Glass Transition and Food Technology - A Critical Appraisal PDF

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Concise Reviews in Food Science
Concise Reviews and Hypotheses in Food Science.
Glass Transition and Food Technology: A Critical Appraisal

M. LE MESTE, D. CHAMPION, G. ROUDAUT, G. BLOND, AND D. SIMATOS ABSTRACT: Most low water content or frozen food products are partly or fully amorphous. This review will discuss the extent to which it is possible to understand and predict their behavior during processing and storage, on the basis of glass transition temperature values (Tg) and phenomena related to glass transition. Two main conclusions are provisionally proposed. Firstly, glass transition cannot be considered as an absolute threshold for molecular mobility. Transport of water and other small molecules takes place even in the glassy state at a significant rate, resulting in effective exchange of water in multi-domains foods or sensitivity to oxidation of encapsulated materials. Texture properties (crispness) also appear to be greatly affected by sub-Tg relaxations and aging below Tg. Secondly, glass transition is only one among the various factors controlling the kinetics of evolution of products during storage and processing. For processes such as collapse, caking, crystallization, and operations like drying, extrusion, flaking, Tg data and WLF kinetics have good predictive value as regards the effects of temperature and water content. On the contrary, chemical/biochemical reactions are frequently observed at temperature below Tg, albeit at a reduced rate, and WLF kinetics may be obscured by other factors. Keywords: glass transition, glassy state, amorphous regions, relaxation, WLF, water activity
Introduction
HE HUGE VARIETY OF POSSIBLE APPLICATIONS OF GLASS TRANSITION
in food science and technology was highlighted in the 1980s by Levine and Slade. Stimulated by an extensive series of papers and presentations from these authors (Levine and Slade 1986; Slade and Levine 1988, 1991) and by theoretical and experimental progress in materials science, a constantly increasing number of studies in the food area refer to glass transition. It seems timely to review current literature, in order to discuss the extent to which it is possible to understand and predict the behavior of foods during processing and storage on the basis of glass transition-related phenomena. Most food products with reduced moisture content are partly or totally amorphous. Depending on the storage temperature and their composition (mainly water content), they are glassy and may be expected to be rigid (eventually crispy) and stable, or contain a rubbery or liquid phase and then be soft and prone to physical and chemical changes. Processes such as baking, air- and freeze-drying, extrusion, and flaking may also operate through the glass transition range. Since the theoretical basis of glass transition that are of interest to food science were already reviewed (Angell and others 1994; Perez 1994; Simatos and others 1995b) a few points will only briefly be mentioned here. We will focus on experimental data dealing with food related materials.
uid, for low molecular weight materials. The GLT is a kinetic and relaxation process associated with the so-called relaxation of the material. At temperatures above the GLT the material, if submitted to a perturbation, can recover after a characteristic relaxation time (): the supercooled melt is in a metastable state. The liquid-like structure of the melt is frozen in the glass, which is an out-of-equilibrium state (Figure 1). The GLT region is the temperature range where the relaxation time of the material is similar to the experimental time scale.
Mobility above GLT

A characteristic feature of mechanical properties of the supercooled melt is the strong temperature dependence in the temperature range above the glass transition temperature (Tg): the apparent activation energy (Ea) commonly attains 200 to 400 kJ.mole-1; it decreases when temperature increases. The most popular expressions to describe this behavior are the Vogel-Tammann-Fulcher (VTF) [1] and the Williams-Landel-Ferry (WLF) [2] expressions: T = 0 exp(B/ (T-T0)) log(T /Tg ) = -C1g (T-Tg)/ (C2g + (T-Tg)) (1) (2)
Glass transition and molecular mobility Definition

Glass transition (or glass-liquid transition GLT) is the name given to phenomena observed when a glass is changed into a supercooled melt during heating, or to the reverse transformations during cooling. Both are non-crystalline states; but while the glass is a rigid solid, the supercooled melt, which is observed between the GLT and the melting point, can be a viscoelastic rubber in the case of a polymeric material, or a mainly viscous liq2444
where T and Tg are viscosities at T and Tg respectively; 0, B, T0, C1g, and C2g are phenomenological coefficients. Both expressions can be inter-converted. Expressions similar to Eq 1 and 2 can be written with the obtained for example with mechanical spectroscopy (Figure 2). C1g and C2g can fluctuate (Ferry 1980) around the universal values given by Williams and others (1955) (17.4 and 51.6 respectively) as a function of the considered material. The variations of C2g and of B correspond to the classification proposed by Angell (Angell and others 1991, 1994) of strong/fragile materials according to the variation of their dynamic properties through the glass
2002 Institute of Food Technologists
JOURNAL OF FOOD SCIENCEVol. 67, Nr. 7, 2002
Glass transition in food . . .

transition. The fragility parameter m was introduced to differentiate fragile systems (m between 100 and 200) which are highly sensitive to temperature changes above Tg, from strong ones (m between 16 and 100) which are less disturbed when passing through the glass transition. By definition, m is the slope of the scaled Arrhenius plot of the viscosity when the temperature approaches Tg from above, Ea being the apparent activation energy (kJ.mole-1): m = Ea/ (RTg ln10) (3) ran in sucrose (Blond 1994; Shamblin and Zografi 1998). In contrast, increasing the weight fraction of fructose in glucose-fructose mixtures also resulted in a decrease of the aging rate, although Tg was depressed (Wungtanagorn and Schmidt 2001a).
Relaxation time
Relaxation times obtained by means of various techniques can be represented as a function of temperature in a mobility map (Figure 4). Besides the characteristic relaxation time , 2 other empirical parameters are used to describe the relaxation processes associated with GLT. Non-exponentiality. The process cannot be described by a single relaxation function. To represent the distribution of relaxation times, a somewhat arbitrary but mathematically convenient expression is most frequently used, a so-called stretched exponential (KWW expression): (t) = exp [ (t / ) (5)
This parameter m can be calculated with the VTF and WLF coefficients: m = C1g + C1g2 T0 ln10/ B or m = (C1g/ C2g) Tg (4)
or it may be deduced from DSC or mechanical spectroscopy data. A discussion of the application of various methods to estimate m for food materials can be found in Simatos and others (1995b). Low molecular weight sugars can be classified as rather fragile materials. They seem to be located in a narrow domain of the fragility diagram (Figure 3). For proteins, the scarce experimental data seem to indicate a strong behavior: m 40.5 for poly-L-asparagine (15 to 25% water) (Angell and others 1994) and similar values for elastin and gluten (Simatos and others 1995b). Pullulan-starch blends were found to show strong behavior (m 42 to 51) increasing with water content (Biliaderis and others 1999). Fragility was reported to increase in the order: pullulan<dextran and phytoglycogen<amylopectin, and to decrease for amylopectin with increasing water content (Borde and others 2002).
where is the property studied as a function of time (t). The parameter is close to 1 for strong liquids (nearly exponential relaxation). For fragile liquids it changes from near 1 at high temperature to a value close to 0.3 to 0.5 near Tg. is generally lower (broader distribution of relaxation times) for polymers than for low molecular weight materials, and for mixtures. Non-linearity. The characteristic relaxation time is changing with time t and with the material structure, which depends on its previous history. This dependence is commonly represented by the following expression: = 0 exp [x h/ RT + (1-x) h / RTf ] (6)
Mobility below GLT

