Water sorption and glass transition temperature of spray dried açai (Euterpe oleracea Mart.) juice

Sorption isotherms and glass transition temperature (T_g) of powdered açai juice were evaluated in this work. Powders were produced by spray drying using different materials as carrier agents: maltodextrin 10DE, maltodextrin 20DE, gum Arabic and tapioca starch. The sorption isotherms were determined by the gravimetric method, while the T_g of powders conditioned at various water activities were determined by differential scanning calorimetry. As results, experimental data of water adsorption were well fitted to both BET and GAB models. Powders produced with maltodextrin 20DE and gum Arabic showed the highest water adsorption, followed by those produced with maltodextrin 10DE and with tapioca starch, respectively. With respect to the glass transition temperature, Gordon–Taylor model was able to predict the strong plasticizing effect of water on this property. Both a_w and T_g were used to determine the critical conditions for food storage, at which powders are not susceptible to deteriorative changes such as collapse, stickiness and caking.     

Glass transition phenomena in molasses

Glass transition phenomena were investigated in molasses obtained from five Australian sugar mills. The transition temperatures (midpoint), T_g, ranged from −75 to −35 °C, while the change in heat capacity was from 0.68 to 0.84 J/g⁻¹/°C. The five molasses varied in moisture, sugars and acidity, and this variation affected the T_g. The predicted T_g of the anhydrous form from the models of Fox, Pochan-Beatty-Hinman and Fried, and from a linear model shows that the molasses with the highest moisture gave the lowest transition temperature. The glass transition parameters of anhydrous sucrose, glucose and fructose did not accurately predict the transition temperatures of the molasses.     

Mechanical spectra and calorimetric evaluation of gelatin–xanthan gum systems with high levels of co-solutes in the glassy state

Mechanical properties of gelatin–xanthan gum (XG) mixtures with high levels of co-solutes were examined by dynamic mechanical analysis (DMA). The mechanical spectra of the samples were modeled according to the Williams–Landel–Ferry (WLF) equation/free-volume theory, which requires an entropic lightly cross-linked network. For the α dispersion, E′ and E′′ superposed with the horizontal shift factor a_T, which was temperature-dependent according to the WLF equation; no other secondary dispersion mechanism was detected. The addition of XG to gelatin networks with high levels of co-solutes changed the glass transition temperature (T_g) and kinetics of glass transition and glassy states. In the glassy state, the WLF equation was unable to follow progress in the mechanical properties, which were better described by the Andrade equation. The calorimetric measurements of the gelatin–XG systems were made using a modulated temperature differential scanning calorimetry (MTDSC) to improve the determination of T_g. The samples were exposed to two cooling and heating cycles to provide a controlled recent thermal history in the temperature range of 40 °C to −70 °C. The T_g values of the samples were determined from the second heating cycle in the reversing heat signal. The calorimetric T_g values increased with increasing glucose syrup:sucrose ratio due to increased crosslinking, whereas mechanical T_g decreased with increased XG content due to network formation.     

Effects of methylcellulose,xanthan gum and carboxymethylcellulose on thermal properties of batter systems formulated with different flour combinations

The functionalities of hydrocolloid–flour mixtures in terms of the thermal properties of their resulting batter systems were investigated, and the effects of different thermal processes such as cooking–freezing–thawing (CFT) and freezing–cooking (FC) on thermal properties of the various batter systems were determined in this study. Differential scanning calorimetry (DSC) was used to determine thermal property parameters including gelatinization temperature (T_G), total enthalpies of gelatinization (ΔH_G), glass transition temperature (T_g), melting peak temperature (T_m), and total melting enthalpies (ΔH_m). The different thermal processes did not significantly affect either T_G or ΔH_G of batter systems, but they influenced the glass transition behavior and the ΔH_m of batter systems. The thermal processes also showed different effects on the batter systems containing different hydrocolloids such as methylcellulose (MC), carboxymethylcellulose (CMC), and xanthan gum (XG). The hydrocolloids shifted T_G upwards, depressed T_g, and increased T_m of batters. The effect of these hydrocolloids on glass transition temperature was more pronounced in raw samples (FC process) than in cooked samples and increased with increasing levels of CMC and MC used in the formulations. Batters with MC showed increased ΔH_m for all the thermal processes. CMC only showed significant effect on ΔH_m for cooked samples (CFT process). MC and CMC showed more pronounced effects on T_g for raw uncooked rice- and corn flour-based batters than on raw uncooked wheat flour-based batters. However, this special effect was not obvious in the batters containing 0.2% XG.     

