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RBEOLOGY OP STIRRED YOGURT

By

A thesla aubmltted to the F.cully of Gradute Studles and Research ln partial

lulftllment of tbe requlrements for the dearee of

Master of Science

Deparbnent of Food Science and ACrlcultural Chemlstry


McGW Unlvenlty. Macdonald Campus

Montreal. Cu.da

June. 1991

ii

ACKNOWLEDGEMENTS

The author wtshes to accord her deepest sense of graUtude and


apprectaUon to Dr. H. S. Ramaswamy for his guidance and inspiration
throughout the course of this study.
The author also extends her slncere thanks to Dr. F. R van der Voort for
his encouragement and for providtng access to sorne equlpment used ln
the current work and to Mr. Thibaud Pilet-Will for the translation of the
abstracto
The financia1 support for the research from the Operating Grants
Program of the Natural Sciences and Engineering Research Councll of
Canada is gratefuUy acknowledged.

The author would I1ke to express her apprectaUon for the cooperation.
understandtng and the necessary support of a1l the members of her
fam1ly and her frtends in the department.

iii

ABSTRACT

Rheologlcal behavior of two commercial bmnds of sUrred yogurt were


tnvestJgated usJng a Haake RV 20 rotatJonal vtscometer. Shear stress was measured
under a programmed 3-cycle up and down shear rate at 100 s-1 /min from 0 to 500 s-1
(5 min). as well as under steady shear at selected rates (l00-500 s-1). Tests were
carrled out at several temperatures.
For samples from both brands. the upward shear-rate flow behavior generally
followed the Herschel-Bulkley model and the downward flow

cUlVe~ w"r~

Imear. They

demonstrated progressive structural degradatJon with repeated f.heartng. In the steady


shear rons. ail samples exhlbtted apparent thlxotroplc behavior and dld not attain the
equlllbrlum conditJon even after 60 min of contlnuous sheartDg. The Ume dependent
stress decay behavtor of all samples were accurately descrlbed by Weltman's
10garlthmJc Ume model. The rheological properUes of both yogurt brands were
qualJtatlvely sim1lar. Both Arrhenius and Turlan models were found sultable

~o

assess

the temperature influence ln the range 10-250 C.


The influence of pectJn (0.0 to 0.5%) and fruit concentrates (raspbeny and
strawberry) 1640 B. 0 to 10%) on the rheology of stJrred yogurt were evaluated. A steady
increase in sorne parameters (consistenC'.f coefficient and apparent viscosity) were noted
with the addition of both pecUn and fruit concentrates. The study indicated that several
rheologtcal parameters could be used to model the flavor yogurt rheology.
The Influence of storage Ume at 20 C up to a perlod of four weeks on the
rheological properUes of the two brands were evaluated. The study tndicated that the
effect of storage on chemJcal composition (acidlty. fat. molsture. proteln. lactose) was
small but slgnlficant (p<0.05). However. the resulUng efTect on vanous rheologlcal
parameters was generally non-signlficant.

iv

RSUM

Les caractristiques rhologiques de deux marques de yaourt brass commercial


ont t ludies e&i utJIlsant un viscosimtre rotatif Haake RV20. Les forces de
cisaillement ont t mesures au cours de trois cycles croissant / clcrolssant de taux
de clsaUlement pralablement programms de 0 500 s-1 raison rie 100 s-l/min (5
min) ainsi que pour des taux constants (100 - 500 s-I), diffrentes tempratures.
Pour les deux marques. les courbes obtenues avec des taux de cisaillement
croissants suivent globalement le modle Herschel-Bulkley. alors que pour les taux
dcroissants elles sont Unalres. Une dgradation progressive de la structure est
apparue au fur et mesure des tests. A taux de cisaillement constant. tous les
chantillons ont montr un comportement thixotrope et n'ont pas atteint l'quUibre
mme aprs 60 min de cisaillement continu. La consistance de tous les chantillons

suivait

av~c

prcision le modle logarithmique de Weltman. Les proprits rhologiques

des deux marques taient qualitativement similaires. Les modles d'Arrhenius et de


TuIian conviennent pour estimer l'Influence de la temprature (10 25

OC).

L'Influence de pectine (0.0 0.5%) et de concentrs de fruits (frambOise et fraise


- 64 0 B. 0 10%) sur la rhologie du yaourt brass a t evalue. Une augmentation
constante de certains paramtres (coeffiCient de consistance et viscosit apparente) a
t constate lors de l'ajout de pecUne et de concentrs de fruits. L'lude a montr que
plusieurs paramtres rhologiques pouvaient tre utilJss pour modliser la rhologie
du yaourt aromatis.
L'Influence du temps de conservation 2 0 C. Jusqu' une dure de 4 semaines,
sur les proprits rhologiques des deux marques a t evalue. L'lude a montr que
l'effet de l'entreposage sur la composition chimique (acidit, matire grasse. humidit.

protines, lactose) est faible mals significatif (p<0.05). Par contre, l'effet sur divers
paramtres rhologiques n'est gnralement pas significatif.

------------------------------------....
v

TABLE 01' CONTENTS

ACKNOWLEDGEMEN'TS ..................................................................................... .

11

ABS~C'r..........................................................................................................

Ut

RSUM ............................................................................................................ .
LIST OF TABLES ................................................................................................ .

viU

LIST OF FIGURES .............................................................................................. .

lx

CfIAPI'ER 1. INrRODUC110N ............................................................................. ..

CHAPTER Il. LITERATURE REVIEW ON CONCEPTS IN RHEOLOGY.................. ..

Types of Vlscous Behavior...................................................................... ..

T1Ine Independent Flow.............................................................. ..

PlasUc or BlnghaDl Flow .................................................. ..


PseudoplasUc Flow........................................................... .
Dilatant Flow.................................................................... .

7
9

TiIne Dependent Flow .................................................................. ..

11

ThixotroplC Flow.............. " .............................................. ..


RheodestrucUve and Rheopectlc Flow ............................... .

11
12

Vlscoelastlc Flow ......................................................................... "

13

Rheologtcal Models.................................................................................. .

14

TUne Independent ModeL'S .......:................................................... ..


TUne Dependent Rheologtcal Models ............................................ .

14
17

Factors Influencing Viscoslty................................................................... .

20

Temperature ............................................................................... .
Concentration.............................................................................. .

20
23

CHAPTER Ill. YOOURT: CLASSIFICATION. MANUFACTURE AND RHEOWGY.....

24

1'ypes of Yogurt ....................................................................................... .

24

Manufacture of Yogurt ............................................................................. .

27

vi
."

Fort1ficatlon of Yogurt Mllk.......................................................... ..


Addition of StabUlzers.................................................................. .
Sweeteners................................................................................... .
Homogeni1..aUon ........................................................................... .
PasteuI1zaUon .............................................................................. .
Coollng and InoculaUon............................................................... .
Incubatlon................................................................................... .
Cooling and Storage .................................................................... ..
Addition of Fruit and Flavor......................................................... .
Storage........................................................................................ .

27
28
28
29
29
30
30
31
32
33

Rheology of Yogurt....... ........... ............... ............... ............ ............ ...........

33

Effects of Processlng Variables on Rheology...................................


Rheological Measurements.. ......... ... ........... ............... ..................

35
38

CHAPTE.R IV. T1ME INDEPENDENT RHEOLOGY OF STIRRED YOGURT..............

40

Abstract.................................... ...............................................................
IntroducUon.............................................................................................
Matertals and Methods.............................................................................

40
40
41

Results and Discussion........... ...... ......... ............... ............... ....................

44

CharactertzaUon of Flow Curves................................................... .


ModeWng of The Flow Curves....................................................... .
Effect of Temperature on Flow Behavior....................................... .

47

Conclusions... ............ .............................. ............ ......... ...... ......... ...... ......

53

CHAPrER V. TIME DEPENDENT RHEOLOGY OF snRRED YOGURI'...................

55

Abstract......... ............................................. .............................................


IntroducUon.............................................................................................
Matertals and Methods............. .............................................. ..................

55
55
56

Results and Discussion............................................................................

58

Stress Decay Comparison of the two Conunercial Yogurts. ...... .......


Modelling of the Flow Curves.........................................................
Effect of Temperature on Flow Behavior........................................

58
58
65

Conclusions.... ................. ......... .................. ............ ............... ..................

72

CHAPTER VI. RHEOLOGY OF RASPBERRY FIAVORED YOGURT...................... ..

73

Abstract. ................................................................................................. .

73

44
51

vii
Introduction.. ...... ....... ........ ... ...... ............ ... ...... ...... ......... ... ...... ...... ...... ....
Matertals and Methods.............................................................................

73
74

Results and Discussion........... .................................................................

75

A Model for FabrtcaUng Flavored Yogurt Rheology............. ............

85

Conclusions............... ..............................................................................

88

CHAPTER VII. RHEOLOGY OF STRAWBERRY FlVORED YOGURf...... ..............

89

Abstract......... ............... ...........................................................................


IntroducUon.............................................................................................
Matertals and Methods............. ................................................................

89
89

Results and Discussion........... ...... ............ ............... ................................

91

A Model for FabrtcaUng Flavored Yogurt Rheology.........................

101

Conclusions.............................................................................................

103

CHAPTER VIII. RHEOLOGICAL BEHAVlOR OF STIRRED YOGURr DURING

104

Abstract......... ..........................................................................................
IntroducUon.............................................................................................
Matertals and Methods.............................................................................

104
104
105

Results and Discussion............................................................................

106

Effect of Storage on Rheological parameters..................................


Effect of Storage on Chem1ca1 ComposiUon....................................

106
112

Conclusions.................. ............ ...............................................................

114

REFERENCES.....................................................................................................

115

SroRAGE AT 2 oC .................................................................... ..

90

viii
LIST 0 .. TABLES

\
Table 1.

ComposlUon of the two commercial yogurts employed ln the study

44

Table 2.

Rheologlcal constants (or the three successive up-curves for two


brands of yogurt uslng Herschel-Bulkely model.. ................... ,.... ..

49

Rheologlcal constants from three successive down-curves for two


commercial brand yogurts usJng a llnear model.. ........................ ..

49

Rheologlcal constants of Brand 1 yogurt (three up-curves) at


d11Terent temperatures usiDg the Herschel-Bulkley model... .......... .

52

Rheolog,lcal constants of Brand 1 yogurt (three down-culVes) at


dlfferent temperatures Ulltlng a lInear model.. ............................... .

52

Activation energy (kcal/mole) of flow from dynamlc shear


expertInents............................ ,......... '" ....................................... ..

54

Weltman model regression parameters (or conunercial stirred


yOgUts at 10oe ........................................................................... .

62

Stress decay constants (or stirred yogurt (Brand 1) at difTerent


shear rates and temperatures ..................................................... ..

66

Table 9.

Activation energy ofvlscoslty decay for stirred yogurt (Brand Il.... .

71

Table 10.

Mean and standard devlations ln rheological parameters of stirred


yogurts as Influenced by the addition of pecUn and concentrate....

79

Table 3.
Table 4.
Table 5.
Table 6.
Table 7.

Table 8.

Table Il.

of effect of pectln and concentrate on the rheologlcal


parameters of stlrred yogurt (analyses of variance)......... ............ ...

80

Table 12.

Multiple regresslon coefficients for rheologlcal parameters.............

86

Table 13.

Mean and standard devlatlons ln rheologlcal parameters of stlrred


yogurts as Influenced by the addition of pecUn and concentrate....

95

Sigruf1cance of effect of pectln and concentrate on the rheologJcal


parameters of stlrred yogurt (analyses of variance)... ...... ...... ... ... ...

96

Table 15.

Multiple regression coefficients for rheologlcal parameters.............

103

Table 16.

Changes ln rheological parameters durtmg storage at 2 oC...........

110

Table 17.

Slgntflcance of effect of storage on rheologlcal parameters of


Brand 1 and Il yogurts...................................................................

112

Changes ln chemJcal composition durlmg storage at 2 oC............ .

113

Table 14.

Slgntflcanc~

Table 18.

ix
UST OF FIGURES

Figure 1.

Idealized flow curves for vanous rbeologtcal systems................... ..

Figure 2.

Types ofyteld values found with sorne plasUc fluids .................... ..

Figure 3.

Ideallzed flow curve for a pseudoplasUc fluid on logarttbmJc


coordinates ................................................................................. ..

10

Figure 4.

TiIne dependent flow bebavior...................................................... .

11

Figure 5.

Ideal flow cUlVes for thiXotropic and rbt."OdestrucUve dispersions ...

13

Figure 6,

Sbear stress - shear rate relaUonshtps (flow curves) for two


commercial yogurts durtng a programmed 3-cycle (10 mJn each)
up and down sbeartng between sbear rates of 0 and 500 s-I ........ .

45

Flow cUJves for Brand 1 sUrred yogurt durtng a first run 3-cyc1e
up and down sheartng and a sunHar rerun after one hour of
relaxaUon ........... " ... " ........ ,................... '" .................................... .

48

Typical Herscbel-Bulkley (for upward curves) and ltnear (for


downward) plots for Brand 1 sUrred yogurt durtng a 3-cycle up
and down sbeartng....................................................................... .

50

Stress decay curves of two conunerctal sUrred yogurts over a 10


min. sbear al seleclt"d sbear rales.................................................

59

Stress decay curves of Brand 1 sUrred yogurt over a 60-min shear


al selected sbear rates..................................................................

61

Stre~s decay parameters as a funcUon of sbear rate for lwo


cOIl1Illercla1 stlrred yogurts................ ............... .............................

64

Weltman A values as a funcUon of temperature and sbear rale for


Brand 1stirred yogurt...................................................................

67

Weltman B values as a funcUon of temperature and sbear rate for


Drand 1st1rred yogurt...................................................................

68

Arrhenius plots of vtscosity (A/1) decay at selected shear rates for


Brand 1st..!..'"I'ed yogurt...................................................................

70

Typlca1 upward and downward flow cUlVes of sUrred yogurt al


vartous levels ofpectln and no raspberry concentrate....................

16

Typlcal upward and downward flow cUlVes of sUrred yogurt al


vartous levels ofpectln and 5% raspbeny concentrate...................

77

Figure 7.

Figure 8.

Figure 9.
Figure 10.
Figure Il.
Figure 12.
Figure 13.
Figure 14.
Figure 15.
Figure 16.
.n"'-.>-

Figure 17.

Typlcal upward and downward flow curves of stirred yogurt at


vartous levels of pectln and 10% raspbeny concentrate................ .

78

Figure 18.

Upward flow conslstency coefficient and flow behavtor Index of


sUrred yogurt as in11uenced by added pectIn.................................

81

Downward flow shear stress ~d apparent v1scoslty of stirred


yogurt as lnf1uenced by added pectln............................................

82

Typical flow curves showIng structure breakdown of stlrred


yogurt ln a 3-cycle upward and downward sheartng sequence.......

83

Stabllity Index (raUo of tPe third and flrst cycle apparent


vtscositles. 1'13 / 1'11) of sUrred yogurt as tnfluenced byadded pectJn
and raspberry concentrate.......... ..................................................

84

Apparent vlscosity of stlrred yogurt as a functlon of added pectJn


and raspberry concentrate............................................................

87

Typlcal rheograms of sUrrt;d yogurt at various levels of pectln and


no strawberry concentrate.............................................................

92

Typical rheograms of sUrred yogurt at various levels of pectln and


5% strawberry concentrate................ "..........................................

93

Typlcal rheograms of sUrred yogurt at various levels of pectln and


lOCAl strawberry concentrate ........................................................ ..

94

Upward flow consistency coefficient and flow behavtor Index of


sUrred yogurt as in11uenced by added pectJn and strawbeny
concentrate........................................................... ........................

98

Downward flow shear stress and apparent viscosity of stlrred


yogurt as influenced by added pectln and strawbeny
concentrate....................... ......... ............... ....................................

99

Weltman parameters of stlrred yogurt as influenced by added


pecUn and strawbeny concentrate................................................

100

Three-dimensional mulUple regression model of apparent


viscoslty of stirred yogurt as a funcUon of added pecUn and
strawberry concentrate.................................................................

102

Typical upward and downward flow curves of two commercial


sUrred yogurts following storage at 20 C for various pertods...........

109

Typical stress decay curves of two commercial stirred yogurts


followtng storage at 2 0 C for vartous pertods...................................

111

Figure 19.
FIgure 20.
Figure 21.

Figure 22.
Figure 23.
Figure 24.

Figure 25.
Figure 26.

Figure 27.

Figure 28.
Figure 29.

Figure 30.
Figure 31.

CHAPTER 1

INTRODUCTION

In recent years. fennented da1:ry products have gained a special Importaul'C III
the Nmth American di eL Among the varlous femlented mllk products. yogurt. a
thennophilic semi-soUd coagulum. has attracted a widespread attention on (he
international scene. The exact origln of yogurt is not well known. but lilerature rcVt'als
that fermentation of mtlk with IacUc acid bacteria Is one of the oidest known mcthod o(
food processmg and preseIVatton used by mankind. The nature and fonn of yogurt b
detennined by geographicallocation. ecology. diet and social structure of the place.
Yogurt was originally consldered to be a I-i.ghly ethnie and local food item alld
rated as "lnsipid and unenjoyabIe" because of ils lart taste and characlerlslle nully
naVal'. Now. il is generally accepted as a 1I0urishing d/et and has gradually becolJlc a
mainstream food. With the advent ofvastly Improved processlng technology. il lias

IJC(,11

possible to carefully control the fermentation process to produce yogurt wilh supcrior.
nutritional. functional and sensory qualiUes. As a result. ils consumptlon has Increasl'd
tremendously in North America: in Canada. for example. the consumptlon has lrlpled ln
la st 10 years (Hoppner and Lampi. 1990). Hershorn and Lemay (1989) prcdtctcd tha( by
1995 the total market value of yogurt based products may rcach as hl,((l1 as 1 blllioll

dollars in Canada Le. four tlmes the present value. The major reason behlnd thls huge
populariLy is the introduction of fruitjflavored yogurt products (Valemky. 1978: Daily
Field. 1984). Although. the blending of yogurt with fruit has been known for a long lime
(Kosikowski. 1977). il is only in recent years that the product has undergone the
tremendous improvement in tenns of quality and variety. and the product ts enjoytng
an ever increasing popularity (Eden. 1988). NutriUonal quaIiUes of yogurt has bccn weIl
documented (Ayebo. 1980:

GUIT.

1984 and Kaup et al.. 1987). Yogurl has been crcditcd

to be a U) source of essentlal minerais such as calcium and phosphorous (Deeth and


TamJme. 1981). (U) source of more easfly digestible protein than skim m1lk. (UI) more
acceptable daJry base for people who are intolerant to lactose (Holslnger. 1978; Bahrs.
1971). and

Ctv) reduced calorie dlet. Sorne controversles exlst reganllng the therapeuUc

effects of yogurt. yet Its overall nutrttlonal value has never been questioned rramlme
and Robinson. 1985).
Broadly. yogurt can be of classtffed in to three main categories: (1) Plam/Natural
yogurt. (U) Fruit yogurt and

(tU)

Flavored yogurt. Each of them may agatn elther he set

or stIJTed type whlch are dlstinguished from one another by thelr gel charactertsUcs and
manufacturtng process. Recent developments had led to marketing of yogurt in several
dlfTerent forms. namely pasteurtzed/UHr yogurt. concentrated yogurt. frozen yogurt.
drled yogurt. yogurt beverage. yogurt tablets and yogurt confectJonery. Their chemlca1
constituents. physical charactertsUcs and organoleptlc qualitles may vary wtdely

dependlng on the method employed for their processlng.


The organolepttc qual1ty of the yogurt product 1s dependent on physlcal
parameters su ch as texture and/or consistency (rheology) both of whlch depend on the
chemlcal composition and the {ennentaUon process. Rheologlcal propertJes therefore
are key parameters

ln

the development. and qual1ty control of all yogurt based

products. The rheolog1cal properUes will also provlde engineering data necessmy for
product handl1ng during the processlng and for the usage of proper process equlpment.
Rheologlcal propertles such as apparent vlscoslty of most food products are Influenced
by the rate of shear. Contlnuous sheartng even at a constant rate has a detrlmental
effect on the yogurt structure. Temperature Is another important factor Influenclng the
rheologlcal properUes of yogurt. Additives such as starch and pectln added to flavored
yogurt have a profound Influence on the product's rheology. Further. storage Ume and
temperature may affect the rheologlca1 and organolepUc propertles of the product.

Publfshed InfonnaUon on rheology of yogurt. espectally the sUrred type. ts


generally scarce (Martens. 1972; Hell1nga et al . 1986; lnagakt. 1986; NlshUtma and
Inagakl. 1987) and most of these works deal wtth the Influence of dtfferel1t
manufactur1ng steps on rheology. No publtshed lnfonnatlon Is avallable on the t11edependeney of the stJrred yogurt rheology. InfonnaUon on flavored yogurt rheology ts
even more scaree. There Is a complete lack of rheologlcallnvestigatJon on the addition of
fruit concentrates to yogurt.

ObJectives: The overall goal of thesls research was to relate the rheologlcal propertles of

stirred yogurt to Us sensory eharacteristJes. The followtng were the specifie obJectives:
(1).

To study the rheologlcal behavlor of plain sUrred yogurts under dynamlc as well
as steady shear state conditions ln order to evaluate (a) the shear stress - shear
rate relatlonshlp.

(b)

temperature effects on rheologlcal parameters and (c) the

stress decay behavtor as a funeUon of steady shear rate, Ume and temperature.
(2)

To Investlgate the effects of peetJn and fruit eoncentrates such as raspbeny and
strawberry on the rheologlcal behavlor of sttrred yogurts.

(3)

To examine the Influence of storage Ume up to a period of four weeks at 20 C on


the physleo ehemleal and rheologleal behavtor of natural stirred yogurt under
the conditions as mentJoned ln (1) above.

The thesls Is prepared ln nlne chapters wlth the ffrst three coverlng Introduction and
lfterature revlew on concepts ln rheology and pertinent Infonnation on yogurt. The next
five chapters (IV-VIII) address speclffe aspects of yogurt rheology: tlme-Independent and
ttme-dependent flow behavtor of yogurts, rheology of flavored yogurls (raspbeny and
strawberry), and finally rheologlcal changes durlng storage. This parUcular fonnat was
used because these Ove chapters have been prepared as manuscripts for publication ln
selentlfle Journals (In proeess). AlI references are l1sted ln the final Chapter lX.

CIlAPTERD

CONCEPTS IN RBBOLOGY

The

m~or1ty

of foods range from simple dilute solutions to complex: mulUphase

systems conslsUng of water. oll. soft fats. hJgb polymers lIke flbrous materlal. protelns
and carbohydrates. Because of the diverse nature of the consUtuents. foodstuffs
generally valY ID texturaI characterisUcs as weU as phySIca1 states. They are
characterized by varlous texturai properttes sucb as fluldity of lIquld and semlsolld
Coods. hardness oC candy. crlspness of vegetables. Juiclness of Cresh fruits. viscosity of
t.hick puree. tendemess ofmeats and other simUar tenns (Tung. 1978; Boume. 1982).
The tenn texture, meaning "intelWeave" ln Latin. bas been used ln the past to
descrtbe the closeness or roughness of pictures or painUngs (Sone, 1969). Rheology

mvolves the study oC the deformation (texture) and flow of matter under the influence of
extemal force/stress. Drinking. blUng. swallowlng. chewing etc. provide the Corce/stress
to the food whlle eaUng and ln processing of food products they are a consequence of
pumping. mixing. bomogenizatlon. etc. Rheological behavior of food products play an
Important raIe in their acceptabilJty. quallty control. product development. processlng
and handllng.
The rheologlcal bebavior of substances that flow is charactertzed by the
measurement of viscoslty wbich is defined as the internaI friction or resistance
experienced by the fluid. as ft moves over another layer of the fluld. An ideal viscous
fluld Is incompressible. non-elastlc and possesses isotropie structure. It is Important to
note that a fluld under the Jnfluence of applied stress like in m1x1ng or pourlng. will not
retum to Us original state even on removal of the applied force. However ft will conUnue

to flow during the applicaUon of the stress.