In the glass, long range cooperative motions are restricted. Motions (vibrations of atoms, reorientation of small groups of atoms) are mainly local, not involving the surrounding atoms or molecules. The temperature dependence of dynamic properties is generally considered to obey Arrhenius law, with an apparent activation energy that is lower than at T>Tg but still rather high (Perez 1994). Several sub-Tg relaxations can be observed in biopolymers and low molecular weight sugars ( and relaxations). Their origin is still being discussed. As observed in polysaccharides they could correspond to rotation of lateral groups ( relaxation at low temperature) or to local conformation changes of the main chain ( relaxation closer to T) (Montes and others 1998). The Ea values range between 40 to 70 kJ.mole-1 for relaxation in maltose and glucose. When a glassy material is stored between T and Tg, a microstructural evolution may take place, which corresponds to the system approaching the metastable equilibrium, with some extra loss in enthalpy and volume (Figure 1). This physical aging, also named annealing when carried out to develop desired properties, can be regarded as a continuation of the relaxation. From observations in the field of materials science, it is known that the more compact molecular organization and the strengthening of interactions result in changes in many physical properties: increased rigidity and brittleness, decreased dimensions, and transport properties. Physical aging is expected to be of importance for the stability of low moisture products and is currently receiving a lot of attention. Experimental study of the process allowed the determination of the relaxation parameters (see below). The rate of enthalpy relaxation was decreased, as expected, upon addition of a substance with a higher Tg, for instance dext-
Figure 1Evolution of enthalpy (or specific volume) (a) and of heat capacity (or of thermal expansion coefficient) (b) versus temperature in the vicinity of glass transition, during cooling (1), rewarming (2) or after physical aging during time t (3). Tgo and Tgm are the 2 points (onset, middle) that are commonly used to define Tg. TfA and TfB are the fictive temperatures characteristic of the glass structure in states A and B. Vol. 67, Nr. 7, 2002JOURNAL OF FOOD SCIENCE 2445

The fictive temperature Tf, for a material being at the actual temperature T, is considered to represent its structural state (Figure 1). The parameter x (0 < x < 1) defines the relative contributions of temperature and structure to (if x is close to 1, mainly depends on the aging temperature) h is the activation energy at Tg for the supercooled material. The parameters , , x can be estimated from enthalpy relaxation experiments using DSC after varying annealing times (Hodge 1994). This was done for maltose (Lammert and others 1999, Noel and others 1999) and glucose-fructose mixtures (Wungtanagorn and Schmidt 2001b). Increasing the fructose weight fraction in the blend induced an increase in x (linearity increase) and a decrease in (broader distribution of relaxation times). The value of and the evolution of Tf with time can give an indication about the relative structural stability of materials (Shamblin and others 1999). For a more accurate assessment of the theoretical relevance and technological usefulness of parameters and x in the food area, there is a need for more experimental data with different material types. to their respective sorption isotherms. Moreover, this study points to the fact that distinct Tgs (or T) may exist in multiphasic systems, not only because of distinct Tg for the components themselves, but also because of the water distribution. Most real foods are multiphasic systems. More attention should be given to the effect of microstructure on glass transition related properties and to possible phase transitions occurring in components such as lipids. As it appears that common techniques (DSC, mechanical spectroscopy) often give an indication of a transition at a macroscopic level, a correct understanding of the glass transition related phenomena implies resorting to different techniques. Moreover, nuclear magnetic resonance, electron spin resonance, solute translational diffusion, and so on, may give information on the molecular mobility in various phases and microstructural locations. The question of the relevant glass transition temperature in frozen products must be raised. Because of the cryo-concentration process, 2 different glass transition temperatures have to be considered, depending on the storage temperature of the product (Figure 5). The glass transition temperature of the maximally freeze-concentrated phase is considered to occur in a temperature range around Tg. If the product is stored at a temperature Ts below Tg it may be expected to be composed of ice and a freezeconcentrated phase in the glassy state and long-term stability may be anticipated. By contrast, if Ts is between Tg and Tm, the freeze-concentrated phase is more diluted, its concentration Cs being determined on the curve Tm at temperature Ts. The glass transition temperature of the partially freeze-concentrated phase is now Tgs, determined on the curve Tg for concentration Cs (Champion and others 1997a).
Glass transition temperature(s)

Most popular methods to determine the temperature range of GLT currently are differential scanning calorimetry (DSC) and mechanical spectroscopy (or dynamic mechanical thermal analysis = DMTA). Both types of techniques may provide significantly different values (Kalichevsky and others 1992a,b; Biliaderis and others 1999). The discrepancies may be understood by keeping in mind 2 series of factors: i. differences induced by the analysis of experimental data, for instance definition of Tg in the DSC curve (onset, midpoint, endpoint, see Figure1), choice of feature in DMTA (drop in E, maximum of E or of tan ); ii. differences ascribable to the coupling of different structural units (with particular relaxation times) with the imposed perturbations, which may differ as regards the nature of the stress or the experimental time. It is therefore not possible to consider a unique glass transition temperature. Namely, following the convention in use in materials science, the use of Tg designation should be restricted to the DSC value (10 K.min -1), the temperature derived from DMTA being named T (with indication of the measurement frequency). The important discrepancies between published values of Tg may, in addition, originate from uncertainties in the water content and/or chemical degradation (Vanhal and Blond 1999). For practical purposes, the method of measurement should be chosen according to the application. If sensory properties of texture, or dynamic processes such as collapse or agglomeration were of concern, the relevant method would most probably be mechanical spectroscopy or change in the Young modulus or viscosity with temperature (with the relevant experimental time). Although more difficult to determine with many food products, Tg (DSC) may be relevant, once the correlation with the dynamically measured temperature or with the phenomenon of interest has been demonstrated. Determination of glass transition temperature is further complicated with food products because of their chemical and microstructural complexity. Glass transitions often extend over a large temperature range, due to a broad distribution of relaxation times and/or to unresolved transitions corresponding to different components. Distinct transitions associated with different phases can be observed as reported for amylopectin-gelatin mixtures (Mousia and others 2000). The DMTA thermograms exhibited 2 glass transitions, which could be associated with the 2 phases identified by FTIR microscopy. The measured Ts were consistent with the values predicted on the basis of water partitioning between the 2 components according
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Plasticization
The temperature of glass transition is strongly dependent on the molecular weight of the material. The expression: 1/ Tg = 1/ Tg + K/ DP (7)
Figure 2Relaxation time of sucrose solutions versus (TTg) (Tg DSC). The curve is the WLF prediction (Eq. 2) with Tg=1.6x1012 Pa.s, C1g=19.8, C2g=51.6 K obtained from fitting to viscosity data. Experimental points: for water contents 6-18% DMTA (=1/2f where f is the frequency of the loss modulus maximum at T); for water contents 34.742.5% shear viscosity (=/G where is viscosity and G the elasticity modulus at infinite frequency 4x104 Pa). Data from Champion 1998