Determining the effects of annealing time on the glass transition temperature of Pueraria lobata (Willd.) Ohwi starch

To probe the effects of annealing time on the glass transition temperature (T_g) and digestibility of Pueraria lobata (Willd.) Ohwi starch, the starch crystal structure and moisture distribution through the components of P. lobata (Willd.) Ohwi starch were investigated. Annealing times of 0, 1, 3, 6, 12 and 24 h were employed to determine the effect of starch T_g using differential scanning calorimetry (DSC) with the support of ¹H low‐field NMR, polarised light microscopy and ¹³C CP/MAS NMR. The T_g values of the starch increased with longer annealing times. The ¹H low‐field NMR results showed that the T₂ relaxation time decreased and starch–water interactions increased as the annealing time increased. Compared with native starch, annealed starch had higher contents of slowly digested starch (SDS) and resistant starch (RS). The starch crystal structure was not destroyed after annealing, but the relative crystallinity percentage increased slightly.     

The effect of starch gelatinization and solute concentrations on T g′ of starch model system

The effect of starch gelatinization on glass transitions in a starch/water model system and how the concentrations of added solutes (sucrose and sodium chloride) affect the glass transition temperatures of the gelatinized starch solution was investigated. The starch suspension samples were heat treated in a Differential Scanning Calorimeter (DSC) under different time and temperature regimes to achieve different degrees of gelatinization. The gelatinization characteristics (onset, peak and end temperatures and enthalpy) and the glass transition values of a potato starch were determined using the DSC. The results showed that the starch concentrations had no effect on gelatinization characteristics and the T_g′ of the gelatinized potato starch but had clearly increased their ΔC_p in the T_g′ region. Annealing at a temperature slightly below the T_g′ of −5 °C, led to maximal freeze‐concentration in the total/partial gelatinized starch and a higher T_g′ value at about −3 °C was obtained. The T_g′ values of the totally gelatinized starch samples were slightly lower than those of partially gelatinized samples. The T_g′ of the gelatinized starch decreased with increasing concentrations of sucrose or sodium chloride. Sodium chloride had a stronger depressing effect on T_g′ than sucrose. © 2000 Society of Chemical Industry     

Annealing of Granular Rice Starches — Interpretation of the Effect on Phase Transitions Associated with Gelatinization

The effects of annealing on phase transitions associated with gelatinization at different moisture contents of an atypical non-waxy rice starch exhibiting a clearer-than-usual glass transition were studied by differential scanning calorimetry. Consistent with observations on synthetic glassy polymers, annealing at temperatures below the glass transition for limited periods caused an elevation of T_g which is attributed to the slow relaxation of the amorphous regions of the starch granules to their equilibrium glassy states. The crystalline regions were significantly affected only after annealing at temperatures above the glass transition, the resulting increase in crystallite melting temperatures and narrowing of the gelatinization range being ascribed to crystal growth and/or perfection. Passage through the glass transition (which precedes crystallite melting) appears to give rise to an apparent endotherm which becomes even more prominent on sub-T_g annealing of samples at low moisture contents. Annealing of an ordinary rice starch (with no clearly discernible glass transition) at a temperature below its onset gelatinization temperature (T₀) produced effects which paralleled those observed after sub-T_g annealing of the atypical rice starch. The conclusion drawn is that a glass transition is superposed on the crystalline melt at the leading edge of the single endothermic peak observed at high moisture contents. Where biphasic endotherms at intermediate moisture levels are concerned, however, the present results suggest that the first or G endotherm very likely arises from a glassy-to-rubbery state transformation while the second or M₁ endotherm is associated with crystallite melting.     

Rheological evaluation of gelatin–xanthan gum system with high levels of co-solutes in the rubber-to-glass transition region

Effects of moisture content, xanthan gum (XG) addition, and glucose syrup (GS):sucrose ratio on the gelation of gelatin-XG systems with high levels of co-solutes were investigated in the rubbery and the glass transition regions. Frequency sweep tests were performed between 0.1 and 100 rad and the storage (G′) and loss (G″) moduli of the system were measured in the temperature range of 60 to −15 °C. The onset of glass transition region increased with decreasing moisture content. The time–temperature superposition yielded master curves of G′ and G″ as a function of timescale of measurement. G″ and G″ were superimposed with the horizontal shift factor a_T, which was temperature dependent according to the Williams–Landel–Ferry (WLF) equation. Glass transition temperature (T_g) of the samples were determined by dynamic mechanical analysis (DMA) from the peak of tan δ. T_g decreased with XG addition. The energy of vitrification of samples with XG increased compared to samples containing only gelatin. Relaxation spectra of the samples were calculated from rheological measurements using the first and second approximations. The Rouse theory was more closely followed with the second approximation.     

