RECOVERABLE WORK VERSUS ASYMPTOTIC RELAXATION MODULUS IN AGAR,CARRAGEENAN AND GELLAN GELS1

Cylindrical specimens of agar, carrageenan and gellan gels (1&2%) were uniaxially compressed to various predetermined strain levels and then decompressed. In an independent set of tests, specimens of the same gels were compressed to the same strains and then allowed to relax. Both the percent recoverable work, calculated from the stress-strain relationships in the compression-decompression cycles and the magnitude of the asymptotic relaxation modulus, calculated from the normalized and linearized relaxation curves, decreased as the strain increased. In all three gels there was a linear correlation between the percent recoverable work and the magnitude of the asymptotic modulus at corresponding strains, a sign that both parameters are indicative of these gels’ degree of elasticity and the latter's strain dependency.     

Stress relaxation behaviour of high acyl gellan gels

Stress relaxation behaviour of high acyl gellan gels has been investigated, and data were fitted successfully by a seven elements empirical model and a four term modified Maxwell model with three fixed relaxation times (20, 200 and 2000 s). In addition, the effect of testing parameters on stress relaxation characteristics and the relationship between those characteristics and intrinsic gel properties were studied. High acyl gellan gels were tested in stress relaxation with different cross‐head speeds (0.1–10 mm s^?1) to applied strains (3–30%). The results showed that the cross‐head speed had little effect on stress relaxation behaviour of gels. With increasing the applied strain, the initial stress and the equilibrium stress increased. The equilibrium stresses from relaxation measurement were positively related to the hardness from TPA tests (R² = 0.991). Relaxation appeared to be associated with the shifting of cross‐links in the gel matrix.     

Polymer and Ion Concentration Effects on Gellan Gel Strength and Strain

Failure stresses and strains were measured in compressive, tensile and torsional modes on gellan gels at four polymer (0.6–1.8% w/v) and seven Ca⁺⁺ (1.5–60 mM) concentrations. Shear stresses at failure were equal in all three testing modes and proportional to gellan content. Low calcium gels increased linearly in strength with Ca⁺⁺ concentration until it reached a level of about 0.5 calcium ions per repeat tetrasaccharide unit of gellan gum polymer. Gel strength decreased linearly with Ca⁺⁺ at higher concentrations. Low calcium gels were extensible with failure strains decreasing as the logarithm of Ca⁺⁺; whereas high calcium gels were brittle and failed at a constant strain, the value of which was twice as high in compression and torsion as in tension.     

Aeration of model gels: Rheological characteristics of gellan and agar gels

Model food sols containing gellan and agar at different solid concentrations were aerated. The rheological characteristics of the setted gels were determined. These were the compression characteristics (fracture strain/stress/energy, firmness and the total energy for compression) and the stress relaxation characteristics (extent of relaxation and relaxation time). Fracture strain of gels increased due to aeration indicating that the aerated samples exhibited a delayed fracture due to the presence of incorporated air. The extent of increase in fracture strain for aerated agar gels over the corresponding non-aerated samples is 1.7-23.1% while it is 4.3-15.1% for gellan gels. The extent of relaxation increased due to aeration while relaxation time (λ) decreased. Relaxation time for aerated agar and gellan gels is 9.6-40.7% and 19.6-37.6% lower than the non-aerated samples. At a low concentration of hydrocolloid, the effect of aeration was usually non-significant (at p ? 0.05) while prominent changes in rheological behaviour occurred at a high concentration. Aeration of food gels offered the possibility of rheological modifications to suit the consumer requirements in developing specialty fabricated gels.     

