Int, Datty Journal 5 (1995) 661-671 © 1995 Elsevier Science Limited Printed in Ireland. Al rights reserved (0958-6946,95,59.50 ELSEVIER 0958-6946(95)00047-6 Rheological Behaviour of Low-fat and Full-fat Stirred Yoghurt L. De Lorenzi. S. Pricl & G. Torriano Department of Chemical. Environmental and Raw Materials Engineering, Unive Trieste. Piazzale Europa 1, 1-34127 Trieste, laly (Received January 31 1994: revised version accepted November 5 1994) {BSTRACT The rheological properties of a low-fat and a fill fat voghurt were investigated under continuous and oscillatory flow conditions with a rotational coaxialeevlinder viscometer at different temperatures. In continuous shear flow tests, flow instability phenomena were detected helow a critical shear rate value. Flow curves were correlaied with the shrce parameter De Kée Turcone model, and the temperature dependence of the relevant parameters way demonstrated, The non-linear viseoclas- tie properties of hoch types of yoghurt were described, at first approximation, in rerms of the complex mudulas G* and phase lag 6. The effects of temperature on weakening of the voghurt structure was illustrated. INTRODUCTION Yoghurt is material with non-Newtonian flow properties and with strong time- dependence of both the thixotropic and viscoelastic types. The Now curve shows yield value at zero shear. This plastic material is characterized by the presence of a labile structure, which is broken down under shear and slowly and only partially builds up in rest conditions or in conditions of lower shear. Flow prop- erties are temperature dependent The flow properties of yoghurt have been the subject of investigations by several authors. Approaches to the rheological characterization of yoghurt may be quite different, depending on the aim of the research, the experimental techniques adop- ted or the experimental data treatment. The microstructure of yoghurt is the main subject of papers. where the flow, properties play only a secondary role (Kalab & Emmons, 1974: Teggatz & Morris, 1990). In other works, the flow properties were correlated with the parameters of the manufacturing process (Labropoulos ¢# al.. 1981: Labropoulos e7 a/.. 1984: Olson & Bottazzi. 1977: Schmidt ¢7 al., 1980); addi- 661662 L. De Lorenzi et al tion of texture modifiers, like pectin or fruits (Ramaswamy & Basak, 1992); sensory properties (Biliaderis ¢7 al,, 1992; Rohm, 1989) or composition (O'Neil ef al., 1990: Windhab, 1991). Some kinetic aspects of the coagulation time were investigated in connection with the flow properties (Sharma er al., 1989; Dannenberg & Kessler, 1988). The logarithmic time model of Weltman (1943) and the Herschel-Bulkley model (1926) were applied in recent investigations, aimed at a general characteriza- tion of yoghurt rheology from steady flow tests (Ramaswamy & Basak, 1991a, Ramaswamy & Basak, 1991b). A flow characterization was also attempted by means of oscillatory flow tests (Zoon ef al., 1988; Zoon et al, 1989; Steventon et al., 1991; Bohlin ¢7 al.. 1984), whereas the works of De Kée & Turcotte (1983) and De Kée & Turcotte (1990) and of Benezech & Maingonnat (1992) presented an approach to the description of the time dependent properties of yoghurt at constant shear rate on the basis of a state equation, a kinetic equation and the parameter, introduced to describe the structural state of the material as a function of the shear rate and time, as previously suggested by Cheng & Evans (1965) The aim of this work is to make a contribution to the knowledge of the rheo- logical properties of both low-fat and full-fat stirred commercial yoghurts, with particular focus on the effects of temperature variation, for which little informa- tion is available in the current literature. MATERIALS AND METHODS The full-fat (4% fat content) and the low-fat (0.4% fat content) yoghurts studied in this work were two commercial samples. obtained from Torvis Latterie Friu- lane, Cervignano (UD), Italy. The corresponding total solids contents were 14.6 and respectively, as ascertained by drying the samples at 72°C, under vacuum, to constant weight All rheological measurements were carried out with a rotational rheometer Haake Rotovisko RV 100 (Haake Mess-Technik, GmbH, Dieselstrasse 4, D-7500 Karlsruhe 41. Germany), measuring head CV100, mounted with a coaxial cylin- der sensor system ZB 15 (Couette type). with Ri/Rz = 1.078, RyRy = 0.545mm (Ry = radius of the rotating cup. Ry — radius of the stationary bob) Continuous shear flow tests were performed in the 0.3-300 s~' range. The application of a stepwise procedure of constant shear rates does not lead to stress constant values in a reasonable time (De Lorenzi & Torriano, 1991; Doveri ef al., 1992). Therefore, recourse was made to the technique of the hysteresis cycles, since