0.1 1.1 0.1 2.7 0.2 1.6 0.1 1.2 0.1 3.0 1.7 1.2 3.0 1.8 1.2

Yield stress Yield stress (Pa) (Pa) 51 37 38 18 19 54 29 30 19 20

Synthetic lecithin

where Ho = o,CA/(g), and y is 0 at the film surface and y = H at the solid vertical surface. Equation 14 is valid in the shearing region from Ho to the solid surface at y = H. The value of the velocity from the film surface to Ho is the maximum velocity of

(15) The velocity profile of milk chocolate with no added emulsifier (Table 2) is illustrated in Figure 7. The plug region, with fluid traveling at the maximum velocity, is at the surface of the film. To reinforce the difference in flow behavior of Casson fluids relative to Newtonian fluids, the velocity profile of a Newtonian fluid is also shown. The Newtonian fluid has a viscosity equivalent to the apparent viscosity of the milk chocolate at a shear rate of 1 s1(59.2 Pa s). The average velocity over the film, for Eq. 11, is calculated by integrating Eq. 14 and 15 over the relevant region and dividing by the film thickness. In Figure 7, the Newtonian fluid has an average velocity of 18 mm/s; the average velocity of the Casson fluid is 13 mm/s, which is 28% lower due to the yield stress. The final step in extending the drainage flow analysis to Casson fluids is to determine the film thickness during the enrobing process. The local film thickness, h(x,t) is substituted for H in Eq. 14 and 15 for the unsteady state mass balance (Eq. 11). This partial

differential equation (Eq. 11) was solved numerically for Casson fluids with a MatLab finite difference program using central difference for the time derivative and central difference for the spatial derivative (Haberman 2004). The finite difference program was validated by limiting cases (for example, Newtonian fluid) and by decreasing t/x to ensure numerical stability. The average film thickness over a 20-s time interval is illustrated

E: Food Engineering & Physical Properties

Figure 7Steady state velocity for a film thickness of 5 mm for milk chocolate melt with a plastic viscosity of 14.6 Pa s and Casson yield stress of 15.0 Pa (solid line) and for a Newtonian fluid with the same apparent viscosity (59.2 Pa s) at 1 s1.

Figure 8Average film thickness as a function of time for (a) milk chocolate with soy lecithin and (b) milk chocolate with synthetic lecithin, YN. The solid line is 0% emulsifier, the dashed line is 0.1% emulsifier, and the dotted line is 0.3% emulsifier.

Flow behavior of milk chocolate melt . . .

in Figure 8 for each of the milk chocolate samples using the Casson parameters determined by MRI-based viscometry (Table 2). The higher viscosity fluids have greater film thickness. As the emulsifier level increases, the film thickness decreases. The predicted average film thicknesses at t = 20 s are given in Table 4, with the experimental average film thicknesses ( 1 standard deviation). The unsteady state mass balance (Eq. 11) yields a good approximation to the experimental values. Experimentally, the film thicknesses are lower due to the draining that took place during the 30 min in the controlled temperature chamber. The experimental film thicknesses were approximately 30% lower than the film thicknesses would have been had they been measured at 20 s. This approximation is based on weighing the chocolate mass that collected in the tray beneath the draining plates. Specifically, 62 g chocolate was collected after the synthetic lecithin trials; a total of 217 g had adhered to the 9 plates. y H-y z axial direction Greek letters pressure drop, Pa shear rate, s1 apparent viscosity, Pa s Casson viscosity, Pa s CA viscosity, Pa s melt density, kg/m3 shear stress, Pa yield stress, Pa , CA Casson yield stress, Pa

