Water Sorption and The Plasticization Effect in Wafers

International Journal of Food Science and Technology 2004, 39, 555562
555
Water sorption and the plasticization effect in wafers

Nuria Martnez-Navarrete, Gemma Moraga, Pau Talens & Amparo Chiralt*
Food Technology Department, Polytechnical University, Camino de Vera s/n, 46022 Valencia, Spain (Received 30 May 2002; Accepted in revised form 20 November 2003)
Summary
Wafers are low moisture food products whose crunchiness or crispness is considered a primary textural attribute, highly aected by the products physical state (glassy or rubbery). The water activitywater contentglass transition relationships for commercial wafers are reported, using Gordon and Taylors equation to model the water plasticization eect and also Brunnaver-Emmett-Teller (BET) and Guggenheim-Anderson-DeBoer (GAB) sorption models. BET monolayer moisture content was 6.2% and the moisture limit to t this model was about 11.5%. Critical water activity and critical water content for the glass transition of the product at 20 C were 0.591 and 0.118 (mass fraction) respectively. Abrupt changes in the mechanical product properties, evaluated from a threepoint bend test, could be observed at these limits. Moisture levels between 6 and 11% give rise to a glassy state matrix in the product and so to acceptable product crispness. Below this range, the glassy matrix seems to turn fragile and, above this range, the product becomes rubbery.
Crispiness, critical water activity, critical water content, glass transition, mechanical properties, sorption isotherm.
Keywords
Introduction
Wafers are produced in huge quantities and this makes it dicult to maintain a consistent product. The keeping properties of the wafers are critical. A wafer that quickly becomes soggy or leathery rather than brittle is unlikely to please the consumer. The nature of the ingredients used, in particular the our, and the processes used to make the wafer can greatly alter its shelf-life. However, the wafer structure and the factors that give it the correct texture are not fully understood (Beckett et al., 1994). Wafers are produced by baking a liquid batter consisting of a mixture of our and water, with small amounts of butter, sugar, salt and sodium bicarbonate. The batter is far more complex than might at rst seem likely. Factors such as the order in which the ingredient are added, the water temperature and the degree of mixing can aect the processing and the nal characteristics of the
*Correspondent: Fax: (34) 963877369; e-mail: dchiralt@tal.upv.es doi:10.1111/j.1365-2621.2004.00815.x
2004 Blackwell Publishing Ltd
product. Once mixed, the batter is deposited on a hot plate and another hot plate closes on top of it. Temperature and batter viscosity are critical at this step. Therefore, to assure a homogeneous quality in the product many variables must be continuously monitored and controlled throughout the process (Beckett et al., 1994). Once the wafer is made, its mechanical properties need to be tested. Two important textural characteristic of a wafer are how it snaps during the rst bite and how it subsequently breaks up and dissolves in the mouth. Wafer crunchiness or crispness is considered a primary textural attribute (Attenburrow & Davies, 1993). Nevertheless, brittleness also aects the physical stability of the product during handling and transportation. Water aects the texture of this kind of product by plasticizing and softening the starch/protein matrix, which alters the strength of the product (Katz & Labuza, 1981). However, the molecular mechanism which accounts for the textural change is not clear; dierent authors have taken dierent criteria to dene the critical moisture content and the values are thus not coincident. Katz & Labuza
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Water sorption and plasticization in wafers N. Martnez-Navarrete et al.