it was experimentally observed that consecutive repeating of up and down cycles leads to + (shear stress) values which, at corresponding shear rates, become closer and closer to one another. Practically, we have observed that the values given in the down-curves of the filth and sixth cycles of 6+ 6 minutes are so close for both yoghurts studied that it may be assumed that conditions very near the true equilibrium are reached in the down part of the sixth cycle. Accepting this approximation allows flow curves to be determined on the basis of the values of the down part of the sixth cycle, Data repeatability was assessed by running each test in triplicate: the differences between the higher and lower shear stress values at the corresponding shear rates never exceeded 5%. Oscillatory shear flow tests were carried out both at constant frequency w and strain 7. Instrain sweep tests, 7 was varied between 7% and 240% at the frequencies w of 1.88Rheological behaviour of low-fat and full-fat stirred yoghurt 663 rads ‘and 6.28 rad s_', respectively. For the frequency sweep tests, frequency was varied between 0.314 rad sand 12.56 rads‘ at the strains of 12, 24 and 240%. The results of the oscillatory flow tests were analysed, at the first approximation, on the basis of the viscoelastic quantities G* and 0. where G*. the complex modulus, measures the proportionality between the applied sinusoidal strain and the resulting stress; 6 is the phase lag, defined as arcig(G" ‘G'); G’ is the real in-phase component of G* and G" is the imaginary, 2/2 out-of-phase component, of G*. For the correlation of the continuous flow curves three models were tested: the Herschel & Bulkley (1926). the generalized Casson (Tscheuschner & Wiinsche, 1979) and the De Kée-Turcotte model (De Kée & Turcotte, 1980; De Kée & Turcotte, 1983), Model parameters were calculated with the non-linear least square method by using the Marquardt algorithm and minimizing the following objective function: 8 (Yexp — Yeut)- The quality of fitting was expressed in terms of average standard deviation, ASD, i.e. [Yeap — Yeai” AN ~ p)]!®. where N is the number of the experimental data and p the number of the model parameters. RESULTS AND DISCUSSION Continuous shear flow tests Flow curves between 0-3 and 300s‘, obtained at different temperatures, are reported in Figs | and 2 for the low-fat and the full-fat yoghurt, respectively. In both cases, the curvature of the stress profiles displays a discontinuity in a narrow shear rate range around 10 s |. Similar phenomena of discontinuity in the flow curve are reported in the literature and attributed to different causes. like dry friction of the material on the viscometer surfaces. slip at the wall, fracture, non homogeneity with secondary flow or plug flow (Windhab, 1988; Magnin & Piau, 1990). In the case of the yoghurts examined, the phenomenon may be mainly due eur stress (Pi aoe eaph fe gaa . f8 Be ¢ a c Bhs 8 a gee 5 0c. 1 _ se tn + 5 he Tan Shear rate (1) Fig. 1. Flow curves for the low-fat yoghurt at different temperatures: (Ill) 4°C, (2) 8°C, (@) 12 C. (A) 16°C. (A) 20 C(O) 24-C. (@) 28°C664 L. De Lorenzi et al 100 peth w an Oe 38 Shear stress (Pa oo é bi tT 0 Tow Too Shear rate (s") Fig. 2. Flow curves for the low-fat yoghurt at different temperatures: (I) 4°C, (0) 8° @) 12°C) 16 © (a) 20°C, (0) 24°C, (@) 28°C to the progressive evolution of the shear flow into a plug flow, when shear rate is progressively decreased toward the critical shear rate value. By correlating the flow curves with the above mentioned models, at shear rates above the critical shear rate range. in which fluid discontinuity phenomena develop. the best fitting was obtained with the De Kée-Tureotte model, eq.(1): r=t+mie % a where 1, (Pa) is the yield stress, 1; (Pa.s) is a viscosity parameter, correlated with the structural state of the material. 1, (s) is a time parameter, that may be useful in the study of time-dependent properties of materials. The ASD, for the De Kée-Turcotte model was found to be from two to three orders of magnitude better in comparison with the Herschel Bulkley and exten- ded Casson models. Thus, all further considerations in this work concern this model only. De Kée- Turcotte model parameters and the relevant ASD values are reported in Table | for the full-fat and low-fat yoghurts, at seven temperatures between 4 and 28 °C. An examination of data in Table | reveals a singular behaviour of zt, with temperature. Indeed, the model gives r, values decreasing with temperature for low-fat yoghurt, whereas for full-fat yoghurt a maximum around 16 or 20°C is indicated. It may be suggested that. in absence of shear, increasing temperatures weakens the structure of the low-fat yoghurt; consequently, t, diminishes. The presence of milk fat inverts