Food Research International 32 (1999) 319325

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Rheology of tapioca starch

C.R. Chen1, H.S. Ramaswamy*
Department of Food Science, Macdonald Campus of McGill University, Ste. Anne de Bellevue, PQ, Canada H9X 3V9 Received 24 September 1998; accepted 18 May 1999

Abstract Rheological properties of tapioca starch solutions were evaluated using a computer controlled rotational viscometer in relation to four factors: temperature, 2080 C; concentration, 26%; pH, 48 and cooking time, 535 min. All test solutions showed powerlaw ow behavior. A second order composite design was used to investigate the eects of concentration, temperature, pH value and cook time on rheological property parameters (consistency coecient, m, and ow behavior index, n), and develop second order multiple response models of parameters related to concentration, temperature, pH value and cook time. # 1999 Published by Elsevier Science Ltd. All rights reserved.
Keywords: Tapioca starch; Rheology; Concentration; Temperature; pH; Cooking

1. Introduction Design of food processing operations (mixing, pumping, heating, cooling) requires data on rheological properties. The ow characteristics of a pumpable food product are dependent on the uid viscosity and density. Calculation of thermal treatment times for processing of liquid foods containing particulates is complex because the residence time distribution (RTD) of particulates and carrier uid are inuenced by concentration and the type of carrier uid as well as other process parameters (time, temperature, pressure, and the system conguration). Data on rheological characteristics, relative velocity between uid and particles and uid to particle heat transfer coecients are needed for optimizing the heat exchanger and holding tube designs in aseptic processing of liquid foods containing particulates (Dail & Stee, 1990a,b; Ramaswamy, Abdelrahin, Simpson & Smith, 1995). Starches are commonly added to popular foods such as soups and sauces to increase their consistency and improve mouth-feel characteristics. The thickening activity of starches results from the swelling of starch granules occurring at gelatinization temperatures (Self, Wilkin, Morley & Bailey, 1990). Recently, modied cross-linked starches
* Corresponding author. Tel.: +1-514-398-7919; fax:+1-514-3987977. E-mail address ramaswamy@agradm.1an.mcgill.ca (H.S. Ramaswamy) 1 Visiting Professor, Department of food science, Zhejiand University, Hangzhou, People's Republic of China.

have been used to simulate carrier uids in aseptic processing of liquid foods containing particulates (Abdelrahim, Ramaswamy & Van de Voort, 1995; Harrod, 1989a,b,c). Tapioca starch is widely used in delicately avored puddings, pastry llings and baby food products (Whistler, Bemiller & Paschall, 1984). Of non-cereal starches, tapioca has ranked rst in order of importance in North America (Kerr, 1950). There have been many research reports on the rheological properties of starch solutions (Bhattacharya & Bhat, 1997; Bhattacharya & Bhattacharya, 1994, 1996; Biliaderis, 1991; Dail & Stee, 1990a,b; Harrod, 1989a,b,c; Ramaswamy, Busak, Abbatemarco & Sablani, 1995; Sandhya & Bhattacharya, 1995; Taylor, 1979), but no published information is available on the rheological modeling of tapioca starch solutions. Further, the majority of reported experimental data on rheological properties focuses on the eects of temperature and concentration, and little on those of pH value and cook time. The objective of this work was, therefore, to study the eect of concentration (26%), temperature (2080 C), pH (48) and cook time (535 min) on the rheological properties of tapioca starch solutions and develop predicting models for the rheological parameters. 2. Materials and methods Tapioca starch was obtained from a local market (modied waxy starch, powdered form, produced by Yat Loong Company, Hong Kong, China, packed and

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distributed in Canada). The pH value of water was initially adjusted by adding acid (citric) or NaOH. Appropriate amounts of starch and water were mixed thoroughly and brought to boiling in a steam-jacketed kettle. The mixture was then allowed to slowly simmer at $100 C for selected time intervals (cook time from 5 to 35 min) under atmospheric conditions. The solution was covered during cooking to minimize loss of moisture during cooking. The lost moisture (about 510% by weight) was added back at the end to maintain the concentration level. Rheological measurements (shear rateshear stress data) were made using a rotational viscometer (Haake Model RV20; Haake Mess-Technik, Karlsrulhe, Germany), equipped with an M-05 OSC measuring head and MVI (radius of the rotor, Rb , 20.04 mm; height, h, 60 mm, radius of the cylindrical cup, Rc , 21 mm) rotor assembly interfaced to a microcomputer for control and data acquisition. The sample compartment was kept at a constant temperature using a water bath/circulator (Haake, Model FK-2). For each test, the lled sample cup and spindle were temperature equilibrated for about 20 min and sheared at a programmed rate linearly increasing from 0 to 200 s1 in 10 min. Shear stressshear rate data were collected continuously at 12 s intervals throughout the test. Flow curves (rheograms) were evaluated by the instrument operating software (Haake RV20 version 2.3) using the following models. 1X ower lw model X ' m n I