Using Dielectric Relaxation Spectroscopy to Characterize the Glass Transition Time of Polydextrose

Dielectric relaxation spectroscopy was used to characterize the glass transition time, t_g, of polydextrose, where the glass transition temperature, T_g, and water activity, a_w (relative humidity), were held constant during polydextrose relaxation. The t_g was determined from a shift in the peak frequency of the imaginary capacitance spectrum with time. It was found that when the peak frequency reaches 30 mHz, polydextrose undergoes glass transition. Glass transition time, t_g, is the time for polydextrose to undergo glass transition at a specific T_g and a_w. Results lead to a modified state diagram, where T_g is depressed with increasing a_w. This curve forms a boundary: (a) below the boundary, polydextrose does not undergo glass transition and (b) above the boundary, polydextrose rapidly undergoes glass transition. As the boundary curve is specified by a t_g value, it can assist in the selection of storage conditions. An important point on the boundary curve is at a_w = 0, where T_g0 = 115 °C. The methodology can also be used to calculate the stress‐relaxation viscosity of polydextrose as a function of T_g and a_w, which is important when characterizing the flow properties of polydextrose initially in powder form.     

Effect of protein concentration on the surface composition,water sorption and glass transition temperature of spray-dried skim milk powders

The effects of dilution of protein content in skim milk (34–8.5% protein content), by lactose addition, on the surface composition, water sorption property and glass transition temperatures of spray-dried powders were investigated. The X-ray photoelectron spectroscopy (XPS) study of spray-dried powders showed preferential migration of proteins toward the surface of the milk particles whereas the lactose remained in the bulk. Sorption studies showed that the lower protein concentration in milk powders is linked to an increased water adsorption property and lowering of water activity (a_w) for lactose crystallization. Analysis of glass transition temperature (T_g) of the powders sorbed at different humidities showed no distinct change in T_g values, indicating the dominant effect of lactose on the glass transition temperature of all the powders.     

Effect of oligomeric or polymeric additives on glass transition,viscosity and crystallization of amorphous isomalt

The main purpose of this study was to further improve the stability of the amorphous state of isomalt by the addition of high molecular weight compounds. Differential scanning calorimetry (DSC) was used to determine the glass transition temperature T_g of a series of polyol mixtures containing isomalt as a function of water content. As expected, for each mixture T_g decreased with increasing moisture. Only with the addition of more than 75% of higher molecular weight compounds to isomalt an increase of T_g could be achieved. Moisture content and time dependent phase transitions in the metastable amorphous state of the mixtures strongly affect the storage stability of isomalt hard candies. Storage tests indicated a markedly accelerated water absorption and crystallization when oligomeric or polymeric compounds were added to amorphous isomalt. Rheological experiments showed that in contrast to pure isomalt melts, the viscosity of melts containing oligomeric or polymeric additives deviated from the model curve predicted by the Williams–Landel–Ferry-kinetics (WLF) with increasing water content.     

The effect of sodium chloride on the glass transition of potato and cassava starches at low moisture contents

The effect of NaCl on the glass transition of cassava and potato starches at low water levels (<20% dwb) was investigated. Sodium chloride (up to 6% of the starch dry weight) was mixed thoroughly with cassava and potato starches using a twin-screw extruder. The samples were equilibrated over saturated salt solutions (LiCl, CH₃COOK, MgCl₂, NaBr, CuCl₂ and NaCl) to give a range of moisture contents. The addition of sodium chloride caused a considerable reduction in the DSC measured glass transition temperature for both starches. For example, the T_g of cassava starch without and with 6% NaCl equilibrated at relative humidity of 11% was 166 and 136 °C, respectively. Similar reductions were found for potato starch. Although the starch sorption isotherms are affected by the addition of salt when T_g is plotted against water content as opposed to relative humidity a T_g reduction on salt addition is still observed. The possible reasons for the plasticization of starch by salt are discussed.     

