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Effect of Glass Transition Temperature on Sticky Point and Agglomeration- a review

Shah N
M.Tech (1St Year), College Of Food Processing Technology & Bio Energy, Anand Agriculture University, Anand

This paper emphasized the significance of the glass transition temperature by highlighting its effects on sticky point and agglomeration. The study revealed that the low molecular weight sugar (principal component of fruits) and some organic acids will influence the glass transition temperature of the food. Moreover, glass transition temperature is an important parameter for determining the optimum processing conditions to dry the products. In general, Tg affects the physical properties of food such as stickiness, caking and agglomeration. The effect of moisture content on glass transition temperature was covered by almost all studies focusing on Tg of foods. In term of test methods for determining the glass transition temperature of foods, it seems that not all test methods are suitable for certain type of foods, accordingly, more study on the recommended test methods should be carried out. Keywords: Glass transition temperature (Tg), Water activity (aw), Agglomeration, Sticky point

Phase transitions govern changes in the physical state of materials. In foods, they are important in determining the physical state during processing, storage, and consumption (Roos & Karel, 1991; Roos, 1995). In various food and biological materials the solids may be in an amorphous metastable state which is very sensitive to changes in temperature and moisture content. This amorphous matrix, which may be formed of food polymers and other food components, such as sugars, may exist either as a very viscous glass or as a more liquid-like rubber. The change from the glassy to the rubbery state occurs as a second-order phase transition at a temperature known as the glass transition temperature (Tg). In recent times, the importance of the rubber to glass transition and the development of the glassy state became widely appreciated in understanding and controlling the quality of materials (Allen, 1993; Shalaev & Franks, 2002). Agglomeration Agglomeration is basically a physical phenomenon and can be described as the sticking of particulate solids, which is caused by short-range physical or chemical forces among the particles themselves as a result of physical or chemical modifications of the surface of the solid. This phenomenon is triggered by specific processing conditions, or binders and substances which adhere chemically or physically on the solid surfaces to form a bridge between particles

(Pietsch,2003). According to this definition, even caking of moisture-sensitive raw materials during storage can be regarded as a kind of undesired agglomeration. Agglomeration has many applications in food processing and major applications include easy flow table salt, dispersible milk powder and soup mix, instant chocolate mix, beverage powder, compacted cubes for nutritional-intervention program, health bars using expanded/puffed cereals, etc. The main purpose of agglomeration is to improve certain physical properties of food powders such as bulk density, wettability, flowability, dispersability, and stability (K. Dhanalakshmi, 2011). Sticky Point Sticky point can be defined as a state after glass transition where particles become sticky from rubbery behavior. And the temperature at this point is called sticky point temperature (Ts) which is always higher than the glass transition temperature. To overcome the problem of stickiness during drying of fruit juices due to low Tg value, additives having high Tg such as isolated protein or maltodextrin can be added. To improve the handling properties of the powders, food grade anti-caking agents (e.g., tricalcium phosphate, silicon dioxide, silicates, phosphates, salts of stearic acid and modified carbohydrates) are also often added together with the drying ingredients (Peleg and Hollenbech 1984; Roos and Karel 1991a; Slade and Levine 1991; Roos 1995; Bhandari et al. 1997; Jaya and Das 2005; Jaya et al. 2006).

Method of Measurement
Glass transition characterization methods are as follow: Differential Scanning Calorimetry [DSC], B. Modulated Differential Scanning Calorimetry [MDSC], C. Dynamic Mechanical Thermal Analysis [DMTA], D. Rheological Determinations And Thermal Mechanical Analysis [TMA], E. Thermal Mechanical Compression Test [TMCT], F. Dielectric Thermal Analysis [DEA]), G. Nuclear Magnetic Resonance [NMR], And H. Electron Spin Resonance [ESR]

A. Differential Scanning Calorimetry [DSC]:

DSC detects the change in heat capacity occurring over glass transition temperature range. DSC determines the enthalpy and temperature changes between a sample and reference during the phase and state transitions. An empty, sealed aluminum pan is used as a reference in each experiment. A common procedure for DSC determinations involve a thermal scan of a small quantity (*10 mg) of food over a selected temperature range, dependent upon the food composition and water content. Calorimetric or spectroscopic techniques have some limitations in terms of sample size and shape, and water content control. In some cases, for example in case of starch it is less sensitive.