Isaac Newton fonnulated the basic law of viscometry whlch states that shear

"

stress (0) 18 dlrectIy proportlonal to shear rate of (y) an Ideal Uquld (Scott-Blair. 1969):
0=

".y

(1)

The proportionallty constant (11) 18 called vtscoslty coefficient. absolute vtseoslty.


dynam1c vtscosfty or apparent vtscoslty.

n'PES OF WSCOVS BEIlAWOR

Dependmg on the flow behavtor under 1mposed sheanng forcf's. flulds can be
classlfted Into two main categories namely. Newtonlan and non-Newtonlan. For
Newtonlan type of rheologlcal behavtor. the fluid maintatns a constant consistency
trrespectlve of the rate of shear. The flow behavtor can thus be expressed by Eq.( 1). The
flow curve (rheogram) shows a linear relatlonshlp between shear stress and shear rate
(Figure 1). and the slope detenntnes the flutd vtscosfty. Water. mtlk. dOute sugar syrups.

honey. edtble oils. fIltered Jutee. carbonated beverages and watel)' beverages e.g. tea.
coffee and beer are examples offlutds exhtbttlng Newlonlan flow. In pracUce. however. a
majorlty of lIqu1d and semJsolid foods encountered in the food system do not exhlbit
Newtonian character. So they do not bear a linear relaUonshtp between shear stress
and shear rate. For these flutds. the vtscostty whtch changes wlth shear rate. 1s temlcd
apparent vtscostty (l1a)' The term apparent ts used to Imply a NewtonJan type of
measurement to a non-Newtonlan system. Recent studles have revealed that nonNewtonJan flow behavtor occurs only when macromolecular chalns are sufTIcJently long
to entangle. In order to allow thls to happen. the molecular weJght of the polymer must
be of a criUcal value whtch ts not dependent upon shear rate (SabJa. 1964). Examples of
non-Newtontan systems are concentrated solution of macromolecules Uke starch.
pectln. gums and other hydrocollolds. collotdaJ systems such as emulslons. pastes and
suspensions.

The non-NewtonJan flow behavtor Is broadly c1ass1fled loto three main groups:
(1)

1lme-independent flow ln whJch the shear stress depends only on the shear rate

(dllute purees and colloldal systems), (2) 1lme-dependent Oow in whJch the shear stress
can be a funcUon of magnitude and du ration :lf the shear rate as weU as the Ume lapse
between two consecutive applications of sheartng treatment (egg albumbl and
gelaUnlZed foodstuffs), and (3) VlscoelasUc flow ln whlch the fluld exhlblts the property
of partial elasUc recovery upon the removal of the shea.nng stress (gel, dough and sorne
egg products).

Tlme-lDdependeDt "Iow
The ttme-independent flow behavlor ls further charactertzed as a) plastic. b)
pseudo-plastic and c) dilatant flow dependlng on the Influence of shear rate on the
shear stress.

Sheu RIIe

...,ure 1. Ideallzed 00. Cun'U for YarlO1ll rbeolo,lcai .,stems

Plastic or Bfnllham Flow: This type of flow Is dtsplayed by flulds whlch behave Uke a
soUd untll a mtntmum shear stress known as the "yteld stress" ts overcome before the
flow can beglns. Blngham and Green (1919) observed thls type of properties ln oU
patnts. hence such materlals are termed "Btngham plastiC'. Elastlc defomlatlon Is
exhlblted at stresses below yteld value. whUe the plastic flow 15 observed at hlgh shear
stresses (Figure

1).

This system ls characterlzed byan offset stratght-Une relatlonshlp

between shear stress and shear rate. and shows a decreaslng vtscoslly wlth an
lncreaslng rate of shear after yteld value Is exceeded.
The physlcal behavtor of

mater1~:"

wlth a yleld stress Is usually explalned ln

terms of a three-dimensional tntermolecular bondtng structure that Is capable of


preventlng fluid motion for small shear stress. When the appUed shear stress exceeds
the value of yteld stress. the internai structure collapses and allowtng the fluld to flow.
In actual practlce. tt Is dlfflcult to flnd a pure Btngham body. In most cases. a "m'"ed
type" (ElUs fluld) flow behavtor Is commonly observed in whlch the shear

stress-~~ ,~ar

rate plot 15 non-linear above the yleld stress (FiglUe 1). Plastic flow 15 not always as
simple as shown ln FiglUe 1. Accurate estimation of yleld value Is difficult. because the
flow curve of shear stress vs shear rate actually shows three yleld values at low shear
rates for a non-Btngham body (Houwlnk, 1958) as represented ln FtglUe 2. The
extrapolation of the experlmental straJght-line to zero shear rate shows the plastic or
Blngham nature of the flow. The shear stress at whlch curvature beglns in the shear
stress-shear rate plot 15 deflned as "Upper yleld value or Upper Houwlnk value"; the
lntercept ln the vertical axis from the extrapolation of the stralght Une of the curve Is
known as the "extrapolated yield value or Bingham value" and the actuallntersecUon of
the shear stress-shear rate plot on the vertical axis 15 known as the "Lower yteld value
or Lower Houwink value".
The concept of yleld stress ln Btngham plastic was quesUoned by Barnes and
Walters (1985) who proposed that glven a sufilclent Ume. such flulds will not exhibtt a

yteld stress. However, su ch a tJme allowance Is not possible ln practlce especlally ln


food processlng operations. Therefore, the yteld stress parameter can not he avolded.
The magnitude of yteld stress ln sorne semlSolirt (oods such as sauces, spreads, baby
(oods, cultured and fennented daJry products etc.. Is an extremely Important cI1terion
ln detennlnlng Its quaUty.

t"'....-~-

Extrlpollted yleld 'Ilue (IlnpllD)

-J1..
r i)

ri)

- Lower ,teld Yllue (HouwInk)

$beuRlle

...,ure 2. Type. of ylel4 ftlaea loand wlth aome ,Jude OuJda.

Pseudoplastfc Flow: Pseudoplastic Dow behavtor Is the most cOllullonly

observed among the non-NewtonJan flulds. This Is charactertzed by shear-thtnntng over


a largl" range of shear rate; thus the apparent vlscoslty decreases wlth the increase in
shear rate (Figure 1). Shear stress-shear rate curve shows a concavtty and follow a near
linear relaUom:hlp at very hlgh and Jow shear rates. The slopes of the IInear portion of
the CUlVe at low and hlgh shear rates are referred to as "zero shear vtscosity" (110) and
"iIiftite shear vtscosity" (11...,) respectively. The reglon of constant vtscoslty at Jow shear

rate may not be obseJVed

under conunon testing, conditions because

of Jack of

sensltMty at low shear rates of most commonly used rheometers. The Intennedlate
concave reglon represents the shear-thlnning property. On logarlthmlc coordlnates.
these three reglons are more noUceable as represented by the apparent vtscoslty vs
shear rate plot in Figure 3. The pseudoplasUc Dow behavtor Is generalJy charactertzed by
a power law model.
Pseudoplastic behavtor 15 posslbly explatned by the existence of an Interaction
between particles and polymer chalns. Su ch interaction may Involve Van der Waal.
electrostatic and other sunHar types of interactions or they may be due to the allgnment
of rtgld and very asynunetrlcal rnacromolecules or partlcles ln the direction of flow. At a
glven shear stress. a quasi-instantaneous equiltbrlum between the breakdown of
orientation and buHd-up Is reached; an lncrease ln a shear rate results ln the shtftlng of
the equillbrlum towards less orientation. Such a phenomenon Is tnstantaneously and
completely reverslble. and the orientation of parUcle Is random (Doubller and Lefebvre.
1989; Tung. 1978). Sorne common examples of pseudoplasUc Dow are colloldal
suspensions. dispersions. soups. purees etc.
Dilatant Flow: Dilatant flow Is opposite of pseudoplasttc Dow and therefore the

apparent vtscoslty of the Duid Increases (shear-thlckentng) wlth an Increase ln shear


rate {Figure 1}. 1\vo types of dllatancy are observed namely. volumetrie dtlatancy and
rheologlcal dilatancy. The term volumetric dllatancy Is used when "swelllng" of the fluld

10

takes place durtng sheartng. Rheologlcal dllatancy reCers to an lncrease ln the apparent
v1scosUy 10 tncreastng shear rate.
Dilatant behavtor Is shown in densely packed partlcles in whlch there 15 only
sufllclent IJquld to flU the volds. As the shear rate Is fncreased. thfs dense packtng must
be broken down to penott the partJcles to Dow past one another. The resulting
expansion leaves Insumclent lfquld to flll the volds and Is opposed by surface tension
forces. Because of Its mabllfty to saturate the system to the space. the vtscoslty
Increases. This type of behavtor Is exhlblted by Uqulds contalnfng a hlgh percentage of
Insoluble I1g1d parUcles ln suspensions. Sorne examples of thls type are solld. raw
starch suspension. sorne chocolate syrup etc.

lb

Ji

"0

"'""

"\

"e

$bar Race (101 suie)

".,ure 3. IdeaUzed Dow cUJ'Ye for 1 pseadoplasUc fJald

GD

lo,arlthmlc coonUDatea.

Il

Tlme-Dependent Flow

The fluids ln this category exhibit shear rate as a funcUon of both the magnitude
and the duration of shear. and Ume lapse between successive sheartng action. The
apparent vtscosity for such a system depends on its prevtous sheanDg hlstory.
Thfxotropfc Flow: Thixotropic flow Is charactertzed by a reverslble decrease ln
shear stress wlth Ume at constant shear and temperature (Flgwe 4). This phenomenon
Is explatned by the break down of forces that extst between the partlcles of a system

whlch later refonn on standing. Hahn et al. (1959) assumed thlxotroplc system as
conslstlng of two types of molecules. a non-Newtonlan type that Is exlended entangled
and Newtontan type that Is coUed and dlsentangled. In actual pracUce. onlya part of
the long molecule may rernatn as entangled whlle the oilier part is untangled. The
cUsentangled molecules are contafned in entangled molecules formlng a threedlmenslonal network. The equtUbrtum constant detennJnes the relaUve amounts of
entangled and disentangled components. The position of the equUlbrtum Is shtfted by
hlgh shear stress. whlch destroy the network. changtng a saUd to Uquld Uke substance.

Rheopedlc

Thlxotrop.c

nme
'ICare 4. TIlDe depeDdent Dow behaYior.

12

When a sample 1s subJected to a contlnuously Increastng shear rate followed


tmmedlateJy by the conUnuousJy decreaslng shear rate. the resuJUng flow curve
encompasses a hysteresls Joop. The area enclosed by the hysteresls loop ts taken as a
measure of the thixotroplc effect or the magnitude of structure breakdown. Sheth
(1976) demonstrated that the structure breakdown may be completely reverslble.
parttally reverstble or irreversible. as detennlned by the extent of recovery of the original
structural vlscoslty. Other researchers (Hahn et al.. 1959; Van Wazer et al.. 1963;
Cheng and Evans. 1965) have also defined thbcotropy as a completely reverslble
process; however. the majOrlty of food products exhlblt only partlally reverslble or non
reverslble character. A fluld may exhlblt thtxotroplc behavlor in addition to other
vlscous propertJes. Yleld stress Is often assoclated wlth thbcotroplc shear thlnning
behavlor termed as viscoplastiC flow. Cheng and Evans (1965) and Harris (1972)
charactertzed a thixo-viscoelastic behavtor of a fluld whlch

undergc,~s

structure

breakdown. Thixo-vfscoelasticity Is consldered to be present ln varytng degrees ln real


matertal.
Rheodestructwe and Rheopectfc Jlow: The t1me dependent loss of structure ln

many flulds Is not recoverable and flulds that permanently lose structure are called
rheodestructive (Mozes anct Vamos. 1966). This shear thlnntng behavtor Is also termed

as rheomalaxts as proposed by Reiner and Scott-Blair (1967). Examples of thls behavtor


are egg albumen. sorne gum and starch pastes. Ideal thixotroptc and rheodestructive
flulds are compared ln Figure 5. Rheopectic behavlor Is the reverse of thlxotropy (F1gure
4) and that Is why It Is also known as anttthixotropy. The apparent viscoslty Increases
wlth an Increase ln shear rate and the structure soUd1C1es wlth the progress of flow.
ACter resUng. the system retums back to Its Original state of vlscoslty If no phase or
cht:m1cal changes has taken place. RheopecUc behavtor Is observed ln egg white foam

and whlpped cream.

13

'.'

..1

>

t
~

Rheodestl1ldloa
C4nstaat $br.r Rite

No RfCOVa,

Nosbear

nme

Fleure S. Ideal Oow CUlYU ror thbotroplc Uld rbcodestrucUye dispersion.

Vlscoelaatlc Flow
A viscoelasttc fluld possesses both the propertJes of an elasttc (soUd Uke) and
vtscous a fluid (l1quld l1ke) slrnultaneously. For thls type of rnateriaJ. a partial elasUc

recovery 15 obtatned once the stress 15 removed. The flow behavtor of this fluid i5 aIso
Urne dependent but di1Ters from thixotropic fluid as non-lnstantaneous. In partJcular.
the 1n1Ual defonnauon rate of a vtscoelasUc matertal 15 controlled by the inerUa of the
fluld. whereas the 1n1Ual deformatlon rate of a thlxotroplc materiaI depends primartly on
Its iniUal vtscoslty. This dual nature Is ev1dent for sorne flulds and semJsoUds such as
flour dough. cake batters. melted cheese. honey and aged condensed rnUk.

14

JUOLOGlCAL MODELS

Tl1tIE-INDEPENDENT MODEl.S

Several mathematical models have been proposed to charactertze the flow


behavtor of fluids. Most models are based on relatlng shear stress to shear rate under a
given set of conditions. Such models are useful in quantlfytng the rheologlcal behavtor
for varlous applications. The Original Newtontan model (Eq. 1) in which shear stress and
shear rate are linearly related Is too simplistlc to explain the rheological behavtor of
most foods. The more popular and extensiVely used model relatlng shear stress and
shear rate is the power-law model represented by Eqs. 2 &. 3.

a = myn

(2)

or 11 = a/y = mi n-1

(3 )

where: n (flow behavtor index) and m (consistency coefllcient) are constants relating the
shear stress (a) or apparent vtscosity (11) and shear rate (r). The flow behavtor Index
gives a convenlent measure of shear th1nnlng (n< 1) and shear thickenlng (n> 1) nature
of the pseudoplastic flow. In the special case where n

= l,

the behavtor becomes

Newtonlan. The power-law model results in a linear plot on logarithmic coordlnates.


This model ls applicable to several fluld foods over a range of intermedlate shear rates
(Holdsworth, 1971; Rao, 1977).
One of the early models whlch charactertzes the shear stress/shear rate
behavtor for a fluld exhlblUng a yield stress is the classlcal Bingham Plastic [Eq. 7],
(J - a o = llB'

Yfor a

>

(Jo

(4 )

The rheogram of Bmgham plastic flow would be l1near on artthmetlc coordlnates of


shear stress versus shear rate having yield stress as the constant and T'lB, the plastic

viscosltyas slope. Although most foods do not follow a true Blngham plastic flow, this
model has been used to describe the flow behavtor of apr1cot puree, mtnced fish paste

15

and cooked cassava paste (Schaller and Knorr. 1973; Nak.'lyama et al.. 1980 and
Odigboh and Mohsenin. 1975).
One limitation of ab ove equation is that it does not account for the yield stress
which Is the minimum stress necesscuy to cause the fluld to flow. A modifled power law
equatlon accommodatlng the yteld stress (00) is the Herschel-Bulkley model represented
below:

- 00 = m.f1

(5)

The yteld stress is generally determined by extrapolation of the flow curve to zero shear
rate (HaImos and T1u. 1981). The Herschel-Bulkley model has been appUed to several
food systems at 1ntennediate ranges of shear (Rao, 1977; Rao et al .. 1981; Duran and
Costell. 1982; Barbosa Canovas und Peleg. 1983; and Dervisoglu and Kokinl. 1986).
Casson model (Casson, 1959) relatlng the square root of shear stress to the
square root of shear rate has been applied successfully for the characterizaUon of
molten chocolate. This model as shown below is parUcularly applicable for nonthixotropic suspension of attractlng partic1es:
0

1/ 2 -

Kac = Re. i l / 2

(6)

The casson yield stress Roc 2 has been used by many researchers (Charm, 1963: Tung
et al . 1970: Hennansson. 1975 and Rao et al., 1981) as parameter in the HerschelBulkley model.
M1zrahi and Berk (1972) (Eq. 6) model is a modifjed Casson model used to
describe the flow behavior of suspended parUcles in an aqueous medium eontaining
dissolved sugars, salts. acid and peclins.
0

1/ 2 - RoM

= KM f1M

17 )

In this equatlon. K2 0M denotes the magnitude of the yield stress which is influenced by
the concentration of suspended parUc1es. dlssolved peelins and other factors. The
constants, KM and nM detennine the rheological properties of the solvent. henee. nM 1s
0.5 for Newtonian fluids and less than 0.5 for pseudoplasUc fluids. Mlzrahl and Berk

16

(1972) noted that this general1zed method Is in better agreement wtth a exper1mental

data over a wide range of sheartng rates. Mlzrahl and Flrstenberg (1975) reported that
Mlzrahl-Berk model fltted more closely than the Herschel-Bulkley model for the
rheologlcal behavlor of low pulp concentrated orange Julee.
The models d15cussed above. are best applicable for lntermedlate shear rate
range. Since. shear thlnn1ng Oulds dlsplay a Newtonian v1scoslty at very low and high
shear rates. their rheologlcal properttes can not be fully described in tenns of the above
models. The Powell-Eyring n!~del (Eq. 8) was developed to descrtbe the flow behavtor of
a shear thlnning flulds based on a zero shear and an 1nfIn1te shear vtscoslty
represented by T'lo and T'loo' respectively. This model (Eq. 8; b as a constant) has been
found sultable to descrtbe the rheology of food systems (Rozema and Beverloo. 1974).
o

= T'llIOi

[(T'l o - T'loo)/Pl stnh- I

(Pi)

(8)

Doublier and Launay (1974) appUed the model developed by Cross (1965) to
characterize the flow behavtor of guar gum solutions over a wtde range of shear rate
(0.16 - 17.6005- 1).
(9 )

Ellis model (Eq. 10) has been round useful to descrtbe pseudoplastlc flow at low
through Intennedlate shear rate because the model lnc1udes zero shear apparent
vlscoslty.
1/11 = 1/'l0 [1 +

(0/00. s) a-Il

(10)

where: 00.5 corresponds to the sbear stress for non-Newtonlan vtscoSlty of 0.511 0 , The
parameter a indlcates the shear thlnning reglon of the pseudoplastlc rheogram.
Michaels and Bolger (1962) postulated that the stress requlred to produce
defonnation or flow at a constant rate conslsts of three parts as shown below:
(11)

where: On and Ocr are stresses required to break the network structure and structural
bonds formed by shear tnduced collision of partides and 0v! 15 the stress needed to

17

overcome the Vlscous resistance to produce flow. This model explains the flow of
mechanlsm of suspension of fruit puree. At zero shear rate. the network zero yteld
stress. Gn Is equlvalent to Go' and Ger Is equlvalent to Gb (Btngham yteld stress) at
hlgh shear rate. The avt equlvalent to 1100' the vtscous flowat Infinite shear rate. The
prtnclple contribution of thls modells the Introduction of the three parameters

0'0'

O'b

and "00' and the roles played by the partlcle concentration and partlcle propertles. This
model has been successfully applled by Duran and CosteU (1982) and glu and Rao
(1988) to evaluate the flow behavtor of apple sauce. aprlcot puree etc.
Recently. Ofoll et al. (1987) proposed a versatile rheologlcal model conslsUng of
four parameters for viscomet.ric flow as stated below:
" = [(O'o/y) nI + 1'\00 'f'2 -nI] l/n 1

(12)

where: nI and n2 are functions of shear stress. yteld stress and shear thlnnlng as weU
as related to fluld flow behavtor. This model Is bel1eved to represent accurately the
shear stress vs. shear rate or apparent vtscoslty vs. shear rate relaUonshlp for several
nonelasUc food matertals. AlI the convenUonal rheologlca1 models can be obtaJned from
the above model by approprtate specification of the four parameters.

TlME-DEPENDENT RlOLOGlCAL MODELS

The conunon approach employed to characterize the Ume dependent flow


behavtor Is either (i) to evaluate the stress decay under a steady shear over a speclfled
Ume. or (U) to measure the hysteresls Joop. the area between up and down curves wlth
the shear rate progranuned to vruy as a funcUon of Ume. The flrst approach glves a
more complete infonnation on the Ume dependent rheologlcal behavtor and can easlly
be evaluated by the Single point vlscoslty measunng dev1ces used conunonly ln food
research.
The followtng model was proposed by Weltman (1943) to descrlbe the change ln

18

apparent viscostty wlth Ume,

" = Al

- BI log

(13 )

(t)

where: Ails the shear stress at unit tlme (l) and BI ts the tlme coemc1ent of thixotropic
breakdown. This model descriiles the continuaI decay oC stress, wlthout reachlng the
state of equlllbr1um even on prolonged shear1ng.
A second model developed by Hahn et al. (1959) to Inc1ude an equllIbrium shear
stress that followed the ftrst order type relattonship was used by Duran and Costell
(1985) and Paredes et al. (1988):
(14 )

Longe et aI. (1966) studled vlscoslty of custard systems contalnlng sugar uslng a
slmllar equaUon:
ln hl - 'le}

=Ct

(15)

where: C is the rate of structural breakdown and 'le Is the apparent v1scoslty at
equlhbrium at a glven shear rate. A modifted Hahn et al. model, ln the fonn of Eq. 16.
was reported to better descr1be the tlme dependency of sorne foods (Tung et al . 1971):
log (" -Tle) = Al - BI log (t)

(16)

Cheng and Evans (1965) proposed a model based on theorettcal consideraUons


related to state and rate:

il Y

State Equation:

(7

Rate Equation:

d/dt = g (, il

= TI (A,

( 17a)
(17b)

where: A Is a structural parameter ranglng from zero to one, and g Is another structural
parameter whlch is a functlon of both i and

The vtscoslty and rate of breakdown are

treated as a function of shear rate and structural parameter in the above equatlons.
Cheng and Evans (1965) reported that these equaUons are applicable to any single
process of structural change.

Woodmann and Marsden (1966) Introduced the followlng empirical relatlonshlp

to describe the stress decay of a thixotropic phannaceuttcallotton:

19

(18)

where: (JI and (J2 represent shear stresses at tlmes t1 and t2 respecUvely. The rate
constant, k, was reported to remain approxtmately constant at shear rates below 200
s-l. This equaUon reveals a contlnuous destrucUon of structurt' for a long sheartng
Ume.
Higgs and NomDgton (l971) detennined the rate of structural breakdown of
sweetened condensed m1lk, by measurtng the coefficient of thlxotroplc breakdown wU.h
Ume, "B" and the coefflcient of thlxotroplC breakdown due to Increasmg shear rate. "M"
(Green, 1949; Wllkinson. 1960) as glven by the foUowmg equaUons:
B = (lh M = (lh -

1'I2)/ln (t2 / t1)


'I2)/ln

(19)

(N 2 / N 1 )

(20)

where: TIl and 112 were v1scosltles at tlmes t 1 and t2 (Eq. 19). and at the angular speeds
NI and N2 (Eq. 20), respecUvely.

nu and Bolger (1974) proposed a rheo-klneUc model to descrtbe the rheologlcal


behavior of mayonnaise whlch exhiblts a yteld stress, pseudoplastlc behavtor and Ume
dependent characterlsUcs. This model was based on Herschel-Bulkley mode! (Eq. 3)
modified to include a structural parameter .. rangmg from an iniUal value of untty for
zero shear Ume. to an equ1l1brlum value. .e belng < 1.