this trend up to a certain critical temperature, beyond which the temperature weakening effect on structure prevails. The values of t, are comparable with those reported by other authors (Ramaswamy & Basak, 1991a, Ramaswamy & Basak, 1991b). Parameters 1 and t; display a regular behaviour with the temperature, the former decreasing, as it could be expected, the latter increasing with increasing temperature. Figure 3 shows an extension of the De Kée-Turcotte model in comparison with the relevant experimental data for full fat yoghurt at 4°C and low fat yoghurt atRheological behaviour of low-fat and full-fat stirred yoghurt 665 TABLE t and Full-fat Yoghurts: Parameters and ASD according to De Kée-Turcotte Model Low-fat yoghurt Full-fat yoghurt ac 20°C 4c 20°C t, (Pa) 10-237 x, (Pa) 7-618 1, (Pa) 7-421 ty (Pa) 9-663 my (Pa, 8) 0162 (Pas) 0-124 ny (Pas) O-15S 1m (Pa. s) 0149 1 (3) 0.001898 1, (s)_ 0.002427 1 (s) 0-001394 1, (s) 0.002426 ASD 0.000487 ASD 0.00027 ASD 0.000441. ASD_—_0-000470 ac wc ac 24°C 1, (Pa) 10.035 ¢, (Pa) 6-772 1, (Pa) 8-250 t, (Pa) 8641 mm (Pas) 0155 1p (Pa. s) 0-126 ny (Pas) 0-140 (Pa. s) 0-143 1 (Ss) 0-002003 1, (s) 0.002791 1 (s) 00014351, (s) 0.002608 ASD — 0.000389 ASD 0.000325 ASD 0.000455 ASD 0.000444 12°C 2c Ine 28°C (Pay 9-128 x, (Pa) 6633, te (Pa) 9-031 % (Pa) 7.0100 mh (Pa.s) 0-148 (Pa. s) 0-107 n (Pas) 0-186 (Pa. s) 0-145 (3) 0-002191 1 (s) 0-002 648 f(s) 0002079 ty (8) 0-003 124 ASD 0.000406 ASD 0.000179 ASD — 0-000487 ASD_—_0-000684 16c 16 4 (Pa) 8.958 1, (Pa) 9-632 m (Pa. s) 0-144 my (Pa, s) 0-153 1 (8) 0.002.468 f(s) 0-002 241 ASD 0.000417 ASD 0.000512 For Definition of Parameters see eq. 1 in text Lo on v 7 To Too Shear rate (}) Fig. 3. Experimental flow curves and De Kée Turcotte model curves for low-fat and full- fat yoghurts: LFY, 8 C. experimental (@), model (—-), FFY, 4°C, experimental (Q), model (- - -).666 L. De Lorenzi et al 8 C, as examples of the model application. The discontinuities in the experi- mental flow curves around the shear rate of 10s”! and the anomalous behaviour at lower shear rates, with regard to that predicted by the De Kée—Turcotte model, are clearly evident. The validity of the De Kée-Turcotte model was ascertained up to 300s | Oscillatory flow tests Tests performed under oscillatory flow conditions are useful tools for the characterization of the viscoelastic properties of materials, Generally, the first step in a routine oscillatory analysis consists in assessing the extension of the linear viscoelastic regime by means of a strain sweep test at constant frequency of oscillation «. For both low-fat and full-fat_ yoghurts, no linear viscoelastic region was observed. even at the lowest strain imposed, independently of the applied frequency. as evidenced in Fig, 4. The complex modulus G* clearly decreases with increasing strain. The rate of decrease of G* with > is more pronounced at lower ©. and in the low strain range. This seems to suggest that the linear viscoelastic region for both yogurt samples is confined to very low strain values. well beyond the experimental window explored. Moreover, this marked strain. sensitivity allows to classify yoghurts as very weakly structured fluids. Nevertheless, in the non-linear region the canonical viscoelastic quantities, such as the complex modulus G* and the phase lag 6, can be still employed as first approximation terms for a comparison among similar systems. In this sense, Fig. 4 shows that the presence of milk fat results only in an increase of the G* values, whatever the strain applied. Temperature variations do not modify the non-linear characteristics of both types of yoghurts. Figure 5 shows that, for the low-fat yoghurt, a temperature 00) on iw r To Strain Fig. 4. Complex modulus G* vs. strain curves for low-fat (LFY) and full-fat (FFY) yoghurts at two different frequencies of oscillation: (I) 1-88 rad/s LFY, (C1) 628 rad/s LEY.(A) E88 rad s FFY, (4) 6-28 rad’s FFYRheological behaviour of low-fat and full-fat stirred yoghurt 667 G* (Pay 007 aie 10 Strain Fig. 5. Complex modulus G* ys. strain curves for the low-fat yoghurt at o = 1-88 rad/s and different temperatures: (MI) 4 C. (C1) 8 °C. (@) 12°C, (0) 16°C, (A) 20°C, (a) 24°C and (x) 28°C. increase leads only to a quantitative downward shifting of the G* curves. Analogous considerations can be extended to the full-fat sample. In order to separate the viscous and elastic contributions to the total stress response of these materials, 6 was plotted vs } for both the low-fat and the ful yoghurts at different temperatures and at constant frequency w = 6-28 rad s~ ‘As can be seen from Fig. 6, increasing strain results in a progressive structural so] | 0) Bey 1 nT aio t 0 Steain Fig. 6, Phase lag 6 vs. strain curves for low-fat (LFY) yoghurt and full-fat (FFY) yoghurts at = 