B. Modulated Differential Scanning Calorimetry [MDSC]: Modulated differential scanning calorimetry (MDSC) is an extension of conventional DSC. Modulated DSC is more sensitive in the detection of glass transition temperatures than conventional DSC, due to the rapid heating rate produced by sine wave modulations. The underlying principle of MDSC is that sine wave modulations deconvolute the total heat flow to reversible heat flow events related to heat capacity and non-reversible heat flow signals related to irreversible events during heating. The experimental protocol involves thermal scanning of a food over a selected temperature range similar to DSC experiments. Dynamic Mechanical Thermal Analysis [DMTA]: At temperatures near to or greater than the glass transition temperature, the solid state is transformed to a supercooled liquid state with rapid time-dependent flow. In DMTA, sinusoidal oscillatory strain or stress input is applied in foods, and the resulting stress or strain is determined. DMTA describes the viscoelastic characteristics of food materials by determining the storage modulus, loss modulus and mechanical loss factor.

D. Thermal Mechanical Analysis [TMA]: Softening or loss of mechanical rigidity of low-moisture solids during state transitions of food systems may be determined by a thermo-mechanical analyzer (TMA). TMA is a simple and relatively inexpensive methodology. In TMA, changes in physical dimensions (volume, length) of the foods under non-oscillatory stress are recorded as a function of temperature and time during temperature scanning. TMA provides greater sensitivity than DSC in recognizing state transitions of amorphous and semicrystalline food components. Disadvantages of TMA include water loss during sample preparation and heating, difficulty in controlling the heating and cooling rates, and inaccuracy in assigning glass transition temperatures in porous foods.
E. Thermal Mechanical Compression Test [TMCT]:

Glass transition characterization is carried out in a thermally controlled cell using a thermal compression test in creep mode, where food is subjected to a constant compression force while it is heated, and the probe displacement is determined as a function of temperature. At the glass to rubber transition, a sudden increase in displacement is observed. The TMCT was tested with the standard DSC, DMTA/TMA techniques, using skim milk powder adjusted to water contents in the range of 25% (kg water/kg dry solids). The method was found to be accurate and sensitive for the determination of the glass transition temperatures in selected food powders. F. Dielectric Thermal Analysis [DEA]: The DEA/DETA method determines the relaxation behavior of a food system as it is subjected to a temperature scan over a selected polarizing frequency range. The dielectric cell used in DEA/DETA varies dependent on the application and material of interest. Experiments are performed with a dielectric analyzer. G. Spectroscopic (Nuclear Magnetic Resonance [NMR]:

Nuclear magnetic resonance (NMR) is a spectroscopy technique based on the magnetic properties of atomic nuclei and is used to detect molecular motion by determining the relaxation characteristics of the NMR active nuclei, such as 1H, 2H, 3H, 13C, 17O, 23Na and 31P. Using 1H NMR, the mobility of water was examined with respect to the Tg. H. Electron Spin Resonance [ESR]: Electron spin resonance (ESR) spectroscopy is a good method for the study of molecular motion in biological glasses and provides information on the rotational mobility of dissolved spin probes. The rotational mobility of the probes is expressed in the rotational correlation time. ESR is closely related to nuclear magnetic resonance spectroscopy. The use of ESR for observation of state and phase transitions in food systems is limited.

Review of Literature
Glass Transition The molecular mobility of the molecules within an amorphous matrix increases with increasing temperature. Thus, the previously rigid glass-like substance is becoming first rubbery and later viscous-plastic (Roos and Karel, 1991b). During this transition the liquid-like (viscous) properties are more and more dominating over the solid-like (elastic) texture components. This change is called the glass transition (Slade and Levine, 1991). Glass Transition Temperature Glass transition temperature is the temperature above which hard amorphous solids will transform into soft, rubbery materials due to increase in mobility/decrease of viscosity. As the temperature is increased above glass transition temperature, various properties of the materials may change, like an increase in the molecular mobility and a decrease in the viscosity, often resulting in a crystallization event of the added solute increasing also food deterioration (Gallegos Infante et al., 2005; Roos, 1995; Shah and Schall, 2006). Therefore, the Tg determines the product stability during storage (Katkov and Levine, 2004). Effect Of Glass Transition Temperature On Agglomeration And Sticky Point In case of fruits, Principal components present are low molecular weight sugars and some organic acids. They have low glass transition temperature (Tg) as shown in the graph fig.1.1 and are very hygroscopic in their amorphous state, so the dry product becomes sticky. Water acts as a plasticizer and decreases the glass transition temperature of the product with the increase in moisture content and water activity as shown in fig.1.2. To overcome this problem, ingredients having high glass transition temperature (Tg) value, such as maltodextrin, and food grade anticaking agents were added to prepare vacuum dried fruit powders. The relationship between T g

and a w provides a simple method for prediction of safe storage temperature at different relative humidities environment.