= (0 + K

f1)

(21)

Accordlng to Petrellis and Flumerfelt (1973), the rate of decay of structural parameters
foUowed a second order rate equatlon:
rl/dt

= -k1 (-

for

- e) 2

Since apparent viscoslty Is defined as '1 =0/"1,

> -e

wlU

(22)

be related to viscoslty as.

='Iy/oo+K'f

(23)

Under equlllbrium conditions. . and 11 are replaced by .e and 11e' Another form of
equatlon was obtained from Eqs. 22 and. 23 relating apparent vtscosity and Ume:

l/hl - 'le) =

1/(1'1 0

'le) + aIt

(24)

20

This model was shown to be in agreement wtth the behavior exhlllted by Ume
dependent emulslons l1ke fruit purees (Ford and Steffe, 1986), soft cheese (MassaguerRoig et al . 1984; MarUnez-Pad1lla and Hardy, 1989). It was also polnted that ooly a
Umlted part of the curve namely at the 1n1t1al perlod when lt behaves ln a ltnear fashlon,
should be used to evaluate the rate constant (MartJnez-Padtlla and Hardy, 1989).
Xu et al. (1984) proposed a more sophtsUcated model, whlch employs a series of
two ftrst order rate functions (denoted by subscl1pts 1 and 2) yteldtng a sum of two
exponentlal functions:
G-(Je

= (Go, I-Ge, 1)

exp(-K1t) + (Go, 2-CJe, 2) exp(-K2 t )

(25)

Recently, Martlnez-Padnla et al. (1989) Introduced an emplr1cal relation


correlattng the thlxotroplc behavlor wtth three variables namely, shear stress, shear
rate and tlme via multiple regresslon. Llke the power law (log s vs log g), the tlme etTect
Is also Included ln the 10ganthm1c fOTm of th15 model. Another signttlcant aspect of thts

model 15 the inclusion of yteld stress. This proposed relationshlp 15 based on the
Herschel-Bulkley model whlch includes the Ume effect:
CJ - Go

= K

.yn

t-P

(26)

where p represents a thlxotroplc stress parameter.


Mottar et al. (1989) estimated the reslstance to structural (R%) breakdown by
the companson of up ('11) and down ('12) viscoslty at spec1flc shear rates:
R (%)

=100 ('12/'11)

(27)

FACTORS INFWENClNG VlSCOSlTY

Temperature
Temperature has an inverse effect on the vlscoslty of llqulds. This effect ls

explatned by the reaction rate theOly of viscoslty (Eyrlng, 1936; Ewell, 1938) whlch
postulates that the energy of activation for a Dow process results from the formation of

21

a number of "holes" or extra spaces. The total volume occupled by the holes, tenned as
"free volume". allows the Molecules to flow lnto. Any factor llke temperature. whlch
changes the free volume will affect the vtscoslty. At lower temperatures. the fluld
becomes thlck. so a larger hole or htgher activation energy Is necessary for flow and, as
a result. the vls(!oslty Increases. On the other hand. at hlgher temperatures. the fluld
becomes thtnner, needs a smaller hole to flow and thus the vtscoslty decreases.
Slnce the vlscoslty of a fluld Is hlghly temperature dependent. the Imowledge
concemlng the etTect of temperature on the vlscOSlty has a special stgnlflcance ln
determlnlng the conditions of precessmg to be adopted durtng evaporaUon.
pasteurlzaUon,

sterlllzaUon,

concentraUon

and

handlmg.

Recent

work

by

Anantheswaran and Rao (1985). Rao et al. (1985) and Telxelra and Manson, (1983)
revealed that heat transfer to and from non-NewtonJan flulds can be best analyzed if the
pertinent rheologlcal parameters are fully establlshed.
For Newtonlan behavlor, the ArrhenJus equaUon has been employed to descrlbe
the effect of temperature on vlscoslty (Saravacos, 1970: Rao and Anantheswaran, 1982:
and Rao et al., 1984):
TI

= F exp (Ea/RO

(28)

where: TI = vlscOSlty, Ea = activaUon energy for vlscous flow, R = gas constant, T =


absolu te temperature and F = frequency factor. The acUvaUon energy of flow ts deClned
as the mlnlmum energy necessary to be overcome before the flow beglns.
Rao et al. (1986) found Fultcher (Eq. 29J model to be more sultable for the
temperature dependence of hlgh sugar food products such as syrups and concentrated
fruit jutces at low temperature:
ln 1'1

= A + BIO' - Tol

(29)

ArrhenJus equaUon Is also employed for non-Newtonlan flulds with sorne


modificaUons. Thus, TI should be replaced by 1'Ia to represent the apparent vlscoslty at a
specifie shear rate.

22

Corey (1972) found that the actiVaUon energy and concentrations (C) of
suspensions were related by the general equaUon lA. B and a were constants):
E = A exp (-B Ca)

(30)

The value of constant "a" was reported to he 1/2. 1, 3/2 and 2 for a minerai 011.
propylene glycol, slUcone oU and 61 <Srtx sucrose soluUon respecUvely.
Turtan (1964) related the flow parameters, such as m and n, to temperature in
an attempt to evaluate thetr temperature dependence:
log m = log IDa - AT
n=Ilo+ BT

(31)

(32 )

During the heat ster1lIzaUon, a fluld Is subJected to both htgh temperatures and
shear gradients. Power law model and Arrhenius equaUon have been comblned as
follows (ChJ1stiansen and Craig, 1962; Harper and El-Sahrlgt. 1965):
(7

(7

=KTC (C exp EaC/ROn


=Km exp (EaH/ RO Cn

(33 )

(34 )

where, n ls an average value for data of a1l the temperatures. Though not identlcal
(VItali and Rao, 1984), the two activaUon energles are inteITelated as follows:
EaH

=n EaC

(35)

Harper and EL-Sahrlgl (1965) proposed the foUowtng model to combine the
effects of temperature and concentration of tomato Julce concentrate:
1'Ia

=a

exp (Ea /Rl1 C ~

(36)

where: a and p are constants and C ls concentration ln Darlx. In most practice, thls
equaUon Is vaUd only over a Umlted range ofvartables (VItali and Rao, 1984).
Rao et al. (1981) comblned the Arrhenius model and the exponential fonn of the
effect of concentration to obtaln apparent vlscoslty,
1'Ia =A exp (Ea /Rl1 exp (B C)

(37)

The coefficients A and B are obtalned experlmentally by multiple regresslon. In the


above equaUon, conslstency Index may replace apparent vlSCosity (Rao et al., 1984).

23

ConcentntloD
Extensive studles have been carried out on the efTect of sollds concentration on
vtscosity at a glven temperature. The flow character of many food systems may be
greatly modlfled by the changes ln the concentraUon of one or more soluble soUds. In

general. vtscoslty increases wlth tncreastng concentrations. Higher concentration of


soluble soUds can lead to non-Newtonian or plasUc dUatant flow behavlor. This Is
explained by Increased partlcle-partlcle or parUcle-medlum interaction and by the
competiUon amung the various solutes present for the avallable water.
The early theoreucal work relaUng Vlscostty to volume concentration may be
attrtbuted to Einstein (1906. 1911) who proposed that.
1'\ = 'Ils ( 1 + a+)

(38)

+Is the volume concentraUon of the parUc1es. and a Is a constant havlng value 2.5. This

......

equatlon 18 val1d only for dUute suspension where 4 Is less than 0.05 and no parUclepartlcle InteracUon occurred. and partlcles are uncharged.
The flow behavtor of suspensions at hlgher concentration devlates from the
Einstein equatlon due to hydrodynarntc interactions between partlcles and the vlscoslty
increases exponentlally. Two general equaUons have been proposed to relate vlscoslty
and concentration (Harper and El-Shartgl. 1965; Rao et al . 1981).
K=K 1 CAI

(39)
(40 )

where: C 15 the concentraUon and Al and A2 are constants. The power law equaUon
(Eq.39J hru; been appUed to pureed fruit and vegetable prad ucts whlle the exponenUal

forrn fltted data for apple Julce (Vitali and Rao. 1982: Harper and EI-Sahrlgl. 1965 and
Rao et al . 1984). A modtfied exponentlal equation was proposed by (barz et al. (1989)
for the rheology of clarlfled pear Jutce as in1luenced by concentration and temperature :
11 = KI exp (Ea/RT + AC + BC2)

(41)

24

CIlAPl'ERm

YOGlJRT: CLASSIFICATION, 1IANlJII'.ACTORB AND RBEOLOGY

Yogurt ls one of the oldest processed food products, yet until recently the
product has been very poorly deftned and understood in the Uterature (Krager, 1989). A
single common definJUon for yogurt ts dlftlcult ln view of the large vartety of products
presently avaJlable

in

market place, ail

diffenng

in

chemical composlUon,

mtcroblologlcal status (active or Inactivated starter culture), blochemical characterisUcs


and organoleptic properUes. In the general sense, yogurt may be referred to as a
semtfluld fennented mtlk product with a smooth texture and a mtldly sour taste and
navor. The bacterial culture for the fermentation usually conslsts of selected straJns

Streptococcus thennophilus and LactobacUlus bulgart.cus. The characteristic navor of

yogurt Is due to the aroma compounds acetaldehyde, acetone, ethanol, butane-2-one,


diacetyl and ethyl acetate, wlth lactic ac1d contribuUng to the acid taste.
The organolepUc characterisUcs of yogurt ls dependent on the physicaJ
characterisUcs of end product such as conslstency/viscoslty, texture, ftrmness, body,
taste and flavor. These characterisUcs are ln tum jn11uenced by the chemicaJ
consUtuents of milk such as fat, protein, lactose and mtnerals (ash). Of these
consUtuents, fat produces a rich and creamy texture wlth an excellent mouthfeel to the
yogurt. Proteln ls mostly responsible for the viscoslty or conslstency of the product.
Lactose provides the source of energy for starter organtsms. The sensory properttes of
the yogurt depends therefore on the type and composition of mtlk.

TI'PES OF YOGURT

Several types of yogurts are available commercially whlch can be c1assified in

25

different ways based on (1) chemlcal consUtuents (U) method of producUon (lU) nature of
the flavor present and finally (Iv) on the nature of post IncubaUon process. Yogurt may
also be categortzed based on thelr physlca1 fonn.
ln tenns of chemtcal consUtuents (malnly fat) yogurts are classlfled into three
groups: fuU. or highfat. parttaUy sktmmed or medtumfat and sktmmed or low fat yogurt.
Based on the method of production. yogurts may elther be set or sHrred type.
For set type yogurt. the gel structure ts fonned dlrecUy in the container durtng the
fennentatJon/incubatJon step. leadlng to the fonnatJon of a contJnuous seml-soUd
mass. For the stirred type. on the other hand. the IniUally fonned gel structure Is
broken by agitation durtng the coollng process. yielding a smooth and seml-vlscous
product (Tamime and Robinson. 1985). A third type of yogurt. jlufd yogurl. Is a sUrred
yogurt of low viscoslty and low soUd content obtatned by mbdng yogurt and water.
Yogurts may he dtfferentiated on the basts of fruit or navor added. Thus. they
can be of three types. namely plain or natural, jruU and jlavored. Plain yogurts are
natural fonn of yogurt wfthout any additives except sugar or sweetentng agent ln sorne
cases. They posses a dIstinct nutty arorna and sharp acldlc taste. Fhdt yogurts are
made by the addition of fruits in the fonn of preserves. purees. Jams or concentrates
and sugar or sweeteners. These yogurts may elther be sundey or swlss style. The fonner
ls made from set type of yogurt wlth the fruit at the boUom of the container whereas for
latter. the addtUves are Incorporated untfonnly ln the sUrred yogurt. Flavored yogurts
are those whtch are

enrtched wtth fruit juices/concentrates. synthettc/natural

flavorings. colortngs. sweetening agents and stabllizers.


Yogurt Is marketed 111 severa! forms followtng the fennentation/incubaUon
process to extend thetr shelf-life: pasteurtzed. frozen. or dried product. Such
modtflcaUons

would

result

in

changes

of chem1ca1

compositions.

physlcaJ

charactertstics and organoleptJc propertles of the end product. UHT/pasteu.rlzed yogurt


ts a heat treated product to reduce the mlcrobtal level and may result ln the level of

26

volatile compounds that are assoclated with navor of yogurt. Frazen yogurt. elther as a
hard or soft pack. ls sold Uke lce cream or a frozen sUck. and Is popular due to the
deUghtful taste and health reputatlon. Hlgh quantity sweeteners and emuls1flers/
stabll1zers are needed to malntaJn the structure during the freez1ng process.

Concentrated/ condensed/ stTatned yogurt are prepared by the parttal el1minaUon


of whey from yogurt. Thetr rheologlcal properUes and characterisUcs differ from those of
original yogurt because of the changes in their physlcal form. These concentrated forms
of yogurt are consurned directly or as Ingredients ln the preparation of many types of
daJJy products ln sorne parts of the world (mainly Middle East and Europe).
Drled yogurt is another form of yogurt obtatned by the post incubaUon

dehydration by sun, spray or freeze drying. "Kashak" a typlcal ex:ample of sun drted
yogurt. containtng herbs as extra Ingredients. avatlable in the Middle East. The nature
and quality of the drted yogurt depends on the number of viable cells ln the product

which ln tum determtne thelr appllcaUons as starter culture or as an Ingredient. Two


fonns of drted yogurts are commercially avallable. One of them (reconstituted yogurt)
requlres incubation to fac1l1tate gel formation whereas the second one lmown as
"Instant Yogurt" needs only a short pertod of Ume for coagulation due ta Us increased

hydrophilllc nature.
A recent addition ta the llst Is the drinktng yogurt. prepared by m1x1ng low-fat
yogurt with fruit julce, sugar or sweeteners and stabU1zers su ch as pectin. Pasteurtzed
drink1ng yogurt can be stored at room tempe rature up to 6 months. These yogurts are
I1ght (reduced calorie) and refreshlng but not thirst quenchtng unless carbonated.
Low calorie yogurt

Is prepared by fermenttng low fat m11k

(l %

or less fat) and

blended wlth additives such as carrageenan, gelattn. etc., for building the texture.
Another variaUon 15 the low lactose yogurl achleved by the use of an enzyme, p-D-

galactosidase, whlch hydrolyzes the lactose leading to a sweeter product. This product
15 parttcularly suitable for lactose Intolerant (hypolactasla) people.

1
27

MANVFACTVRE OF YOGURT

The art of maktng yogurt. has been known to manktnd slnce anclent Umes but
sclenttflc detalls of the manufacture, untU recently, were not clearly understood. Since
the mllk necessary for the manufacture of yogurt may be procured from several
mammallan sources. thefr chemlcal constituents and consequently the physlcal
propertJes of the end product will durer wtdely. This causes the necesslty of
standardtzation and fortification of yogurt milk.
Clar1fication 1s the first step in the processlng yogurt mllk to rernove the visible
dirt and somatic cells by either filtration or ln a specially deslgned separator ln the
yogurt lndustry. Followtng this, the fat content of rnUk 1s standardtzed (1 to 4%)
accordlng to legal composltlonal standard that may vary ln dlfferent parts of world.

Fortification of yOlurt mllk


The major alm of forttficatlon of milk 1s to increase the level of proteln content
thereby enhanclng the conslstency/vtscoSlty and firmness of the end product. The
fortification can be carrled out elther by addiUon of proteln rich powder (soUds-not-fat.
SNF) or by concentration of mllk.
SNF ln the yogurt lndustry Is mainly of dairy ortgln ego milk powder (skinuned),
caselnate. co-precipltate and whey proteln concentrates/powders. Sorne UrnJted
application of plant proteln to enrtch total solid content 15 also reported ln the literature
(Schmidt et al. 1980).
Supplementation with skJrn mJlk powder (3-4%) 1s a common pracUce to
lncrease the SNF of the yogurt milk. Excessive use of sktm mllk powder lnduces a
powdety flavor to the yogurt and leads to the production of an increased level of acld
during storage. Yogurt may also be fortlfled wlth butter mflk but Us use Is not very
common because of Its limlted avatlabllity. Caselnates dlrectly lncrease the level of

28

proteln. However hlgher level (>2%) of casemates in the basic m1x results in an
undestrable and uncontrolled thickness of the product. Tae level of whey powder
generally recommended is around 1-2%. Higher level 15 avotded to prevent undestrable
whey flavor and butld of lactose content. Evaporation and concentration by reverse
osmosis have also been resorted to increase the solids level in the yogurt mtlk.

Addition of atabWzera

Stabtlizers or hydrocollotds are often mlxed duJ1ng yogurt manufacture. Such


additions bear a greater stgn1ficance partlcularly durtng the mechantcal treatment such
as pumping, m1x1ng etc. of yogurt gel after incubation. StabU1zers may be natural,
modiJled or synthetic gums but their use must have prior sanction from appropriate
authortties and Is subJect to leglslation and regulation. Stabiltzers function as
thlckeners or geUing agents due to their hydrotion property and stabiltzing action on the
proteln leadlng to restrlcted movement of water molecule. The chemtca1 nature of the
stabilizers determtnes the exact step at which theyare to be added. Thus, stabUlzers
may be incorporated to elther cold mtlk before pasteurtzation, or to the hot mtlk
bnmedtately after pasteurtzation or to gel/coagulum after incubation. Appropriate
selection of stabUlzers and its level of concentration play a major role to achteve the
desired charactertstics. Flavored yogurt, UlIT/pasteurtzed yogurt, frozen yogurt and
other yogurt based products require stabUizers to lmprove their qualtty.

Sweetenen

Sweeteners are routinely added durtng the manufacture of fruit or flavored


yogurt and plain sweetened yogurt in order to mask the actdlty and to enhance the
added flavortng matertal (i.e. fruit or beny). The amount of added sugar varies from 3-

(,

4% for plain YOgUrt to 8-12% for frult-based yogurt (McGregor and White, 1987). The
addition of sugar ts desirable before the heat treatment as the damage to m1lk coagulum

29

Is mlI1JmJZed. The level of added sugar should be carefuUy controlled to prevent an

extensive proteolys1s leadtng to bitter flavor (Slocum et al. 1988). Alternate sweeteners
such as hlgh fructose corn syrup. sorbitol. cyclamate. saccharin. fructose have also
been used (HyvOnen and Slotte. 1983: McGregor and White. 1986),

Homogenizatfon
eonunercially. homogentzation Is generally carrled out at 60-700 C under 100200 kg/cm2 pressure prlor to heat treatment. HomogenJzation reduces sizes of fat
globules

l.O~)

whlch gets adsorbed onto the casein mtcelles ('ramime and Robinson.

1985), This increases the effective total volume of suspended malter which in tum
ttnproves vtscoslty1consiStency of the product.

Pasteurization
Mllk may be pasteurlzed by several techniques: vat pasteurizatton (85 e for 1040 minutes). htgh-temperature short Ume or HTST treatment (98 oe for 0.5-1.87 minI
and ultra high temperature or mIT treatment (l400 e for 2-8 sec). UI-IT processlng of
mtlk offers certain advantages in tenns of better process control. sanitation. potenUal
energy. Ume savlng over the conventlonal batch type heaUng. The role of above heat
treatment ls to destroyany pathogenic microorganlsms present ln the yogurt milk. Il
produces certain factors that can stlmulate the acUvity of starter culture and aJso
red1stribute calcium. phosphorus and magnesium conta1ning mlnerals between the
soluble and colIoidal parUcles whlch affect the fonnatton of curd parUcles and help to
decrease the rate of coagulation. Besides the above functlons. heat treatment of yogurt
milk alsa changes the physico-chemical structure of m1lk proteins. an Important aspect

related to yogurt texture.


Milk prote in 1s composed of casein which exists as colloidat aggregates and
globular whey or serum prote1n in solution. The interaction between denatured whey

30

proteJns and caselns detennlnes the stabllJty of the yogurt gel.


ScannJng electron microscopie studies reveal that the size of the casetn micelles

Increases gradually on heatlng and fonn a chain matrtx (Kalab and HaIWalker. 1973).
As a result. partlcles are un1fonnly dlstrlbuted throughout the yogurt entrapping

aqueous phase withln the network. The resulUng coagulum becomes ftnn and less
susceptible to synerests. On the contraJY. unheated mIlk ytelds weak coagulum of
coarse network by fOnnlng aggregates with unevenly distr1buted proteins whlcb impairs
immoblUzation ofwater (Kalab et al . 1983).
The degree of denaturaUon of whey proteln 15 an important factor a1fecttng the
texture of end products. The deslred level of denaturatlon depends on the type of the
product manufactured. Plain yogurt with the minimum content of total soUd (9.5-12%)
needs extensive denaturatlon of whey prote1n whlle yogurt contalning b1gher level of
total soUds (above 14%) or frult/flavored yogurt require less denaturation (Puban.

1988).

Coolfng & Inoculation


The treated _uilk Is cooled to the optimum Incubation temperature of starter
culture: 40-4SoC (shvrt Incubation method) or 300 e (long incubation method). The
next step 15 Jnoculatlon whlch Is canied out with a fresbly made bulk starter or deep
frozen drted form of concentrated starter and IlXed at a rate of 2-3% under the desired
conditions of temperature with mllk. Conunonly mixed starter culture consists of a
mixture of S.thennophillus and L. bulgartcus ln al: 1 ratio. The cholce of starter culture
15 not

solely restrtcted to the above two.

Incubation
Immediately after Inoculation. the wann m1x 15 pumped Into fermention vessels.
the nature of whlch depend on the type of yogurt desired: set or stlrred. For production

31

of set type yogurt. the fennentaUon/lncubaUon ts can1ed out ln the retatl container.
The containers are Incubated at the approprlate temperature tn a cabinet or a tunnel.
In case of sUrred yogurt. the Inoculated mllk 18 dellvered Into a fermentation tank for

bulk Incubatlon at the opUmum temperature for 3-6 hr. This fermentaUon process can
be elther of batch-type or of conUnuous type. the former belng more

COnunOll.

The

conUnuous fennentaUon procedure 18 carr1ed out ln two stages. In the first stage.
known as pre-fennentation of mJlk. bacterlal multipUcatlon takes place. the pH belng
kept constant with the addition of fresh mUk. In the subsequent stage. formation of
texture occurs wtth further acidification. In a completely conUnuous process. the
fonnation of a good structure ln the final product Is difficult to obtatn.
Durmg Incubation. lactose 18 converted to lacUc acld by the lactose
dehydrogenase present ln the S. themwphJJ1us and 1... bulgarlcus. The lactlc acld
destablltzes the caseln micelles by convertlng the colloldal calcium phosphate complex
..~.. JI

in the nUcelles to the soluble form. The resultlng graduai loss of calcium from the
micelles leads to coagulation of casein at pH 4.6-4.7 and formation of the yogurt
gel/coagulum.
The incubation temperature and urne both affect the texture of the coagulum
fonnation (ropiness or roughness). the organoleptlc propertles (aroma production) and
also the degree of proteolysls. ExcessiVe proteolysls may result ln synerasls and
undestrable navors (Slocum et al . 1988).