Effect of addition of sucrose and aspartame on the compression resistance of hydrocolloids gels

The effect of adding sucrose (5–25% w/w) and aspartame (0.04–0.16% w/w) on the compression resistance of three hydrocolloid gelled systems: κ‐carrageenan, gellan gum and κ‐carrageenan/locust bean gum at three different concentrations (0.3, 0.75 and 1.2% w/w) was studied. Sucrose addition increased true rupture stress in the three‐gelled systems, this effect being stronger in gellan gels. The deformability modulus increased with sucrose concentration in gellan gels, but not in the other systems. Rupture stress and deformability modulus increased with the addition of sucrose only in the harder gels (0.75 and 1.2% w/w). The effect of sucrose addition on the true rupture strain was significant but, in general, not important, mainly for lower gum concentrations. Aspartame addition did not affect the compression parameters.     

Compressive textural attributes, opacity and syneresis of gels prepared from gellan, agar and their mixtures

Gellan, agar and their mixed gels at an equal proportion of both were subjected to uniaxial compression to determine the textural attributes including fracture characteristics, opacity and syneresis. An increase in concentration of hydrocolloids increased opacity but decreased syneresis. Highly transparent gellan gels with opacity less than 8% were obtained; opacity of agar gels was highest, and was between 5% and 30% for their mixed gels. Syneresis as low as 1.5% was observed with the mixed gel containing 2% each of agar and gellan. The maximum stress and energy for compression increased with the level of gelling agents while instantaneous relaxation in height decreased. Binary combinations or mixed gels containing agar and gellan can provide unique textural and physical characteristics like syneresis and opacity.     

THE RHEOLOGICAL PROPERTIES of RICE GRAIN

For rice kernels uniaxial compressive modulus function, the time-temperature and time-moisture content shift factors, the bulk compressive creep modulus, the uniaxial compressive stress relaxation modulus, and the uniaxial compressive failure stress were experimentally determined, while the shear modulus and Poisson's ratio were calculated from the available experimental data.
Uniaxial compression tests were carried out at deformation rates of 0.254.0.0508 and 0.0127 cm per min for five temperatures in 11C increments from 25 to 69C for each of the four moisture levels of 12, 17, 22 and 29% (d.b.). Stress relaxation and bulk compression tests were performed at the same four moisture levels and at the temperature of 25C.
Master curves for uniaxial compressive modulus and failure strength were developed as functions of reduced time where the temperature and moisture effects were transformed to equivalent time effects by the method of reduced variables. the brown rice kernel was found to have only one time-temperature and one time-moisture shift function showing that the material is thermo- and hydro-rheologically simple.     

Compression resistance,sweetener's diffusion and sweetness of hydrocolloids gels

The effects of the type and concentration of two hydrocolloids—κ-carrageenan and gellan gum—and of the type and concentration of two sweeteners—sucrose and aspartame—on the gel resistance to compression, on the sweetener diffusion and on the intensity of the gel sweetness and the relationships between the gel physical properties and their perceived sweetness were studied. The gels true rupture stress increased with hydrocolloid concentration, this increase being higher for gellan gels. Gellan gels showed lower true rupture strain values, which in contrast with carrageenan gels, decreased on increasing hydrocolloid concentration. The addition of sucrose produced a bigger increase in gel strength at the higher hydrocolloid concentration. The main effect detected on the sweeteners’ diffusion constant was the higher value observed in low concentration (3 g L⁻¹) κ-carrageenan gels. Gellan gels were perceived as sweeter than κ-carrageenan gels. The decrease in sweetness due to an increase in hydrocolloid concentration was greater in gellan than in carrageenan gels. Variations in sweetener concentration, true rupture strain, and deformability modulus values explained 93% of the variability in sweetness for gels with sucrose and 94% for gels with aspartame.     