where DP is the degree of polymerization, K a constant, Tg the high molecular weight limit of Tg, is used to describe the molecular weight dependence of Tg in an homogeneous polymer series. It has been proved to apply to carbohydrates (Orford and others 1989). For a compatible mixture a single GLT is observed, the temperature of which taking an intermediate value that depends on the mass fraction of components (Tg curve on Figure 5). In food, plasticization (Tg decrease) is mainly due to water, but other small solutes may also act as plasticizers. One among numerous applications is the addition of glycerol to raisins to keep them soft at a low water activity when mixed with cereals. Branching in polysaccharides may work as internal plasticization, inducing a small decrease in Tg when compared to linear chains (Bizot and others 1997). To the contrary, cross-linking is known to strongly raise the glass transition temperature; for instance, calcium tetraborate was found to significantly raise both Tg and T of alginate/poly(vinyl alcohol) blends (Miura and others 1999). The literature is replete with figures showing the variation of Tg (or T) versus water content for food components or real products. The semi-theoretical Couchman and Karasz expression: lnTg = 1n (mi cpi lnTgi) / 1n (mi cpi ) should allow the prediction of Tg from mi the mass fraction, Tgi the glass transition temperature and cpi the increment in heat capacity at Tgi for each component i. However, given the uncertainties in the Tgi and cp i for biopolymers and the somewhat poor agreement with experimental values, particularly when one component is water, the empirical Gordon-Taylor expression is most often preferred: Tg = (m2 Tg2 + k m1 Tg1) / (m2 + k m1) where m2 et m1 are the mass fractions of solid and water respectively, Tg2 and Tg1, their glass transition temperatures and k a fitting parameter. A problem with both relations is that the glass transition temperature of water is still uncertain (Velikov and others 2001), it is sometimes taken as a fitting parameter in the Gordon-Taylor expression. kJ.mole-1, thus showing a total decoupling of the water diffusivity from the macroscopic viscosity. The diffusion was faster in matrices of the oligomeric chains of the glucose syrups than in maltose matrices at equal water content (Tromp and others 1997). Similarly, NMR measurements of the water self-diffusivity did not show any important evolution at Tg. At this point, Dtrans was around 4x10-11 m2.s-1 in pullulan with 19.1% water content (Ablett and others 1993). These results follow the same line as former studies (Bruin and Luyben 1980; Furuta and others 1984), which had shown the water diffusivity varying continuously with water content and exhibiting relatively high values in glassy materials. An heterogeneous distribution of water is sometimes desired in food products, for instance to associate soft and crispy / crackly textures, as in pizza, ice-cream + cone, mixtures of cereals plus raisins. To maintain this texture differential, it is necessary to limit the transfer of water from the soft (moist, rubbery) domain to the rigid (dry, glassy) one. The rate of transfer is proportional to both the diffusivity of water and the difference in water potential (or water activity) between each domain. Water diffusivity remains relatively high even in the glass so that the transfer has to be reduced by means of edible films or barriers. Appropriate formulations of the 2 domains may allow reductions in the difference in (apparent) water activity while keeping the difference in water content and texture. A good example of application of the glass transition concepts to food technology is designing a confectionery with a core rich in fructose within a sucrose envelope. With the same aw the glass transition temperature is higher for sucrose than for fructose. The core (supercooled liquid) can then be soft within the rigid (glassy) coating.
Mobility of solutes
Physical data. In liquid systems well above Tg, the translational diffusion (Dtrans) and rotational diffusion (Drot) of molecules can be predicted from the so-called Debye-Stokes-Einstein
Mobility of water around Tg. multi-domains foods

Experimental results evidence that the mobility of water remains high in glassy food systems. From NMR measurements of the rotational mobility in oligo and polysaccharides, the trends can be summarized as follows (Ablett and others 1993): the water has a higher degree of mobility than the solute, even below Tg; the water mobility at Tg increases with increasing molecular weight of the solute; the higher the molecular weight of the solute, the lower the temperature below Tg at which the mobility of water is observed to begin to increase (also see Figure 6a). The rotational mobility of water in a maltose glass is estimated to be only 10 5 times lower than that of liquid water (Hemminga and others 1999) whereas the viscosity is about 1015 times greater in the sugar glass than in pure water. Figure 6 illustrates the difference in mobility for water (no significant enhancement of the temperature dependence near Tg, mobility increasing with the molecular weight of the solute) and for the matrix (significant enhancement of the temperature dependence near Tg). Similar conclusions can be derived from studies about water translational diffusion (Dtrans or Dapp). The diffusion coefficient obtained from desorption experiments in dried glucose syrups and maltose was shown to follow Arrhenius behavior above and below Tg, with the same apparent activation energy of 60
Figure 3Fragility diagram: Arrhenius representation of viscosity where T is scaled to Tg. From: (a: SiO2 , b: glycrol and h: triphenylphosphite) Angell and others 1994, (c: sucrose) Champion 1998, (d: fructose and e: glucose) Ollett and Parker 1990, (f: maltose) Noel and others 1991, (g: trehalose) Magazu and others 1998. Water content (%) as indicated in the inset. The relaxation time scale applies for sucrose 8%. Vol. 67, Nr. 7, 2002JOURNAL OF FOOD SCIENCE 2447

relations (DSE): Dtrans = kT / 6rc Drot = kT / 8r3 c (7) mers (Blackburn and others 1996; Fujara and others 1992; Hall and others 1998; Le Meste 1995). The values of Dtrans for probes dispersed in polymers are greatly dependent on the probe size and shape (Hall and others 1998). They may also be affected by the existence of interactions such as hydrogen bonds between the probe and the polymer (Hall and others 1999). By contrast, rotational diffusion data, obtained from a variety of techniques, always appear to scale with the matrix relaxation dynamics (excepted when probes dispersed in a polymer are smaller than a minimum size (Hall and others 1998)). The decoupling between translational and rotational diffusions has been explained by the spatial heterogeneity of supercooled materials, comprising domains with varying mobility, both types of motions being differently sensitive to the local variations of relaxation time (Blackburn and others 1996; Fujara and others 1992; Hall and others 1998). The decoupling temperature being in the range where and relaxations merge (Perez and Cavaille 1994), suggests that the translational diffusion of the probe could be facilitated by local motions of the matrix when the temperature approaches Tg (Champion and others 1997b). The practical importance of this decoupling has to be emphasized, with regard to the stability of amorphous products: in the vicinity of Tg, the translational diffusivity may be 2 to 5 orders of magnitude higher than predicted from the viscosity and the Stokes-Einstein equation. The temperature dependence also is much weaker (apparent activation energy =59 kJ.mole-1 for the Dtrans of fluorescein in sucrose below 1.2 Tg).
where k = Boltzmann constant, T = temperature, = viscosity, r = hydrodynamic radius of the diffusant, c = coupling factor between the molecule and the matrix. A relaxation time associated to the translational mobility (D) may be defined as the time necessary for the lateral motion of a structural unit on a distance equal to its characteristic dimension (Perez 1992). With small molecules the latter may be taken as the molecule diameter (2r): D = (2r)2 / Dtrans (8)
The DSE equations are not valid to describe the diffusion of a small solute dispersed in a polymer network where the macroscopic viscosity (commonly measured) does not reflect the local environment of the diffusing species and is not the factor that controls diffusion. The translational and rotational mobilities of small probes dispersed in concentrated sucrose solutions (57.5%) were not significantly affected, or were only slightly reduced, upon addition of respectively 1% or 10% polysaccharides, in spite of the large increase in viscosity (Contreras-Lopez and others 2000). To check the validity of Eq. 7 in systems where the diffusing probe was of a size similar to that of the matrix material, Dtrans of fluorescein was measured in concentrated sucrose solutions (3090%) in a temperature range from -15 to 20 C using the FRAP method (fluorescence recovery after photobleaching) (Champion and others 1997b). The evolution of the fluorescein Dtrans with temperature did follow Eq. 7 when the temperature was higher than 1.2 Tg (Tg / T = 0.86) (Figure 7 and 8 ). The D trans values measured in solutions of various concentrations are all on the same curve, which demonstrates that D trans is effectively controlled by viscosity. When the temperature was closer to Tg, the diffusion of fluorescein was faster than predicted from Eq.7. The decoupling of translational diffusion and viscosity in the same temperature range, (between Tg and 1.2 Tg) had been 1st reported for probes dispersed in various organic liquids or poly-
Ts
Tgs
Cs
Figure 4Arrhenius representation of the characteristic relaxation times for maltitol deduced from viscosity, mechanical and dielectric spectroscopies. Faivre and others 1999 2448
Figure 5State diagram of the sucrose-water system. Tg and Tm indicate the temperatures of glass transition and of equilibrium freezing/melting respectively, versus sucrose mass fraction. Tg=glass transition temperature of the maximally freeze-concentrated phase (here defined as the intersection of curve Tg (DSC Tg onset) and curve Tm (UNIQUAC model). Cs and Tgs=concentration and glass transition temperature of the partially freeze-concentrated liquid when the product is stored at a temperature T s>Tg. From Blond and others 1997