Cooling and Storage


As soor. as the deslred acidlty is achleved. the yogurt coagulum Is cooled 10

<lOoe. The main purpose of cooling is to reduce the actlvity of microorganisms and is
achieved elther by one phase or two phase methods. In the one phase method. the
yogurt Is cooled dlrectIy from Incubation temperature to below IOoe. In two phase
cooling, the temperature ts lowered filst to 15-200 C and flnally to below 100 e. the latter

32

being perfonned in the retaJl contaJner

10

avoid any damage to the vlscoslty. Bulk

cooltng can take place elther in incubation vessels (in-tank cool1ng) or ln tubular or
plate heat exchanger, the latter betng faster. The rate of cooUng detennines the
conUnued act1v1ty of the mtcroorgarusms and Is therefore Important wlth reference to
the acldlty of the end product. For cooltng of set yogurt, a cold air tunnel or cabinets Is
employed. On the other hand, for stJrred yogurt, c:I1fferent processes are adopted to
attaln desired vlscoslty (Anon, 1977) through the foUowtng steps: (1) breaklng ..he
coagulum in incubaUon tank Ull homogeneous, (U) pre-cool to 240 C and packaged (UI)
final coollng at 5-60 C ln the cold store. The manufacture of sUrred yogurt needs careful

consideration because of the potenUal danger of serum separaUon ln the final product
(Webb and Whltter, 1970).

Addition qffruit andftauor


A varlety of different ingredlents (fruit preserves, canned/frozen fruit, syrup,
puree, concentrate, natural or syntheUc flavors, colonngs etc.) can be incorporated into
the yogurt to fmpart the deslred characterisUc.
For flavored yogurt, flavonng agents (sol1ds or essence) are i&dded to the yogurt
basic m1x before IncubaUon. This Is not possible ln case of fruit or honey yogurt as
lacUc acld fennentaUon Is affected by the large amount of sugar. In sundae style set
yogurt, 15-18% by weight of fruit puree, fruit preserve or syrup Is poured on to the
boUom of the container foUowed by the inoculated m1lk. The containers are sealed and
Incubated.
For mixlng of yogurt with fruit two main types of methods are followed. In batch
system, yogurt and fruit are blended together ln the tank elther manually or
mecharucally. In contlnuous systems, thls Is done by uslng pumps and in-line staUc
mixers.

33

Storage
The temperature at whlch the yogurt product Is Onally stored detenntnes tls
shelf ltfe. The conunon storage temperature ts around SoC. At thts temperature. the
qualtty can be preselVed for a period of 3-4 weeks. A cOlIUllon consequence of storage Is
the over acldlty resulUng from the metaboltc activity of the starter culture. The hlgh
actdtty will lead to Increase ln proteolysts and a hlgher level of free amtno acld whlch
may he of precursors for undeslrable flavors such as blttemess (Groux. 1976; Vlanl and
Honnan. 1976). Production of excess lactic ac1d durlng storage also results ln a strong
undestrable acld taste. Over acldlty can also modlfY the physlcal characterisUcs of
yogurt and alter the product conslstency/vlscoslty (Orlessen. 1988). Another Important
aspect of storage 15 the increased ltpolytic acUvity of the starter organtsms resulttng ln
hydrolysls of fat and production of more free fatty aclds.

RIIEOLOGY OF YOOURT

or the two types. set yogurt may be consldered as a vlsco-elastic soUd where
elasticlty Is pronnent; whereas. stlrred yogurt 1s essenUaIly a vtsco-elasUc lIquld
meanlng vtscoslty Is predominant. Thus. both contaln an elastlc component as well as
viscous component. but thetr relative proporUon varies conslderably from one another.
MaJority of the pubUshed Uterature on yogurt relates to set type yogurt
(Galesloot. 1958; Webb and Whlttler. 1970; Nlelson. 1972; Prentlce. 1972; Dannenberg
and Kessler. 1988a.b; Rohm. 1989). A few studles have also been carrled out on sUrred
yogurt (Martens. 1972; InagakJ. 1986; NlshUlma and Inagaki. 1987; Hellinga et al.
1986.). especlally on the studles relaUng to stress decay behavlor. Yogurt has been
generally recognized as having a non-Newtonlan. thixotroplc. Ume-dependent. shear
thinning flow behavtor wtth an assoclated yleld stress. 1t Is commonly observed that
shear stress increases rapidly at the beginntng showing a yield point. This phenomena

34

tndicates a strong btndlng Corce glVlng ft the character of an elastlc soUd. In less flnn
and soCt yogurts, the gel structure undergoes only elastlc defonnatlon; but at high
shear rates exceedlng the yield value, gel structure undergoes a breakdown resultlng ln
viscous flow behavtor (Dannenberg and Kessler, 1988b).
To evaluate the flow behavtor of sttrred yogurt, Casson and Herschel-Bulkley
model has been more widely employed (lnagakl, 1986). lIellinga et al. (1986)
charactertzed rheological propertJes ln tenns of a modUled power-Iaw equatlon of
Ostwald-de Waele. They calculated the initial values of viscoslty by extrapolatlng the
curves to zero Ume.
Yogurt has also been charactel1zed as undergotng a stress decay behavtor wlth
tbne of shear showtng htghly irreversible decrease oC vtscoslty

(Nlsh~1ma

and lnagald,

1987: HelUnga et al., 1986; Driessen, 1988). The obselVed dlm1nJshlng stress
corresponds to the decreasing average hydrodynamic dlameter of protein partlcles,

whlch Is a Cunctlon of shearing Ume and rate of shear for a given sample. Korolczuk and
Mahaut (1989) charactenzed the stress decay behavlor of acld type cheese whlch have a
sbnllar structure to stlrred yogurt, by ustng Weltman logarithmic time-Ioganthmic
vlscoslty model. The magnitude of structural breakdown was quantlfled by comparison
oC the vlscoslty oC upward and downward curves and expressed as per cent of shear

reslstance (Mottar et al., 1989). The area oC under the hysteresis loop was used to
evaluates the Ume dependent thinnlng of gel structure (Dannenberg and Kessler,
1988b). The structural regeneratlon of yogurt gel 1s not complete (Ramanauskas and
Urbene, 1973; Fol<eev, 1973) and Is llkely to be dependent on the process shear hlstory
and other process variables (Steventon et al. 1990; Rohm, 1989). However, accordtng to
Bottazzl (1976) such a recovery ls complete. Steventon and co-workers (1990) studied
the effect of processlng and shear on the vlscoslty of yogurt under the conditions which

sbnulate the manufacturing system.

35

BffecQ of proce....., ftI'Iable.

OD

rbeolOO

The texturaI charactertstics of the yogurt gel depend on each step ln the
manufacturtng technology dlscussed earller, namely standardlzation, heat treatrnent,
cholce of culture, Incubation temperature and Ume, etc.
Hlgher total solld content ln the yogurt has been assoclated Wlth hlgher
vlsCosity/finnness of the gel (Puhan. 1988; Wolfschoon-pombo et al. 1983: Becker and
Puhan, 1989; Rohm, 1989; Tamime. 1977; Tamime and Deeth. 1980). A small
dlfference (-1 %) ln the soUds could result ln stgnlflcant dlfTerences ln vtscoslty of
yogurts (Dannenberg and Kessler, 1988b: Becker and Puhan. 1989). Caselnate acts as
a stablUzer and Increases the vtscoslty and conslStency of the product (Tam1me and
Robinson, 1985). In the Na-caseinate forUfied yogurt. the gel strength ls enhanced as
compared Wlth sklm milk powder and whey prote ln (Modler et al. 1983; Robinson and
Tamlme, 1986). Beyond a certain leve1. whey proteln glves soCter coagulum ln
comparlson to other dalry proteln mixes (Modler and Kalab. 1983; Tratnlk and Krsev.
1988). Gassem and Frank: (1990) found that mllk treated wlth mtcroblal proU nase had
significantly htgher finnness and viscoslty compared to untreated yogurt or yogurt
treated with plasmtn. Non canvenUonal protelns (peanut. soyand sunflower protein)
have been shown to influence the viscoslty of yagurt (Schndt et al. 1980; Bllanl et al ..
1989).
TIle vlscosity of stlrred yogurt Increases with lncrease ln homogenJ1.atlon
pressurf, (Puhan. 1988} due lo a decrease ln the slze or rat globules.
The heat treatment appears to have a slgnlflcant influence on the rheologlcaJ
propertles of yogurt gel caused by the denaturation of milk protelns. The yogurt
prepared from the vat processed milk has a greater apparent yjscoslty and flnnness
because the 1evel of whey proteJn denaturaUon ls greater campared to the UHT
treatment (Puhan. 1988; Schmidt et al . 1985; ParneU-Clunies et al .. 1986; SalJI el al ..
1984). Several addlUonal studJes have also demonstrated the ln1luence of heat

36

denaturation of whey proteln and caseln micelles on the vtscoslty and f1nnness of
yogurt gel (Kalab et al., 1983; Emstrom, 1974; Mottar et al., 1988; Pamell-Clunies et
al., 1986, 1988; Labropoulas et al., 1981, 1984). Recently, Dannenberg and Kessler

(l988a,b) and Rohm (1989) correlated denaturation of P-lactoglobulln(LG) and physlcal


properUes of gel. Mottar et al., (1989) polnted out that at the InJtlal stage of the heatlng
process, a considerable proportion of both p-LG and a-lacatalbumln(LA) assoclate wtth
IC-casslen. But at the later stage, denatured p-LG fonns a filament on the surface of the
rnIceUe. thereby parUally prevenUng the micelle fusion to take place dunng the
fennentation of the mIlk; thls results ln a texture of lnferlor quallty. However at a hlgh
heat Intenslty, a-LA preclpltates on ta the micelle thereby mllng the gaps between the
two consecutive filaments. This produces a smoother texture of yogurt.
Other processlng variables whlrb 1nf1uence the rheologlcal propertles ts the

nature and proportion of the two starter cultures. the incubation temperature, pH
durlng coollng and the coollng rate (Martens, 1972). Sorne straJns of the starter culture
produce polysaccharides of hlgh thlckenlng abllity (roplness). This gtves rlse to the
yogurt product of hlgh viscoslty and smooth appearance (Dellagllo, 1988; Teggatz and
Moms, 1990: Vlahopoulou and Bell, 1990; Robinson. 1988). The gels produced by ropy
stralns glve weaker vlscoelastlc structure compared ta non-ropy straJns (Vlahopoulu
and Bell. 1990). It has also been noted (Yuguchl et al., 1989) that HIe rate of
fermentation procedure may also affect the vlscoslty among many other physlcal
properUes. This Is because the size of the partlcles of the yogurt curd depends on the
rate at whlch yogurt Is fennented. Frozen culture produces a smoother texture because
of Its slower initial growth. Whereas fast-set cultures produce a grainy structure for the
coagulaUon of proteln ln large partlcles (Duame, 1979). It Is a1so reported that any large
variations from the optlmum ratio of 1: 1 of the two rnIcroorganJsms may produce poor

rated yogurt ln terms of conslstency or flavor (Kroger and Weaver, 1973: Kroger, 1975;
Nlelsen, 1975).

37

several handl1ng operations durtng the yogurt manufacture also may Influence
the gel structure of the product. Ourtng the commercial preparation. stirred yogurt as
subJected to several mechantcal treatments between the incubation tank to the
packaglng machine. Several types of equlpments 5uch as agltators. pumps. coolers.
pipes. extractors and packaglng units are used. ln addition. fruit meterlng/mbdng
machines are Included for fruit/flavored yogurt. Durtng the course of the above
treatments. the three dfmensional net work of the coagulum Is damaged. resultlng ln
smaller caseln partlc1es. The sUrrlng step ln the preparation of stlrred yogurt plays a
key role. Excessive sUn1ng w1I1 cause a slgntncant reducUon ln vtscoslty contrary to the
formation of rough structure ln case of InsulIlclent stlrrtng (Onessen. 1988). Pumping of
stlned yogurt through pipes has a decreaslng effect on vlscoslty (Steenbergen. 1971a).
To control the structural damage. the use of eUher large stroke volume or positive
dlsplacement pumps ls reconunended. The dlmenslons of pipeline also affect viscoslly
adversely (Steenbergen. 1971b). Thus the viscoslty decreases wfth lncreaslng pipe
length if the veloclty and the dlameter of the pipe are kept constant. On the other hand.
keeptng the length of the pipe constant causes minfmum structural damage ln wlder
pipe. Nodules. conunonly tenned as lumpy or granular ls consldered as one of the
texture defects in yogurt. Guirguls et al. (1987) found that nodulaUon ls reduced wtth
increastng speed of stirrtng leadlng to the decrease in vlscoslty.
Use of stabllizers or viscosity modiflers such as starch. pecUns and oUter
hydrocollolds to lmprove vlscostty of fruit/flavored or other types of yogurts
(UlIT/pasteurized. drtnk etc.) has long been a cOllUllon pracUce Of vanous products
used. pectln flnds Wldespread application largely oWlng to Ils thlckening and gelfonnlng ablllty. Use of modlflers brings about stablllzaUon of acid mJlk products
(Iversen. 1984). Wtth yogurt drink. addlUon of pecUn helps to keep the casein micelles
in suspension (Pllnik. 1990). Accordtng to Hooydonk et al. (19821. the best stabUtziDg
action wtth least sedimentation can be achieved with approximately 0.4% pecUn level

38

whlch brtng about 70% of fortification. It seems most probable that pecUn stab1zes the
proteln by tncreastng the vlscoslty of the serum phase and volume fraction of the
dlspersed materlal. Low methoxy pecttns are potenUally of more useful because of thelr
hlgher gellIng ablllty with calcium Ions and at low soluble solld contents (Kratz et al .
1989). The use of carrageenan to rebulld vfscoslty. Rnnness. as well as conslstency ls
also a common practice (Petersen. 1989). Vartous types of natural star".h are also
employed as yogurt modlflers and all of them tmprove the viscoslty (Hansen and
Annagost. 1990; Chawla and Balachandran. 1986: Vanderpoorten and Martens. 1976).
Application of synthetic modl1lers such as propylene glycol alginate. carboxymethyl
cellulose are also clted ln the llterature but thelr use ls much llmlted because thelr
adverse eO'ect on the quallty (Foley and Mulcahy. 1989: Shukla et al. 1988). Dependlng
on the time of coagulation and the raUo of starter culture. the addition of 0.2% sodium
alginate Induces a saUsfactory texture at room temperature (Rao et al. 1982).

(
Rheologlcal measurements
Since yogurt represents a very dellcate gel. Its rheologtca1 measurements present
many dlf1lcultles. Such a measurement must he very precise. as ft ulUmately
detennines the organolepUc properUes. Several fundamental types of viscometers and
other related Instruments are currently employed for the

~easurement

of conslstency.

finnness and other rheologlcal parameters.


To measure the fimmess of set yogurt. penetrometers are wtdely used rramlme
and Robinson. 1985). For set type of yogurt. measurement of elastic property ln tenns
of finnness and spreadabiUty are a conunon pracUce. These are expressed as force
necessary to penetrate the sample to a glven depth. AltemaUvely. It can be assayed ln
terms of penetration depth achleved ln a spec1fled Ume. Penetrometers measure the

force-penetrauon curves from whlch such parameters as brealdng force and flow
coemclent are evaluated. Bostw1ck and Adams conslstometers are employed to evaluate

39

the spreadlbiUty and fiuldlty of set yogurt .


Measurement of Viscostty/ conststency of both set and sttrred type yogurt

as

rouUnly carrted out by uslng vlscometers based on coaxial cyltnder and cone and plate
system under controlled shear rate or shear stress. For SUrred yogurt. the rheologlcal
properUes are almost solely expressed tn tenns of vtscoslty stnce It possesses hlgher
vtscous properUes than elasttc properUes. Rotatlonal Viscometers Mahopoulu and Ben.
1990. Kynast. 1972; Rasic and Kunnann. 1978) and Posthumus funnel (Posthumus.
1954) have been largely used ln recent years for the measurement ofvtscoslty ofyogurt.
Several parameters Inc1uding apparent vtscoslty. yteld stress. Ume dependency and
shear thlnntng can be assessed wlth rotaUonal Instrument. A major UmltaUon of
Posthumus funnel Is that a range of shear stress ts applted to the sample. Durtng the
measurement. shear rates vary with Ume and locaUon. Helltnga et al. (1986) used a
mathemaUcal model to quanUfy them.
To obtain the dynamlc measure of the gel structure. an osclllatory vlscometer
(cone and plate system) ls used (Steventon et al. 1990; Vlahopoulou and Bell. 1990;
Helltnga et al. 1986; Noel. 1988). Such an Instrument provtdes more lnfonnaUon about
structure of yogurt gel as weil as viscous and elasUc properUes.
Ali the methods described above are elther fully or partly destructive in nature.
Recently. sorne methods have been reported for measurtng rheologlcaJ properUes of
yogurt gel tn a non-destrucUve manner (Jearcocke et aJ.1988; Yuguchl et al. 1989). One
of these methods (Jearcocke et al. 19881 15 based on the measurement of apparent
moment of inerUa and angular veloclty under the Influence of a standard torque. ft has
been shown that the viscoslty and amount of lnerUa bears a lInear relaUonshlp to one
another.

40

CIIAP'l'ER IV

TIME-INDEPENDENT RBBOLOGY 01' STIRRED YOGVRT

ABSTRACT

Rheologtcal charactertsttcs of

two commerdal brands of sttrred yogurt were

evaluated ustng a HaaJce Rotoutsco Model RV 20 wUh an MS-Ose measur1ng head and
MV-1 rotor assembly from measured shear stress values wu1er a programmed. a-cycle upand down-shear rate at 100 s-1/ m tnjrom. 0 to 500 s-1 (5 mtn). The upward shear-rate
jIDw behaulDr of the yogurt samples could be described by a Herschel-Bu1Jcley model

while the downward shear-rate curoes were essentlally ltnear. Bath upward and

downward shear rate curues demonstrated progressive structural degradatiDn with


repeated shearing. The dependency ofrheological parameters on temperature in the range
10-25 0 C foUowed bath Arrhenius and 1rtan models.

lNTRODucnON

Yogurt. a fennented dairy product. bas achieved special promtnence and


economic Importance ln recent years due to its positive nub1t1onal attributes. A varfety
of new flavored yogurt-based products are appeartng on the market. Yogurt is mainly
avaUable in two fonn&: set-type and st1rred-type. bath in plain or flavored fonnat. The
characterfstic gel-structure of the set-type of yogurts fs allowed to form in containers
durtng the fermentation/incubation phase wblle in the sUrred-type the gel structure
fonned durfng bulk incubation 1s nonnally destroyed by agitation dunng cooling to gave

the product a smooth and semt-viSCous flow bebavtor (Tamlme and Robinson. 1985).

41

Several studles have evaluated the texturai charactertsUcs of set-type yogurts


(Dannenberg and Kessler, 1988; Ga!esloot, 1958; Martens, 1972, Nielson, 1972:
PrenUce, 1972; Webb and WhltUer, 1970), but there has been no detaUed pubUshed
study on sUrred yogurt rheology (Hellinga et al., 1986; lnagaki, 1986; NishiJbna and
Inagakt. 1987). MaJortty of studies on sUrred yogurt are limited to evaluaUon of the
conslstency, apparent vtscosity or flnnness as lnfluenced by Ils chencal composlUon:
especially fat, protein and carbohydrate (lactose) content (Blanchl-SaJvadort and
Zambrlnl, 1988: Onessen, 1988: Galesloot, 1958; Martens, 1972; Nlelsen, 1972;
PrenUce, 1968). Becker and Puhan (989) reported that small dtfTerences (-1%) ln
protein and nonfat sol1ds could result in signiflcant dtfTerences ln vtscoslty of yogurts.
Yogurts exhtbit a complex, shear-thtnntng, ttme-dependent fiow behavtor, and therefore
yogurt rheology 1s of Importance with reference to the Ir processlng, handUng, process
design, product development and quallty control aspects.
The objectives of this research were {il to study the ttme-independent dynamlc
flow behavtor of stJrred yogurts, i.e., to evaluate the nature of relaUonshlp between
shear stress and shear rate. and (U) to study the effect of temperature on the evaluated
rheological parameters.

JlATE.RlAI.S AND METHODS

Several samples of conunercially avaUable plain sUrred yogurts produced by two


dlfferent manufacturers (Agropur Co-operaUve Agro-AllmentaJre. Granby. PQ, and
Del1sle Food Ltd . Boucherville, PQ) were obtatned from a local supermarket. In Quebec.
the retaU containers arrtve at supermarkets with a shelf-Ufe of about 4-5 weeks
UdenUfied by thelr expiration dates on the containers). Ali samples were obtaJned 3-4
week before their expiration dates and were stored at 2 0 C until use (maximum one
week). Prior to testing they were gently mtxed by hand using a spatula to get a unJfonn

42

sarnple and handled carefully to m1nJInize any structural breakdown. They were held in
the sample cup for ternperature equmbratlon (about 20

m1n)

before measurements were

made. Sarnples frorn the two commercial brands were compared at IOoe. whlle
addlUonal tests were perfonned wtth only one brand to evaluate the Influence of
temperature.
Rheologlcal measurements were made uslng a Haake RV20 rotatlonal vtscometer
(Haake Mess-TechnJk GmbH u. Co.. Karlsruhe. Federal Rep. Germany) equlpped wlth
an M5 ose rneasurtng head and MV1 rotor (20.04

DUn

00; 60 mm hetght) ln a

concentrlc cyltndrtcal cup (21.00 mm ID) assembly Intenaced to a mlcrocornputer for


control and data acquisition. The rotor and cup assembly was Jacketed to maintaln
sarnple temperatures and a controUed ternperature water bath/circulator was used to
pass water through the Jacket. AlI samples were malntalned at the des1red ternperature
before tesUng and ail expeliments were trtpl1cated each Ume uslng samples from

dlJTerent containers.
Test samples of yogurts were subJected to a simple hannonlc (dynamlc) shear at
a progranuned rate of 100 s-l/mln Itnearly Increasing frorn 0 to 500 s-l

ln

5 min and

subS'!quently decreaslng from 500 to 0 s-1 tn another 5 min. This cycle of upward and
downward shear rates was repeated two more Urnes wtth the same test sarnple to study
the structural breakdown resulUng frorn successive up and down shear-cycles.
Temperature effects on flow curves were evaluated for one of the Brands by subJecting
the samples to dynarnlc shear as descrlbed above whUe mainta.ln1ng the samples at the
varlous temperatures (100 e. 150 e. 200 e and 250 e). Wlth the other Brand. experlments
were carrled out only at IOoe. AIl expeliments were repl1cated three Urnes.
The flow curves were evaluated by one of the followtng rnodels (prevtously
detatled ln Chapter 11):

43

1. Power law model:

= min

(4-1)

(4-2)

(4-3)

2. Casson model:
C

1/ 2

3. Herschel-Bulkley model:

4. Unear model (only downward curves):


0'

(4-4)

The Arrhenius equation was used to study the effect of temperature on rheologlcal
propertles:
lla

F. exp (Ea/RT)

(4-5)

The activation eneJgy of flow (Ea at constant shear-rate) was evaluated at each of the
selected shear-rates for both up- and down-CUIves from the regression of natural
loganthm of apparent vlscosity vs. reciprocal of the absolute tempe, 'ature.
The flow-behavior index and consistency coefficients of the up-curves were also
related to temperature by Turtan (1964) approach:

log (m) = A - B (T)

a+b(T)

(4-6)

(4-7)

For the linear down-culVes. the resulting yield stress and viscoslty were related to
temperature by a stmilar approach employtng Turlan model:

=
=

A-B(T)

a+b(T)

(4-8)
(4-9)

CheJnical composition (fat. proteln and lactose) of yogurt samples from each
container was evaluated in trtplicate by the rapid IR spectrophotometrlc melhod of van

.....

de Voort (1980) ailer adjusting the pH to 6.5 uslng IN NaOH. Moisture content of each
replicate was determined by drytng in a vacuum oven at 700 C for 24 hr.