X1 C 4Y

X2 T 50a15Y

X3 P 6Y

X4 t 20a7X5
Table 1 Experimental factors and levels Factor Coded 2 variable (Xi) 1 0 1 2

Concentration temperature pH Cook time C (%) T ( C) value P t (min) 2 3 4 5 6 20 35 50 65 80 4 5 6 7 8 5 12.5 20 27.5 35

where ' is the shear stress (Pa),  is the shear rate (s1), m is the consistency coecient (Pasn), and n is the ow behavior index (dimensionless). 2X rershelfulkley model X ' '0 m n where '0 is the yield stress. 3X gsson model X ' 0X5 k0 0X5 k1  n 0X5 Q P

Fig. 1. Comparison of ow curves of three starch solutions: tapioca, maize and potato at a 4% concentration level.

where k0 and k1 are Casson yield stress and Casson viscosity, respectively. A shear analysis test as recommended in Stee (1992) was used to assess the validity of using the power-law model for test data. A second order central composite design (Gacula & Singh, 1984; Piggott,1986) was used in order to develop predictive models of rheological parameters. The experimental factors and levels are shown in Table 1. The tted response model is: Y b0 bi Xi bii X2 bij Xi Xj i i 14Y j 14Y i T j R

The relationships between coded variables and practical variables(Table 1) were as follows:

Fig. 2. Typical ow curves of tapioca starch solutions: (1) T=10 C, C=4%, pH=7, t=20 min; (2) T=20 C, C=4%, pH=7, t=20 min; (3) T=20 C, C=4%, pH=7, t=40 min; (4) T=20 C, C=4%, pH=4, t=20 min.

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3. Results and discussion 3.1. Rheological characterization of tapioca starch Fig. 1 shows the ow curves for tapioca, sweet potato and maize starch solutions under the same conditions.

The curves for sweet potato and tapioca were experimentally obtained at a 4% concentration after a 20 min cook time. The maize starch data are from Ramaswamy, Basak et al. (1995) also at a 4% starch concentration level. From Fig. 1, it was found that the shear stress for tapioca starch solution was much higher than those for

Table 2 Comparison of dierent models for the rheology of tapioca starch solutions at dierent temperatures (T), concentrations (C), pH values and cook times (t)a
Typical conditions T=10 C, C=4%, pH=7, t=20 min T=20 C, C=4%, pH=7, t=20 min T=20 C, C=4%, pH=7, t=40 min T=20 C, C=4%, pH=7, t=20 min Model Powder lawb HerschelBulkleyc Cassond Power lawb HerscheBulkleyc Cassond Power lawb HerschelBulkleyc Cassond Power lawb HerschelBulkleyc Cassond mk1 1.02 1.08 0.97 0.87 0.86 0.84 0.64 0.639 0.621 0.168 0.167 0.159 n 0.417 0.413 0.843 0.691 0.684 1.401 0.602 0.701 1.422 0.778 0.780 0.1692 'o ko 0.95 0.92 0.49 0.42 0.41 0.38 0.10 0.19 R2 0.98 0.95 0.96 0.99 0.97 0.97 0.98 0.96 0.98 0.97 0.96 0.97

a b c d

The number of data points regressed is 50. Power law model: ' m n . HerschelBulkely model: ' '0 m n . Casson model; ' 0X5 k0 0X5 k1  n 0X5 .