Sensory quality of low-sugar orange gels with gellan, xanthan and locust bean gums

Effects of reducing the sucrose content (from 55 to 30 ^°Brix in the final product) and of the use of gellan gum or a mixture of gellan, xanthan and locust bean gums (3:1:1) on the mechanical characteristics (maximum rupture force and deformation at rupture) of orange gels prepared with 15% w/w fruit pulp, sucrose and different amounts of hydrocolloids (0.25, 0.4, 0.55 and 0.7% w/w) were studied by uniaxial compression. The concentration of aspartame needed to compensate for sweetness loss was determined by a paired-comparison constant-stimulus method. Sensory characteristics (texture, appearance and flavour) of low-sugar orange gels (30 ^°Brix) with 0.5% w/w aspartame and different amounts (0.55 and 0.7% w/w) of gellan or the mixture of gums were analysed by the free choice profile method in comparison with the high-sucrose reference material (55 ^°Brix and 0.4% w/w gellan). Use of the mixture of gums permitted the obtention of low-sugar orange gels showing mechanical characteristics similar to those of the reference gel, though some differences in texture were perceived. The low-sugar gels were slightly lighter in colour and slightly more bitter and refreshing than the reference sample. Received: 29 November 1995/Revised version: 13 May 1996     

Rheological properties of cereal starch gels and Mesona Blumes gum mixtures

The effect of Mesona Blumes gum (MBG) was examined on steady and dynamic shear of MBG/rice starch and MBG/wheat starch gels. In addition, stress relaxation and creep tests were performed for two types of cereal starch gels. The flow curves of both MBG/starch gels exhibited pseudoplastic behavior at shear rates between 0.01 and 10 s⁻¹, and the data were fitted into the power law model (R² = 0.91–0.98). Dynamic mechanical spectrum showed that all gels were strong gels in frequency between 0.1 and 10 Hz. Stress relaxation data at different strains indicated a strain‐softening phenomenon for both gels. Data were fitted into Maxwell model (R² = 0.91–0.98). Creep curves were conducted at the shear stress 6.4 Pa within linear viscoelastic region of both MBG/starch gels. Data were fitted into Burgers model (R² = 0.91–0.98). Apparent viscosity η, storage moduli G′, equilibrium stress relaxation modulus G_e and zero apparent viscosity η₀ of MBG/rice starch gels decreased in the following order: 6/0>6/0.5>6/0.35>6/0.1 (starch/gum w/w). Whereas η, G′, G_e, and η₀ of MBG/wheat starch gels increased gradually along side the increase of MBG contents. The stress relaxation time λ of MBG/rice starch gels increased in the following order: 6/0<6/0.5<6/0.35<6/0.1 (starch/gum w/w) while λ of MBG/wheat starch gels decreased gradually with the increase of MBG level. The influence of MBG on two examined cereal starch is totally opposite.     

ASSESSMENT OF COHESION IN GRUYERE-TYPE CHEESE BY RHEOLOGICAL METHODS

The quantitative assessment of cohesion in unripened hard cheese was studied using static methods (uniaxial compression and tension, 3-point bending, and cutting) and transient methods (stress relaxation and creep). The two levels of cheese cohesion (denoted as weak and strong, according to the judgement of the cheesemaker) were obtained by two different manufacturing procedures. Statistical analysis showed that all static methods can be used to discriminate various levels of cohesion. Uniaxial tension proved to be the most powerful test to assess quantitatively the cohesive properties of hard cheese since the values of all parameters (fracture stress, fracture strain, work to fracture, modulus of deformability, and apparent flow modulus) depend significantly (α < 0.01) on the level of cohesion. Stress relaxation and creep tests were not as powerful as the rapid static methods in distinguishing the two levels of cheese cohesion.     

RHEOLOGICAL BEHAVIOUR OF BUTTER AT LARGE DEFORMATIONS

Eleven traditionally produced butter samples were evaluated for rheological properties at large deformations by lubricated and nonlubricated uniaxial compression with varying sample geometries and compression rates, by stress relaxation in shear and creep experiments in compression at 5–20C each. Compression forces required to deform cylindrical samples in nonlubricated conditions were higher than in lubricated cases. Correction of shape changes in nonlubricated stress-strain curves resulted in good agreement with lubricated experiments at low compression rates up to stress maxima or yielding. As frictional forces were relatively smaller at high deformation rates, lower stresses were obtained in nonlubricated conditions. Samples with higher height/diameter ratios showed more pronounced stress maxima. A biaxial extensional viscosity, η be , was computed for nonbrittle, soft samples. Typical slopes in logarithmic plots of viscosity against strain rate were approximately -1. At strains of about 0.01 creep compliance depended on compression stress. The average ratios of recovered to initial instantaneous compliance were between 0.31 and 0.59, and increased with sample temperature. A calculated ηBE from creep compression showed fair agreement with ηBE from static compression experiments. At comparable strains, a conversion of creep compliance to the stress relaxation modulus by an approximate method showed a good fit of experimental results.     