44

RESULTS AND DlSCUSSlON

The chemical composition of yogurt sample& from the two commercial brands
employed ln the study tndlcated only marginal dJfferences between them (Table 1) wlth
Brand Il contalnJDg sllghtly htgher fat and protetn than Brand 1. The composftional
tnfonnatlon prtnted on containers confinned these ftndtngs and also Indlcated that the
samples contaJned only milk sollds and bactertal culture wtthout any added stabllJzer.

Table 1. Composition of the two commercial yogurts employed ln the study.

Yogurt

Mofsture
(%)

Fat
(%)

Proteln
(%)

Lactose
(%)

(
Brand 1

81.8O.4

1.9O.Ol

6.6O.Ol

6.3O.O2

Brand Il

81.61.5

2.1O.Ol

6.7O.O2

6.4O.O3

ChuacterlzaUon of Dow curYU

Typica1 flow CUNes for the two commercial brands of sUrred yogurts under a
dynamic 3-cycle sheartng sequence are shawn ln Figure 6. The flow patterns are
qualitatively slmUar but have sorne quantitative dlfferences. The overall shear stress
encompasstng the test range of shear rates was about 30% hlgher for the Brand Il

samples than for Brand 1 indlcating a stronger structural rlgidlty wtth the former. The

.....

9OTI----------------------------~

9OTI----------------------------___

Brand 1

80

70

70

80

60

1 50

l 50
1

...
e:.
lA

Brand Il

80

40

m40

30

m30

20

20

10

10

OTI----~--~----,_--~----~

200
Shear Rate

400
(S 1 )

o~I----~--~--------~~--~

200

400

Shear Rate (s )
'

JI'tture 8. Sbear .ua .beu rate re..do_h1,. (00W' carYea) for two commercial
yOlarta d1ll'lD& pl'O,rammed 3~cle (10 mIa eacb) ap . .4 40W11 .hea"

betweea .heu ..te. of 0 . .4 800 1.


~
(JI

46

shape of the Dow curves lndlcate the presence of a yleld stress. shear thlnnlng
(thixotroplc) nature of the test samples ln consistent wtth flndlngs by Inagald (1986).
The figure also demonstrates that a major change ln the rheologtca1 behavior appears
after the first shearlng cycle. This Is consistent wtth the characterlstic flow behavior of a
prevlously unsheared virgln sample for CUNe 1 whlJe the other curves represent the
flow behavtor of shear degraded samples. SlmIlar results were reported by Halmos and
Tlu (1981) for several meat and yeast extracts and by Paredes et al. (1988) for salad
dresslngs.

The area enclosed between the up- and down-curves (hysteresls loop) Is a
measure of the extent of structural breakdown durtng the sheartng cycle. The hysteresls
Joop assoclated wtth the first cycle Is relaUvely larger than that associated wtth the
second or thtrd cycle Indlcating that the Ist sheanng cycle caused the major
degradatton of sample structure. Hysteresls Joop-areas assoclated wtth the 2nd and 3rd

shearlng cycles were also sma1l and comparable. Indlcating slmllar structural changes
wlthln these cycles. However. the three successive up-curves were clearly separated
wlth one lymg below the other (Figure 6) Indlcatlng a continuai breakdown of structure
wlth each shearlng cycle. However. there Is sorne ev1dence that the structural 10ss ln
the upward sheanng process may be partially recoverlng durlng the downward shearlng
as Indlcated by the overlapplng of 2nd and 3rd up-curves wlth thelr precedlng downcurves (Figure 6).
Addltional tests were carrled out to test the recovery of the thlxotroptc structural
breakdown. The sample after the 3-cycle upward and downward contlnuous shearlng
was allowed to rest ln the cup for an hour and then the test was repeated. Figure 7
compares rheograms of the vlrgln sarnple wlth that of the sheared sample followlng
relaxation. The results Indlcate that the apparent thlxotroplc structural breakdown Is

almost irreversible. The first up-ward curve of the shear-relaxed sample Is nowhere near
the first up-curve of the previously unsheared sample. In facto the set of 3 upward

47

CUlVes followtng relaxaUon were below the three upward curves of the first run sample.
Each sheanng cycle resulted ln a sorne nonrecoverable structure loss. SlmUar resulls
were observed with the down-ward flow curves (Figure 7'. The progressive thtxotroplc
breakdown could be character1zed by the steady lowerlng of vlscoslty (slope of the
nearly I1near downward curves' through the six sheanng cycles (vlscoslty values glven
ln Pa.s': 0.10 (down-U, 0.085 (down-2" 0.078 (down-3, first run', 0.073 (down-U, 0.069

(down-2), 0.066 (down-3, second run after relaxaUon).

ModelllD, of the flo. curYe.


The Casson mode! gives a relaUvely poor fit for the experlmental data, especlally
for first up-curves with R2 values rangtng from 0.73 to 0.85. The Herschel-Bulkley
model requlred data on yleld stress whlch sorneUmes Is obtruned from the Casson

.-.

modelO'ung, 1978). This procedure however resulted in a poor fit for Herschel-Bulkley
model. When yleld stress values were from Ilnear regresslon of shear-stress vs. shearrate data at low shear rates, the Herschel-Bulkley model resulted ln a better fit of dala
with R2 values generally above 0.95 (Table 2). TypIca1 Herschel-Bulkley plols for lhe
three upward curves are shown ln Figure 8 uslng Ilnear co-ordinales (the fitted IIne
follows the log-log format of Herschel-Bulkley model'. For the 2nd and 3rd up-curves.
the results from Casson and Herschel-Bulkley models were generally comparable. The
latter mode! was chosen ln the present studies so that a Single model could be used for
all three up-curves thereby provtdlng parameters for comparlng dtfferent test samples.
The downward flow curves cou Id be descrlbed by a simple Unear model showlng
Newtonian flow-charactensUcs (fable 3); typlcal IInear plots for the three successive
down curves are also shown ln Figure 8. Small dev1aUons from IInearity were observed
at the lower and hlgher ends of the shear rate span 50 s-1 and >450 s-I); however.
these end effects were not consldered slgnlflcant slnce the ass",clated R2 values were
generally very hlgh (>0.99; Table 2'.

~~

70

,IIIfIit:.,

70
Top to bOttom

60 ~ Dawn-1, .... run

~~

60~

Down-2. ht run
Dawn-3, tir run

50

-j...

40

s::.

30

50

ail

Down-2. ail., ,eIaIIatJon

CL

11loMn-'. _ _

40

30

1
liS
s::.

CI)

Down-3.all.,,~Uon

CI)

20

20
Up-2. 1Ir ,un
Up-3. tir run

10W

Up-1, after relaxation

10

Up-2. after ' ....tlon


Up-3. 11ft.,

o1
0

200
Shear Rate (S-1)

,"._tlon
1

400

0
0

200

400

Shear Rate (S-1)

FIIure 7. Flow cun'ea for Bnmd 1 atbred yoaurt durlDa Ont nua 3-cycle up and

doWll Iheartna and a Ilmllar renm alter one hou of reluatlon.

~
(X)

49

Table 2. Rheological constants for the three successive up-cUlves for two brands of
yogurt uslng Herschel-Bulkley model.

Bl'UldD

(Pa)

(Pa)

#1

11.2

13.7

0.212 0.97

24.7

28.8

0.129 0.93

#2

9.4

1.46

0.540 0.99

17.1

5.19

0.373 1.00

#3

7.6

1.36

0.538 0.99

13.7

3.62

0.418 1.00

Table 3. Rheologlcal constants from three successive dOWll-curves for two


conunercial brand yogurts uslng a linear model.

Brand Il

Brand 1

.,..
-4-'

'la

(Pa)

(Pa.s)

#1

15.3

0.0887

#2

13.8

#3

12.3

R2

'la

R2

(Pa)

(Pa.s)

0.99

21.3

0.109

0.99

0.0747

1.00

26.0

0.0867

0.99

0.0687

1.00

22.8

0.0797

0.99

......

~i

60.

~,

60.

UnNrModel

50

Ci

60

40

)30
..al

Ci

40

Q.

Q.

)30
..

al

.r;

oS:

lOB

20

Up-eurve 1

Up-curve2

10

Up-c:unre 3

01

200

Shear Rate ($'1)

Oown-curvt 2

00wn-c:uN8 3

00wn-c:uN8 1

400

200

400

Shear Rate (s 1)

Figure 8. Typlcal Henchei-Bulldey (fol' apwud cUI'Yel) uad lIDeu (fOI' down....d)
plot. for Brand 1 .tlrred yogurt dUl'lq 3-cycle ap and dcnm .hurlag.
111

51

The flow behavtor Index and conslstency coemcient were used to comparr the
rheologlcal charactertstlcs of the two commercial samples under repeated sheartng
n'ables 2 & 3). Compared to Brand II, Brand 1 samples had a higher now behavior
Index (n), a lower yleld stress and a lower conslstency coemclent (m), all Indicatlv1' of a
comparatlvely thlcker structural rlgldlty wtth the fonner. Il Is also clear from Table 2
that m decreases and n tncreases w1tb repeated sheartng. Changes ln both m and n
were more pronounced between the Ist and 2nd cycle than between 2nd and 3rd.
IndlcatJng that most structural breakdown occurs in the Ist sheartng cycle. Every
sample possessed yleld stress (fables 2 & 3) even durtng the thtrd successive shearcycle although the values decreased gradually. Stmtlar results were obselVed with
downward curves (Table 3). DurtDg the downward sheartng, the )1eld stress decreased
almost I1nearly from an average value of 15.3 Pa to 12.3 Pa for the Brand 1 samples and
31.4 Pa to 22.8 Pa for Brand II. Yleld stress appears to be an Inherent property of lhis

product even though the test samples have shear-thlnnlng charactertsUcs. The
downward viscosity changes throllgh successive sheartng cycles were almost llnear. The
viscosity of the Brand Il yogurt was higher than that of the Brand 1 consistent wlth the
previous discussion.

Effect of temperature on Oow behavlor


Table 4 shows the Herschel-Bulkley rheologlcal constants of the upward curves
for Brand 1 samples at four temperatures and Table 5 shows the llnear model constants
(downward now) of the same brand yogurt for the same four temperatures. 80th the
Turtan and Arrhenius approaches were round to be satlsfactory to descrtbe the
temperature influence on rheologlcal parameters. Yleld stress. conslstency coefficient
and apparent vtscoslty decreased wllh an Increase ln temperature whlle the now
behavtor index showed an lncreaslng trend wtth temperature.

52

Rheologlcal constants of Brand 1 yogurt (three up curves) at different

Table 4.

temperatures ustng the Herschel-Bulkley model.

UPCURVE2

UPCURVE 1

(Jo

UPCURVE3

(Pa)

(Pa)

11.9 14.6 0.2:07

0.98

8.04

1.82 0.506

0.98

6.94

1.43

0.531

0.99

15 7.65 9.63 0.265

0.98

8.44

1.49 0.513

0.99

7.16

1.21

0.532

0.99

20 4.92 5.56 0.335

0.98

7.47

0.98 0.562

0.99

6.34 0.86

0.568

0.99

25 3.53 3.01

0.96

5.96

0.74 0.577

0.98

5.45 0.61

0.596

0.99

10

0.400

(
Table 5. Rheologlcal constants of Brand 1 yogurt (three dOWllcurves)
at different temperatures uslng a linear mode!.

DOWNCURVE 1

Temp
(OC)

(Pa)

fla

R2

(Pa.s)

DOWNCURVE2

(Jo

fla

(Pa)

(Pa.s)

DOWNCURVE3

R2

fla

R2

(Pa)

(Pa.s)

10

14.8

0.090

0.99

13.4

0.074

1.00

11.9

0.068

1.00

15

14.5

0.078

0.99

12.9

0.065

1.00

11.4

0.060

1.00

20

12.1

0.069

1.00

10.5

0.058

1.00

9.87

0.053

1.00

25

9.67

0.057

1.00

8.83

0.049

1.00

8.27

0.045

1.00

53

Uslng the Turtan approach (equatlons 6 and 7) for charaeterlzing the


temperature dependence of Herschel-Bulkley parameters. it was possible to lncorporate
the Influence of temperature on the shear-slress vs. shear-rate relaUonship
single model (comblnlng equaUons 3. 6 and 7).

~lcal

ln

to a

relaUonshlp for the 8rst up-

cUlve 15:

log (0 - oal = (l.64 - 0.0459 ml + (0.141 + 0.0130 ml log (it

(4-10)

A s1mllar relatlonshlp for the downward curve by combln1ng equatlons 4. 8 and 9

Is

glven below:

= (19.0 - 0.356 (1')) + 10.112 + 0.0022 ml (it

(4-11)

In order to use the Arrhenius approach to descrtbe the effeet of temperature on


the flow behavtor of stlrred yogurt. apparent vlscosltles were evaluated at selected shear
rates of 100. 200. 300 and 400 s-1 and regressed aga1nst the reclprocal absolule
temperature. The assoclated actiVaUon energles (Ea) of Dow are sununartzed ln Table 6
whlch showed that the Ea values gradually decreased as the shear-rale lncreased in the
Orst up-curve (Virgtn curve). The Ea values at vartous shear rates the second and third
up-curves and the three down-curves varled only sUghtly. The range of calculaled
values (or Ea was 4.2 to 5.2 (5.8 to 8.95 kcal/mole Wlth the fkst up-curvel.

CONCLUSIONS

SUrred yogurt rheology can be descrtbed by Herschel-Bulkley and Unear models


durlng succesSive up-ward

and down-ward

sheartng

sequence. Temperature

dependence of rheologlcal parameters follow Arrhenius and Turlan models. SUrred


yogurt charactertsUcally exhlbtts parUally reverslble thtxotropiC flow behavtor with a

54

recurrtng yleld stress. Characterlzatlon of stlrred yogurt rheology Is the fnt step ln our
overall objective of developlng scjentlflc procedures for fabrtcating the des1red
conststency ln flavored yogurt-based beverages by blendtng the stlned yogurt wlth
hydrocollotds and flavor concentrates.

Table 6. Activation energy (kcal/mole) of flow from dynamic shear expertments.

UPCURVE 1

UPCURVE2

UPCURVE3

Ea

R2

Ea

R2

Ea

R2

100

9.0

0.99

5.1

0.98

5.1

0.98

200

7.7

0.99

5.2

0.97

5.0

0.98

300

6.5

0.99

5.0

0.97

4.9

0.99

400

5.8

0.98

4.8

0.98

4.7

0.99

Shearrate
(s-l)

DOWNCURVE 1

DOWNCURVE2

DOWNCURVE3

Ea

R2

Ea

R2

Ea

R2

100

5.2

0.95

4.6

0.93

4.3

0.95

200

5.0

0.96

4.6

0.96

4.3

0.98

300

4.9

0.96

4.6

0.98

4.3

0.98

400

4.9

0.97

4.5

0.98

4.4

0.99

Shear rate
(s-l)

55

CIlAP'l'ER V

TIME DEPENDENT RBEOLOGyor STIRRED YOGURT

ABSTRACT

Stress decay behaviDr of two sttrred yogurt samples was evaluated at vartous
shear rates (l00-500 s-l) and selected temperutures (lO-2S 0 C) usUlg a Haake RotatfDnal
viscometer. Results sfwwed that ttme-dependent shear thlnning was evtdent wu1er aU
testUlg conditions and an equUibrtum shear stress was rwt reached even afler 60 min oJ
conttnuous shearing. Welbnan's logarttlunic ttme model accuralely descrtbed the stress
decay behavior at each sheartng condttfDn and the temperature trifluence on Weltman
parameters showed a ltnear trend. 111e temperature influence could also he eualuatcd

using the Arrherus model and resulting activation energies ranged from 4.9 to 14.6
kcal/mole.

INTRODUCTION

N pointed out in the prevtous chapter. there has been very lJttle publlshed

study on sttrred yogurt rheology desptte the fact that these products have attained
signlficant conunercial importance in recent years. Most publJshed tnfonnaUon deaJ
with the evaluatlon of the consJstency. apparent vtscostty or finnness as lnfluenced by
tts chemJcal composttion. The shear th1nn1ng behavtor of rheology of sUrred yogurt was
detatled earUer. Yogurt has also been known to ex1btt Ume dependent flow behavlor
(Tam1me and Robinson. 1985; HeUtnga et al.. 1986) whtch Is an Important factor to

56

charactertze the rheologtcal propertles of the final product.


The obJectJves of thls research was to evaJuate a possible methodtcaJ approach
for the study of stress decay behavior of sttrred yogurt as a funcUon of steady shear
rate. Ume and temperature. Such an approach wiU be useful in assesstng the structural
damage due to product handl1ng as weil as structural stabillty of fonnulated yogurt
based products.

MA'JZRlAI.S AND METHODS

TIme dependency of the rheologlcaJ charactenstlcs were evaJuated uslng an


Haake RV 20 rotaUonal viscometer (detailed in Chapter IV) by subjecting test samples to
a 10 min (or 60 min ln sorne runs) shear at each of the followfng fixed shear rates: 10.
100. 200. 300. 400 and 500 s-l. A fresh sample was used for each measurement.

Temperature effects on the Ume dependent behavtor were evaluated by subJecting test
samples to steady shear at four temperatures: 10. 15. 20 and 2SoC. AU samples were
maintaJned at the desired temperature before tesUng and a11 expertments were
trtplicated each Ume uslng samples from different containers.
The stress decay behavior of test samples was evaluated uslng a modified
logarithmic-Ume model suggested by Weltman (1943):

cr = A - B (log (t/lm)); t ~ lm

(5-1)

where:
(J

= Shear stress (Pa)


= Time (s)
= TIm.! at maximum obselVed shear stress (12 s in the present study)

(
B

= Intercept when log (t/tm) =0 or t =tut (Pa)


= Siope (Ume coefficient of thixotroplc breakdown. Pa)

57

The constants A and B were obtained from regresston of (J vs log (t). The nature
of relationship of these constants. A and S. wtth shear rate were explored by regresslon
techniques (both Unear and logartthmtc).
The Arrhenius equation (detatled elsewhere) was also used to study the effect of
temperature on rheologtcal constants and ta evaluate the activation energy of vlscoslty
decay:

" = F e (Ea/R'O

(5-2)

The viscosfty value (ll) for the Arrhenius equation was obtatned as a raUo of A
value to the rate of shear (yi: " = A/y. thus II represented the apparent viscoslty of the
sample followmg sheartng for t = lm (12 s. in these studles). In a second set of analysls.
the Ume coeftlcient. S. whfch indtcates t'he magnitude of stress decay over a ten fold
change in the shearfng ttme was also used ln the viscosfty computation: II
in

thls situation represented a change ln apparent viscostty (due

(0

= BIY. thus II

structural damage)

through one log-cycle of shear ttme (between 12 and 120 s. for example). The acUvation
energies (Ea ) were evaluated from the regressfon of natural logarfthm of II vs. reclprocal
of the absolute temperature.
Weltman parameters. A and B. obtatned at each shear rate were also related to
temperature by the Turian (1964) approach:

A=Al

+~ (T)

B =Bl + B2

(5-3)
(5-4)

where Al, A2. BI and B2 were parameters obtalned from llnear regressfon of A and B vs
,.....

temperature.

58
RBSVLTS AND DISCUSSION

Stre dec.J compariloD of the two cODUllerclal yo,urta

Typtcal stress decay curves for the two conunerctal brand sUrred yogurts dul1ng
a 10 min steady shear at selected shear rates are compared in Ftgure 9 whtch generally
tndtcate that the two samples exhlbtt somewhat sunHar flow patterns. There were small
dtfferences tn thelr magnitudes: the shear stress assoctated wlth Brand II was sUghtly
htgher than that of Brand 1 at the htgh shear rates (400 and 500 sl) whlle these
dtfferences were small at the lower shear rates. The 10 mJn sheanng period employed in
these studtes was tnsuffictent to achteve an equ1Ubl1um stress condtUon tn any test
run. Stress decay behavtors at dtfferent shear rates were s1ln1lar, and the d11Terences in
the stress values tnttlally obser...ed wtth reference to vartous shear rates persJsted

(...

throughout the 10 min shear tesUng. although they narrowed to sorne extent toward
the end. At the low shear rate of 10 s-I, shown wlth Brand 1. the magnitude of stress
decay was relatlvely small. In the hand mtx1ng of samples used to get a untform sample
prior to testll1g ln our studtes, the sheartng cou Id be expected to be mu ch smaller.
Hence, the extent of structure breakdown of samples due the brief hand mixing was
constdered negUglble.

MOdeUlD, of the Dow carves

1 he stress decay curves were next. analyzed ustng estabUshed mathematlcal

models: Weltman (1943). Hahn et al. (1959) and nu and Boger (1974). The two latter
models requtred data on the equtUbrium shear stress (oe) followlng long tlme sheanng.
Most reported lJterature data tndtcate that equlltbl1um condtUons are generally achteved

wlthtn the first 30 min of sheartng (Weltman. 1943; Tiu and Boger. 1974: Massaguer-

59

'

120

120

110

Brand Il

110

Brand 1

100

100

90

90

Shear rate (s-l)

ca 80

Q.

=10

"...

~60
ca

"

~SO

40
30
20

20

10

10
0

10

lime, min

lime, min

l'l,ure 9. Stress decay cunel of two commerclalltlrred yo,urts Clver. 10 min.

shear at lelected shear ratel.

10

60

Roig et al .. 1984: Ford and Steffe. 1986. Rao. 1977: Tung et al. 1970). However. our
results demonstrated that even after 60 min sheartng at various shear rates between
100 and 500 s-l. test samples of stlJTed yogurt contlnued to show structural decay

(Figure 10). Hence. ln our studtes. we chose to use the 10gartthmic-tJme model
(Weltman. 1943) to descrtbe the tJme dependency of shear stress under constant shear.
Figure 10 1llustrates the goodness of fit (R2

= 0.97-1.0)

of thls model to exper1mental

data (shown as points) up to 60 min under each of the three shear rates (Unes show the
fitted log-Ume regresslon models).
Weltman model regresslon parameters. A and B (Table 7). were used to compare
the stress decay behavtor of the two commercial samples. For both samples. the
Weltman model accurately descrtbed the stress decay behavior (R2 > 0.98). IndlcaUng
slrnHartty ln thetr flow behavior. Up to a shear rate of 300 s-l. the A values for both

brands were comparable. whlle at the two htgher shear rates (400 and 500 s-I). Brand
Il had a htgher lntercept coefficient lA value) than the Brand 1. These results suggest a
slightly hlgher start up viscoslty wtth Brand Il. especlally at the htgher shear rates.
Sinee a zero-Ume stress or vlscoslty Is non-existent ln the logartthmtc Ume model (s
reaehes Inflnlty as Ume tends to zero). the Intercept coefficient represenUng the

~tress

at the Ume. t = lm. when il reaehed a maximum value was used ln the compartson (12 s
ln our measurements). This Ume.

lm.

Is usually a funcUon of the Instrument's data

acqulslUon/measunng system and as weil as scan Ume.


The manufacturer (Haake) suppUed data acquisition software permitted
gatherlng 50 data pairs ln any given shear/ttme scan. hence tm actually represented
the second data point in our 10 min test runs. The flrst data point wtth shear stress
about half of this maximum was not Ineluded ln the analysls. Zero-Ume shear stress
(00)

(.

for each condlUon was separately obtained by a linear graphical procedure as

outllned by Massaguer-Roig et al. (1984) to compare the results of thls study with
dynamtc shear experlments descrtbed previously in Chapter IV. Weltman A values

61

65

60

--

55

co

50

f i)

(1)

45

( 1).

40

Q.

ns

Brand 1
Shear rate (s-1)

500

Q)

.s::.

en

35
30
25

o o.

100

20
0

40

20

60

Time (min)

r.,ure 10. Stress decly cunel of Brand 1 at1rred J'o,urt over a 50-min Ihear at
Hlected Iheu ntel.

62

Table 7: Weltman model regresslon panuneters for conunerctal sttrred yogurts at lOoe.