Encapsulation
In the food industry there is a growing interest for encapsulation technologies, which are designed to protect the encapsulated material (or active) and to allow only controlled release. This is particularly the case for flavoring components, which are prone to loss by evaporation, oxidation or ingredient interactions. Although a variety of methods have been proposed to encapsulate flavors, spray-drying and extrusion are still the most common techniques. A great number of studies have been devoted to the retention of aroma during drying, freeze-drying, extrusion, or storage of dried products. It is well known that in favorable conditions, aroma can be retained to a much larger extent than expected from their volatile character (see Flink 1975 for a review). At low water content the diffusion coefficient for organic compounds drops rapidly, even more rapidly than that for water. This selective diffusion process (Thijssen 1971), with some modifications, is generally accepted as the main process explaining the retention of aroma being entrapped in glassy materials (carbohydrates or proteins) (King 1988). Release of volatiles is promoted by temperature and water content conditions that bring the dry glassy material to the rubbery state ( To and Flink 1978; Whorton and Reineccius 1995). The potential interest of glass transition in view of controlled release from glasses was the basis of a patent (Levine and others 1991). The study of release kinetics is complicated by the structure of dried/extruded products and changes induced by plasticization. The release of propanol from freeze-dried sucrose and sucrose-raffinose matrices was shown to increase with (T-Tg) following WLF kinetics with the universal coefficients, in a range of (T-Tg) approximately 10 to 30 C (Levi and Karel 1995b). Actually the release kinetics appeared to be controlled by crystallization (in the sucrose matrix) or by collapse (in the sucroseraffinose matrix). The release of volatiles was also associated with the collapse of spray-dried maltodextrins ( Whorton and Reineccius 1995). Volatiles loss during rehumidification of freeze-dried foods models was interpreted in terms of a diffusion-based model where the web thickness within a sample increases with time because of structure collapse (Omatete and King 1978). The introduction of an effective diffusion coefficient, which should be time-dependent, was suggested to obtain a realistic description of processes above Tg (Karel and others 1993). While the completion of collapse results in a decline of the release rate, crystallization is accompanied by a total loss of the volatiles (Levi and Karel 1995b; Senoussi and others 1995). For flavors encapsulated in carbohydrate matrices by an extrusion process, it was concluded that release (at low water contents) due to diffusion through the matrix was relatively slow as compared to release due to matrix cracking (Gunning and others 1999). With undercooled maltose-water mixtures where a more regular macroscopic structure could be expected, and with steady water content, the release of volatiles could be modeled as a Fickian diffusive process (Gunning and others 2000). Close to the glass transition of the material, the temperature dependence of the apparent diffusion coefficient showed a decoupling from viscosity similar to the one described for probes in sucrose-water mixtures. The dependence on water content of the effective diffusion coefficients of water and ethanol in maltodextrins films could be fitted to the model developed originally by Fujita (1961) from the free volume theory to express the concentration dependence of the diffusion coefficient of a solvent in a synthetic polymer (Furuta and others 1984). However, the comparison of the curve fitting parameters to other data would be necessary.
Edible films and barriers

Edible films and coatings are expected to be concerned by glass transition, as both their mechanical and barrier properties are strongly affected by temperature, ambient humidity and plasticizer content. There is an abundant literature on glass transition temperature of biopolymer films and on the influence of water and other plasticizers. Nevertheless, quantitative data correlating their functional properties to glass transition phenomena are scarce. In an extensive study on polyol-plasticized pullulan-starch blends (Biliaderis and others 1999), the permeability to O2 and CO2 could be fitted to Arrhenius behavior both below and above Tg. The Arrhenius plots showed a distinct break in the temperature range of Tg (DSC) and T (drop in E). The apparent activation energy for permeability (Ea P) was larger above glass transition than below, amounting to 74 to 113 kJ.mole -1; it decreased for increasing water contents. These values, however, are small when compared to the apparent activation energy for the relaxation, which was between 226 and 296 kJ.mole-1. Even smaller values of EaP above Tg were reported for O 2, CO2, and ethylene permeability in gluten films (20 to 56 kJ.mole-1) (Mujica and others 1997). Similar features were described for the permeability or diffusion coefficients of gases in natural and synthetic polymers. Consistent with the predictions from the free-volume theory of diffusion, experimental observations showed that as
Figure 6NMR relaxation time T2 (a) and second moment M2 (b) versus (T-Tg) for freeze-dried maltodextrins (DE 2, 21, 40) equilibrated at a water activity of 0.4. T2 represents the rotational mobility of the more mobile protons (mainly water). M2 is considered to be inversely related to mobility of the less mobile protons (matrix protons + possibly some water protons). Data from Grattard and others 2002 Vol. 67, Nr. 7, 2002JOURNAL OF FOOD SCIENCE 2449

the weight fraction of small molecules increases (for instance, increase in water content in the above examples) the apparent activation energy of diffusion above Tg decreases and the inflexion at Tg becomes less apparent (Duda 1999; Ramesh and Duda 2001). Although the free-volume theory for diffusion allows, at least qualitatively, to explain the temperature and water content dependence of permeability, it should be remembered that permeability (P) is the product of diffusivity (D) and solubility (S) of the diffusant in the matrix: P=DS The activation energy for P is: EaP = EaD + HS where HS is the dissolution enthalpy. Depending on the respective hydrophilic/hydrophobic character of the film and the permeant, EaP may be variously affected. geot and Blond 1991), dried white bread and extruded flat bread (Fig. 9). As a first explanation, the crispness loss was directly related to glass transition (Ablett and others 1986, Slade and Levine 1993, Roos 1995). Crispness is associated with a low-density cellular structure that is brittle and generates a high- pitched noise when fractured. The loss of brittleness was attributed to the drop in rigidity modulus that is characteristic of the glassrubber transition in polymers. Due to the plastifying effect of water, the temperature of glass transition was assumed to be decreased to the ambient temperature where crispness was assessed. A glass transition could indeed be recognized in a real food product such as bread using thermomechanical analysis (TMA) and later DMTA (Le Meste and others 1992, 1996). It was shown, however, that the water content at which the loss of sensory crispness, as well as the brittle to ductile transition observed in mechanical tests, occurred in white or extruded breads, corresponded to a glass transition temperature (T)much higher than the testing temperature (Le Meste and others 1996, Roudaut and others 1998) (Figure 9). Similar results were obtained with corn cakes (Li and others 1998) and with starch extrudates (Attenburrow and others, 1992, Nicholls and others 1995). This most important texture change thus takes place while the material is in the glassy state. It was suggested that it could be best modeled without any relation with glass transition, by empirical expressions such as the Fermi equation (Peleg 1996) (Fig 9). The underlying microstructural events are not elucidated yet. Secondary relaxations are evidenced by DMTA and dielectric spectroscopy below glass transition in dry and extruded breads (Le Meste and others 1996, Roudaut and others 1998, 1999) (Fig 10). It is difficult to definitely relate these features with the texture changes, because the latter result from a variation in water content at ambient temperature, whereas the former are detected in a temperature / frequency scanning at constant water content. The values of tan (DMTA),however were shown to increase from the water content (9%) at which the acoustic emission drop was initiated, which allows to conclude to a significant increase in mobility in the glassy state, coinciding with the crispness loss
Oxidation kinetics
The relatively high mobility of water and oxygen in glassy matrices is responsible for the limited shelf-life of encapsulated materials or dried food products. The permeation rate of oxygen into a freeze-dried (sucrose-maltodextrin-gelatin) matrix was found to show Arrhenius behavior (EaP = 74 kJ.mole-1) below and above Tg and to control the oxidation kinetics of the encapsulated oil (Andersen and others 2000). Evidently, the permeation rate is influenced by the matrix structure (crystallinity, porosity, tortuosity) and the distribution of oil in the case of an emulsion. Glass transition appears to only have a weak direct impact on the diffusivity of small molecules such as gases and water. A number of studies however show that the structural modifications induced by glass transition significantly affect the actual permeation. Crystallization of the matrix was shown to induce the release of the encapsulated oil, thus enhancing its oxidation (Shimada and others 1991). Oxidation of saffron carotenoids and of the beetroot pigment betanin encapsulated in polymer matrices was observed in conditions of water content and temperature where the matrices were glassy, confirming the permeation of O2 in the glass. The lower degradation rates were actually observed when the matrix was collapsed (Selim and others 2000; Serris and Biliaderis 2001). Depending on the experimental conditions, partial or total release of the oil may result from collapse; while the released oil is oxidized, the fraction remaining entrapped appears to be protected (Labrousse and others 1992; Grattard and others 2002). Glass transition knowledge may be beneficial to encapsulation, edible films, and coating technologies by helping to define processing parameters and especially the matrix formulation. More investigations are necessary however, to better understand the mobility of small solutes in glassy and rubbery matrices and particularly the influence of water. Moreover, it must be kept in mind that in practical situations release or permeation kinetics may be affected by events such as collapse or crystallization.
Structure and Texture Texture of low moisture products

