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Original article The viscoelastic properties of soybean curd (tofu) as affected by soymilk concentration and type of coagulant
Yongqiang Cheng,1 Naoto Shimizu2 & Toshinori Kimura2*
1 China Agricultural University, Now Doctoral Program in Agricultural Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba-shi 305-8572, Ibaraki-ken, Japan 2 Graduate School of Life and Environmental Sciences, University of Tsukuba, Tennodai 1-1-1, Tsukuba-shi 305-8572, Ibaraki-ken, Japan (Received 15 March 2003; Accepted in revised form 17 August 2004)

Summary

The viscoelastic properties of dierent types of tofu were investigated. Soymilk concentrations were 5, 6, 7, 8 and 9%. Coagulants used were 30 mm CaSO4 or 30 mm glucono-delta-lactone (GDL). As the concentration of soymilk was increased viscosity and handling diculties increased. A high concentration of soymilk in tofu gave a high break stress and produced hard tofu. The four-element Burgers model tted the creep behaviour and both viscous and elastic parameters could be acquired from model analysis, reecting changes in elasticity and viscosity of tofu. The constant viscous parameter in the model increased with increasing soymilk concentration. The viscous parameters of viscoelastic materials like tofu gel, obtained from small deformation tests, seemed to correlate, to some extent, with the break stress obtained from large deformation tests. For hard tofu production increasing the soymilk concentration within a certain range and the partial replacement of calcium sulphate coagulant by GDL could be eective options.
Burgers model, creep behaviour, hard tofu, true strain, viscosity.

Keywords

Introduction

The healthy eects of soy products have aroused the attention of many researchers and consumers (Hawrylewicz et al., 1995; Hasler, 1998). The protein intake in China is still inadequate, even today. Because of the high nutrient value of soy protein, soy products are considered as excellent protein resources. As a soy product, tofu is a traditional product in some Asian countries like China and Japan. Promoting the production of tofu in China could be a good way of solving the problem of protein intake there. Generally speaking, the Chinese seem to prefer hard tofu. Currently, there are still some problems in the industrial production of hard tofu in China (Cheng et al., 2000). To improve tofu production, texture evaluation of tofu products is necessary.
*Correspondent: Fax: +81 29 855 2203; e-mail: toshibio@sakura.cc.tsukuba.ac.jp doi:10.1111/j.1365-2621.2004.00935.x
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Break stress behaviour alone cannot reect both the elastic and viscous properties of food materials. For hard tofu manufacture, a study of the eects of processing on the texture of tofu is necessary. In a creep test, a load is kept constant and the strain increases with time, causing creep behaviour. Analysis of the creep behaviour by models can give both elastic and viscous parameters. Knowledge of changes in elasticity and viscosity, as aected by dierent processing conditions, could help to improve hard tofu production in China. The creep properties of agar gels (Isozaki et al., 1976), 20% soybean gel and egg white gel (Kuwahata & Nakahama, 1975), whey protein gels (Katsuta et al., 1990) and porcine serum-myosin gel (Ni & Hayakawa, 2001) have been investigated and tted to dierent models. Kuwahata & Nakahama (1975) investigated the creep behaviour of a 20% soybean gel and compared it with an egg white gel and a 1.5% agar gel. They reported that the creep behaviour

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of the three types of materials could be tted by a four-element model. However, up to now, few studies have been reported describing the creep properties of tofu with dierent soymilk concentrations and coagulants. In this study, the creep properties of dierent types of tofu were investigated and analysed by viscoelastic models. Based on the results of creep tests, ways to improve hard tofu production in China are also described.
Materials and methods

dierent concentration was measured in order to determine the inuence of concentration on viscosity. A LV2000 viscometer (Cannon Instrument Company, State College, PA, USA) was used, and the rotation speed was 30 r.p.m. for all the tests. The experiments were repeated more than three times and the coecients of variation for all determinations were <10%. Texture prole of tofu made in the laboratory Stress-strain and creep properties of tofu were evaluated using a TA-XT2i Texture Analyzer (Stable Micro Systems Ltd., Godalming, Surrey, UK) tted with a 5 kg load cell. The cylindrical tofu samples were 30 mm in height and 36 mm in diameter. A 70 mm diameter at plunger was used and the compression speed for the stress-strain test was 1 mm s)1. Tofu was compressed to 80% deformation in the stress-strain tests. Considering the cross-sectional area expansion during compression, a Henckys true strain was calculated from the original data as follows (Peleg, 1984; Nussinovitch et al., 1989): eT t ln H0 H0 DH 1