(1981) reported that a water content greater than the BET monolayer value results in a decrease in the macromolecular interaction that contribute to the crunchiness sensation, because of the water water interactions. Water uptake above the monolayer moisture content reaches a critical value beyond which point the consumer perceives a textural change. The acceptance limit is better established as a function of water activity (Katz & Labuza, 1981). The level of critical water activity after which products with similar characteristics to wafers lose their crunchiness/crispness has been stated as 0.360.51 for potato chips, saltines or popcorn (Katz & Labuza, 1981), 0.500.57 for krispies (Roos et al., 1998), 0.60 for biscuits (Hough et al., 2001) and 0.600.68 for breakfast cereals (Sauvageot & Blond, 1991; Peleg, 1994; Mart nez-Navarrete et al., 1998). These values are in the water activity (aw) range where amorphous to crystalline transformations occur in simple sugar food systems and the mobilization of soluble food constituents begins. Removal of water during the processing of many products often results in the formation of an amorphous state, which is a non-equilibrium state with time-dependent properties. In carbohydratebased foods, such as wafers, rapid cooling after baking also produces amorphous states during their elaboration process (Beckett et al., 1994). The physical state of amorphous materials may change from a solid glassy state to a liquid-like rubbery one when the glass transition temperature (Tg) is reached. As the Tg is dependent on water content, a change from a glassy to a rubbery state can also occur as a consequence of an increase in the product water content during its processing or storage. In many food products, glass transition has been linked to changes in the mechanical properties that lead to the loss of crunchiness (Roos, 1995). Nevertheless, relationships between textural attributes and Tg may be dependent on the parameter analysed (Harris & Peleg, 1996; Roos et al., 1998). The glass transition temperature in confectionery products will be dependent on product composition and also on its thermal history, i.e. the rate of cooling and heating during processing. State diagrams showing the relationships between product composition and its physical state, as a function of temperature, are a useful tool in food formulation, in order to establish processing
requirements (equipment and operation variables) or to design package/storage conditions. By taking state diagrams into account, it is possible to optimize product stability and quality in terms of the retention of the desired levels of attributes, such as texture. Exposure of low-moisture foods to high relative humidities often results in water sorption and a detrimental increase in water content. In these products the loss of crispness occurs when critical values of water content (CWC) and water activity (CWA) are exceeded, depressing the Tg of the material to below ambient temperature. As proposed by Roos (1993), a combined use of the Gordon and Taylor equation, to model the plasticization eect of water, and the GAB sorption model allows the evaluation of food stability as a function of product water content and storage conditions. The aim of the present study was to establish the awmoistureTg relationships for wafers in order to establish the CWA and CWC that induce glass transition in the product matrix. Likewise, the impact of product wetting on its mechanical properties was analysed to evaluate the eect of water plasticizing properties on product texture.
Material and methods
Materials Wafers of a commercial brand (Padi galletas) were purchased at a local supermarket. According to the producers specications, the composition of wafers was (% w/w): 79.5 carbohydrates, 10.9 proteins and 2.9 lipids. Likewise, the ingredients specied on the label were wheat our, sucrose, dextrose, emulsier (E-322), foaming agent (sodium bicarbonate and E-4500ai), salt avouring and antiagglomerating (E-341) agents and natural colorant (caramel). The wafer dimensions were 67 65 3 mm and their weight 1.5 g. Moisture conditioning For sample moisture conditioning, six wafers were placed at 20 C in hermetic chambers containing saturated salt solutions with dierent aw (LiCl: 0.113, CH3COOK: 0.230, MgCl2: 0.330, K2CO3: 0.430, Mg(NO3)2: 0.520, NaBr: 0.591, CuCl2: 0.680, NaCl: 0.755 and KCl: 0.845,
557
Greenspan, 1977). The sample weights were controlled till they reached a constant value (mass dierence <0.0005 g), where the equilibrium moisture content of the samples was assumed to be achieved (Spiess & Wolf, 1983). Initial water content of wafers was determined using an infrared balance (AND, AD-4714 A, Tokyo, Japan) and the nal equilibrium moisture content was calculated from this value and from the nal weight of the samples. Instrumental texture analysis A three-point bend mechanical test (A/3PB rig from Stable Micro Systems, SMS, Haslemere, UK) was done by using a Universal Texture Analyser TA.XT2 (SMS). The length between supports of the beam was xed at 12 mm. The wafer samples with dierent moisture contents were exed until fracture, or till 10 mm deformation when they did not break, at 2 mm s)1 cross speed. Each measurement was in triplicate at 20 C. Differential scanning calorimetry analysis A dierential scanning calorimeter (DSC) 220CU SII (Seiko instruments Inc., Tokyo, Japan) was used for the calorimetric analysis of glass transition. Samples conditioned at dierent moisture contents were homogenized and about 10 mg was placed into DSC pans for thermal analysis. Heating rate was 5 C min)1 and temperature range varied between )60 and 100 C, depending on sample moisture content.