Crispness, a popular texture attribute of various low moisture foods, is lost when their water content is raised above a threshold, which was found between 6 to 9% for crackers, popcorn, and potato chips (Katz and Labuza 1981), breakfast cereals (Sauva2450 Figure 7Translational diffusion coefficient (FRAP) of fluorescein in sucrose solutions. The curve is the prediction according to the Stokes-Einstein relation (Eq. 7), with viscosity predicted from the WLF model (parameters in Figure 2 caption). Water contents indicated in the inset. Champion and others 1997b

(Figure 11). The loss tangent increase could result from sub-Tg relaxations becoming possible at 25 C when the water content is raised above 9%, or could be associated with motions just preceding the onset of glass transition ( relaxation) (Roudaut and others 1998). Fracture tests evidence another important event in glassy cereal products: an hardening effect is observed, beginning at about 5% and maximum between 9 and 11% water content with dried and extruded breads, which is also detected in sensory analysis and which is followed by a softening at higher hydration (Fontanet and others 1997, Roudaut and others 1998). Similar observations have been reported for corn cakes (Li and others 1998) and fat-free apple chips (Konopacka and others 2002). It may be noted that similar effects have also been described for starch extrudates (Attenburrow and others 1992, Nicholls and others 1995) and films (Chang and others 2000). The first change in texture could, therefore, be an increase in fracture stress: being less easily fractured, the product is perceived as less crispy (Roudaut and others 1998). This hardening effect was ascribed to antiplasticization (Roudaut and others 1998; Chang and others 2000). The addition of a diluent to a polymer, although decreasing Tg, can hinder the polymer chain motions, resulting in an increased rigidity (Vrentas and others 1988). This antiplastifying effect of water in starch systems has been attributed to a short-range reorganization (Fontanet and others 1997) resulting in a density increase by filling the defects in the glass structure (Benczedi 1999, Chang and others 2000). It is worth noting that this antiplastifying effect was observed under high deformation conditions. Water at low concentration may therefore act as plasticizer under low deformation conditions and as antiplasticizer under high deformation conditions (Chang and others 2000). This imposes important constraints on drying and storage in the dry state of products with a high relative content of low molecular weight solutes such as sugars, minerals, and protein hydrolysis products. Here again, a controlled caking process (or agglomeration) is used to improve the appearance and handling of powders and their dispersion in water. It is well known that the factors controlling structure collapse, stickiness, and caking are temperature and water content and that these processes are time dependent. The collapse temperature of powders (To and Flink 1978) as well as the sticky point (the temperature at which the force to stir a powder in a tube increases sharply) has been shown to decrease when water content increases. During freeze-drying, structure collapse occurs when, as a result of an increase in water pressure for instance, the heat input exceeds the drying needs, inducing a rise in temperature at the sublimation interface. Structure collapse in the course of freeze-drying was shown to happen when the viscosity of the cryo-concentrated phase had fallen to the range of 107 to 104 Pa.s (Bellows and King 1973). Below this limit, the interstitial network could not withstand the collapsing effects of the capillary forces. The same critical viscosity range was shown to determine collapse in freeze-dried materials (Tsourouflis and others 1976). A similar mechanism was proposed to explain caking phenomena: the formation of interparticle bridges between adjacent particles and then aggregation take place when the surface viscosity reaches the critical range 108 to 106 or 107 to 105 Pa.s for sucrosefructose-maltodextrin mixtures or coffee extract respectively (for particle diameters 3 to 4 m and 30 to 40 m respectively and contact time 1 to 10 s.) (Downton and others 1982; Wallack and King 1988). The connection of collapse and caking with glass transition is demonstrated by the parallel evolution of agglomeration temperature and Tg as a function of water content. The sticky point (Ts) and glass transition temperature of the sucrose-fructose mixture model were observed to be similarly affected by increasing moisture content, with Ts close to the Tgend values, that is about 20C above Tgonset (Roos and Karel 1991a). Similar results were reported for the collapse temperature (Tc) of freeze-dried maltodextrins, but with Tc values about 30 to 70C above Tgonset (Roos and Karel 1991b). It must be stressed that the critical viscosity levels, and then the (T-Tg) values are dependent on the characteristic times of the methods used to monitor the changes. The link between collapse and caking and glass transition is further supported by many observations showing that collapse and caking temperatures are raised as Tg is, when the average molecular weight of the product increases, for instance with maltodextrins (collapse) (Tsourouflis and others 1976; To and Flink 1978; Roos and Karel 1991b) or starch addition in powdered soy sauce (caking) (Hamano and Sugimoto 1978). The increase in Tg of sugar solutions following the addition of maltodextrins was reported to be correlated with an increase in drying yield (thanks to the reduction of product sticking on the spray-dryer walls) (Busin and others 1996). Both collapse and caking have been demonstrated to obey WLF kinetics. The collapse of a freeze-dried sucrose-raffinose model, measured by the decrease in specific volume, was reported to change exponentially with time. The relaxation time values could be fitted to the WLF equation with the universal constants, for a (T-Tg) range between 15 and 30 C (Levi and Karel 1995). Caking of a spray-dried fish protein hydrolyzate was also found to follow a first order kinetic model. The temperature dependence of the relaxation time was characterized by a WLF relationship, with adjustable C1 and C2 coefficients, for (T-Tg) beVol. 67, Nr. 7, 2002JOURNAL OF FOOD SCIENCE 2451
Collapse and caking