Materials Soy protein isolate (SPI) of 90% dry base (84.6% wet base) protein content (FujiproE, Fuji Oil Co., Osaka, Japan) was used to prepare soymilk. Analysis-grade glucono-delta-lactone (GDL) and food-grade CaSO42H2O were purchased from Wako Pure Chemicals Industries Co. (Osaka, Japan). They were used without further purication. Tofu production in the laboratory The tofu production method used in this laboratory was based on the industrial kinugoshi (silken) tofu production method used in Japan (Watanabe, 1997) and was also reported in our previous paper (Cheng et al., 2002). SPI was dissolved in distilled water to prepare 5, 6, 7, 8, and 9% (w/v) protein soymilk. The soymilk was heated to 100 C and kept at this temperature for 3 min, then was cooled to below 10 C. GDL solution or CaSO4 suspension was added as coagulant and the tofu made in the laboratory was referred to as either GDL-tofu or Ca-tofu. Their nal concentrations were adjusted to 30 mm. The soymilk mixture was poured into a steel tank, containing glass moulds (30 mm in height, 36 mm in diameter) to shape the columnar tofu samples. The soymilk was then heated to 75 C in a water bath and kept for more than 40 min to let the soymilk coagulate. Samples were stored at room temperature for 60 min before the viscoelastic tests. Measurement of the viscosity of soymilk Viscosity is a very important index of soymilk concentration. The viscosity of soymilks with

where eT(t)is true strain, H0 is the original height of the specimen and DH is the absolute deformation. After the linear range was determined by stressstrain proles, a creep test was done. A force was maintained for a 10 min period and the change in strain was recorded. The recorded creep curve test was really a small deformation test (no more than 10% in this study) and the cross-sectional area did not change much, so it was not necessary to use the true strain for the calculation. All the parameter settings, operation of the instrument, and saving of data obtained from the measurements were accomplished using a PC with Texture Expert software version 1.0. Experiments were repeated at least three times. Analysis of textural properties From the stress-strain curve, break stress (peak point) and apparent elasticity (the ratio of stress/ strain) can be obtained. After the creep curves of dierent types of tofu were recorded, they were

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Viscoelastic properties of tofu Y. Cheng et al.

387

(a)
E

(b)

(c)
En

E1

Figure 1 Characteristics of the different models. (a) Maxwell model; (b) Vigot model; (c) Four-element Burgers model. E, elasticity of Hookes body; g, viscosity of dash-pot body.

Figure 2 Effect of soymilk concentration on its viscosity.

tted to dierent models. Mohsenin (1986) summarized the rheological evaluation of plant and animal materials in detail and described dierent models for the analysis of stress relaxation and creep behaviour. The Maxwell model (Fig. 1a), with a spring model and a dashpot model in series and the Vigot model (Fig. 1b), with a spring model and a dashpot model in parallel, were used as the primary units. A least square non-linear algorithm in Sigmaplot (Jandel Corporation, San Rafael, CA, USA) was used to t experimental data to the models. The best t was determined on the basis of the standard error and coecient of variation of the parameters, the value of the regression coecient and by comparison of the residual value between the plots of the experimental and tted data. The appropriate type of model was determined on the basis of the dependence criterion for the non-linear algorithm in Sigmaplot. After the model was determined, the parameters of the model were calculated by iteration from dierent initial values using Sigmaplot software.
Results and discussion