COMPARISON BETWEEN PROJECTED MECHANICAL EQUILIBRIUM CONDITIONS OF SELECTED FOOD MATERIALS IN STRESS RELAXATION AND CREEP1

Asymptotic modulus versus strain relationships in stress relaxation tests of potato flesh, cheddar cheese and 1.5% agar gels were compared to similar relationships derived from creep experiments. The asymptotic moduli (or compliance reciprocals) were on the same order of magnitude and their dependency on the strain of a similar character. These suggest that despite the history sensitive response of food materials, their mechanical equilibrium conditions are governed by the same structural features.     

Sweetening power of aspartame in hydrocolloids gels: Influence of texture

Equivalent sweetness of aspartame relative to two sucrose concentrations (10% and 20% w/w) were determined in water and in hydrocolloids gels. The influence of the texture of three hydrocolloids gelled systems—gellan gum, κ-carrageenan, and κ-carrageenan/locust bean gum (LBG)—at two gums concentrations (0.3% and 1.2% w/w) on the equivalent sweetness of aspartame were then studied. For the three gelled systems, the increase in hydrocolloid concentration produced a significant increase in the true rupture stress and in the deformability modulus values. For both κ-carrageenan and mixed gels the true rupture strain values increased when increasing hydrocolloid concentration while for gellan gels, decreased. For the same hydrocolloid concentrations the κ-carrageenan/LBG gels showed the largest strain at rupture and gellan gels the smallest (most brittle). For both soft (0.3% gum) and hard (1.2% gum) gellan gels and κ-carrageenan gels, the concentrations of aspartame needed to deliver a sweetness intensity equivalent to that of gels with 10% sucrose (0.079–0.087% w/w) were similar to those obtained for aqueous solutions (0.084% w/v). For hard κ-carrageenan/LBG gels the corresponding concentration of aspartame was slightly lower. For all gelled systems the concentrations of aspartame needed to deliver a sweetness intensity equivalent to that of gels with 20% sucrose were higher for soft gels than for hard gels.     

Relaxation Time Spectrum of Hydrogels by CONTIN Analysis

CONTIN is a general-purpose program for inverting noisy linear algebraic and integral equations by means of inverse Laplace transform. This study explored the application of CONTIN analysis to determine the relaxation time distribution spectra for food gels, including gellan, carrageenan, whey protein, and gelatin gels, based on stress-relaxation data. CONTIN results represent the continuous relaxation time spectra when the number of the terms in the discrete Maxwell stress-relaxation model approached infinity. The CONTIN results for gellan gels were correlated to the texture properties of gels from compression tests with respect to the effects of calcium concentrations. CONTIN analysis may be a very effective tool in elucidating the microstructural properties of a hydrogel from mechanical testing.     

Rheological characterization of fresh and cooked potato tissues (cv.?Monalisa)

 The rheological properties of fresh and cooked (15 min in boiling water) potato tissue which had been deformed to a lessor or greater extent by uniaxial compression, shear, uniaxial tension, successive cycles of stress relaxation, creep compliance and texture profile analysis were evaluated. Structural failure of fresh tissue under compression always occurred along a single plane of maximum shear stress, while fresh tensile specimens failed under tension. Tensile tests proved better methods by which to determine the failure parameters of cooked specimens since it was possible to observe two differents modes of failure with this technique. Equivalent modes of failure (causing damage to the cell wall or cell separation) and changes in structural components caused by cooking proved easier to idetify with tensile tests. The six element Burger's model incorporating two discrete Voigt-Kelvin units was the most suitable for defining tissue creep behaviour. The instantaneous elastic modulus could be related to the internal cell pressure, and gelatinization of starch and viscoelastic units appeared to reflect the viscoelastic properties of pectic sustances and hemicelluloses, respectively. Received: 1 December 1997     