The changes in mechanical properties related to glass-liquid (or rubber) transition are the governing factors in many food processing operations. Structure collapse of the product during airor freeze-drying, or during the storage of dried products, is responsible for the reduction in volume and porosity, which results in the loss of desirable appearance and volatile substances and in poor rehydration. It is generally considered that structure collapse should be avoided, although it may be credited of some beneficial aspects such as a reduced sensitivity to oxidation. Powder stickiness and caking are phenomena related to collapse.
Figure 8Translational diffusion coefficient of fluorescein in sucrose solutions (Cf. Fig. 7) to show the decoupling of Dtrans from viscosity for Tg/T>0.86. (T/Dtrans =constant when the DSE law is obeyed: solid line). Champion and others 1997b

tween about 20 and 80 C (Aguilera and del Valle 1995). Because of the rather narrow (T-Tg) range, in the 1st example, the C1, C2 values may not be meaningful. What is most important, however, is the high level of the mean apparent activation energy (>200400 kJ.mole -1), which points to the large temperature dependence of the phenomenon. Prevention of collapse or caking is 1st based on low temperature and/or low water content. This means, for instance, cooling the walls of the spray-dryers and the design of towers with dimensions large enough so that the droplets would not reach the walls before being in the non-sticky domain. The beneficial action of anticaking agents, which has been recognized for long, is explained by several mechanisms, the rise in glass transition temperature by increasing the average molecular weight of the amorphous phase being only one of them (Aguilera and others 1995). It may be concluded from the presently available evidence that structural collapse, stickiness and caking/agglomeration, being primarily dependent on flow rate, are successfully explained using the glass transition concept. From the current literature, it appears that these phenomena are never observed in the temperature/water content domain below glass transition. Even in cases where some chemical evolution in the glassy state was reported, collapse could not be observed at T<Tg. Their kinetics can be described based upon the equations characterizing the dynamic properties, such as viscosity or relaxation time, above Tg, although coefficients specific to the product should be determined. The glass transition temperature measured, for instance, by DSC appears to be a good predictive parameter of their domain of occurrence. Some shift above this value may however be observed. The anticaking action based on a physical barrier between particles, cited above, is one example. It has also been shown that addition of small amounts of high molecular weight substances may prevent the collapse during freeze-drying, without changing the DSC Tg (Le Meste and others 1979). 30 C above Tg, viscosity being of the order of 107 to 108 Pa.s under these conditions (Fan and others 1994).
Crystallization
Crystallization is a very important process regarding the quality of food products. Depending on the product, the absence or presence of crystals, as well as their size and shape, are critical factors, for instance to the desired texture properties of confectioneries or ice-creams and for the free flowing characteristics and dissolution of powders. Moreover, crystallization may promote the release of substances entrapped in the glass, for instance water, which will increase the water content of the remaining amorphous phase. Crystallization comprises 2 steps: nucleation and growth. Nucleation is the formation of a crystalline phase in the melt or in a supersaturated/supercooled solution. According to classical nucleation theories, the probability of appearance of nuclei, J, is a function of a thermodynamic and a kinetic terms J = A exp [- (G* + G/ RT] G* is the critical free energy required for the formation of a nucleus of the critical size at a given temperature and concentration. G is the activation energy for transport between the bulk solution and the nucleus. When nucleation occurs at a temperature T close to Tm, G* is very high, resulting in a very low J value. The nucleation probability increases with the degree of supercooling (Tm-T). As T decreases however, the term G becomes dominant, the closer T to Tg, the more nucleation is controlled by molecular mobility. The nucleation rate can therefore be expected to take a maximum value at some temperature between Tg and Tm. The crystal growth rate also depends on several processes that are differently influenced by temperature. Schematically the crystal growth implies, on the one hand, incorporation of growth units into the crystal lattice, on the other hand, transport of these units from the bulk to the crystal interface, surface diffusion to an appropriate site and heat transfer in the reverse way. Whatever the mechanism assumed for the incorporation, the 2 processes involved in crystal growth can be expected to be inversely controlled by temperature, resulting in a bell shaped
Drying and extrusion

The transition between the rigid glass and the viscoelastic supercooled melt has many other applications in food processing, particularly aiming at deliberate structures. Drying of plant products may be carried out with rough initial conditions, allowing an external layer to pass suddenly from the fully hydrated state much above the glass transition to the dry glassy state. This rigid external layer helps in maintaining the original product shape and in developing an internal porous structure favorable to the final drying and to a fast rehydration. With some materials however, this layer may work as an impermeable crust, which can be desirable or not depending on the end-use of the product. The formation and thickness of the crust are controlled by the relative rates of drying and collapse. A predictive model could be proposed, by accounting for viscoelastic deformations and change in Tg during drying (Achanta and Okos 1995). Compression is, on the contrary, used to reduce storage and transport volume of freeze-dried products. Water content and temperature during compression can be adjusted according to the glass transition concepts. In the snack and cereals industry, this knowledge is used to design the operations of flaking, puffing, extrusion-cooking, although published studies are scarce. The expansion during extrusion-cooking was modeled using the WLF variation of viscosity above Tg. The influence of extrusion temperature and initial water content on the final density could be satisfactorily predicted. Simulation showed for instance that bubble growth can start to occur when the temperature is about
2452
Figure 9Glass transition temperature and crispness of extruded flat bread as a function of water content. The solid line is the fitting of Fermi equation to crispness data: P=P0/[1+exp ((w-wc)/b)] where P and P0 are magnitude of crispness, respectively for water content w and in the dry state, wc is the characteristic water content where P=P0/ 2, b is a constant describing the steepness of the transition.

curve with a maximum at some temperature between Tg and Tm. To describe the variation of the overall rate of crystallization as a function of temperature, several semi-empirical expressions were proposed, particularly for polymers, such as the following one (Lauritzen and Hoffmann 1973): K1/n = A exp [-U* / R(T-T)] exp (- N / T T f ) (9) Tg) but also by hampering the incorporation of the growth units in the crystal lattice, an effect depending on the molecular structure of the additives. It is well known that in mixtures of sugars, the crystallization rate is depressed, compared to that of pure materials. In dried products, it is generally considered that crystallization proceeds through nucleation and growth (Saleki-Gerhardt and Zografi 1994), the amorphous state of the freeze-dried samples being checked by X-ray diffraction (Kedward and others 1998). On the contrary, in frozen products all the freezable water has generally been transformed into ice during the freezing stage. The issue is then the coarsening of the ice structure during frozen storage, which is considered to occur through several mechanisms, including accretion, migratory recrystallization (or Ostwald ripening), where differences in the stability of crystals, based on size differences, cause small crystals to disappear and large crystals to grow, and finally isomass rounding, which is also based on differences in stability for surfaces with different curvature radii (Hartel 1998). Several studies with fructose solutions (Sutton and others 1996) and with ice creams (Hagiwara and Hartel 1996) suggested that ice recrystallization was driven by a non-convective diffusion process, as the time dependence of the mean crystal size could be described by the expression: r = r0 + K t1/3 where r is the mean crystal radius, r0 the initial value, K the crystallization rate (Hartel 1998). The temperature dependence of K was checked for WLF kinetics, using a constant temperature (Tg or an arbitrary temperature T0 obtained by fitting). The authors reported the fit of K to WLF kinetics was reasonably good, although recognizing that the range and the number of tested storage temperatures (-20 C to -5 C, that is 14 C to 29 C above
K is the isothermal crystallization rate constant at temperature T derived from the Avrami equation: Xt = 1-exp (- K tn) where Xt is the fraction of the material that has crystallized at time t and n the Avrami index. A is a preexponential constant that includes all terms independent of temperature. N is a constant that was related to the surface energy in the case of polymers, T(=Tm-T) is supercooling, f = 2T / (T+Tm). U* is a constant related to the activation energy for the transport of crystallizing units. T is a hypothetical temperature below which such transport is inhibited and has been found in practice to be approximately 30C below Tg. The transport term in [9] has the form of the VTF expression. For large supercooling, when this term is controlling the crystallization rate, the process can therefore be observed to exhibit VTF / WLF kinetics. Considering a broader temperature range, the interplay between transport and adhesion to the crystal surface is expected to again result in a bell shaped curve between Tg and Tm. The (time-dependent) crystallization temperature (Tcr) in amorphous sugars determined from DSC with a heating rate of 5C/min was reported in a number of studies to be approximately halfway between their Tg and Tm respective values (Roos and Karel 1991a, 1992; Saleki-Gerhardt and Zografi 1994; Gabarra and Hartel 1998). The effect of water was found to be about the same on Tcr and Tg as indicated by a fairly constant value of (Tcr-Tg) (Roos and Karel 1991a). The time to complete crystallization (tcr) in samples of lactose with water content between about 1% and 8% could be fitted to a WLF type equation: Log tcr = log tg + C1 (T-Tg) / (C2 + T-Tg) where the universal values were used for C1 and C2; the time tg was determined by curve fitting (Roos and Karel 1992). The (TTg) range in these experiments was 10 C to 45 C. A LauritzenHoffmann-like fit was found to apply to crystallization rates measured for dry sucrose and lactose with water content about 3% to 7% in temperature ranges between 25 C or 50 C to 90 C or 130 C above Tg (Kedward and others 1998, 2000). This model was also applied to crystallization in a 50% aqueous starch gel (Marsh and Blanshard 1988) and to the retrogradation of waxy maize starch extrudates (Farhat and others 2000). It is generally believed that crystallization over practical time scales occurs exclusively above Tg; however the drug indomethacin was reported to undergo crystallization over a time scale of days or hours down to temperatures 30 C below its Tg, provided the material had been triturated in the glassy state (Yoshioka and others 1994). The possibility of inhibiting the crystallization in dried products by raising Tg through the addition of high molecular weight compounds was explored in many studies. Mixing the crystallizing sugar with other substances effectively reduces crystallization rate, although a connection with a change in Tg can not be demonstrated ( Jouppila and Roos 1994; Gabarra and Hartel 1998). In lactose-trehalose mixtures, crystallization was delayed without any increase in Tg (Mazzobre and others 2001). It is most probable that the additives interfere with crystallization not only by decreasing molecular mobility (connected with an increase in
tan 106
Figure 10Storage modulus (E), loss modulus (E) and loss factor (tan ) for extruded bread with 5% water content showing and relaxations. Measurement frequencies: 5, 20, 40 Hz Vol. 67, Nr. 7, 2002JOURNAL OF FOOD SCIENCE 2453