Table 3 Second order design matrix and calculation results of rheology parameters: consistency coecient, m, and ow behavior index, n Order 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 x0 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 x1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 2 2 0 0 0 0 0 0 0 0 0 0 0 0 0 x2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 2 2 0 0 0 0 0 0 0 0 0 0 0 x3 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 2 2 0 0 0 0 0 0 0 0 0 x4 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 2 2 0 0 0 0 0 0 0 x1 x2 1 1 1 1 1 1 1 1 1 1 2 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 x1 x3 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 x1 x4 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 x2 x3 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 x2 x4 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 x3 x4 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 x12 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4 4 0 0 0 0 0 0 0 0 0 0 0 0 0 2x2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 4 4 0 0 0 0 0 0 0 0 0 0 0 x32 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 4 4 0 0 0 0 0 0 0 0 0 x42 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0 0 0 0 0 0 4 4 0 0 0 0 0 0 0 m (Pasn) 0.423 0.38 0.531 0.470 0.321 0.301 0.387 0.360 1.043 0.883 1.109 0.950 0.632 0.611 0.721 0.703 0.38 0.98 0.88 0.336 0.321 0.613 0.35 0.33 0.558 0.549 0.63 0.661 0.583 0.559 0.513 n 0.512 0.522 0.49 0.495 0.613 0.625 0.587 0.608 0.201 0.231 0.181 0.195 0.471 0.465 0.389 0.372 0.602 0.214 0.289 0.62 0.651 0.211 0.615 0.626 0.471 0.469 0.458 0.471 0.423 0.498 0.514

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the other two starch solutions at the same shear rate. Tapioca starch solutions thus had much higher viscosity than the other two starch solutions which is one of the reasons for selecting tapioca sample in this study. Typical ow curves for tapioca starch suspensions under dierent test conditions are shown in Fig. 2. A comparison of dierent rheological models as shown in Table 2 for describing the ow behavior of starch suspensions under typical conditions indicated slightly better R2 of 0.970.99 with the power law model. The power law model generally gave a higher R2 and showed a better t for data points under most other circumstances as well. Shear rate corrections to the experimental data were applied, for a range of test conditions, as outlined in Stee (1992) and the power law coecients were recalculated. The recalculated values of m and n did not dier much from those calculated from the software (most were within 2% of the software calculated value while in one case it was 7% higher). Hence, the software calculated values were retained and used for all subsequent analysis in this study. 3.2. Regression models of rheological parameters (m, n) From a practical stand-point, it will be useful to describe the eects of temperature, concentration, pH and cook time by one composite model. In literature, the Arrhenius model has been frequently used to model
Table 4 Analysis of variance for regression models
Source of variance DF m (Pasn) SS Total Model Linear b1 b2 b3 b4 Quadratic b11 b22 b33 b44 Interaction b12 b13 b14 b23 b24 b34 Error Lake of t Experimental
a b c

the eects of temperature, while the eect of concentration has been described by either an exponential or a power relationship (Ramaswamy & Basak, 1991). However, Abdelrahim et al. (1995) found the Arrhenius model to be less desirable for describing the temperature dependence of power law parameters for starch especially at the low concentration levels because the associated coecients of determination were generally less than 0.7. The alternative is a Turian approach taking into account the eects of both temperature and concentration on consistency coecient and ow behavior index (Ramaswamy & Basak, 1991). However, none of the above studies take into account the eects of pH and cook time on rheological properties. In this study, m and n were related to temperature, concentration, pH and cook time by a multiple regression analysis. The following predictive equations involving temperature, concentration, pH and cook time were developed using a second order response methodology: m 0X579 0X195X1 0X118X2 0X051X3 0X02X4 0X047X12 0X027X22 0X011X32 0X046X42 0X055X1 X2 0X0006X1 X3 0X0129X1 X4 0X0015X2 X3 0X021X2 X4 0X001X3 X4 R2 0X95Y SyYx 0X0693 T

n MS 0.1093 0.913 0.336 0.062 0.009 0.064 0.021 0.004 0.062 0.049 0.0 0.003 0.0 0.007 0.0 0.0048 0.0075 0.00013 F Ratio 21.06a 175.98a 64.76a 11.95a 1.73c 12.336a 4.048c 0.77 11.951a 9.455a 0.0 0.57 0.0 1.349 0.0 5.625 SS 0.669 0.609 0.310 0.162 0.060 0.0 0.016 0.003 0.008 0.035 0.013 0.001 0.0 0.001 0.0 0.0 0.06 0.054 0.006 MS 0.0435 0.310 0.162 0.060 0.0 0.016 0.003 0.008 0.035 0.013 0.001 0.0 0.001 0.0 0.0 0.0038 0.0054 0.001 F Ratio 8.38a 59.75a 31.23a 11.56a 0.0 3.084c 0.579 1.540c 6.746b 2.50c 0.193 0.0 0.193 0.0 0.0 5.40

30 14 1 1 1 1 1 1 1 1 1 1 1 1 1 1 16 10 6

1.613 1.530 0.913 0.336 0.062 0.009 0.064 0.021 0.004 0.062 0.049 0.0 0.0003 0.0 0.007 0.0 0.083 0.075 0.008

p40.01. p40.005. p40.1.