References
Aeschlimann JM, Beckett ST. 2000. International inter-laboratory trails to determine the factors affecting the measurement of chocolate viscosity. J Texture Stud 31:54176. Arola DF, Barrall GA, Powell RL, McCarthy KL, McCarthy MJ. 1997. Use of nuclear magnetic resonance imaging as a viscometer for process monitoring. Chem Eng Sci 52:204957. Beckett ST. 2001. Model for chocolate, friends or foe? Manufactur Confection March:617. Bird RB, Stewart WE, Lightfoot EN. 2002. Transport phenomena, 2nd edition. New York, N.Y.: John Wiley & Sons. Chevalley J. 1975. Rheology of chocolate. J Texture Stud 6:17796. Chevalley J. 1991. An adaptation of the Casson equation for the rheology of chocolate. J Texture Stud 22:21929. Chevalley J. 1999. Chocolate flow properties. In: Beckett ST, editor. Industrial chocolate: manufacture and use, 3rd ed. Oxford: Blackwell Science Ltd. Choi YJ. 2003. Application of tomographic techniques for rheological properties and process control [PhD dissertation]. Davis, Calif.: Univ. of California, Davis. 257 p. Availability of Choi, YJ dissertation: http://wwwlib.umi.com/dissertations/search. Cisneros-Zevallos L, Krochta JM. 2003. Dependence of coating thickness on viscosity of coating solution applied to fruits and vegetables by dipping method. J Food Sci 68(2):50310. Groenveld P. 1970. Withdrawal of power law fluid films. Chem Eng Sci 25:157985. Gutfinger C, Tallmadge JA. 1965. Films of non-Newtonian fluids adhering to flat plates. AIChE J 11(3):40313. Haberman R. 2004. Ch 6, Finite Difference Numerical Methods for Partial Differential Equations. In: Applied partial differential equations with Fourier series and boundary value problems, 4th ed. Upper Saddle River, N.J.: Pearson Education, Inc. p 222-31. [IOCCC] Intl. Office of Cocoa, Chocolate and Sugar Confectionery. 2000. Viscosity of cocoa and chocolate products, analytical method 46. Brussels, Belgium: Assn. of the Chocolate, Biscuit & Confectionery Industries of the EU. Jackson K. 1999. Recipes. In: Beckett ST, editor. Industrial chocolate: manufacture and use, 3rd ed. Oxford: Blackwell Science Ltd. Lang ER, Rha C. 1981. Determination of the yield stress of hydrocolloid suspensions. J Texture Stud 12:4762. McCarthy MJ. 1994. Magnetic resonance imaging in foods. New York, N.Y.: Chapman & Hall. Powell RL, Maneval JE, Seymour JD, McCarthy KL, McCarthy MJ. 1994. Note: Nuclear magnetic resonance imaging for viscosity measurements. J Rheol 38:146470. Sadikin S. 1999. Viscometric measurement by nuclear magnetic resonance imaging [MS thesis]. Davis, Calif.: Univ. of California, Davis. 209 p. Availability of Wichchukit dissertation: http://wwwlib.umi.com/dissertations/search. Steffe JF. 1996. Rheological methods in food process engineering, 2nd ed. E. Lansing, Mich.: Freeman Press. Tallmadge JA, Gutfinger C. 1967. Entrainment of liquid films: drainage, withdrawal, and removal. Ind Eng Chem Res 59(11):1834. Yoon WB, McCarthy KL. 2002. Rheology of yogurt during pipe flow as characterized by magnetic resonance imaging . J Texture Stud 33:43144. Yoon WB, McCarthy KL. 2003. Flow behavior of processed cheese melt. J Food Process Eng 26(6):55976. Van Rossum JJ. 1958. Viscous lifting and drainage of liquids. Appl Sci Res Section A 7:12144.

Conclusions
he flow behavior of molten milk chocolate was evaluated experimentally using an MRI-based tube viscometer. The chocolate was best characterized by the Casson model; as the emulsifier level increased from 0% to 0.3%, the Casson yield stress values decreased from 15 to 1.9 Pa and Casson viscosity values decreased from 14.6 to 6.0 Pa s. Deviation of the Casson parameters between the MRI-based method and rotational viscometry was due to uncorrected wall slip during the rotational measurements. The MRIbased viscometer Casson parameters were incorporated into an unsteady state mass balance to predict the average film thickness of the milk chocolate during enrobing. As the emulsifier level increased from 0% to 0.3%, the predicted enrobing thicknesses decreased by 60%. Experimentally, this trend was verified.

Acknowledgment
We appreciate the donation of chocolate from Hershey Foods Corp.

Notation
g H Ho h L P r R t TE TR u v x y gravitational constant, 9.8 m/s2 steady state film thickness, mm or m film thickness supported by the yield stress, mm or m unsteady state film thickness, mm or m pipe length, m pressure, Pa radial direction pipe radius, mm or m time, s echo time, ms pulse repetition time, ms film velocity, mm/s or m/s pipe velocity, mm/s or m/s flow direction of film, read direction direction perpendicular to flow direction of film

E: Food Engineering & Physical Properties