Results and discussion
0.30
we(g water/g dry solids)
0.25 0.20 0.15 0.10 0.05 0.00 0 0.2 0.4 0.6 0.8 1
aw
Figure 1 Water sorption isotherm of wafers, at 20 C. Experimental points and GAB model tted.
aw 1 C1 aw ; wo C 1 aw we wo C aw 1 C2 K1 C 2 aw aw : wo C wo C we wo CK
1 2
Water activitywater contentglass transition temperature relationships Water content in commercial wafers was 7.00 0.02%, which agrees with the compositional data specied on the products label (main solids 93.3%). Equilibrium moisture contents (we) at the dierent aw of the samples are plotted in Fig. 1, which shows the sorption isotherm (at 20 C) of wafers. The points were well tted by BET (for aw 0.520) and GAB models. To this end, linearized equations (eqns 1 and 2, respectively) were used.
From the BET model tting (r2 0.987), the monolayer moisture content (wo) was 0.062 g g)1 dry solids (d.s.), very near to that obtained from the GAB model tting (r2 0.958) (wo 0.069 g g)1 d.s.). C parameter values were 27.9 and 16.9 for BET and GAB models respectively. Likewise, K in the GAB equation was equal to 0.841. The monolayer moisture content was lower than 10 g/100 g d.s., which is the maximum value reported for food materials (Tsami et al., 1990). The aw value at which the BET monolayer moisture content was reached was 0.17, a security value beyond which deteriorative reactions may be accelerated in the product. The water activity predicted for the studied commercial product, with 7.5 g water/100 g d.s., was 0.22, near to the security value commented on above. In Fig. 1, the predicted curve of the GAB model has been plotted, and the close tting of the equation can be seen. Over the aw range investigated, the typical sigmoid shape curve of a type II isotherm (Brunauer et al., 1940) was observed. Equilibrium moisture content increases slowly at low water activities where sorption mainly occurs on the solid matrix formed by biopolymers (polysaccharides and proteins). From an aw higher than 0.75, the curve shows a steep rise, which was attributable to the dissolution of sugars in the incipient product aqueous phase (Tsami et al.,
558
1990; Hubinger et al., 1992; Maskan & Gogus, 1998; Vazquez et al., 1999). The eect of solution interactions on wateraw relationships begins to be evident from aw 0.60, which was the limit from which point on the BET equation did not t the points properly. Therefore, it is expected that product properties suer a great change from this aw value, at which the equilibrium moisture content is about 13% dry basis (d.b.). Figure 2 shows the glass transition, as analysed by DSC; the observed change in sample specic heat at a determined temperature is shown. Samples with higher aw (from 0.520) show a small endotherm in the typical temperature range of starch gelatinization (Fig. 2). This can be attributed to an incomplete gelatinization of native granules during the baking process, as aected by sugar content (Mizukoshi, 1990), or to retrogradation phenomena which occur throughout the storage time (Keetels et al., 1995). As expected from the moisture levels reached and the product composition, no freezable water was detected by DSC, as deduced from the thermograms. Table 1 shows the onset and midpoint temperatures for glass transition of the dierent samples.
The Gordon and Taylor equation has proved to be a reliable predictor of glass transition temperatures of sugars at various water contents. Application of the equation requires its previous tting to experimental data. To this end, linearized equation of the Gordon and Taylor model (eqn 3) may be used. wTgw Tg : 3 Tg Tgs k 1 w The above equation was tted to experimental Tg (midpoint)-moisture (w) data (r2 0.928), considering )135 C to be the Tg of pure water (Tgw, Roos, 1995). The value obtained for the parameter k was 5.54, while Tg of the anhydrous solids (Tgs) was estimated as 133 C. This value is lower than values reported for dry starch, which range between 151 and 243 C (Roos, 1995); this is as expected taking into account the plasticizing eect of sugars (Roos, 1995), which will reduce this value in products like wafers. Figure 3 shows experimental data (midpoint values for Tg) and the predicted curve, where the close tting of the model can be seen. The plasticizer eect of water can be observed, especially at water contents
Figure 2
Thermograms showing the DSC analysis for obtaining the glass transition values (Tgo onset, Tg midpoint).
