Journal of Food Engineering 84 (2008) 307312 www.elsevier.

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Glass transition and state diagram for fresh and freeze-dried Chinese gooseberry
Haiying Wang, Shaozhi Zhang, Guangming Chen *
Institute of Refrigeration and Cryogenics, Zhejiang University, Hangzhou 310027, China Received 15 October 2006; received in revised form 12 May 2007; accepted 14 May 2007 Available online 26 May 2007

Abstract The glass transition temperature and freezing temperature of Chinese gooseberry, which is also called kiwi fruit, prepared at various water activities at 25 C were determined by dierential scanning calorimetry (DSC), and used to plot the state diagram for the Chinese gooseberry sample. High moisture content (>0.45, dry basis) samples obtained by adding liquid water into freeze-dried samples, were also analyzed. The state diagram was composed by the freezing curve and the glass transition line, which were tted according to ClausiusClapeyron model and GordonTaylor model, respectively. The maximal-freeze-concentration point was calculated to be at a moisture content of X 0s 0:153 (g water/g wet basis) and at this point T 0m 41:8  C, T 0g 57:1  C. The state diagram could be used to predict the stability during storage and the necessary storing conditions for Chinese gooseberry products. 2007 Elsevier Ltd. All rights reserved.
Keywords: State diagram; Glass transition; Freeze-dried; Chinese gooseberry

1. Introduction One of the explanations for the behavior of food materials during processing and storage is based on the food polymer theory (Rahman, 1995). According to this theory, before freezing completely, most products experience glass transition. The glass transition phenomenon happens not at one temperature point but in a temperature range during which the products become non-crystalline solids from a rubbery or leathery state and the products stability increase greatly. When the storage temperature is above the glass transition temperature, some molecules will be mobile, leading to undesirable reactions. State diagram assists in predicting food stability during storage as well as selecting a suitable condition of temperature and moisture content for processing (Rahman, 1995; Roos, 1995). A state diagram usually shows freezing curve and glass transition line, and maximal-freeze-concentration

Corresponding author. Tel./fax: +86 571 8795 1680. E-mail address: gmchen@zju.edu.cn (G. Chen).

point can be found on it. Dierential scanning calorimetry (DSC) is often used in state diagram research. Since real foods are complex multi-component mixtures which have variable compositions even for the same breed, very little data about their state diagrams have been accumulated compared with pure solutions. However, as the importance of state diagram is better recognized, more studies have been carried out for real foods during recent years. State diagrams of processed apple (Aguilera, Cuadros, & del Valle, 1998; Bai, Rahman, Perera, Smith, & Melton, 2001; Sa, Figueiredo, & Sereno, 1999), pineapple (Telis & Sobral, 2001), tomato (Baroni, Sereno, & Hubinger, 2003; Telis & Sobral, 2002), cornstarch (Zhong & Sun, 2005), tuna meat (Rahman, Kasapis, Guizani, & Al-Amri, 2003) and garlic (Rahman, Sablani, Al-Habsi, Al-Maskri, & Al-Belushi, 2005) have been reported. Chinese gooseberry (scientic identication: Actinidia Chinensis, which is also called kiwi fruit) is rich in vitamin C, carbohydrate, bre, folic acid, pantothenic acid, calcium, protein, magnesium, iron, vitamin B6 and carotene. It is even described as king of the fruits for its high nutritive

0260-8774/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.jfoodeng.2007.05.024

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H. Wang et al. / Journal of Food Engineering 84 (2008) 307312

Nomenclature aw C C1, C2 K K E DHm R2 T 0g T 00 g T 000 g Tgm Tgs Tgw TF T 0m water activity GAB parameter general constants in WLF equation GAB parameter GordonTaylor parameter molecular mass ration of water to solids (kw/ks) melting enthalpy (J/g) signicance of correlation coecient maximally freeze-concentration glass transition temperature (C) characteristic temperature of intersection of glass transition and freezing lines (C) characteristic glass transition temperature measured by DSC (C) glass transition temperature of mixture (C) glass transition temperature of solids (C) glass transition temperature of water (C) freezing temperature (C) end point of freezing (C) T0m Tw Xm X 0s X 00 s X 000 s X0 s Xs Xw b kw s sg maximally freeze-concentration freezing temperature (C) freezing point of water (C) moisture content at fully occupied active sorption sites with one molecule of water (g/g dry basis) solid content at the maximally freeze-concentration (g solids/g wet basis) solids mass fraction at T00 (kg solids/kg sample) g solids mass fraction at Tg000 (kg solids/kg sample) initial mass fraction of solids in equation (g solids/g wet basis) mass fraction of solids (g solids/g wet basis) mass fraction of water (g water/g basis) molar freezing point constant of water (1860 kg K/kg mol) molecular mass of water time constants for crystallization at Tgi time constants for crystallization at T