R2

Shear rate

Initial stress

A value

Bvalue

(s-I)

(Pa)

(Pa)

(Pa)

55 ;t 6.5
70 12.0
77 14.1
89 13.6
100 ;t6.1

53 5.6
65 2.0
70 1.9
80 3.4
9015.9

11.6;t 1.6
15.610.5
17.611.3
21.811.2
24.4;t 1.5

0.98
0.99
0.99
0.99
0.99

47 14.7
72 ;t4.1
80 ;t 7.6
99 ;t9.6
125;t 9.2

46 3.7
67 3.9
74 9.3
90 9.9
115 8.4

8.3 ;t0.5
15.7 ;t2.1
18.4 ;t2.9
23.0 ;t2.6
32.7 ;t4.2

0.98
1.00
1.00
1.00
1.00

Brand 1
100
200
300
400
500
Brand Il
100
200
300
400
500

showed a hlghly correlated IInear relatlonshlp wlth these zero-Ume shear stress values
(hereafter referred to as 1n1Ual stress):

Brand 1:

A = 0.87 ao + 7.6,

R2 = 0.99

Brand Il:

A = 0.89 ao + 3.2,

R2 = 0.99

This should be expected slnce both Weltman A (stress at t

= 12 s)

and ao (at t = 0 s)

were measures of stress at specifie times. The Ume coefficient of stress decay (Weltman
B value) was generally comparable between the two brands up to a shear rate of 400 s-

I, whlle at 5005- 1 Brand Il had a hlgher B value than Brand 1. These dtfferences ln A
and B values were statisUcally non-slgnlficant (p>0.05) except at the htghest shear rate

63

(500- 1). The small composlUonal d1fferences between these two brand yogurts support
these observations. The dltTerences ln Weltman parameters between the two brands
from two dlfferent manufacturers were therefore consldered to be characteriSUc of
sample to sample variation and for the purpose of evaluaUng the stress decay. the two
brands were assumed to be behavtng slmJlarly and represenUng slmtlar product types.
Ali the above parameters. the 1n1Ual stress too) as well as A and B values were
found to be Unearly related to the shear rate. i (Figure 11). Our earl1er studles under
dynamJc shear testlng condlUons Indlcated that the flow behavlor of sUrred yogurt was
weil descrtbed by a Herschel-Bulkley model (Chapter IV) whlch relates the logartthm of
shear stress to logarlthm of shear rate (log(oo-o)

= log m + n

log (i)). CharacterlsUcally.

slnce Weltman parameters represent different. measures of shear stress. one would
expect su ch a logarlthmic relaUonshlp behavlor between them and the shear rate ln
the present studies. with ooly Cive shear rates employed for tesUng ln the range of 100
to 500 s-l. the logarlthmic model offered no slgniflcant advantage over the Unear model.
all yielding high R2 values. For simpUcity. the Ilnear models were chosen to characterlze
variations ln A and B as funcuon of t.

Brand 1:
A

44.5 + 0.090 i.

R2 = 0.99

=
=

8.68 + 0.032 i.

R2 = 0.99

45.1 + 0.110 i.

R2 =0.99

29.4 + 0.16 i. R2

=
=

2.80 + 1).056 y.

R2

29.3 + 0.18 i.

R2 = 0.94

0
Brand Il:

=0.97
=0.96

64

130----------------------~

1~~---------------------~

120

120

Brand 1

110

110

_100

_100

e:..90

e:..

ca

ca

80

E
t! 70

80

A value

~ '10

:.

ll-

1:
!

l:
~

fit

90

CD

Ci)

1)

Brand Il

40

) 30

40
) ~

20

20

B value

10

Or-~--~_r--r_~~~,_~

100

200

300

Shear rate (S-l)

400

B value

10
500

O~----~~~~~~--~~

100

200

300

400

Shear Rate (S-1)

Vl4ure 11. Stre.1 dec.)' puameterI. functioD of .heu rate for two
comlDerclalltlrred )'o,urtI.

500

65

Effect of temperature OD Bow behavlor


Temperature sensltlvtty of the rheologlcal parameters O"able 8) of yogurt samples
from Brand 1 were analyzed by the TuI1an model and the ArrhenJus approach: both
were found to be satlsfactory. An Increase ln temperature decreased both A and B
values. and slmilar results were observed wh,.n these A and B values were converted to
thelr vtscosfty counterparts (Ali and B/it lndlcaUng that the apparent vlscoslty of test
sarnples decreased as the temperature lncreased.
Hlgh R2 values (>0.97) were obtalned for the Turfan approach I1nearly relatln't A
and B values to temperature at vartous shear rates. 51nce both these paramelers were
also I1nearly related to shear rate as discussed earUer. the comblned Influence of shear
rate and tempe rature on A as well as B was evaluated uslng a mulUple regresslon
technJque. The resulUng equaUons showed slgnfflcantly hlgh correlations for both A and
B as funcUons of shear rate and temperature (T. expressed ln

A = 64.2 + 0.089 i
B

- 1.98 T

= 16.2 + 0.030 i - 0.67

OC):

= 0.98
R2 = 0.98
R2

The three-dimensional plots of A and B values as funcUons of t~mperature and


shear rate are shown in Figures 12 and 13. With thls approach. Il will be possible to
lncorporate the influence of temperature on the stress-lime relatlonshlp ln to a single
model. AbbrevtaUng the coefficients obtalned above ln a general manner as Al' A2' A3'
BI' B2. and B3' the comblned equaUon cao be wI1tten as shown below:

(5-5)

..

66

Table 8. Stress Decay constants for sUrred yogurt (Brand I) at dUJerent shear rates and
temperatures.

Shear rate (s 1)

Temp Parameter

10

15

(
20

25

100

200

300

400

500

A (Pa) Mean 48.9


s.d
1.5

63.6
1.7

69.8
1.1

82.4
2.5

87.2
0.7

B (Pa) Mean 10.6


0.3
s.d

15.7
0.6

17.5
1.6

22.6
0.9

24.3
0.4

R2

0.98

0.99

0.99

0.99

0.99

A (Pa) Mean 44.4


s.d
0.4

54.2
1.5

63.7
1.3

74.5
3.7

78.6
1.7

B (Pa) Mean 8.55


s.d
0.3

11.7
0.6

15.1
0.3

18.9
1.3

20.7
0.8

R2

0.97

0.99

1.00

1.00

1.00

A (Pa) Mean 31.0


0.8
s.d

43.0
2.4

54.7
0.9

61.3
0.5

63.6
1.8

B (Pa) Mean 4.90


0.3
s.d

8.32
0.6

12.2
0.6

14.5
0.6

15.7
0.2

R2

0.95

0.99

1.00

1.00

1.00

A (Pa) Mean 22.2


s.d
0.6

33.3
2.1

42.4
3.0

52.3
5.5

57.6
2.3

B (Pa) Mean 2.96


s.d
0.2

5.20
0.3

7.58
0.3

11.1
1.6

12.8
0.4

R2

1.00

1.00

1.00

1.00

0.92

67

..

soo

Temperature (C)

FI,ure 12. Weltman A value. . . . funCtlOD of temperature and .heu rate for
Brand 1 lt1rred fO,urt.

68

20

~
.!

15

~
ID

li

10

.: ......
...-, ....

" " . e".

"

........ .
o

'

..

13

.:....

500

"

"

'.

..... .....
19

':,...

,..

.'
"

....

.'

....
22

25

Temperature (C)

n,ure 13. Weltman B valuel . . . functloD of tempenture and .heu nte for
Brand 1 IUrred JO'url.

69

In order to use the Arrhenius approach to descrlbe the effect of temperature on


the flow behavtor of sUrred yogurt. apparent vtscosltles were evaluated as A/y raUos at
the dlfferent shear rates of 100.200.300.400 and 500 s-l. and regressed agaJnst the
reciprocal absolu te temperature. A typica1 Arrhenius plot ts tUustrated ln Figure 14
which shows the effect of temperature and shear rate on the apparent vlscosUy. The
assoclated activatlon energies (Ea1 of stress/vtscoslty decay are summartzed ln Table 8
whlch showed that the Ea values gradually decreased as the shear-rate lncreased. The
range of calculated values for Ea uslng the A/i approach was 4.9 to 9.1 kcal/mole.
These values were simllar to the activaUon energies reported elsewhere (Chapter

IV)

for

the same yogurt brand whUe obtaJning shear strss-shear rate data under a 3-cycle
programmed upward and downward ramp sheartng sequence (5.8 lo 9.0 kcal/mole wtlh
the ftrst up-curve). ActivaUon energies calculated using the iniUaI vtscostty values (oo/i)
showed resulls similar to those calculated ustng A/i (5.5 - 9.3 kcal/mole). Since both A
and

00

values are estimates of shear stress prlor lo structure decay. the activation

energy from A/y and oo/y can be expected to malch activation energies of flow found in
the earlier studies. These Ea values lhus show the temperature sensiUvlty of the
inherent sample viscosity.
Activation energies were a1so calculated uslng the Ume coefficient of apparent
viscoslty (B/y values) whlch showed a trend slmllar to that observed whlle uslng the AfY
values (Table 9): the magnitudes were. however. mu ch larger (7.4 to 14.6 kcal/mole).
B/y values. unllke A/i. are a measure of vtscoslty decay over a glven Ume and therefore
represent a stablltty parameter. The activation energies found from the B/y values.
therefore. represent lemperature senslUVity of sample Viscosity when subJecled to a
constant shear. IncreaslllP' temperature can therefore be consldered to have a dual
eiIect on vtscosJty of a sample subJected to a steady shear: a decreased start-up
viscosity and a less pronounced vlscoslty decay.
',/,

70
,

0
-0.2
-0.4
"i'"

-0.6

g:

-0.8

;;
u
en

en

1.2

',...

1.4

--

u;

en

:>

500

-1

cG

Q..

Shear rate (s-l)

300

200
100

1.6
1.8
-2
2.2
2.'-2.6
0.00335

0.J0341

0.00347

0,00353

Temperature (1/K)

Fl,ure 14. ArrheDfus plots of mcilty WiJ decay at lelected Iheu rates for
Brand Iltfrred yo,urt.

(...

71

Table 9. Activation energy ofvtscosity decay for sUrred yogurt (Brand 1).

Viscosity parameter

A/y value

CJo/ivalue

Ea

Ea

Blivalue

Shearrate

(s-l)

(kcal/mole'

(kcal/mole)

(kcal/mole)

100

9.1

0.95

9.3

0.94

14.6

0.97

200

7.3

0.99

7.9

0.99

12.3

0.98

300

5.5

0.94

5.5

0.97

9.1

0.92

400

5.2

0.99

6.2

0.99

8.0

0.99

500

4.9

0.98

5.8

0.98

7.4

0.99

A =Weltman A value; B
y= shear rate

=Weltman B value; (Jo =Initial stress;

72

CONCLUSIONS

The stress decay behavtor of stJrred yogurt under a constant shear (100-500 s-l)
can be adequately descl1bed by the Weltman loganthm1c-Ume model for up to 60 min.
Weltman parameters show linear trends with shear rate and temperature. and hence
can be incorporated in to a composite model. Temperature effects can also be descrtbed
by the Arrhenius approach which gives acUvation energies ln the same range obtainable
under dynamic shear tesUng conditions. The tnJUal stress or start-up vtscoslty
decreases with Increasing temperature and Is partly compensated by a lower vtscosity
decay rate.
Characterization of the stress decay behavior constitutes an Important step ln
our overall objective of developiDg procedures for fabrtcating the desired consistency

and stabll1ty ln flavored yogurt-based products by blendlng stirred yogurt w1th


hydrocollolds and flavor concentrates.

73

CIlAPTERVI

RHEOLOGY OF RASPBERRY FLAVORED YOGURT

ABSTRACT

The influence of pectin (0.0-0.596) and raspbeny concentrate (64 0 B: 0-1 (116) on the
rheological characteristics of commercial sttrTed yogurt was evaluated using a computer
controUed Haake RV20 equipped with a M5

ose

measurtng head and MV l rotor. The

study indicated a steady iI1crease in the conststenctj coe1ficient (upward Jlow) alld
apparent viscosity (downward flow) with the addi.t1on of pectin and concentrate. TIll?
study also tndicated that the of the raspbeny flavored yogurt could be Jabrrcated

Wltll

desired rheological properties by postjermentatinn mixing of stUTed yogurt wUh pectUi


and raspberry concentrate.

INTRODUCTION

Data presented by Valenzky (1978), Ryan et al. (1984), McGregor and White
(1987) and Eden (1988) flavored yogurt. drtnks would be accepted by a major segment of
the North AmeIican consumer market and that the most popular flavor is raspbeny.
Due to Us positive nutrttional attribute. a vartety of new flavored-yogurt producls are
filling commercial vending machines. Flav,Jred yogurts are made by prior addition of
flavortng substances like fruit concentrates or syrups along with such additives as
pectln etc. to improve tht" viscosity before/after the fennentaUon process. Added flavor
Ingredients decrease the consistency of the product and therefore lhese producls are
often stabilized with viscosity modiflers such as slarches or pect tn (Tamime and
Robinson, 1985).

74

The objective of the present lnvesUgaUon was to study the effect of pecUn and
raspbeny concentrate on the rheologlcaJ behavtor of sUrred yogurt ln order that the
deslred product vlscoslty cou Id he achJeved by mlxtng pecUn and concnentrate to the
sUrred yogurt.

MATERIALS AND l'tIETHODS

Citrus pectin (methoxy content. 9.5%: Sigma Chemlcal Co.) and raspbeny
concentrate (640 B) were used as additives for test sampi es of sUrred yogurt obtatned
from the local market. A stock soluUon of pectln (5% by welght) was prepared by
dlsperslng ft ln wann dlstilled water to facllJtate addition. A full factorlal deSign of
expertments wlth six levels of pecUn (O. 0.1. 0.2. 0.3.0.4 and 0.5%) and three levels of
concentrate (O. 5 and

10%)

was employed wlth three rppllcates. Each test sample was

prepared by addleJg approprtate amounts of pecUn stock solution (O. 2. 4. 6.8 or 10 g)


and concentrate (O. 5 or 10 g) to 80 g of yogurt and made up to 100 g t.slng dtstilled
water. Prior to tesUng they were mixed genUy to get a unlform sample and handled
carefully to m1nmuze any structural breakdown. They were held at IOoC ln the sample
cup for 20 min before measurements were made.
The methodology for obtalnlng rheologlcal data durlng a programmed 3-cycle
continuous upward and downward sheartng sequence uslng the Haake RV20 rotational
vlscometer and the models used for thelr treatment (Herschel-Bulkley for the upward
curves and llnear model for the downward curves) are deta1led ln Chapter IV. The
rheologlcal parameters m. n. a o and 11 were used to assess the Influence of added pectln
and concentrate on the flow behavioT of test samples. The breakdown of rheologtcal
structure due to repeated shear was evaluated by compartng the apparent vlscoslty

(downward shearlng) of test samples obtatned from the thlrd shear-cycle to those from
the ftrst cycle.

75

RESVLTS AND DISCUSSION

Figure 15 shows the first upward and downward flow curves for test samples of
sUrred yogurt contairung dlfferent concentrations of pecUn wlthout added raspbeny
concentrate. Figures 16 & 17 show sunHar curves for samples contain1ng 5% and l001b
raspberry concentrates. AU test samples exhiblted typlcal thlxotroplc fiow behavlor will,
yield stress. In conflnnaUon wlth our earller findings (Chapter

IV).

the fust upward

curves of all samples could be adequately descnbed by the Herschel-Bulkley mode)


(R2_0 .99. Table 10). Il ts evident from Figures 15-17 that pecUn and concentrate had a
considerable effect on the flow behavtor of sUrred yogurt. Addition of pecUn resulted ln
an upward shifting of the flow cUIVes (butldlng up of structure leading to increased
sample viscosity). This behavtor was enhanced by the addition of raspbeny concenlratc.
Slmtlar results were obseIVed wtth the downward CUIVes whlch were essenUally
linear over the broad range of shear rates employed ln the study (Table 10). Since the
slopes of these cUIVes Indicate thelr apparent viscoslty (ah = Tl). the relaUve elTects of
added pectin and concentrate on the viscoslty of test samples could be Ca3lly vlsualtzed
from these curves; the trend was essenUally the same.
An analysls of variance of the fully randomtzeu factonal design (Table Il)

indicated both pecUn and concentrate to be signiflcant parameters (p<O.O 1) influenclng


all rheological parameters (m. n. (Jo and Tl). As expected the three repltcates were not
slgnificantly (p>O.05) different in any analysls. In addition. alltwo-way Interactions were
also found to be non-signtficant (p>O.05) except the pecUn-concent.-ate Interaction with
the apparent viscosity. The effect of added pecUn was non-linear and was somewhat
stmtlar with reference to the conslslency coelTtclent (m) from upward curves and the
yleld stress (aal from downward CUIVes as shown ln Figures 18 ar:d 19.

76

100
Pectln ('rom top to bottom)
0.5"-

90
80

--
1
a.

Concentrate 0%

0.4"-

70

0.3"-

60

0.2"-

.a 50j
!

1i

0.1"0.0"-

40

en

30

'!

"

20
10
0

Figure

100

us.

Typlcal upward and downward Oow cUlVes of st1rred yogurt at varlous

200

300

400 500 400


She.r rate (.-1)

300

200

levels of pectlD and DO raspbeny CODcentrate.

100

77

100

PeCUn (from top to bottom)


0.5%
0.4%

90

80

-CI

a.

i.
CI

Concentrat. 5%

70
60
50
40

II)

30
20
10
O~mnrnmTImmmmnmmnmnmmrrmnmmwmwm~~~~~~~

100

200

300

400 500 400


Shl.r rate (1-1)

300

200

100

Figure 16. Typlcal upward and downward Dow curves of stlrred yogurt at varlous
levels of pectlD and 5% raspberry concentrate.

78

100

.-,.
~

50

1
1:

tn

~"

0.5%
0.4%
0.3%
0.2%
0.1%

90
80

Concentrat. 10%

Pietin (from top to bottom)

70
60

~,

,,~
'<l99

40

,"9

9~

30

20
10
0
0

100

200

300

400

500

400

300

200

100

Shr rate (1-1)

n,ure 17. Typlcal upward and downward Oow carves of stlrred yo,urt at varlous
levels of pecttn and 10% raspberry concentrate.

i...

79

Table 10. Mean and standard deviatJons ln rheologlcal parameters of stJrreO jogurts as
tnfluenced by the additJon of pecOn and concentrate.

:"
",

PeeOn Rasp
cone.

(%)

(%)

(Pa)

0.0

0.1

0.2

0.3

0.4

0.5

0.0

0.1

0.2

0.3

0.4

0.5

0.0

10

0.1

10

0.2

10

0.3

10

0.4

10

0.5

10

R2

Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.

1.31
0.04
1.18
0.11
1.37
0.05
1.60
0.04
1.81
0.02
2.57
0.04

0.46
0.01
0.53
0.03
0.53
0.01
0.53
0.01
0.53
0.00
0.51
0.02

0.97

Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.

1.67
0.23
1.58
0.16
l.78
0.04
2.06
0.25
2.47
0.42
3.49
0.37

0.45
0.02
0.50
0.01
0.52
0.01
0.52
0.02
0.53
0.03
0.49
0.02

0.98

Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.

2.07
0.14
2.30
0.17
2.24
0.27
2.59
0.31
3.45
0.09
3.80
0.17

0.44
0.00
0.46
0.01
0.50
0.02
0.50
0.02
0.49
0.01
0.50
0.01

0.99
0.99
1.00
0.99
1.00

0.99
1.00
1.00
0.99
0.99

0.99
0.99
0.99
0.99
0.99
0.98

R2

TI

(Pa)

(Pa.s)

3.97
0.17
3.80
0.48
4.30
0.30
5.30
0.48
6.08
0.37
7.91
0.11

0.043
0.001
0.056
0.003
0.071
0.003
0.087
0.002
0.102
0.001
0.121
0.003

0.99

4.39
0.<"4
4.40
0.14
5.49
0.61
6.07
0.22
7.60
0.14
9.37
0.16

0.049
0.001
0.064
0.002
0.085
0.005
0.099
0.002
0.121
0.001
0.141
0005

0.9f}

4.75
0.04
5.12
0.28
5.16
0.31
6.03
0.21
8.32
0.47
11.06
0.61

0.058
0.003
0.075
0.002
0.093
0.002
0.110
0.003
0.135
0.002
0.166
0.002

0.99

1.00
1.00
1.00
1.00
1.00

1.00
1.00
1.00
1.00
1.00

1.00
1.00
1.00
1.00
1.00

80

Table Il. Sigruflcance of effect of pectln and concentrate on the


rheologlca1 parameters of sUrred yogurt (analyses of variance).

d.f.

1'1

1'13/11 1

PecOn

Concentrate

RepUcate

ns

Ils

Ils

Ils

ns

PecOn-Conc.

10

ns

Ils

os

ns

Rep.-Conc.

ns

Ils

os

os

ns

Pec.-Rep.

10

ns

Ils

Ils

Ils

ns

Source
ofvartaUon
Main Effects

1Wo-Factor
Interacttons

Total
Ils

53
not slgnlficant. p > 0.05
slgntficant. p < 0.01

The flow behavtor index (n) increased up to a pecUn concentraUon of 0.3% and
decreased thereafter (Figure 18). The apparent viscosity (11) from the downward cUlVes
varied linearly wlth pecUn concentraUon (Figure 19). The effect of addlUon of raspbeny
concentmte on all these parameters could be described by a linear fun cUon within the
range (0-10%) employed ln the study. This was somewhat expected because raspbeny
fruit jutce concentrates have been descrtbed to exhibit Newtonian flow charactertstics in
the low 300 B) concentration range (Sarvacos. 1970; Rao. 1977; lbarz and Pagan.
1987).

81

..

... ~ .....

3 a ~.!.:.................................; ..............................

:
:
3.4 ................................ ............... ............... :.
. :
..
~

_.~

......... _.

~.~ .......................... _.................................. ..

'.

1
:
:.
t 2.1 -)............................... 1............. ;....................... I .
i:

1i
a

::

~:

2.2 ~.~............................... ~ ............... ~.... .....

1.4 1-', ...........

0.53

} .............

~T ...... ......
.

1" . . _.
~.

.. :.... ..... .......... ...

! .... , ....... !.

.-

..

..,

. .!

i. . . . . ' ' .' . . T . . 1" .


r""""'' ' .. . . . .... .
.

'-

.-

.,

n.{ .......... ... . .... ...

~f:

1:

1.8~11 . 1
0.55

-.

. .....

.....

...... -

0.51 _.;..........: ..... ; ............

........

et 0.47

...............

~.~

;
.
+~ ...............::............................
_
..... , ......... .

l'

li: 0.45 :_.~............................... ;................ ; .............. _................... .


:
:
.
.

' . '
"
.
0.43 ~.~................ i...... ~ ........o
;................. :............... .;. ........ ...... ~...... ............
0.3
0.5
0.2
0.4
o
0.1

....... -

.Il

Peetln (%)

Ftlure 18. Upward fiow conslstenc)' coemclent ad fiow behavlor index of &tlrred

yoturt u lnOuenced by added pectln.

82

J.'.::':::.:::.:r::.:.:.::. or:.::::::.:r. ::....:.:. :~:.....:::-':"L:: .:-:-.::1:"::':::.:::r:


! '!'
.
.r:-:-:-:-:-:-:-r:-....:-:- ':-"'j':-"':-:-" .:-y. :-. . . :-.L...:-..... 'I"(" .... ...... .t ...... ..... .~.
t.. t ..... i. . . . . . . . !.......... .....:......... ..... .. ............ ~ ..............:.