Gelling Temperatures of Gellan Solutions as Affected by Citrate Buffers

Effects of citrate buffers at pH 3.5 and 5.0 on gelling temperatures of gellan solutions with 0.4–1.8% gellan and 1.5–60 mM Ca²⁺were studied. Partial dissociation of the carboxyl groups in gellan polymer in pH 3.5 solutions resulted in weakened gels. The pH 3.5 buffer exhibited weak chelating ability for Ca²⁺. The gelling temperature of gellan solutions at pH 3.5 was quantitatively related to polymer and cation concentrations using a similar model to that for gellan water solutions. The pH 5.0 buffer exhibited strong chelating ability. Gelling temperatures at pH 5.0 were generally lower than those at pH 3.5, except at low calcium concentrations.     

COMPARATIVE STUDY OF LARGE STRAIN METHODS FOR ASSESSING FAILURE CHARACTERISTICS OF SELECTED FOOD GELS

Vane rheometry was compared with uniaxial compression and torsion in evaluating the effects of strain rate on failure shear stress and deformation of soybean protein (tofu) and gellan gum gels. A Haake VT 550 viscotester was used for torsion and vane tests, and compression was performed with an Instron/MTS universal testing machine. Strain or angular deformation at failure was independent of strain rate in the three testing modes. In vane rheometry, failure shear stress increased with increasing low shear rates (< 0.100 s ⁻¹) and was rate independent at higher rates. This strain rate dependency was also evident in compression, varying with the material. For torsion, fracture stress appeared to be rate independent. Shear fracture stresses measured in torsion and compression were in good agreement at strain rates above 0.025 s ⁻¹ and 0.100 s ⁻¹ for tofu and gellan gels, respectively. Shear stresses from the vane method were lower than shear stresses of torsion and compression. Similar texture maps of the food gels studied were generated by plotting stress and strain or angular deformation values of the three testing methods. The findings validate the vane technique as an alternative to torsion and compression for rapid textural characterization of viscoelastic foods.     

Mechanical Properties of Gellan Gels in Relation to Divalent Cations

Mechanical behavior of gels formed with gellan polymer crosslinked by calcium and magnesium ions was studied to determine the influence of divalent ion type and polymer concentration. Failure strength and deformation were measured in compression and related to concentrations of gellan and bound cations in gel matrices. Insufficient cations formed weak, extensible gels. Maximum gel strength was achieved at 0.5 divalent cations/repeat tetrasaccharide unit, assumed to be the condition for maximal numbers of complete junction zones. At optimum cation levels gels with Ca⁺⁺ were about 1.2 times stronger than gels with Mg⁺⁺ at the same polymer concentration. Excessive cations weakened the gels. Twice as much reduction in gel strength resulted from additional Ca⁺⁺ as compared to the same additional amount of Mg⁺⁺. Differences between strengths of the gels may be attributable to polymer configurations at junction zones in relation to cation size.     

Rheological studies on commercial egg white using creep and compression measurements

The gel properties of commercial egg white (EW) with high gelling ability were compared with those of standard type using creep and compression measurements. The effects of heating time, temperature, and protein concentration on gel properties were investigated at pH 7.5. The experimental creep curves were analyzed using four elements of the Maxwell–Voigt model. The difference in rheological properties of the two types of EW was reflected in the values of elastic modulus and viscosity. The experimental stress–strain curves for all EW gels were fitted using the BST equation with high accuracy. This equation contained two fitting parameters, i.e. Young's modulus and the elasticity parameter n_BST. The elasticity parameter n_BST characterized non-linear elastic behavior for large deformation. At 80°C, n_BST of both types of EW gels did not change with increasing heating time. However, n_BST decreased with increasing temperature in a range of 70–85°C.