the DSC Tg, for ice creams; -20 C to -10 C, that is, 25 C to 35 C above Tg for fructose solutions) were too small to allow exact determination of the best model for temperature dependence. Moreover a constant reference temperature appears irrelevant to check WLF kinetics in this situation where the composition of the amorphous phase and therefore its Tg value are variable in the tested temperature range. Actually, commenting on the data for the ice crystal growth in frozen beef, as well as other processes of deterioration in frozen foods, we stressed the point that the temperature dependence of these processes was much too weak to be correlated with the drastic decrease in viscosity above Tg, as a result of the WLF effect associated to ice melting (Simatos and Blond 1991). We suggested that (besides using more appropriate WLF parameters C1 and C2) this discrepancy could be solved using Tg values much lower than Tg. Indeed, to take into account the dilution induced by the melting of ice, the temperature taken as reference (Tg in Eq. 2), should be the variable Tg s (Figure 5) (Simatos and Blond 1993). When added at a rather high concentration to solutions of low molecular weight solutes, polymers induce an increase in the temperature commonly considered as Tg on DSC curves. Evidence has been presented, however, for the onset of molecular mobility remaining close to the glass transition temperature of the small solutes solution (Simatos and others 1995a). Macromolecules (various polysaccharides and gelatin) are commonly added to ice cream mixes as stabilizers as they are known to exert a beneficial effect on the texture of the final product. At the very low concentrations that are used in the ice cream industry, these stabilizers do not induce any visible effect on the DSC Tg values (Levine and Slade 1988; Goff and others 1993; Blond 1994). The main mechanism of the favorable effect of these stabilizers on the sensory properties of texture may relate to the perception in the mouth, either through a change in the viscoelastic properties of the unfrozen phase or any other sensory effect. Stabilizers however have been shown to reduce recrystallization rate in ice creams stored at temperatures above Tg (Caldwell and others 1992; Hagiwara and Hartel 1996). The potential mechanisms suggested to explain this inhibition include: restriction of mobility around Tg (Blond 1994); mechanical limitation of the crystal growth related to rigidity of the freeze-concentrated phase (Muhr and Blanshard 1986; Blond 1988); adsorption of the macromolecules on the crystal surface (Sutton and Wilcox 1998). In stabilized ice creams, there was a general trend where the recrystallization rate increased with increasing (T-Tg) but the data did not fit well WLF kinetics (with constant Tg) (Hagiwara and Hartel 1996). For tyrosinase (Chen and others 1999a) and invertase (Chen and others 1999b) (in PVP matrices with various water contents), the increase in the rate of inactivation as a function of (T-Tg) was much less pronounced. Moreover, inactivation was observed to occur during storage below Tg for a number of systems (Schebor and others 1996; Mazzobre and others 1997; Sun and others 1998; Chen and others 1999a,b; Taragano and Pilosof 2001). Alpha () amylase was more stable in rubbery matrices of lactose or trehalose than in a glassy PVP matrix (Terebiznik and others 1998). The protective efficiency of saccharides, maltodextrins and PVPs does not increase with their respective Tg (Rossi and others 1997; Terebiznik and others 1998). Provided that they remain amorphous above Tg, disaccharides are more protective than expected from their relatively low Tg. The stabilizing effect of sugars may be attributed to specific hydrogenbond interactions between the protein and the sugar replacing water (Crowe and others 1993). Dehydration induced conformational change of poly-L-lysine, from a random coil conformation to an extended sheet one, can be prevented either by immobilization (vitrification) resulting from fast air-drying, or by sufficient interaction with a protectant through hydrogen-bonding. Protection was increased in the order: dextran-sucrose-glucose, opposite to the order of increasing Tg, but the same as for the tightness of hydrogen bonds with the polypeptide, as revealed by FTIR absorption spectra (Wolkers and others 1998). The high efficacy of trehalose, which had been related to its highest glass transition temperature among the tested sugars (Green and Angell 1989), could be associated, in addition, with other properties, such as: restricted mobility above Tg and ability to resist to phase separation and crystallization during storage (Sun and Davidson 1998), higher stability of the disaccharide bond (Schebor and others 1999b), existence of solid state polymorphic forms (Sussich and others 2001).
Chemical reactions
To determine the impact of Tg related phenomena on the chemical stability of foods, investigations have been mainly focused on non-enzymatic browning reactions (Karmas and others 1992; Roos and Himberg 1994; Lievonen and others 1998; Bell and others 1998; Schebor and others 1999a; Craig and others 2001). Studies have also dealt with the hydrolysis of sucrose (in
Chemical stability Proteins

It has been suggested that, to ensure the preservation of structure and activity of proteins in the course of freeze-drying or their long-term storage in the dry state, all that is needed is to maintain the system below its glass transition temperature (Franks 1990). The higher the Tg of the matrix, the better should be its stabilizing effect. Experimental results published so far have only partly verified this hypothesis. It has been shown for various dried enzyme preparations that storage above Tg accelerated the loss of activity. The rate of glucose-6-phosphate dehydrogenase inactivation (in a glucose-sucrose matrix) was reported to conform to the WLF relation (with coefficients C1 12.5 and C2 92 for water content 6% to 7%) (Sun and others 1998). The rate of inactivation of a pectinlyase preparation also greatly increased at temperature above Tg (Taragano and Pilosof 2001).
2454
Figure 11Influence of water content on the loss factor measured at 25 C (DMTA 5 Hz) for white bread ( ) and extruded bread (). Roudaut and others 1998.