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Table 1 Values of glass transition temperature (Tg onset and Tg midpoint) and mechanical parameters (force F and distance d at the fracture point) for wafer samples with dierent moisture contents
Glass transition temperature (C) Water content (g water/g wafer) 0.047 0.062 0.070* 0.073 0.088 0.104 0.116 0.133 0.153 0.192 *Commercial sample. Tg onset 65.1 2 55 3 50 2 30.1 1.2 29.5 0.9 8.4 0.5 )8.1 1.7 )26.2 1.3 10.4 0.6 )5.3 1.9 )21.2 1.2 55.9 1.3 32.3 0.9 33 3 Tg midpoint 68.1 2.5 61 5
Mechanical parameters F (N) 18.4 22.1 19.6 23.6 23 21.6 23 18 13.3 8.55 1.7 1.0 1.9 0.6 2 1.4 4 3 1.2 0.10 d (mm) 0.57 0.53 0.62 0.71 0.84 0.97 1.07 0.97 0.92 1.02 0.10 0.05 0.10 0.11 0.13 0.08 0.07 0.11 0.06 0.06
130 100 70 40
100 80 60
0.25 0.2 0.15

CWC
Tg (C)
10 20 50 80 110 140 0.00 0.05 0.10 0.15 0.20 0.25 0.30
Tg (C)
40 20 0 20 40 0 0.2 0.4
CWA
0.1 0.05 0 0.8 1
0.6
w (g water/g product)
Relationship between Tg (midpoint) and moisture content (w) of samples. Experimental points and tted Gordon and Taylor model.
Figure 3
aw
Figure 4 Relationships between Tg, aw and equilibrium water content (w).
below 20 g/100 g product. In the commercial product, with a 0.07 water mass fraction, glass transition occurs at about 54 C. The predicted CWC at 20 C was 11.8%, which implies that samples with greater moisture content will be in a rubbery state at this temperature. This value coincides with the moisture limit in the sorption isotherm from which point onwards an increase is observed, which is related to the beginning of solutesolvent interactions in the system. Figure 4 shows the data of equilibrium water content and Tg together as a function of aw. As can be observed, Tgaw data in the range studied showed a linear relationship (Tg )119.25aw+ 89.75, r2 0.9516), such as has been described in other products (Roos, 1995; Mart nez-Navarrete
et al., 1998; Moraga, 2002). Dierences between the intercept in this equation and the Tg of the anhydrous solids predicted by the Gordon and Taylor model agree with the actual sigmoid relationship between Tg and aw in the complete aw range described for other products (Roos, 1995) and that can also be assumed for wafers. The critical water activity for the glass transition at ambient temperature (20 C) calculated from this equation (0.58), is very close to that calculated from CWC by applying the GAB model (0.61). The equilibrium water content (0.116 0.006 g g)1 wafer) and aw (0.591) of wafer samples equilibrated with NaBr saturated solution are very close to the critical values and so represent the point of change in sample properties dependent on molecular mobility in the system.
w (g water/g dry solids)
560
30 25 aw = 0.230 20 aw = 0.113
aw = 0.330 aw = 0.430 aw = 0.520
Commercial
aw = 0.591
F (N)
aw = 0.680 aw = 0.775
15 10
aw = 0.845 5 0 0 0.5 1 1.5 2

Figure 5 Representative force Fdistance d curves obtained from the three-point bend test, for samples with several aw.
d (mm)
F(N) or F/d (N mm1)
0.6 20 0.4 10 0.2 0 0 0.2 0.4
Mechanical analysis Figure 5 shows the typical shapes of the force distance curves obtained from the three-point bend test for samples of several aw. For clarity, only one of the replicates at each moisture content has been selected for the gure. Samples with low water activity (aw 0.430) showed a similar behaviour with a sharp initial slope and fracture point. After this aw value, samples become more deformable and the initial slope of the curve greatly decreases; the greater the sample aw, the lower the slope. In these cases, no abrupt fracture was observed, although the yield point could be identied. From forcedistance curves, the force (F) and distance (d) at fracture or yield points were characterized for samples with dierent moisture levels (Table 1). The F/d ratios at these points were also calculated. In Fig. 6 the development of F, d, and F/d parameters as a function of sample aw can be observed. An initial increase in F value, in line with sample aw increase, was observed and can be attributed to the progressive increase in sample
aw
0.6
0.8
Figure 6
Development of mechanical parameters (F, d, and F/d at fracture point) as a function of sample aw.
deformability, which in turn increases its resistance to fracture, while it becomes longer. From aw 0.330, F remains practically constant until the aw 0.591 (0.116 water mass fraction) from which point on it suers a sharp decrease. Deformation at fracture (d) shows an increasing sigmoid behaviour, the ascending zone being between aw 0.230 and 0.591 (0.062 and 0.116 water mass fraction respectively), but it reaches a practically constant value from aw 0.591. The increase in d values reects the progressive plasticizing eect of water in the product, becoming more deformable in line with the increase in molecular mobility
d (mm)
The low aw value of the commercial product makes it very sensitive to becoming damp at the usual environmental relative humidity. This implies that there is a requirement for a water impermeable packaging and other precautions during product manipulation to avoid it becoming rubbery, thereby losing its typical characteristics.