'," ....:- . :--r. . :-:-:-:-.;...:-:-:-..~ . .:- . 1 .:- . . ..._.:-:- .... _:-.:- :-:-:-. . . .
-r . . . . . . : . :-:- :-'1':-:-:- J:-:-:- . ~:- .":-... t:-:-:- ..... t:-:-:- .. ,

.J............... ............... ,................. ~................ ~.. ............. ~..... ......... ~ ............. .. ~..

148

~f
~

.. .........

! ............. .1........... .... !............. !............ !..

t.-128 t-.-:-...............
. _................................
.
::................................; . ..... ..
'"1 .:
. :

L'

lU

~:

::

"

. .

! .. .. .. .. .!.-

I
.. ............... :. -

l'

..

~
~:
:
:
:
:
:
.
.
~ lOI I-.~ ................ ~ .................~ ................. ; .................: ................. ;................. :................. :.. -

1:

~!
1
~
~
1
.
i
~ :.: ................ _:.: ................ -.........................................................................................
:.~
;.
'.:
~.'
1
.
;
81
~.':'

~ i

68

:t

t. i. . . .:-.: . :-.L............. 1
... :-:-:-:-. . .L:-. '. :-.

48 .... ';1...............

:.

:-.1. .. :-:-..........
;
~

i. . :-:- . . . .:. . :-. . :-. . . ~

+..................................................
! 1 ;i.................:1............... i
+
o

0.1

0.2
Peetln

0.3

0.4

'l -

I ................

0.5

["J

nlure 19. Downwud Oow .heu .ue.. and appareDt vUcollty of .tlrred yo,urt as
lDfIueDc~d

by added pect1D.

83

Repeated shear cycles progresslvely degraded the rheologlcal Structure of sUrred


yogurt as shown typlca.l1y ln Figure 20 for representaUve upward and downward Cu IVes
of samples conta1n1ng 0.5% pectJn and 10% raspberry concentrate. nIe shear
destruction patterns were sunHar at other condlUons con.'lnnlng our earlter findlngs
(Chapter IV) of continuaI and Irreversible structural decay wlth repeated shear. In order
to

quantitate

the

influence

of

added

pectin

and

concentrate

on

shear

degradablllty/stablllty of yogurt structure. the rheologlcal parameters from the lhlrd


cycle were compared wtth those from the ftrst cycle. A shear stabWty lndlcalor was
defiIled as a ratio (T\3 / ll1) of the apparent viscostUes of thlrd cycle and flrst cycle
downward flow curves. The downward-flow parameter (ll) was chosen because of the
Unear relationshlp between shear stress and shear rale. The raUo of apparent
viscostUes (113 / 1\ 1) as a funcUon of pecUn and concentration are shown ln Figure 21.

100
Pectln 0.5%

Cycl. 1

90

Concentrate 10%

80

--i

70

a.

&0

...

50

40

li
~

J:

en

20

10
0

100

200

300

400

500

400

300

200

100

She.r rat. (s.. 1)

Figure 20. Typlcal fiow curves showlng structure breakdown of stlrred yogurt ln a
3-cycle upward and downwud shearlne sequence.

84

PectJn (%)

0.1

0.3

0.2

0.4

0.5

o'87.
~.!.............. !................ ~ ............. !................ ;.................................;................!.:
:
. :
:: .

0 83

i'

I. . . . . . . : .
~.J. . . . . . . . . 1................L. . . . . . . j................!...............+. . . . . . . .L. . . . . . ..!.~
i
!
!
l
~
!
!
;
!
;
l' : ! j i

o 85 ~.l ............... ;................ l. ................................i................ i.. ....


'!
!
~
:
!!

l.-

0.81

~+

.......... r . . . . . .......... ... .............. ! .............. 1...... .. ..... j.............. ;.!


!
:.
I~

0.79 ~.~ .... ........I~

. . J ... ;................:................:................~ ................:.-

i . : .

>

:.

0.77 1- .:............. :............ .. ( .. .. .... .. , ...... .... 1 .. .. ........ 1........ ....... j ................:

o.
83 ~.~.......
:
1- :

1. :. . . . . . . . . .

. ................. !........................... ;...........................................................'.:

::,..1 ............. ...........

~
1- :

0.82

!.............................:............................ L~

i.

~:I:::. : .,: :.: ':.: ::':::::1':.:::::::::::::.:.:.:::::1:":::::::'. :::':::::::.:i:::.:.:.::.:':":.:.:.::.:::-:~

i
:
1-1- :
!
en 0 81

"T

....
...

1- . .:. ............................ : ............................. :............................

:.
:

.. ......................... l._

i !
!.
o .
.
. .
.
::-.+ ............................ j.............................!.............................;............................ +.::
::
::
:.
:: ..
1-

I-!

"

"

!.............................:...................... ... 1........ .. .. 1 ...... ...... +-

0.8 _ ..

5
10
Raspberry Concentrate (%)

ngure 21. StabWty lndez (ratio of the thlrd and Bnt cycle apparent vtscosltles,

of stln"ed yogurt as InOuenced by added pectln and raspberry concentratc.

85

AnaIysis variance results II1dlcated both pectln and concent.rate to be highly


significant (p<O.OI) factors influencing the shear degradablllty/stabUlty. Thelr Intluence
however were opposite. While pectln tmproved the structural stab1llty (hlgher 113/111
values at hlgher pectln content), the concentrate Increased the sensUivlty of the
samples to shear degradabllity (Figure 21). However, ft should aIso be noted that earller
results (Table 10; Figures 19) Indlcate that addition of both pecOn and conccntrale
increase apparent viscoslty level of test samples. These results show that whfle addition
of pectin favors both viscoslty Increase .md shear stab1llty, addiUon of concentrates will
only result ln an apparent increase ln sample vlscoslty whlch may be mm e eastly
degraded by repeated shear.

A Model for Fabrlcatlng Flavored Yogurt Rheology

In order to develop a model to fabricate the rheology of raspberry flavored


yogurt, the relative influence of the addition of pectin and concentrate on a rhcologlcaJ
parameter need to be quanUfied. Ideally, if m, n. (Jo and 11 could be predlclcd accurately
as functions of added pecUn and concentrate. the upward flow CUIVe could be described
by the Herschel-Bulkley model and likewise the downward curve could be describf'ri by
a linear model. A multiple regression technique with a second order polynomial sultable
for generating a response surface plot (Statgraphlcs StaUstical Graphies System.
STSC, Rockville. MD) was employed to relate the rheologlcal parameters to pecUn and

concentrate levels. The multiple regresslon coefTiclenls for the depcndent variables and
the assoclated R2 values are summarized in Table 12. The regresslon fltUng was good
(R2~0.89) except for the flow behavior Index (R2

= 0.70).

Because of the hlgh R2 value

and the relative ease at whlch il can be detennlned by varlous instrumenls. the
.'~

apparent viscoslty (11) was chosen as the parameter for detenntnlng levels of pecUn and
raspberry concentration in the flavored yogurt formulaUon.

------

------------------------------------------86

Table 12. MulUple regresslon coefficients for rheologlcal parameters.

Coefficient
Parameter

0.70

0.474 0.430

-0.71

0.89

1.340 -2.00

0.94

4.10

0.99

0.04430.109

-4.77

-0.004

0.00

0.005

8.956 0.066

0.124

0.001

25.3

-0.009

0.417

0.00

0.005

0.142

0.093 0.001

Regression EquaUon IP = Pectin (%); R = Raspbeny concentrate (%)1:


Parameter =Cl + P,C2 + p2.C3 + RC4 +R2.CS + P.RC6

Figure 22 shows the three dbnenslonal response plot of apparent vlscoslty as a


function of pecUn and raspbeny concentraUon levels. Also superlmposed on the figure
(shaded) Is the range of apparent viscoslty obselVed wlth commercial raspberry flavored
yogurts. Pectln concentrate requlred to Increase the sample v1scoslty to commercial
levels with no concentrate added Is 0.25-0.4% whlle the range Is 0.1 to 0.25% wh en the
sample contained 10% raspberry concentrate. The exact level of concentrate would
depend on organoleptic propertles of the fonnulation.

87

f V1ICOllty range 0.08-0.10 Pa.1

'f

f
1.

0.12

0.01

1
10.01
t
0.03

",ure 22. AppareDt 'rilcoslty of IUrred JO'urt u fuDCUOD of added pectln and
nspbeny CODcentnte.

--------------------..........
88

CONCLUSIONS

The rheologlcal properties of stJlTed yogurt. were tnfluenced by


pectJn and raspberry concentrate. Upward shear flow

CU Nes

th~

addition of

demonstrated Herschel

Bulkley flow pattern wtth yteld stress, whlle the downward shear Dow CUlVes were
essentlally llnear. The apparent viscoslty from downward CUIVes could be used to
assess the shear degradabUity of yogurt. samples. Pectln resulted ln increased sample
VlScoslty that was more shear stable whUe the lncreased vtscoslty resulted from the
addition of concentrate was less shear stable. The rheology of flavored yogurt could be
fabrlcated by mixing stlrred yogurt. wtth the rtght proportion of pectln and fruit
concentrates.
In this study, the pectln and concentrate have been added to yogurt after the
fennentation process. Further, the prepared yogurt had been diluted to sorne extenllo
faclUtate proper incorporation of pectJn and raspbeny concentrate. Building of the
deslred viscoslty has sUll been possible. In sorne formulations, pecUn or other
stabll1zers are added to the mIlk prlor to fennentatlon whlle the concentrate Is added
followlng the fennentatlon process. In these situations. the amount of pecUn and
concentrate necessruy for achleving the destred conslstency may be somewhat dlfferent.
the concept would still be applicable.

89

CIlAPTERVD

RBEOLOGY OF STRAWBERRY FLAVORED YOGURT

ABSTRACT

The influenct of pecttn (0.0-0.596) and strawbeny conntrate (648: 0-10%) on the
rheological characteTistics of commercial sttrred yogurt was evaluated using a Haake
RV20 wtth an M5

ose

measuring head and MY1 rotor. AU rheograms tncluded an

upward floU) curoe through a linear ramp shear (0 ta 300 s-1 in 3 minJ. a stress decay
curoe al a steady shear rate (10 min at 300 s-l),joUowed by a secondflow curoe throt&gh
a downward ramp shear (300 ta 0 s-1 in 3 mtn). In consistence with previDus flndtngs. aU
upward jlow curoes foUowed the Herschel-Bulkley modeL downward curves were ltnear

and the stress ecay behavior foUowed the Weltman logartthmi.c lime modeL The study
indtcated that (he rheology of j1.avored yogurt was influenced by bath pecttn and
concentrate levels and that the destred product vtscosity could be obtained by postfermentation mtxiTIg oJ stiITed yogurt wtth pecttn and strawbeny concentrate.

INTRODUCTION

Among the flavored yougurts. the second most popular flavor appears to be
strawbeny followtng raspbeny. Flavortng Ingredients as weil as added mod1fiers cao
have profound e1Tect on the rheology of yogurt based products. The objective of the
current investigation was to study the effect of pecUn and strawbeny concentrate on
the rheological behavior of surred yogurt. Once again the ultimate atm was to simulate
the rheology of strawbeny flavored yogurt through the addition of pecUn and strawberry
concentrate to the post-fermented stlrred yogurt.

90

MATERlALS AND METHODS

A full factortal design of expeI1ment wtth six levels of pecUn (O. 0.1.0.2.0.3.0.4
and 0.5%) and three levels of concentrate (0, 5 and 10%) was employed w1th three
repl1cates. Each test sample was prepared by addtng approprtate amounts of pecUn
stock solution (0, 2,4,6, 8 or 10 g) and concentrate (0, 5 or 10 g) to 80 g of yogurt and
made up to 100 g ustng dtstllled water.
Rheological studies were carrted out using an Haake RV20 rotaUonal viscometer
descrtbed earUer. Test samples were subJected to a ramp shear rate of 100 s-l/mln
changlng linearly from 0 to 300 s-I ln 3 min, were held at the maximum shear rate of
300 s-1 for 10 min and then subjected to a ljnear ramp down shear to 0 s-1 ln the next
3 min. The models employed to charactedse the two types of flow curves (upward and
downward) were essenUally the same as descrtbed in previous Chapter. The stress
decay behavior was charactertsed by using Weltnl.ln model whlch Is sllghtly difTerent
from that used in the prevlous study.

Weltman Model:
(J

= A - B log (t); t.>ls


(7- 1)

Since the stress decay was initJated ln a sample that prevlously was brought to the test
shear rate (300 s-I), use of a Ume factor lm as employed in Chapter V was not
necessary. Even so, slnce a zero Ume viscoslty Is non-existent ln the logartthmic-Ume
model, the results would be valld only beyond a certain ume (dependent on the system).
Based on experimetal results. a !!me of 1 s was chosen as the lower UmU and since on a
loganthmic scale thls

J epre'Jents

a zero value (log (1)

= 01.

the shear stress

corresponding to thls Ume Is actually represented by the intercept coefficient (A value)


of the Weltman mod/!l.

91

The rheologtcal parameters m, n, Go' TI, A and B were used to assess the
Jnfluence of added pecUn and concentrate on the flow behavtor of test samp15.

RESULTS AND DISCUSSION

Figure 23 shows the complete rheogram for test sru.npl.es of sUrred yogurt
contatniDg different concentraUons of pectln wtthout added strawbeny concentrate.
Figures 24 & 25 show stmtJar cUlVes for samples contatntDg

~%

and

1 f)%

strawbeny

concentrates. Ali test samples exhtbtted typtcal thtx:otropic flow behavtor with yteld
stress. Further, the cUives were generally stmtlar except for the progressive upward
shilltng as a resuJt of the addltJon of pecUn and/or concentrate. It Is therefore evtdent
that pecUn and concentrate had a considerable effect on the flow behavtor of sUrred
yogurt espectally contrtbuUng to bullding up of structure (tncreased sarnple vtscOSity).

ln conftnnaUon with prevtous ftndtngs (Chapter IV), the upward cUlVes of all samples
could be adequately descrtbed by the Herschel-BulkJey model (R2_0.95, Table 13).
SJmJlar results were obseJVed wtth the downward cUJVes which were essenUally
Unear (R2>0.97, Table 13) over the range of shear rates employed in the study. Stnce
the slopes of these downward CUIves tndicate their apparent viscosity (a/y

= TI),

the

relaUve effects of added pecUn and concentrate on the vtscosity of test sampi es could be
easny vtsualized from these cUJVes: the trend was same as discussed earJJer.
The stress decay behavtor at the constant shear rate of 300 s-1 was obtatned
from the mtddle part of the rheogram (Figures 23-25). The 10garithmJc Ume model
chosen (Weltman, 1943) well descrtbed the stress decay behaVior (R2_0.97, Table 13)
for ail conditJons tested. LogarithmJc stress decay models based on an equiUbrtum
stress (Hahn et al., 1959 and Tiu and Boger, 1974) were not sultable for sUrred yogurt
because of their continuai stress decay wtth tJme as descnbed ln Chapter V.

60 ,-----------------------------------------------------------,
Pectln lev.. (top to bottom): 0.5,0.4,0.3,0.2, 0.1.0%.

50

-e:..
..
..

40

fit

30

.c

fi)

20

10

10

12

14

16

TIm. (min)

FIJure 23. Typlcal rbeoJram. of .t1rred J'OJuR at Yuloua leyeJa of pectln and no
strawbeny concentra te.

\0

tv

i~

r"'-

70~------------------------------------~
Pietin lev.. (top to boIom): 0.1. 0.4. 0.3. 0.2, 0.1 0%.

60

--

50

30

A.

40

.1:

(1)

20

10
O~I--~--r--r--~~--'-~--~--r--r--T-~--~~r--r~

. 10

12

14

16

Tlme (min)

Fl,ure 24. Typlcal rheo,ram. of atlrred yo,urt at yarloua leyela of pectln and 5%
etrawbeny concentrate.

\0
W

e )

.-

80
Pectln level (top to boaom): 0.1, 0.4, 0.3, 0.2, 0.1

.0%.

70
60

-
f!:.

50

40

.r:

30

lit

en

20
10

0
0

10

12

14

16

TIm. (min)

FI,ure 25. Typlcal rheo,rams of stlrred yo,urt at YUlous leyela of pectln and lOOIi
strawbeny concentrate.

\CI
.t;..

95

Table 13.

Mean and standard dev1ations ln rheologleal parameters of stirred

yogurts as tnflueneed by the addition of pecUn and coneentrate.

(
'"

Strawbery
cone.

ID

(%)

(%)

(Pa)

0.0

0.1

0.2

0.3

0.4

0.5

0.0

0.1

0.2

0.3

0.4

0.5

0.0

10

0.1

10

0.2

10

0.3

10

0.4

10

0.5

10

Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mr:an
s.rt.
Mean
s.d.

2.04
0.10
1.86
0.48
2.22
0.28
2.92
0.35
2.52
0.38
2.81
0.59

0.38
0.00
0.44
0.02
0.44
0.02
0.42
0.01
0.48
0.03
0.49
0.03

Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.

2.89
0.33
2.97
0.28
2.66
0.06
3.28
0.56
3.45
0.12
3.58
0.95

0.35
0.01
0.37
0.01
0.43
0.01
0.44
0.03
0.46
0.02
0.48
0.03

Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.
Mean
s.d.

3.82
0.26
4.61
0.38
4.76
0.23
4.12
0.62
4.96
0.38
5.67
1.12

0.33
0.02
0.32
0.01
0.36
0.01
0.42
0.02
0.42
0.02
0.44
0.03

Weltman

Down-curve

Up-culVe
PecUn

R2

0.95
0.97
0.98
0.97
0.99
0.99
0.94
0.96
0.98
0.98
0.99
0.99
0.93
0.96
0.98
0.98
0.99
0.99

(Jo

1'1

(Pa)

(Pa.s)

4.42
0.22
4.32
0.45
4.44
0.23
4.98
0.40
5.97
0.21
6.81
0.29

0.04
0.00
0.05
0.01
0.07
0.00
0.08
0.01
0.11
0.00
0.13
0.00

4.92
0.54
4.66
0.28
5.14
0.19
5.38
0.48
6,69
0.20
7.19
075

0.04
0.00
0.05
0.00
0.07
0.00
0.09
0.00
0.12
0.01
0.14 .
0.01

5.73
0.25
5.27
0.15
5.69
0.09
5.93
0.52
7.32
0.22
9.99
1.02

0.05
0.00
0.06
0.00
0.08
0.00
0.10
0.01
0.13
0.00
0.16
0.00

R2

0.99
1.00
1.00
1.00
0.99
0.99

(Pa.s)

(s-l)

19.8
1.1
24.9
2.6
30.6
0.2
36.1
2.4
45.2
0.6
52.7
0.4

3.41
0.32
4.22
0.39
5.35
0.03
6.20
0.32
7.69
0.33
8.21
0.34

22.8
1.2
27.1
0.6
34.9
0.8
41.8
1.2
52.0

0.99

58.4
4.8

4.70
0.29
5.63
0.09
7.19
0.41
8.17
0.28
9.46
0.57
9.85
1.51

0.99

25.8
0.5
31.4
1.7
40.4
0.7
46.9
2.3
58.0
2.4
71.0
0.4

5.97
0.13
7.40
0.55
8.91
0.21
9.75
0.41
11.5
0.86
12.7
0.48

0.99
1.00
1.00
1.00
0.99

~.8

0.97
1.00
1.00
1.00
0.99

R2

0.97
0.97
0.97
0.96
0.97
0.97
0.97
0.98
0.97
0.98
0.97
0.97
0.98
0.98
0.98
0.98
0.98
0.98

96

An analysis of variance of the fully randomtzed factorial design rrable 14)

indlcated that boUl pecUn and concentrate were slgntflcant parameters (p<O.Ol)
influencing all rheologlcal parameters (m. n.

00,

Tl. A and B). The dtfferences betwecn

the replicates wcre small and generally non-signtflcant n'able 14). ln addlUon. aU twoway interacUons were aIso non-significant except pecUnconcentrate interacUons wlUl
the flow behavior mdex. apparent viscosity and Weltman A value.

Table 14. Significance 1 of eiTect of pecUn and concentrate on the rheologlcal parameters
of sUrred yogurt (analyses of variance).

Source
ofvartaUon

dJ.

2
2

ns

ns
ns

os

os

ns

Ils

os
os

WeltmanA

Weltman B

Main Effects
PecUn
Concentrate
Replicale

os

ns

ns

ns

l'aS

ns
ns

ns
ns
ns

Two-Factor
Interactions
PecUn-Conc. 10
Rep.-Conc.
4
Pec.-Rep.
la
Total
1

os

......

53
Slgnlflcance al 1% level
signlficant
not slgntficanl

ns

97

The overall effects of added pectln and concentrat'! on the various rheological
parameters are shown ln Figures 26-28. The effects were generally non-linear except
wtth reference to the apparent viscosity. and Weltman pararneters. The strawberry
concentrate was a more dominant factor than pecUn content in tnfluenctng the
conslstency coefficient (Figure 26). With reference to the flow behavtor index (n). the
efTects of pecUn and concentrate were opposite. While added pecttn increased the flow
behavior Index. the addition of concentrate caused It to decrease (Figure 26).
The stress constant calculated as the intercept of the downward curves

(00 ,

Eq.

7 -2) varted somewhat exponentially wtth pecUn and concentrate whtIe the apparent
vtscosity (11) varted Itnearly wtth both pectln and strawberry concentration (Figure 27).
Jutee concentra tes at low concentration levels '<300 B) have been generally descnbed to
exhibtt Newtontan flow charactertstics (Sarvacos. 1970; Rao. 1977; Ibarz and Pagan.

(.
'

1987). The non-linear effect of addition of strawbeny concentrate on &'me rhcological


parameters are somewhat ln contrast with the above studles.
Both stress decay parameters. Weltman A and B values. showed a IInear trend
wtth added pecUn and concentrate (Figure 28). Weltman A value increased almost by
three rolds with addition of 0.5% pecttn whUe addition of l00A> strawbeny concentrate
Increased ft. on an average. by about 50%. Somewhat slmt1ar results were observed
wtth Weltman B values.
Weltman A value whlch 1s the shear stress at a Ume equaI to 1 s (in this studyl.
Is a structural parameter that genera11y has a close correlation wtth the yield stress
(Chapter V). Higher values lndicate a stronger resistance to start up shear. The
Weltman B value. usually referred to as the Ume coefficient of stress decay. 1s a
measure of the rate of structure breakdown. Higher B values indlcate that the sample Is
more susceptible to structure loss. In this study. both A and B values increased wtth
the addition of pectin as weIl as concentrate. This tmplies that the addition of pecUn
and

concentrate

helped

building

up

of

the

start-up

vtscosity

and

also

98

8
Strlwbtrry concentrllte

-
l

>0

-!c

5"
0%

(J

0.0

0.1

0.2

0.3

0.4

0.5

0.2

0.3

0.4

0.5

0.5
Strawberry concentrate
Je

-..
->
."
C

0.4

-1

L I.

0.3
0.0

0.1

Pectln (%)

F11ure 26. Upward Dow conslstency coemclent and Dow behavior indu of stlrred
yogurt as lnOuenced by added pectin and strawberry concentrate.

99

10
.lIawberry concentrlte
10"

."

>=

8
7

5
4

.st

0.0

0.1

0.2

0.3

0.4

0.5

0.2
S~awberryconc.~lte

8
1 0.1
"5

J
0.0
0.0

0.1

0.2

0.3

0.4

0.5

Peetln (%)

(
"

n,ure 27. Downward fiow .heu .tre.. and appueDt Ylacoalty of.t1ned )'o,urt as
lDfiueDced by added pectlD and atrawbeftJ' CODceDtrate.

100
*'i"'11
"<$/J'

80
---.
, 70

Strawberry concentrat.

60

.: 50

)40
~ 30

20
10

0.0

0.1

0.2

....... 13
12
......., 11
.a 10

... t...,.