Physicochemical, mechanical and thermal properties of brown rice grain with various moisture contents

The effects of moisture content on the mechanical and thermal properties of either a short‐grain variety (Akitakomachi) or two long‐grain varieties (Delta and L201) of brown rice were studied. Total starch contents of the three varieties were comparable, but the amylose content of L201 was significantly higher than that of the other two varieties. The maximum compressive strength of brown rice grain was much higher than the maximum tensile strength. L201 showed the highest maximum compressive and tensile strengths. The phase transition temperatures (glass transition temperature T_g and melting temperature T_m) were examined by differential scanning calorimetry. The T_g and T_m for L201 were higher than those for Delta and Akitakomachi. The maximum compressive strength, maximum tensile strength, T_g and T_m for the three varieties of brown rice grains decreased with increasing moisture content. The T_g of individual brown rice kernels decreased from 53 to 22 °C as moisture content increased from 12 to 25% wet basis. A statistical model was calculated by using linear regression to describe the change in T_g in terms of moisture content.     

The glassy state phenomenon in applications for the food industry: Application of the food polymer science approach to structure–function relationships of sucrose in cookie and cracker systems

This review of the glassy state phenomenon in applications for the food industry comprises two main parts. The first is a broad but brief overview of the so-called ‘food polymer science’ approach and its importance to food R&D studies of glassy solid and rubbery liquid states and glass transitions in food products and processes. The following elements of this approach are discussed: (i) the glass transition temperature (T_g) and methods for its measurement in foods; (ii) plasticization by water and its effect on T_g; (iii) the concepts of ‘water dynamics’ and ‘glass dynamics’ in non-equilibrium food systems; (iv) Williams–Landel–Ferry kinetics in the rubbery state above T_g, (v) state diagrams; and (vi) the effect of molecular weight on T_g. A comprehensive and up-to-date listing of more than 400 literature references on the glassy state phenomenon and glass transitions in food materials and systems is featured in that part of the paper, and these references are also compiled and tabulated according to specific subject headings. The second part of this review highlights the application of the food polymer science approach in recently reported studies on the structure–function relationships of sucrose in cookie and cracker systems. This part describes (i) the sucrose–water state diagram as a tool in understanding cookie and cracker baking; (ii) shortcomings of the traditional AACC sugar-snap cookie method as a test-baking system, in contrast to a new test system based on a model commercial-type wire-cut cookie formula; and (iii) a revealing illustration of sucrose functionality in cookie baking. The review concludes with a word about future prospects.     

Physicochemical properties of commercial starch hydrolyzates in the frozen state

The physical properties of commercial starch hydrolyzate (varying in dextrose equivalent values, DE, from 0.5 to 42) solutions in the frozen state were related to their composition. At 20% (w/v) hydrolyzate concentration, an inverse linear relationship between DE and apparent glass transition temperature (T_g′) of the unfrozen solute matrix was observed. The T_g′ temperatures remained relatively constant for solute concentrations below 40% (w/v); above this concentration the T_g′ was depressed, possibly due to the plasticizing effect of additional water entrapped in the glassy state during non-equilibrium freezing. Simple predictive models (based on the Flory–Fox equation; 1/T_g=∑{w_i/T_gi}) were found to predict reasonably well the T_g′ value of ‘binary’ monodisperse and polydisperse hydrolyzate mixtures of varying proportions between the two components. Linear relationships were also found between T_g′_measured (by calorimetry) and T_g′_predicted (based on the Flory–Fox model, and using the oligosaccharide composition of the hydrolyzates and the respective T_g′ values of the pure components). The rate of oxidation of ascorbic acid has been measured in the presence of starch hydrolyzates at temperatures between −4 and −16°C. Both the Arrhenius and WLF (Williams–Landel–Ferry) kinetic models were found to describe the temperature dependence of reaction rate constants reasonably well. However, knowing the T_g′ value of the amorphous maltodextrin was not sufficient to predict its cryostabilization behavior.     

Effect of water uptake on amorphous inulin properties

Physical property changes of amorphous spray-dried inulin were investigated during water uptake at 20 °C. Modulated Differential Scanning Calorimetry (MDSC) and Wide Angle X-ray Scattering (WAXS) were used to investigate the evolution of the glass transition temperature (T_g) and the crystallinity index, respectively. The water content, crystallization and thermal properties relationship enabled the identification of three zones in the T_g–water content state diagram. Zone I delimited inulin in a glassy amorphous state, while zone II characterized inulin in a liquid amorphous state. Inulin crystallized and caked when T_g was below the storage temperature of 20 °C, but crystallization (zone III) was not spontaneous and was delayed by the defined zone II. The crystallization led to thermograms with an endotherm close to T_g. Temperature-Resolved WAXS allowed to correctly ascertain the MDSC endothermic peak as a melting peak because the crystallinity index was maximal at onset temperature of the transition, and dropped to zero at the endset temperature.     