F(N)
F/d (N mm1)
d (mm)
50
1.2 1 0.8
40
30
561
eect is clearly observed in the decreasing values of F/d or deformability modulus of the product.
Conclusions
At room temperature (20 C), the product studied showed a glassy state until its moisture content reached 11%. However, for moisture content lower than 6% (monolayer moisture content) the product showed a great fragility and broke at very low deformation. Therefore moisture levels between 6 and 11% are recommended to obtain an acceptable crispy product, with a glassy state matrix, but not too fragile.
Figure 7
Pathway of mechanical parameters at different levels of product water content.
References
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associated with water interactions. The F/d ratio at fracture (yield) point will be related to Youngs modulus of the product. It showed a continuous decrease from aw 0.230 (0.062 water mass fraction), which quanties the loss of stiness of wafers as they become more moist. The observed behaviour of the F/d parameter is very similar to that reported by Attenburrow & Davies (1993) for Youngs modulus of ice cream wafers. These authors found that there was a signicant decrease of the modulus when water content increased above 610% with a stabilization of the modulus value at water contents greater than 25%. Figure 7 summarizes the pathway of mechanical parameters at dierent levels of product wetting. From this analysis, it is possible to conclude that wafers with very low moisture content (lower than about 6%) are very fragile and break with very small deformations. Fragility progressively decreases until moisture content reaches 1112%, when glass transition occurs in the matrix at 20 C, and the product becomes rubbery. At the temperature used in this study (20 C), the resistance to fracture (F) is almost constant (after a small initial increase) while the product remains glassy (moisture content lower than CWC). When the product attains the rubbery state no fracture occurs but there is a plastic deformation of the product matrix, in which resistance decreases as the product water uptake increases. From the BET monolayer moisture content (6%), the water plasticizing
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Maskan, M. & Gogus, F. (1998). Sorption isotherms and drying characteristics of mulberry (Morus alba). Journal of Food Engineering, 37, 437449. Mizukoshi, M. (1990). Baking mechanism in cake production. In: Food Emulsions (edited by K. Larsson & S.E. Friberg). Pp. 479504. New York: Marcel Dekker. Moraga, G. (2002). Aspectos Fisicoqumicos Relacionados n con la Crioproteccio de Fresa y Kiwi. Doctoral thesis, Universidad Politecnica de Valencia, Spain. Peleg, M. (1994). A mathematical model of crunchiness/ crispness loss in breakfast cereals. Journal of Texture Studies, 25, 403410. Roos, Y.H. (1993). Water activity and physical state eects on amorphous food stability. Journal of Food Processing and Preservation, 16, 433447. Roos, Y.H. (1995). Phase Transitions in Food. Pp. 73192. San Diego, CA: Academic Press. Roos, Y.H., Roininen, K., Jouppila, K. & Tuorila, H. (1998). Glass transition and water plasticization eects on
crispness of a snack food extrudate. International Journal of Food Properties, 1, 163180. Sauvageot, F. & Blond, G. (1991). Eect of water activity on crispness of breakfast cereals. Journal of Texture Studies, 22, 423442. Spiess, W.E.L. & Wolf, W.R. (1983). The results of the COST 90 Project on water activity. In: Physical Properties of Foods (edited by R. Jowitt, F. Escher, B. Hallstrom, H.F.Th. Meert, W.E.L. Spiess & G. Vos). Pp. 6591. London and New York: Applied Science Publishers. Tsami, E., Marinos-Kouris, D. & Maroulis, Z.B. (1990). Water sorption isotherms of raisins, currants, gs, prunes and apricots. Journal of Food Science, 55, 15941597. Vazquez, G., Chenlo, F., Moreira, L. & Carballo, L. (1999). Desorption isotherms of muscatel and aledo grapes, and the inuence of pretreatments on muscatel isotherms. Journal of Food Engineering, 39, 409414.

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International Journal of Food Science and Technology 2004, 39, 555562