low pH media: Schebor and others 1995, 1999b, or by invertase: Chen and others 1999; Kouassi and Roos 2001), aspartame degradation (Bell and Hageman 1994), thiamin hydrolytic cleavage (Bell and White 2000), cleavage of peptide bond and unimolecular dissociation of tetrahydropyran (Streefland and others 1998). From these various works, it can be provisionally concluded that the temperature of glass transition does not constitute an absolute stability threshold and that, above this temperature, the reaction kinetics do not obey WLF kinetics. Almost all of the quoted studies reported finite reaction rates in glassy products. The reaction rate increased with the difference (T-Tg) (sometimes with a maximum above Tg: Bell and White 2000). When the variation of Tg however, was induced by changes in water content, the expected single relationship between the rate and (T-Tg) was not observed (Karmas and others 1992; Roos and Himberg 1994; Bell and others 1998). The reaction rate evolution with temperature was most often described as uniform, of Arrhenius type, even within the glass transition temperature range (Roos and Himberg 1994; Lievonen and others 1998). A break in the slope of the Arrhenius plot in the Tg range was identified by Karmas and others (1992). The apparent activation energies however remained low, even at T>Tg : 50 to 100 kJ.mole-1 (Karmas and others 1992), 130 to 140 kJ.mole -1 (Craig and others 2001). These values are quite smaller than the activation energies commonly observed for dynamical properties in the glass transition range. In some systems, reactions in the glassy state may have been rendered possible by a phase separation, resulting in microregions with a higher water content (and then a lower Tg) than the whole matrix. It should be also noted that in most studies, reactants were mixed together during the preparation step, limiting the need for translational diffusion. A decoupling of reactants mobility from the matrix viscosity may also be an explanation for the occurrence of finite reaction rates at or below Tg. Some observations suggest that the temperature itself rather than the difference (T-Tg) controls the non-enzymatic browning kinetics (Roos and Himberg 1994; Schebor and others 1999a). As was recalled by Karel and Saguy (1991) physical chemistry books state that, for reactions that are influenced by diffusion of reactants, the reaction rate constant kapp may be described by the relation: kapp = kact / (1 + kact / D) where kact is the reaction constant observed in well-stirred solutions, which recognizes the fact that only a fraction of potential reactants coming into contact are activated and can react. D is the diffusivity of the reactants (equal to the sum of the individual diffusion coefficients), is a coefficient depending on a collision distance. Both parameters k act and D are temperature-dependent. The reaction can be fully controlled by diffusion if the reaction constant kact is much larger than D (then kapp D), the temperature dependence is the same as for D (possibly WLF kinetics). In the case of reactions that have a high activation energy (as could be for non-enzymatic browning), kact remains low as long as the temperature is not high enough, and consequently kapp is controlled by activation of reactants rather than by diffusion (k app k act). The temperature dependence is of Arrhenius type. The temperature dependence of the alkaline phosphatase activity in frozen concentrated sucrose solutions represented a favorable situation for modeling according to WLF kinetics (with variable Tgs : Fig. 5) probably because the enzyme exhibits a relatively high kact even in concentrated sucrose solutions and at low temperature (Champion and others 2000).
Microbial stability
Slade and Levine (1987, 1991) claimed that water dynamics related to glass transition may be used instead of water activity (aw) to predict the microbial stability of concentrated and intermediate-moisture food products. From an extensive review of the then available knowledge, Chirife and Buera (1996) demonstrated that these expectations were not supported by experimental evidence. Among the arguments that were presented was the observation that many foods, including fruits, vegetables, and milk, are in the rubbery state for humidity conditions (a w) where these foods are known to be resistant to microbial growth. (T-Tg) values, the difference between a typical incubation temperature of 30 C and the product Tg, were estimated to be between 60 C and 100 C for a w values between 0.60 and 0.85. To the contrary, molds were reported to grow in maize and wheat flour in moisture conditions where the products were likely to be glassy. It was concluded that, although mobility factors, in addition to aw, may be useful for a better prediction of microbial behavior in foods, glass transition concepts do not provide any better alternatives than aw as a predictor for this. More recently, germination of Aspergillus niger spores was observed in starch samples for water content/temperature conditions just above Tg, but not in samples below Tg (Kou and others 1999). More research is needed to specify the importance of molecular mobility and glass transition phenomena in controlling the microbial stability of foods, dealing with different types of microorganisms and substrates, not only spores germination but also growth and metabolic activity.
Conclusion
transition concepts to food technology is the lack of an unique Tg. The reasons for that are related to the influence of the experimental time and of the stress nature. Moreover, the glass transition temperature is not an absolute frontier for molecular mobility. Even mechanical properties allow the observation of some mobility below glass transition, which is in connection with sub-Tg relaxations or physical aging, and which may be of prime importance as regards texture properties of some food products. Transport of small molecules also makes high mobility evident in the vicinity, or below, the glass transition. One should further be aware that the glass transition temperature is not sufficient in itself to characterize the behavior of a material in the GLT range. Other parameters, such as width of the transition, fragility, non-linearity, non-exponentiality, have to be collected for food materials, related to chemical or structural attributes and studied as regards their relevance to food technology issues. These problems, however are not specific to food materials. They have to be also overcome for non-food materials, where GLT and related phenomena have proved to be such useful concepts. More particular to the food area may be difficulties resulting from the extreme chemical and structural complexity of many food products. The ubiquitous presence of water may also be an important factor: the large variations in water content and the specific interactions with other food constituents make special investigations and theoretical models necessary. Moreover, at high water content, GLT is no longer relevant. Based on presently available information, glass transition concepts do not seem useful to predict with confidence the microbial stability of foods; further research is needed to assess the influence of water and solutes mobility for controlling growth and metabolic activity of microorganisms in intermediate moisture foods.
Vol. 67, Nr. 7, 2002JOURNAL OF FOOD SCIENCE 2455
NE IMPORTANT ISSUE HINDERING THE APPLICATION OF GLASS

In situations where visco-elastic properties play a dominant role, GLT based technology has proved truly efficient. Both the Tg (or T ) values and WLF kinetics show good capabilities for the understanding and prediction of the effects of temperature, water content and product formulation and can be successfully used to control texture, processes such as collapse and agglomeration, and various technological operations including drying and extrusion. There are circumstances however, where molecular mobility, which may be under the dependence of GLT in low moisture and frozen products, is only one of the factors that control the evolution kinetics. Crystallization and chemical/biochemical reactions offer good examples where glass transition-linked mobility combined with other concepts can provide a satisfactory understanding of the observed kinetics. Important progress may be expected along this line, however much more experimental work is needed to gain a clearer view on molecular mobility, particularly in the vicinity of Tg and below, and its relationships with secondary relaxations or aging. It seems highly desirable to establish mobility maps for food materials showing the characteristic relaxation time for the different types of molecular motions, as a function of temperature and water content. Improved understanding of mobility in the vicinity of Tg should result from the rapidly growing knowledge on heterogeneity in glasses and supercooled liquids (Sillescu 1999). Recent theoretical developments and experimental evidence are leading to a clearer view on heterogeneity in (chemically homogeneous) glass-forming liquids and polymers. Heterogeneity at the nm scale, connected with the distribution of relaxation times, is being studied by various spectroscopic methods and by experiments with colloidal glasses (Ediger 2000). These studies should particularly help in understanding and predicting molecular mobility immediately above glass transition temperature. More attention should also be given to the behavior in the GLT range of complex food products: respective mobility of individual components according to their molecular size (and other physico-chemical characteristics), different glass transition temperatures for various components resulting from the distribution of water, contribution of possible phase transitions (lipids) to the observed macroscopic behavior, and so on. Glass transition in proteins should deserve further research in the food technology context, particularly addressing the questions of glass transition in frozen products, protective actions in the dry state and plasticizing effects in films of sugars and polyols.
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Authors are with the Laboratoire dIngnierie Molculaire et Sensorielle, ENSBANA. Universit de Bourgogne, 21000 Dijon, France. Direct inquiries to author Simatos (E mail: Denise.Simatos@u-bourgogne.fr).
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