tions. In industrial practice, too high a viscosity may cause diculties in transportation in pipes in some cases (e.g. when a centrifugal pump is used). Thus, the viscosity of soymilk should be controlled to an appropriate level. Stress-true strain behaviour of tofu In our previous study, we reported the stress-strain behaviour of dierent tofus (Cheng et al., 2002). However, considering the area change during compression, it would be better to determine the stress-true strain relationship at the same time. The stress-true strain behaviours of GDL-tofu and Ca-tofu are shown in Fig. 3. For the same soymilk concentration, all the GDL-tofus showed a higher break stress than Ca-tofu, as also previously reported by Saio (1979). True strain has been used by many researchers (Lee et al., 1983; Van Kleef, 1986; Kim et al., 2001). Compared with normal engineering strain (Cheng et al., 2002), true strain gave a larger value in all the cases, which meant that a larger break strain was obtained when using true strain, although it did not change the break stress of the dierent tofus. During the compression tests, the area of the tofu sample changed under the compression and thus the use of true strain would give a better indication of the dierent factors inuencing tofu texture. Generally speaking, increasing the soymilk concentration gave a harder tofu (Fig. 3). This result corresponded with the ndings of Saio (1979). The total amount of protein increased with increasing soymilk content, the density of the network becoming higher resulting in a higher break stress. The break stress and strain of 9% GDL-tofu and Ca-tofu decreased a little compared with the 8% tofus. The contents of GDL and CaSO4 were

Change in viscosity with soymilk concentration The viscosity of soymilk increased with increasing soymilk concentration (Fig. 2). As protein was the major component of the solid content of the SPI used, a higher soymilk concentration means a higher protein content. Circle et al. (1964) reported that soymilk viscosity increased exponentially with soymilk concentration. Our study showed a similar trend, particularly at the lower concentra-

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Viscoelastic properties of tofu Y. Cheng et al.

(a)

indicated that the concentration of soymilk and type of coagulant had a great inuence on the texture of tofu gel. Creep behaviour of tofu For texture evaluation, both large and small deformations are used, large deformations in compression tests and small deformations in stress relaxation, creep and dynamic viscoelastic tests. A stress relaxation test on tofu was studied in our previous research (Cheng et al., 2002). The dynamic viscoelasticity of tofu and soybean gel has also been reported previously (Van Kleef, 1986; Kohyama & Nishinari, 1992). Compliance (the reciprocal of elasticity) was used as an index of creep in this study. A typical creep curve is shown in Fig. 4. The compliance increased with time, initially quickly then more slowly. After unloading the sample, a constant deformation remained, which showed that tofu was a viscoelastic material. At the start point, the sudden increase reected the existence of constant elasticity. From the characteristics of the creep curve, a four-element model could be considered. It was found that a four-element Burgers model (Mohsenin, 1986) could t the curve. The model is shown in Fig. 1c. The relationship between compliance and the viscoelastic parameters could be expressed as follows (Kawabata, 1989): Jt 1 1 t t 1 e sret1 En E1 gn 2

(b)

Figure 3 Stress-true strain curves of different tofu. (a) CaSO4-coagulated tofu; (b) GDL-coagulated tofu. Soymilk concentration: d, 5%; , 6%; , 7%; s, 8%; , 9%.

constant at 30 mm for all cases and the protein amount increased. The decrease of break stress and strain for 9% GDL-tofu and Ca-tofu may be because of the decreasing coagulant/protein ratio; i.e. it might be that 30 mm GDL or CaSO4 may be insucient coagulant for 9% protein. For hard tofu manufacture, the results show that use of GDL is better for the production of tofu with harder texture. Saio (1979) reported that the network of GDL-tofu consisted of occulent aggregates and that of Ca-tofu showed a spongy structure with a tight framework. The coagulation mechanisms of Ca-tofu and GDL-tofu are a little dierent although hydrophobic interactions play an important role in both (Kohyama et al., 1995). The existence of gluconic acid in GDL-tofu and calcium ions in Ca-tofu may be important factors that dierentiate between the textural properties of Ca-tofu and GDL-tofu. Because of the acidic taste of GDL-tofu, in the practical production of hard tofu, only partial replacement of CaSO4 by GDL should be considered. These results also

where, J(t) 1/E(t) is compliance (Pa)1); t is time (s); En is the constant elasticity parameter (Pa); E1 is the elastic parameter of the Vigot model (Pa); gn is the constant viscosity parameter; and sret1 is retardation time (s), which is dened as

Figure 4 Typical creep curve of tofu.

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6% 7%

Table 1 Parameters of the four-element Burgers model (Fig. 1c, eqn 2) for the creep behaviour of CaSO4coagulated tofu Soymilk concentration En(10 Pa) E1(103 Pa) g1 (106 Pa s) gn(106 Pa s) sret1(s)
3

Compliance (Pa1)

8% 9%

6% 5.7 5.6 0.38 1.9 68

7% 4.4 7.6 0.26 2.2 34

8% 7.7 7.4 0.10 4.5 13

9% 4.5 8.5 0.16 4.3 19

Time (s)
Figure 5 Creep properties of CaSO4-coagulated tofu from dierent soymilk concentrations: , 6%; , 7%; , 8%; , 9%.