value. Since the production of Chinese gooseberry is restricted by area and season, long term preservation is attractive (Gerschenson, Rojas, & Marangoni, 2001; Lee, Farid, & Nguang, 2006). The objective of this study is to develop a state diagram for Chinese gooseberry by DSC technique. 2. Materials and methods Fresh Chinese gooseberry was bought from local market. Its moisture content was determined by placing small sample pieces in a drying oven (DHG-9070, Jinghong, China) at 60 C for 3 h and then at 100 C for 5 h (Han, 1996). The weights of the samples were recorded each hour until they showed variation less than 0.3% (Sa et al., 1999). The results were given as an average for three samples. In order to prepare samples with dierent water content, fresh Chinese gooseberry were cut into cylinders, with 3 mm in height and 4 mm in diameter. Such cylinders were then put into a freeze-dryer (Self-made, Weng, Zhou, Chen, Wang, & Xia, 2004). The samples were completely frozen at 60 C, followed by drying at about 10 Pa, 20 C for 20 h and then 20 C for 5 h. All the samples were powdered and further dried in a desiccator over P2O5 for 13 weeks for completely dried materials (Roos & Karel, 1991). To get samples with water activity from 0.12 to 0.94, powdered freeze-dried Chinese gooseberry samples were put in DSC pans (45 mg) and equilibrated with saturated salt solutions of constant water activities (Table 1) for 2448 h (Roos & Karel, 1991) and moisture content (dry basis) values were obtained from the weight dierences of the samples before and after equilibration.

Table 1 Water activity of saturated salt solutions at 25 C (Sa et al., 1999; Roos, 1987) Saturated salt solution LiCl CH3COOK MgCl2 6H2O K2CO3 Mg(NO3)2 6H2O NaNO2 NaCl KCl KNO3 a25 w 0.12 0.23 0.33 0.44 0.52 0.61 0.75 0.85 0.94

To get samples with water activity higher than 0.94, water was added directly by micro-syringe into the freeze-dried powder in small aluminum DSC pans and then the pans were sealed and put in a dry desiccator at 4 C for 24 h (Telis & Sobral, 2001). The weight gains after equilibration were measured and used to calculate the water contents of the samples. The relationship between water activity and moisture content (dry basis) is correlated with the Guggenheim Andersonde Boer (GAB) model (Eqn. (1)). Xw X m CKaw 1 Kaw 1 Kaw CKaw 1

where Xw is the moisture content in dry basis; Xm is the moisture content at fully occupied active sorption sites with one molecule of water, which is secure moisture content for high quality preservation of freeze-dried food; C and K are the GAB parameters associated with the enthalpies of monolayer and multilayer, respectively.

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The transition temperatures of Chinese gooseberry samples at dierent moisture contents were measured with differential scanning calorimetry (DSC-Q100, TA, USA). The instrument was calibrated for heat ow and temperature using distilled water (melting point 0.0 C, DHm = 333 J/ g) and indium (melting point 156.6 C, DHm = 28.44 J/g) (Chinese Standard GB/T 13464-92). An empty aluminum pan was used as reference. Samples were sealed in aluminum pans (1.75 mm height; 6.67 mm internal diameter) and nitrogen was used as carrier gas (50 mL/min). Liquid nitrogen was used for sample cooling with a cooling rate of 10 C/min. All the scans were taken at the same heating rate (10 C/min) between 120 and 25 C. Annealing was performed holding the samples at the temperature point T 0m 3.0 C for 30 min (Bai et al., 2001). All the results were given as an average for three samples. The glass transition temperature of foods with low water activities is modeled by GordonTaylor equation (Eqn. (2)) (Bai et al., 2001; Sa et al., 1999; Telis & Sobral, 2001). T gm X s T gs kX w T gw X s kX w 2

1.0

Equlibrium moisture content (g water/g dry basis)

0.8

0.6

0.4

0.2

0.0 0.0

0.2

0.4

0.6

0.8

1.0

Water activity
Fig. 1. Sorption isotherm of Chinese gooseberry (j experimental data; GAB model).