Fig.1.1 Trend of glass transition temperature with molecular weight

(Fitzpatrick, 2007) in his study, produced food powders namely, mango, pineapple, and tomato (34% w.b. moisture content) by mixing with maltodextrin and tri calcium phosphate at predetermined levels before drying. Glass transition temperature of the fruit powders were interpreted in terms of the Gordon-Taylor model for verification. Glass transition and sticky point temperatures were compared by plotting them in a graph against moisture content fig.1.3.

Fig.1.2 Effect of temperature on water activity (J.J. Fitzpatrick, 2007)

Fig.1.3 Comparison of glass transition and sticky point temperature with respect to moisture content

Amorphous, noncrystalline solids are typical of low water content in frozen foods. Solids in these foods, e.g., confectionary, dehydrated foods, cereal foods, and frozen foods, often form nonequilibrium glass-like structures. The glassy state of the solids forms during food processing in a reversible glass transition. Vitrification can occur in numerous glassy states that exhibit various relaxations around the glass transition. The success of freeze drying, spray drying, and extrusion and the stability of dehydrated foods against flow, collapse, and crystallization is based on the control of the glassy state during the dehydration process and storage. Encapsulation processes often use glass-forming materials to entrap dispersed components or improve retention of volatiles. Plasticization of the noncrystalline structures by temperature or water reduces relaxation times exponentially above the glass transition, which results in rapid deterioration. Critical values for water activity and water content express the level of water plasticization leading to glass transition in food storage. In spray drying, Turchiuli et al.(2011) predicted the evolution of drop water content along drying from the measurements of air temperature and relative humidity, at different positions in the dryer. With knowledge of product properties (temperature, water activity, and glass transition temperatures) it was possible to determine regions in the chamber where particles were possibly sticky for agglomeration with other particles. Spray drying consists in atomizing a solution into liquid drops in a hot air flow to get dry solid particles after solvent evaporation. The convective drying at the drop surface leads to a very fast evolution of temperature and water content due to initial high differences of temperature and water vapour pressure between the drop surface and the drying air. During drying, the drop surface viscosity increases due to potentially amorphous polymers reaching a rubbery state. The drop surface becomes sticky with consequences on wall deposit. This sticky behavior which appears in the range of 10 to 30 C above the glass transition temperature (Tg), may be utilized in a positive way for agglomeration of drying particles with dry powders, either recycled fines or new dry powder, to improve instant properties.

The evolution of water content of drops along drying is deduced from measurements of air temperature and relative humidity, at different places in the dryer and used to predict the drying and sticky behavior of two maltodextrin solutions (DE12 and DE21) with different glass transition temperature (Tg). The introduction of dry particles at different places in the chamber allowed validating the method to control agglomeration.

1. Conclusion
Glass transition concept allows to understand agglomeration and stickyness which is dependent on water content (moisture content/water activity)/temperature and time combination. The summery of this study puts forward that, the glass transition temperature is directly proportional to molecular weight of particles and temperature. As the temperature increases, water activity decreases which lead to increase in glass transition temperature so the rubbery and sticky state will be delayed which impart better storage stability and flow properties. While agglomerating amorphous powders it is important and useful to consider the impact of temperature, moisture and agglomeration time.

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2nd Mercosur Congress on Chemical Engineering 4th Mercosur Congress on Process Systems Engineering CALORIMETRIC STUDY AND ADSORPTION ISOTHERMS OF FREEZE-DRIED TOMATO TREE (Cyphomandra betacea (Cav)Send) JUICE Carlos E. Orrego-Alzate1*, Gloria I. Giraldo-Gmez1, Mara E. Gonzlez-Jimnez1 1Departamento

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