Glass Transition Temperatures Determined using a Temperature-Cycling Differential Scanning Calorimeter

Glass transition temperatures, T_g, of polystyrene, polyvinylpyrrolidone, polydextrose, gelatin, corn flakes, pasta, and aqueous glucose/glycine solutions were determined using a differential scanning calorimeter which cycled the temperature while the net temperature increased at a constant rate. Operating conditions of the modulated differential scanning calorimeter^(tm) (MDSC^(tm)) for optimizing the endothermic baseline shift associated with the glass transition were a scan rate of 5°C/min with an amplitude of ± 1°C over a modulation period of 60 or 100 sec. The MDSC successfully separated the glass transition from other irreversible thermal changes in simple food ingredients. While the MDSC did not distinctly determine T_g of complex food systems at low moisture contents, glass transitions were observed for solutions and food systems at higher moisture contents. T_g values from MDSC were reproducible and similar to those from standard DSC.     

Application of compression test in analysis of mechanical and color changes in grapefruit juice powder as related to glass transition and water activity

Physicochemical and structural properties of grapefruit juice powder were studied as affected by water activity. Powdered juice was obtained by freeze-drying and equilibrated at different water vapor pressure atmospheres in order to give samples with water activity in the range of 0-0.84. The mechanical properties of the powder were measured by confined compression tests and the compressed samples, which presented uniform surface and thickness, were subjected to color analysis. The maximum force attained during the compression tests and the color coordinates could be quantified with good reproducibility. The results were related to water activity and to glass transition temperature. The occurrence of mechanical changes in the powder was shown to precede significant color changes with increasing water activity. Considering the susceptibility to stickiness, the stability limit was observed at T−T_g ≈ 2 °C, with a high degree of mechanical changes being detected at T−T_g ≈ 16 °C, whereas for significant color changes this critical temperature difference was around 32 °C.     

Browning,Starch Gelatinization,Water Sorption,Glass Transition,and Caking Properties of Freeze-dried Maca ( Lepidium meyenii Walpers) Powders

The browning, gelatinization of starch, water sorption, glass transition, and caking properties of freeze-dried maca ( Lepidium meyenii Walpers) powders were investigated and compared with a commercial maca powder. The freeze-dried maca powders had lower optical density (browning) and higher enthalpy change for starch gelatinization than the commercial maca. This resulted from a difference in thermal history. The equilibrium water contents of the freeze-dried maca powders were higher than those of commercial maca at each water activity ( a _w ) because of differences in amorphous part. The glass transition temperature ( T _g ) was evaluated by differential scanning calorimetry. There was a negligible difference in the anhydrous T _g (79.5–80.2 ºC) among the samples. The T _g -depression of freeze-dried maca powders induced by water sorption was more gradual than that of the commercial maca due to a difference in water insoluble material content. From the results, critical water activity ( a _wc ) was determined as the a _w at which T _g becomes 25 ºC. There was negligible caking below a _w = 0.328. At higher a _w , the degree of caking remarkably increased with a large variation depending on the samples. The degree of caking could be described uniformly as a function of a _w / a _wc . From these results, we propose an empirical approach to predict the caking of maca powders.     

Glass Transition and State Diagram for Jujube Powders With and Without Maltodextrin Addition

Both water activity and glass transition concepts were used for stability evaluation of jujube powder in this study. The water sorption behaviour at 25, 35 and 45 °C and the relationship between water content (X _w), glass transition temperature (T _g) and water activity (a _w) were investigated for jujube powder with and without the maltodextrin addition. Moisture sorption isotherms of different jujube powders were of type III and BET model was the best for fitting the experimental data. The equilibrium moisture content of jujube powder containing 20% maltodextrin at a given a _w was lower than that of pure jujube powder. However, temperature had no significant effect on the moisture sorption of jujube powders. Values of T _g of different jujube powders were obtained using differential scanning calorimetry and the glass transition line was fitted to the Gordon-Taylor model. A depression in T _g with increasing water content was observed. State diagrams of different jujube powders were established based on the moisture sorption isotherm and the glass transition curve. Results showed that jujube powders with and without maltodextrin addition were stable at 25 °C when the water content was lower than 0.0673 and 0.0566 g/g solid, respectively.