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n 0X455 0X114X1 0X082 0X05X3 0X02X4 0X023X12 0X011X22 0X017X3 0X035X42 0X029X1 X2 0X01X1 X3 0X001X1 X4 0X006X2 X3 0X004X2 X4 0X002X3 X4 R2 0X91Y SyYx 0X0616 The design matrix and calculated results of rheological parameters (mY n) are given in Table 3. The analysis of variance results (Table 4) showed that the lack of t was not signicant for m and n (p b 0X05), and regression models were signicant for m and n (p b 0X05). In addition, the standard residual errors for m and n regression equations were 0.0693 and 0.0616, respectively, this should be accepted in practical application. Hence, it indicated that the tted model was adequate. However, it was easily found that the eects of some regression coecients on m and n were not signicant (p>0.05). In order to improve the accuracy of the models, the non-signicant terms were removed and Eqs. (6) and (7) were simplied as follows: m 0X579 0X195X1 0X118X2 0X051X3 0X02X4 0X047X12 0X027X22 0X046X42 0X055X1 X2 R2 0X94Y SyYx 0X0664 V n 0X455 0X114X1 0X082X2 0X05X3 0X023X12 0X017X32 0X035X42 0X029X1 X2 R2 0X91Y SyYx 0X0532 W And from Eq. (5) (Table 2), the nal form of the relationships were obtained as follows: m 0X183 0X195C 0X0079T 0X051pH 0X0028 t 0X047C 42 1X2 10 4T 502 8X4 10 4 t 202 0X0037C 4T 50 R 0X94Y SyYx 0X0664 IH n 1X057 0X114C 0X055T 0X05pH 0X023C 42 0X017pH 62 0X035t 202 0X002T 50C 4 R2 0X91Y SyYx 0X0532 II 3.3. Eects of concentration and temperature on m and n Fig. 3 indicates the eects of concentration and temperature on consistency coecient m and ow behavior
2

Fig. 3. Eects of concentration and temperature on consistency coefciency, m, and ow behavior index, n, of tapioca starch solutions.

index n (at pH=6, t=20 min). It is clear from the gure that m increased with the concentration and decreased with temperature, and the eect was opposite with n. But the extent of increase or decrease at dierent temperatures or concentrations were dierent because of the interaction between temperature and concentration (Table 4). 3.4. Eects of pH and cook time on m and n Fig. 4 indicates the eects of pH and cook time on consistency coecient m and ow behavior index n (at C=4, T=50 C). It can be easily seen that the eect of pH value on m or n is linear, and cook time non-linear. Moreover, the highest m and the lowest n existed within the experimental range. To obtain this value, we could

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dierentiate Eqs. (10) and (11) with t and equate them to zero: dm 0X0028 16X8 104 t 20 0Y dt dn 0X07t 20 0Y dt t 20min t 18X3min

Hence, the optimum cook times were 18 min to get the highest value of consistency coecient and 20 min to get the lowest value of ow behavior index, respectively. 3.5. Comparison of the predicted m and n values with experimental values The pooled data for experimental m and n vs those predicted by Eqs (10) and (11) are shown in Fig. 5. The regression coecient R2 was 0.96 and 0.94, respectively. The gures indicated that there was good agreement between experimental values and theory values of m and n predicted by models [Eqs. (10) and (11)]. 4. Conclusions The study indicated that the ow behavior of tapioca starch solutions was adequately described by the powerlaw model. The second order response models well described the eects of concentration, temperature, pH value and cook time on the associated rheological properties (m and n). There existed signicant interaction between concentration and temperature. The highest consistency coecient, m, was obtained after an 18 min cook time and the lowest ow behavior index, n, was obtained after a 20 min cook.

Fig. 4. Eects of pH and cook time on consistency coeciency, m, and ow behavior index, n, of tapioca starch solutions.

Fig. 5. Plots for experimental vs calculated consistency coeciency, m, and ow behavior index, n, of tapioca starch solutions.

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