Table 2 Model tting for sorption experimental data Models Freeze-dried apple (Sa et al., 1999) Freeze-dried pineapple (Telis & Sobral, 2001) 7.190a 0.012a 0.815a 0.991a 7.916b 0.010b 0.821b 0.985b Freeze-dried Chinese gooseberry

where Xs and Xw are the mass fraction of solids and water (wet basis), respectively; Tgm, Tgs and Tgw are the glass transition temperature of mixture, solids and water, respectively. Tgw = 135.0 C (Sa et al., 1999); k is the Gordon Taylor parameter. 3. Result and discussion The moisture content measured for fresh Chinese gooseberry was (0.84 0.01) (g water/g wet basis), which was close to the reference data 0.8341 or 0.8382 (g water/g wet basis). The sorption experimental data were tted with the GAB model. Sorption isotherm is shown in Fig. 1. On the whole, the GAB model well ts the experimental data. The empirical parameters and correlation coecients calculated by non-linear regression are listed in Table 2. Since Chinese gooseberry is also a fruit with large content of fructose and small content of polymer, its sorption isotherm presents a shape of J, similar with those obtained by Telis (Telis & Sobral, 2001). Freezing points and glass transitions of samples at different moisture contents were determined from heat ow curves with professional software (Universal Analysis, TA, USA), as shown in Figs. 2 and 3. Here, the onset temperature (Tgi) of the glass transition region is dened as the intersection of the rst and the second tangent and considered as the glass transition temperature. The mid-point (Tgp) is dened as the inexion of the curve part between the rst and the third tangent. The end point (Tgp) is dened as the intersection of the second and third tangent.
Ref.: http://www.mcgill.ca/cine/resources/data/miao/. Ref.: http://www.food-allergens.de/symposium-vol1(1)/data/kiwi/ kiwi-composition.htm.
2 1

GAB model Xm 0.112a C 2.093a K 0.985a R2 0.994a GAB

a b

0.112b 1.955b 0.987b 0.997b

0.459 0.265 0.827 0.987

Parameters from the references (Sa et al., 1999; Telis & Sobral, 2001). Parameters modeled with the data from the references (Sa et al., 1999; Telis & Sobral, 2001).

Fig. 2. Freezing point determination on DSC thermogram (Moisture content 0.504 (g water/g wet basis)).

The freezing point (TF) is taken as the temperature at endothermic peak (Fig. 2). The end point of freezing (T 0m ) is taken as the initial point of ice melting at endothermic peak. (Rahman, 2006; Rahman et al., 2005). The samples with dierent water content behaved dierently during DSC tests. For samples with moisture content less than 0.19 (g water/g wet basis), since much of the water were linked to the solid matrix, only the phenomenon of

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Fig. 3. Glass transition determination on DSC thermogram (Moisture content 0.175 (g water/g wet basis)).

Fig. 5. DSC thermogram for annealed sample (Moisture content 0.333 (g water/g wet basis)).

glass transition could be observed. Tgi decreased from 23.2 C to 60.8 C when the moisture content increased from 0.0 to 0.19 (g water/g wet basis) (Table 3). When the moisture content was in the range from 0.32 to 0.40 (g water/g wet basis), an exothermic recrystallisation (devitrication) peak of unfrozen water was observed as shown in Fig. 4. The devitrication could be eliminated by annealing the sample (Fig. 5). The freezing temperature at the maximal-freeze-concentration point, T 0m , was 41.8C (Table 4). When the moisture content was higher than 0.50 (g water/g wet basis), the glass transition phenomenon disappeared and only the melting peak could be found (Table 4).

Table 4 Glass transition temperature and freezing point of Chinese gooseberry when there is freezable water Solid T gi T 000 = C Tgm/C Tge/C T 0m = C TF/C DHsample/ g content kJ/kg Xs (g solid/ g wet basis) 0.20 0.30 0.53 0.65 0.67 0.69 61.1 59.8 48.1 60.5 55.2 54.9 41.6 55.0 51.6 52.0 39.1 51.3 29.6 33.2 39.6 33.6 41.3 41.8 2.2 2.7 7.7 19.0 21.1 19.7 172.2 170.6 102.4 34.5 33.3 40.1

Table 3 Glass transition temperature of Chinese gooseberry when there is no formation of ice Solid content Xs (g solid/g wet basis) 0.81 0.83 0.85 0.87 0.93 0.95 1.00 Tgi/C 60.8 56.6 60.6 45.2 25.5 24.4 23.2 Tgm/C 55.8 53.4 55.8 40.9 18.7 19.8 35.8 Tge/C 52.2 49.1 52.7 37.3 14.3 13.7 45.7

With the DSC data, the state diagram of Chinese gooseberry esh could be drawn as shown in Fig. 6. The glass transition data were tted with GordonTaylor equation using non-linear regression method and the values of Tgs, Tgw and k are listed in Table 5. ClausiusClapeyron equation (Eqn. (3)) well represents the decreased freezing temperature with the increasing solid

40 20 0

Temperature (oC)

-20 -40 -60 -80 -100 -120 -140 0.0

//' //

Tg =-49.2 C Tg=-57.1 C Tg =-60.8 C

/// o / o

//

Tm=-41.8

G F C

E
0.2 0.4 0.6

Xs =0.835 Xs =0.871
0.8Xs =0.847 1.0
/

Solids (fraction)
Fig. 4. DSC thermogram for non-annealed sample (Moisture content 0.338 (g water/g dry basis)). Fig. 6. State diagram of Chinese gooseberry sample (AB0 : freezing curve; DE: glass transition line; F: glass transition point of maximally freezeconcentration).