6-28 rad/s and different tempepratures: (Q) 4 C LFY, (Q) 12°C LFY, (©) 20°C LY. (A) 28°C LFY, (@) 4°C FFY, (@) 20°C FFY,668 L. De Lorenzi et all break-down and. correspondingly, d increases. converging to the limiting value of 90 . as expected. By combining the experimental evidence for G* and 5, we may conclude that the imposed strain exerts its major effect on the elastic component G', which decreases more rapidly than the viscous one G" with the increasing strain. An alternative for the evaluation of the strain amplitude influence on the mechanical response of the systems under investigation may be the analysis of the frequency dependence of the complex modulus. Figure 7 reports the beha- vior of G* vs. « for both the low-fat and the full-fat samples at 20°C and three different strains. For both yoghurts. doubling 7 from 12 to 24% results only in a quantitative reduction of the G* values, more marked in the case of the full- fat sample, whereas a ten-fold strain variation (24% — 240%) produces also a net change in the relevant G* profiles. Although all data refer to the non- linear region. the shapes of the and G* vs. « curves obtained at 7 = 12 and 24% still resemble those typical of weakly structured materials. On the contrary, S-shaped curves are obtained at very high strains, as a consequence of the strong influence of the amplitude of deformation in the low frequency region The slight dependence of the phase lag 5 on the frequency «», as depicted in Fig 8, implies that all the G* — cy profiles can be decomposed into two parallel curves of Gand G” vs. «; once again, this is an evidence that the systems under inves- tigation exhibit features typical of weakly structured materials (Lapasin ¢f al., 1992), Finally, as can be seen in Fig. 9. temperature variations do not modify appre- ciably the shape of the G* vs. es curves. and only at 28°C a substantial decrease of the G* values can be observed oF r 0 To Frequeney (rad/s) Fig. 7. Complex modulus G* ys. frequeney curves for low-fat (LY) and full-fat (FFY) yoghurts at 20 C and three different strains: ((}) 12% strain LFY, (A) 24% strain LFY, (©) 240% strain LFY, (Ml) 12% strain FFY, (a) 24% strain PFY, (@) 240% strain FRYRicological hchaviour of low-fat and full-fat stirred yoghurt 669 0 val Seeakdiatiy va To Frequency (ralist Fig. 8. Phase lig 0 vs. frequency curves for low-fat (LFY) and full-fat (FPY) yoghurts at 20°C and three different strains: (I) 12% strain LEY, (@) 24% strain LFY, (&) 240% strain LPY. (0) 12% strain FFY. (*) 4% PEY, (+) 240% strain PFY. my nl or iw 1 Frequeney (rad/s Fig. 9. Complex modulus G* vs. frequenc different temperatures (4 C0112 CA) curves for the full-fat yoghurt at 3" = 12% and C(O) BWC. CONCLUSIONS Both full-fat and low-fat yoghurt were found to be pseudoplastic materials with yield value and appreciable clastic components. which were more marked in the full-fat than in the low-fat type670 L. De Lorenzi et al Discontinuity phenomena were observed in continuous flow experiments, when shear rate was decreased under a certain critical } range. It may be suggested that these phenomena be mainly due to the onset of a plug flow at low shear rates. Fitting continuous flow data to adequate models allowed evaluation of rheo- logical parameters to obtain useful information on the rheological behaviour of the materials. In this context the yield stress to is of special interest. Indeed, 7 brings out the presence of different structural states in full-fat and low-fat yoghurts and the relevant temperature effects In the oscillatory flow tests no linear viscoelastic region was observed, even at the lowest strains applied. This means that the linear viscoelastic behaviour is confined to very low strains and suggests to classify yoghurt as a weakly struc- tured material. On the basis of the variation of the phase lag 6 with strain, strain sweep tests at first approximation describe the evolution of the material proper- ties, which change from those of a predominantly viscoelastic solid to those of predominantly liquid with elastic components during the test performance. Moreover, strain sweep tests brought out gradual structural weakening with increasing temperature for both yoghurts. Higher values of G* at low strains were obtained for the full-fat yoghurt in comparison with the low-fat yoghurt The opposite is seen at high strains, For both yoghurts stronger breakdown effects are shown at the lower frequency tested. Frequency sweep tests displayed different behaviours, in dependence on the different strains applied. Although all data refer to the non-linear region, the shape of the G* vs. w at the lower strain and the phase lag 5 dependence on « confirm that yoghurt behaves as a weakly structured material. 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