Table 2 Parameters of the four-element Burgers model for the creep behaviour of GDL-coagulated tofu Soymilk concentration En (10 Pa) E1 (103 Pa) g1 (106 Pa s) gn(106 Pa s) sret1(s)
3

5% 5.0 6.4 0.79 1.5 124

6% 8.3 9.4 0.70 2.6 75

7% 8.7 14.8 1.0 3.8 68

8% 5.2 17.7 0.87 6.9 50

9% 6.1 17.2 0.72 8.9 42

sret1 g1/E1 (g1 is the viscous parameter of the Vigot model). The creep behaviour of Ca-tofu produced from 6 to 9% soymilk is shown in Fig. 5. Tofu from higher soymilk concentration gave lower compliance, i.e. a smaller deformation. For the same measurement conditions, a smaller deformation indicates a rmer material structure. Hence creep behaviour indicated that a higher soymilk concentration resulted in a stronger tofu structure, and this is consistent with the stress-true strain results. A higher soymilk concentration means a higher protein content. It has been suggested that the network of tofu gel may be formed via hydrogen bonding, hydrophobic associations, ionic interactions and electrostatic cross-links and also through some sulphydryl-disulphide linkages of unfolded polypeptides (Catsimpoolas & Meyer, 1971; Utsumi & Kinsella, 1985). Soy protein plays an important role in the gel formation. The total amount of protein increased with increasing soymilk content. For a high protein content, the density of the network becomes higher and this results in higher break stress. Iterative calculations using Sigmaplot software, based on a least square algorithm, gave the creep parameters of the four-element Burgers model (Tables 1 and 2). The regression coecients (R2) in all cases were above 0.99. The constant viscosity parameter, gn, increased with increasing concentration of soymilk, whereas the constant elasticity parameter, En, varied irregularly with concentration. For both Ca-tofu and GDL-tofu, the retardation time (sret1) deceased with increasing
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soymilk concentration. The changes of both gn and sret1 reected the formation of a rmer structure with increase in soymilk concentration, i.e. higher viscosity and shorter retardation time. GDL-tofu had a higher gn than Ca-tofu for the same soymilk concentration, which is consistent with the stress-true strain results shown in Fig. 3. It would seem that the viscous parameters of creep behaviour correlate with changes in break stress, similar to our previous ndings from stress relaxation analysis of tofu (Cheng et al., 2002). Shimoyamada et al. (1999) showed that the gel strength of the freeze-gel formed from soymilk was related to the viscosity of the soymilk before freezing. Although both large deformation properties (stress-strain test) and small deformation properties (stress relaxation, creep, dynamic viscoelastic tests) reect tofu texture, they are not always consistent (Kuwahata & Nakahama, 1975). For analytical simplicity and a better understanding of the models involved, the creep test is a very eective small-deformation measurement. For food gels, eating characteristics as well as functional properties such as handling and cutting are strongly dependent on their larger-deformation and fracture characteristics. To understand the overall properties of tofu, both large and small deformation tests are necessary.

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Conclusions

The results of this study on the stress-strain and creep properties of Ca-tofu and GDL-tofu with dierent concentrations of soymilk suggest the following conclusions: 1 True strain gave larger values than engineering strain and was a more realistic concept, considering the area changes that occur during compression. 2 Higher concentration of soymilk resulted in tofu with a higher break stress. For the same soymilk concentration, GDL-tofu had a higher break stress than Ca-tofu. 3 The creep behaviour of tofu could be represented by a four-element Burgers model. The parameters obtained from the model reect both the elastic and viscous changes in tofu. For both Ca-tofu and GDL-tofu, the constant viscous parameter gn showed a consistent increase with increasing soymilk concentration. The viscous parameters obtained from the small deformation test might have a more consequent relationship with the break stress obtained from the large deformation test. For producing the hard tofu preferred by Chinese consumers, increasing the soymilk concentration within a certain range and the partial replacement of calcium sulphate coagulant by GDL coagulant could be eective options.
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International Journal of Food Science and Technology 2005, 40, 385390

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