H. Wang et al. / Journal of Food Engineering 84 (2008) 307312 Table 5 GordonTaylor model tting for experimental data Parameters Heat pump dried apple (Bai et al., 2001) Freeze-dried pineapple (Telis & Sobral, 2001) 57.75 135.15 0.21 0.954 51.6 52.0 Freeze-dried Chinese gooseberry 23.2 135 5.72 0.972 57.2 41.8

311

above the glass transition temperature, WilliamsLandel Ferry (WLF) equation (Roos, 1995) could be employed to estimate their shelf life. WLF equation is given as follows: log s C 1 T T g sg C 2 T T g 4

GordonTaylor model 41.3 Tgs (C) Tgw (C) 134.8 k 3.59 R2 Results T 0g  C T 0m  C 57.8 50.3

content in the range from 0.2 to 0.7 (g solids/g wet basis) with R2 = 0.928.   b 1 X0 s D ln 3 kw 1 X 0 EX 0 s s where D is the freezing point depression (Tw TF); TF is the freezing point of the sample (C); Tw is the freezing point of water (C); b is the molar freezing point constant of water (1860 kg K /kg mol); kw is the molecular mass of water; X 0 is the initial solids mass fraction (kg solids/ s kg sample); and E is the molecular mass ration of water to solids (kw/ks), E = 0.101. In Fig. 6, line AB0 represents freezing temperature curve and line DE represents glass transition temperature Tgi. Several characteristic points B0 , G, F and C are clearly dened by (Rahman et al., 2005). Point B0 is the maximal-freeze-concentration point, at which the freezing temperature T 0m 41:8  C and the water content (1 X 0s 0:153 (g water/g wet basis). This part of water is considered as unfreezable (Rahman et al., 2005). Point F is the maximal-freeze-concentration glass transition point, its temperature T 0g 57:2  C and its solid content is the same as X0 s at point B0 ; point G (T 00 49:2  C and g X 00 0:871 (g water/g wet basis)) is the intersection of line s AB0 and line DE, which is dierent from the experimental value (Tgi = 45.2 C and Xs = 0.871 (g water/g wet basis)) in Table 3. This dierence is due to the discrepancy of the tted curves from the experimental data. Point C represents the glass transition of high water content samples measured by DSC with annealing, its temperature (T 000 =60.8 C and X 000 =0.835 (g water/g wet basis)). g s There are numbers of factors which can inuence food stability (Rahman, 2006). Among them temperature is prominent. Low temperature cannot only slow down the adverse reactions of microbe, enzyme, respiration and other factors, but also suppress the growth of ice crystals. Big ice crystals may destroy the micro-structures of food product and lead to the decline of food quality. With understanding of the state diagram, the best storing condition for products could be proposed. For example, for Chinese gooseberry dried to water content of 0.1 (g water/ g wet basis), it had better be stored below its glass transition point, 38.3 C. For products that have to be stored

where sg and s are time constants for crystallization at Tg and T, respectively; C1 and C2are general constants. According to Sun (Sun, 1997), for the system which has a freezing point much higher than its glass transition point, C1 = 20 and C2 = 155. The storage period under glass state, sg, is estimated as follows: since the growth rate of ice crystal under glass state is estimated as 1 mm per 103 years (Hua, Li, & Liu, 1999), it will take 2030 years for a trivial crystal to grow big enough to destroy the Chinese gooseberry cells whose typical diameters are about 20 30 lm, therefore sg equals 2030 years. As an example, lets consider dried Chinese gooseberry product with water content Xw = 0.1 (g water/g wet basis), its glass transition temperature can be found from the diagram to be 38.3 C. According to (Eq. (4)), the shelf life of this product at 5 C can then be calculated to be 3.2 and 5.0 days. It is easy to make similar estimation for products with other water contents and stored at other temperatures. 4. Conclusions Chinese gooseberry is one of the most popular and nutritive fruits that is worthy for storage. The state diagram of freeze-dried Chinese gooseberry was drawn according to DSC data in this paper. It is composed of freezing line and glass transition line. The glass transition temperature for the maximal-freeze-concentrated condition, T 0g , was found to be 57.2 C. T 0m , the freezing temperature for the maximal-freeze-concentrated condition was found to be 41.8 C. The unfreezable water fraction was found to be 0.153 (g water/g wet basis). The state diagram obtained here may be helpful in developing better products made of Chinese gooseberry. Acknowledgements The authors acknowledge the nancial supports from National Natural Science Foundation of China (No. 50076039) and National Foundation for Scholars Returning from Abroad. References
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