0.4

0.5

Strawberry concentrat.

'i

"

0.3

m 9
c 8
ca

7
8
5
4
3

0.0

0.1

0.2.

0.3

0.4

0.5

Pectlr. (%)

n,ure 28. Weltman parameten of .t1rred )'o,urt a. IDOueDced byadded pectln


and .trawbeny concentrate.

101

Increased thelr sensittv1ty to stress decay. The Viscosfty of pecUn and concentrate
enr1ched samples remained htgher through out because of the more dominant effect on
structure buUd-up. For example, the average start up shear stress ln samples
conta1n1ng 0.5% pectln was -60 Pa as compared wl1..n -22 Pa for samples without
pectln. The correspond mg average B values were apprmdmately 10 and 4.5 s-1
respecUvely. The calculated vtscosfty of the former wou Id thus be hfgher (0.07 Pa.s as
compared to 0.007 pa$) even after contlnuous shearfng for four loganthmic tlme cycles
(10000 s or about 2.8 hr) at 300 s-l.

A Mode. for Fabrlcatln, Flavored YoJUrt llbeololY

In order to develop a model to fabrtcate the rheology of strawbeny tlavored


yogurt, the relative influence of the addition of pectin and concentrate on a rheological
parameter need to be quantified. Ideally, if m, n, (Jo and '1 could be predicted accurately
as functions of added pectln and concentrate, the upward tlow curve could be descrtbed
by the Herschel-Bulkley model and lJkewise the downward curve could be descrtbed by
a llnear model. A multiple regression technique with a second order polynOmial suftabk
for generating a response surface plot (Statgraphics Statistical Graphies System,
STSC, Rockville, MD) was employed to relate the rheological parameters to pectin and
concentrate levels. The multiple regression coefficients for the dependent variables and
the associated R2 values are summartzed in Table 15. The multiple regression fitting
was especially good (R2>0.9) With the apparent viscosity and Welbnan parameters.
Because of the high R2 value and the relatiVe! ease at which ft

Call

be determtned by

vartous Instruments. the apparent viscosity (TI) was chosen as the parameter for
detenntntng levels of pectln and strawbeny concentration in the flavored yogurt

fonnulation. Figure 29 shows the three-dtmensional response plot of apparent viscosity


as a function of pectin and strawbeny concentration levels. AIso superimposed on the

102

V1scoslly range: 0.08-0.10 P8.1

-----r------'?fdJ~~~

0.11
0.15

e:..i
,
\

0.12

0.01
0.06

0.03

',etln (%)

" '..... 29. "r1afCe-4\IDCIII,ooal ...oItlpte


.dll

e4

o
o4C' of appare ' _a1'lY of

se.-,. . . .

"""" .. (aocUoO of actcte4 pecU...4

.~r<7 _cee"'''

103
Table 15. Multiple regresslon coemcients for rheologtcal parameters.
cocmlent
Parameter

R2

Cl

C2

0.74

2.06

0.483 2.27

0.75

(Jo

C4

C5

C6

0.0489

0.0155

0.0896

0.384 0.279 -0.147 -0.00327

-0.000413

0.00633

0.84

4.72

0.00974

0.293

fi

0.98

0.04060.105 0.136 -0.000156

0.000054

0.00604

WeltmanA

0.97

20.5

37.5

54.3

0.0303

2.35

WeltmanB

0.94

3.31

11.0

-2.40 0.228

0.00431

0.325

C3

-5.83 20.7

-0.0205

0.178

Regression Equation IP = Pectin (%); R = Strawbeny concentrate (%)):


Parameter= Cl + P,C2 + p2,C3 + RC4 +R2.C5 + P.RCe.

figure (shaded) Is the range of apparent viscoslty obselVed wlth commercial strawbeny
flavored yogurts. Pectin concentrate requlred to tncrease the sample viscoslty to
conunerclal levels wtth no concentrate added Is 0.3-0.4% whtle the pectln range
requlred Is 0.2 to 0.3% when the sample contaJned 10% strawbeny concentrate. The
exact level of concentrate would depend on organoleptlc propertles of the fonnulation.

CONCLUSIONS

The rheologlcal properttes of stirred yogurt were tnfluenced by the addition of


pecUn and strawbeny concentrate. Both pectin and strawbeny ccncentrate Increased
the sample viscoslty. Although the shear stabUfty of the pectln and concentrate treated
samples were lower, the beneftclaJ effect could be real1zed under practical conditions
due to the htgher start-up vlscoslty. The rheology offiavored yogurt could be fabrtcated
by mtxlng sUrred yogurt wtth the right proportion of pecUn and fruit concentrates.

104

...

CIlAPTER vm

RBEOLOGICAL BEBAVIOR OF STIRRED YOGURT DURING STORAGE AT 20C

ABSTRACT

The influence of storage al

:zoc up

ta 4 weeks on the rheologtcal charactertstics oJ

commercial stirred yogwt was el.lluated usfng the Haake RV20 rotattonal vtsclJmeter.
The jlow behavior was evaluated wu:ler dynamtc shearing with a 3-cycle programmed
upward and downward shear rates (0 to 500 s-1: 5 min) as weU as al a selected steady
shear rate of 300 s-1. In conststence with previous findtngs. aU upward flow curves
JoUowed Herschel-Bulkley model while the downward cumes were linear. and stress
decay behavior JoUowed the Weltman logartthmtc modeL The study indicated only
marginal changes (generaUy rwt signlflCanI.. p>O.05J in the flow behavior parameters oJ
yogwt under dynamic as well as steady shear during the storage. The chemtcal
composition also changed oruy slightly during the storapp, although the results werc
statisttcaUy signlficant (p<O.Ol).

INTRODUCTION

Due to Us increasing popularity as a nutnUous food. yogurt and yogurt based


products su ch as fruit yogurt (Swiss style), set and sUITed fruit flavored yogurts. yogurt
dI1nks. yogurt ice-cream etc.. are becoming more aVailable in the market. Accordtng lo
Agriculture Canada (1988). the per captta consumpUon of yogurt has tncreased by two
folds in the last fjve years.

Yo~urt

Is a penshable food and has a shelf-Hfe of about four

weeks under refrigerated conditions. Deterioration of quaJUy and functtonaltty of lhe


<,

product poses a major problem for the widespread use of yogurt and relaled products.

105

ConUnued mtcroblologlcal acUvlty ln yogurt based products during storage has


been assoclated with sorne chemtcal changes: sourlng (Slnha et al. 1989; Jordano et al.,
1988), proteolysJs ofmilk protelns rramJme and Robinson, 1985: Lacroix and Lachance,
1990) and hydrolysts of fat (DeUagUo, 1988). These chemJcal reacUons may adversely
affect the sensory, rheologlcal as well as funcUonal properUes of yogurt. Low
tempe rature storage obvtously Js the cholce for control1ing these changes.
LaUc et al. (1987) have demonstrated that the duraUon of storage of yogurt at a
constant tempe rature (80 C) affects the rheologtca1 characterisUcs whlch in turn
changes the organolepUc propertJes. O'Nell et al. (1979) reported that the acldlty and
conslstency Increased sllghtly durtng a 2-week storage at 4 0 C. At the same tJme they
reported that fat and total solJd contents varted dependlng on the nature of the
conunerclal yogurt used.
The current study was undertaken to InvestJgate the influence of storage tlme of
up to four weeks at 20 C on the physJco-chemtcal and rheologlcal behavtor of sUrred
yogurt under dynamJc and steady shear testlng condiUons.

MATERlALS AND METHODS

The same two commercial brands of yogurts (Brand 1 and Brand II) reported
earUer were used in the current study. They ail had a resldual shelf-llfe of four weeks
based on the expiration date on the containers and were stored at 20 C for varlous
pertods prlor to analyses.
Rheologlcal evaluaUons were made durtng a programmed 3-cyc1e contlnuous
upward and downward shearlng sequence (descrtbr.d in Chapter IV) as weIl as at a fixed
shear rate of 300 s1 (detatled in Chapter V) uslng the Haake RV20 rotattonal

(
J

vtscometer. The models employed to evaluate the upward and downward flow curves

106

and the Ume dependency were essentially the same as dlscussed ln the earller chapters.
Rheologlcal parameters m, n,

0 , ", "3/'1 l' Welbnan A and Weltman B values were

used to assess the Influence of storage Ume on the flow behavtor of test samples.
Molsture content was esUmated from the oven drytng method of AOAC method
(1980), with a sUght modification: drytng was done ln a vacuum oven at 700 C for 24 hr
Instead of usual 4 hr at lOOoC.

Th,~

loss ln wetght of the sample expressed as a

percentage of the Initial weight was taken as the wet basls molsture content. The pH of
the

~amples

was detenntned uslng a Digital pH meter (Chemcadet model 5984-50).

TItrable acidlty was evaluated by titration wtth O.IN NaOH accordtng to the AOAC
method (1980). Acldity was expressed as percentage lactic acid. Fat. protein and lactose
contents were analyzed usJng the rapid IR spectrophotometric method (van de Voort.
1980) uslng a Multispec MKI tnfrared mtlk analyzer from measured absorbance values
at respective wavelengths (for fat (5.73 J.lDl). prote ln (6.461JIll) and lactose

(9.61~mn.

The

samples were adJusted to pH 6.5 using IN NaOH prior to the IR measurements.


Rheologlcal evaluatlons and chemtca1 analyses were perfonned on samples from
both Brands at three day Intervals during storage for four weeks at 2 o C.

RESULTS AND DISCUSSION

Effect of storaie on rheolo,lcal parametera

Figure 30 1llustrates typlca1 upward and downward flow curves of test samples
from Brand 1 and Brand II foUowtng storage at 2 0 C for selected pertods. AU curves
confirmed a thixotropiC, shear thlnnJng behavtor wlth an yleld stress: however, they
showed no specifie trend with respect to storage Ume. The overall pattern of the flow
curves for the two brands rematned qua1JtaUvely sim1lar but sorne quantitaUve

107

dlfferences were noticeable. In agreement to our prevfous flndJngs (Ramaswamyand


Basak. 1991a). test samples of Brand

n exhiblted a sl1ghtly htgber Vlscoslty compared

to that of Brand 1 as tndtcated by the assoclated larger shear stress at a gtven shear
rate. Ali upward curves for both brands could be weU descrtbed by a Herschel-Bulkley
Model (R2_0.99; Table 16). Wlth Brand l, the magnitudes of rheologlcal parameters, So
and m both Increased up to mldway through the storage, beyond whtch they gradually
decreased and nearly retumed back to thelr ortglnal values by the end of the storage.
The reason for thls 1s not c1ear. In contrast for Brand n, there were no speclflc trends
for the rheologlcal parameters durtng the entire pertod of storage. The vaiue of n sbowed
a slm1lar pattern but in the opposite direction, i.e., they decreased Orst and then
fncreased. The downward flow curves of test samples from both brands were lInear
(Figure 30, Table 16, R2_0.99; Brand 1 showing sltghtly lower v1scoslty than Brand Il).

As previously noted ail the test samples showed progressive degradation of

rheologlcal structure on repeated shear. In order to make a quantitative measurement


of the shear degradation of yogurt structure and to assess how ft 1s influenced by
slorage, the values of the apparent vlscoslty from the thlrd cycle were compared with
those from the flrst cycle. The ratio of these two vlscoslties, h3/h l' was deflned as a
shear stabUity index, hlgher values lndlcating larger stabUity. Durtng the storage, the
stabillty index ranged from 0.79 to 0.81 for Brand 1 and from 0.76 to 0.78 for Brand Il
IndicaUng oruy marginal dUferences between them and smaIJ changes to be assocfated
Wlth storage.
Stress decay curves for the two commercial brands durlng a 10 min steady
shear at the selecled shear rate of 300 s-1 are shown 10 Figure 31. Weltman regression
parameters A and B values were used to compare the stress decay behavtor of the two
test samples. Weltman A value whlch Is the shear stress at tlme

study),

1s

=lm

(12 s ln thls

a structural parameter that generally bas a close correlation wfth the yteld

108
,"

stress (Ramaswamy and Basak. 1991b). Hlgher values tndlcate a stronger res1stance to
start up shear. Weltman B values 1s usually referred to

2S

the Ume coefflc1ent of stress

decay. and 1s a measure of the rate of structure of breakdown. IUgher B values Indlcate
that sample Is more susceptible to SL.1"\lcture loss. For both Brands. the stress decay
behavtor was accurately descrtbed by Weltman model (R2 = 1.0) As observed prevtously
(Ramaswamyand Basak. 1991b). the stress curves for the two samples were nearly
s1milar but thetr magnitudes dtffered sUghtly. The effect of storage Ume on the Weltman
parameters A and B are gtven ln Table 16. Weltman A values showed a trend slmtlar to
the yield stress. It must he stressed that these changes durtng storage were qulte small
5% on the average) to have any real impact on the overall rheologlcal property of the
sample. SlmUar trends were aIso obselVed for the other Weltman parameter B.
Results of the analysls of variance for the changes ln rheologlca1 parameters
dunng storage of the two conunerclal yogurts are shown ln Table 17. For Brand 1. the
rheologtca1 parameters 00 and m showed no slgntflcant change durlng storage whereas
the changes wlth reference to the flow behavtor Index. n. werc slgntflcant (p<0.05). Wlth
Brand Il. aIl these rheologtca1 parameters were non-stgnificant. Wlth reference to the
downward CUlVes. for Brand 1. values of both stress constant and apparent vtscoslty
were slgntflcant (p<O.Ol). For Brand Il. on the other hand. stress constant was
signtftcant (p<O.05) but not the apparent vtscoslty. The storage Ume was not a
signiftcant factor tnfluenclng shear degradtblty Istab1l1ty (113 / 111) ln both cases. The
analysis of variance also revealed that the storage Ume dld not have any slgntflcant
effect on the values of Weltman A or B. In splte of the staUsUcal slgn1flcance. the
magrutudinal changes ln major rheologtcal parameters were consldered small.
especlally as related to the influence other major factors. Overall. the parameter values
changed by less than 7% (except for yield stress whlch varted by up to 18%) durtng the
enUre storage pertod. RelaUvely. thls represented a change of smaller magnitude than
',>.

contrtbuted by. for example. a 5C change ln sample temperatures (Chapters IV & V).

109

70

dayQ

--

day12
day18

50

Je

tG

0-

:a

day6

60

da~1

daY27

40

30
20

10

Brand 1

4
5
Time (min)

10

.-

l,

-,

90

-:a
tG

0-

( J)

dayQ
day6
day12
day18

80
70
60

Je

da~1

daY27

50

40
30
20
10

Brand Il
0

6
5
Time (min)

10

",ure 30. Typlcal apwud and downward 00. c,,"el of two commerclalltlrred
yo,urtI foUowbl, Itonle at 2 0 C for nrI0Ul perlodl.

110
Table 16. Changes ln rhealogtcal parameters durtng storage at 2C

Upcurve
Time

0
3

6
9
12
15
18
21
24
27

1'I3I"l1

Weltman
B
A

0.09

0.80

65.4

18.1

(a.b)

(a)

(a)

(a)

0.09

0.81

64.6

17.4

(a.b.c)

(a)

(a)

(a)

6.92

11.8

0.24

14.9

(a)

(a.b)

(a.b)

(a)

10.2

11.5

0.25

16.3

(a,b)

(a.b)

(a.b)

(a.b.c)

0.09

11.3

11.9

0.24

16.6

0.80

62.3

15.9

(a,b)

(a.b)

(a.b)

(a.b.c.d) (a.b)

(a)

(a)

(a)

11.4

15.5

0.21

18.8

0.09

0.80

72.6

20.1

(a,b)

(a,b)

(a)

(d)

(c.d)

(a)

(a)

(a)

12.8

14.2

0.21

18.7

0.09

0.79

71.1

19.5

(a,b)

(a.b)

(a.b)

(c.d)

(c.d)

(a)

(a)

(a)

13.6

11.6

0.25

18.2

0.09

0.80

65.6

18.0

(b)

(a.b)

(a.b)

(c.d)

(d)

(a)

(a)

(a)

10.9

12.4

0.24

18.0

0.09

0.80

72.7

19.2

(a,b)

(a.b)

(a.b)

(c.d)

(a.b.c)

(a)

(a)

(a)

9.86

12.9

0.23

17.8

0.09

0.81

64.8

16.8

(a,b)

(a.b)

(a.b)

(b.c.d)

(a)

(a)

(a)

(a)

7.00

16.1

0.20

17.7

0.09

0.80

65.9

17.6

(a)

(b)

(a)

(b.c.d)

(a.b.c)

(a)

(a)

(a)

9.35

10.7

0.25

15.4

0.09

0.79

68.6

18.8

(a,b)

(a.b)

(b)

(a.b)

(a)

(a)

(a)

(a)

14.9

16.3

0.21

23.4

0.10

0.78

73.8
(a)

(a)

(a)

(a.b)

(a.b.c)

(a.b)

(a)

15.7

17.2

0.21

23.3

0.10

0.78

75.2

19.2
(a)
20.5

(a)

(a)

(a.b)

(a.b)

(a.b)

(a)

(a)

(a)

14.5

16.9

0.21

23.5

0.10

0.78

74.0

19.7

(a)

(a)

(a.b)

(a.b.c)

(a.b)

(a)

(a)

(a)

18.3

19.9

0.18

26.7

0.10

0.77

(a)

(a)

(a)

(b.c)

(a.b)

(a)

17.2

19.1

0.19

25.6

0.11

(a)

(a)

(a.b)

(a.b.c)

(a.b)

14.0

14.9

0.23

23.5

0.10

0.77
(a)
0.78

81.1
(a)
80.5

(a)

(a)

(b)

(a.b.c)

(a.b)

(a)

15.5

16.8

0.21

24.7

0.10

0.77

(a)

(a)

(a.b)

(a.b.c)

(a.b)

(a)

21

14.9

14.5

0.21

22.3

0.10

0.77

74.1
(a)
79.7
(a)
73.0

21.3
(a)
21.4
(a)
19.4
(a)
21.8
(a)
19.1

(a)

(a)

(a.b)

(a)

(a)

(a)

(a)

(a)

24

16.4

15.7

0.22

24.8

0.10

0.78

73.0

19.5

(a)

(a)

(a.b)

(a.b.c)

(a.b)

(a)

(a)

(a)

17.4

19,1

0.20

27.4

0.11

0.76

72.2

19.2

(a)

(a)

(a.b)

(c)

(b)

(a)

(a)

(a)

3
6
9
12
15
18

27

....

Down curve
Oc
1'1

(a)

"'For each brand. column values nOI sharing a common letter are slgmficanlly dlffcrcnl (IKO.OI)

111

85~------------------------------------~

(i

Q.

80 -
75

70 .,..

Brand 1

..

,.,

65
60 55 ~
50-

III

III.:.!!...
"".!!!!t..
.',

&&&

dayO
day6
day12
day18
day21
day27

'=+..
"

11'1111111

:::=:::~::: +~~.IIIJ.'I.II'I*J.1
1(

:+++++
+ ++.++++.

Ji

45~---r------,-------~--~------,-------~--~--~~==~~~B~,-~
2
4'
10
8

Time (min)
100.-------------------------------------~
95. t
Brand Il

lU
Q.

...~
CI)

iS

90 ,a
85 -
80 - ,

75 70 l'!'II
65 60
55
50

0
2
4

dayO
day6
day12
day18
1(
day21
++11',.", al 1111 day27
IIIIIIISIIIIII
~

'l, .....

.'!!!""".,,.",.......
.

".
10

TIme (min)

n,ure 31. Typlcalltre.. dec., CUI'VU of two commercial atlrred YOIurU foUowin,
atonte at 2C for ftrlou perlocll.

(,..

112

Table 17. Slgn1flcance of effect of storage on rheologlcal


parameters of Brand 1 and II yogurts.

ParUculars

Up-cuIVe parameters

Parameter

Il

ao

ns

ns
ns
ns

ao
1\
113 / 111

ns

ns
ns

A value
Bvalue

ns
ns

ns
ns

Down-curve parameters

Weltman parameters

ns

Brand Brand
1

ns

signillcant, p <0.05
slgnillcant, P <0.01
not slgn1ficant, p>0.05

Effect of storage OD chtmical composition

The 4-week storage influenced the relative amounts of prInclpal consUtuents of


the two yogurt brands tested to a small extent (Table 18). Su ch effects though smaJ! was
not negUglble. Among all the major consUtuents. the levels of titrable acidlty increased
with storage time 0.58-1.62%, for Brands 1 & II) and ln consislence wilh a gradualloss
in the lactose content whlch upon hydrolysls Is expected to yield lacUc acid (6.30-

6.21%, Brand 1; 6.37-6.23%, Brand II). The lncrease ln acidity showed a corresponding
decrease in the pH of the product (4.19-4.09. Brand 1; 4.21-4.10. Brand 11).

113

Table 18. Changes in the chemical composition ofyogurt during storage at 2~.

Brand

Brandi

Time
(days)

3
6
9
12
15
18
21

24

27

Brand Il

0
3
6
9
12
15
18
21

24
27

(")

Protein Lactose Lactic pH


&cid (%)
(%)
(%)

1.85
(g)
1.84
(f.g)
1.82
(e,f)
1.83
(f,g)
1.81
(d,e)
1.81
(c,d,e)
1.80
(b,c,d)
1.80
(h,c)
1.79
(a,b)
1.78
(a)

6.S4
(e)
6.51
(e)
6.42
(d)
6.42
(d)
6.38
(b,c)
6.39
(c,d)
6.36
(a,b,c)
6.35
(a,b)
6.35
(a,b)
6.33
(a,b)

6.30
(d)
6.31
(d)
6.26
(c)
6.25
(b,c)
6.24
(a,b,c)
6.23
(a,b,c)
6.22
(a,b,c)
6.21
(a)
6.21
(a,b)
6.21
(a)

1.58
(a)
1.59
(h)
1.60
(c)
1.60
(c)
1.60
(c,d)
1.61
(d,e)
1.61
(e)
1.61
(t)
1.61
(t)
1.62
(g)

2.07
(d)
2.04
(c,d)
2.03
(b,c)
2.02
(a.b,c)
2.02
(a.b,c)
2.02
(a,b,c)
2.01
(a.b)
2.01
(a.b)
2.01
(a.b)
2.00
(a)

6.68
(d)
6.62
(c)
6.57
(b)

6.37
(e)
6.31
(d)
6.29
(c,d)
6.28
(b,c,d)
6.27
(b,c,d)
6.27
(a,b,c)
6.27
(a,b,c)
6.25
(a,b,c)
6,25
(a,b)
6.23
(a)

1.58
(a)
1.58
(a,b)
1.59
(a,b,c)
1.59
(b,c)
1.59
(c,d)
1.60
(d)
1.60
(e)
1.61
(e)
1.61
(t)
1.62
(g)

Fat

6.S7
Cb)
6.57
(b)
6.57
(b)
6.56
(a,b)
6.54
(a,b)
6.53
(a)
6.53
(c)

4.19
4.18
4.17
4.17
4.16

Moisture

(%)
82.1
(a)
82.0
(a)
82.5
(a)
82.2
(a)

82.S
(a)

4.14
4.13
4.11
4.10
4.09

4.21
4.19
4.18
4.17
4.16
4.14
4.14
4.13
4.11
4.10

For each brand, column values nol sharing a common lelter are
significanlly different (p<O.OI)

82.4
(a)
82.1
(a)
82.4
(a)
82.5
(a)
82.3
(a)

80.3
(a)
82.8
(b,c,d)
82.2
(b,c)
83.0
(d)
82.8
(b,c,d)
82.9
(c,d)
82.1
(b)
83.0
(d)
82.6
(b,c,d)
82.7
(b,c,d)

114

The other principal components ego proteln and fat also decrea.sed sllghtly
during storage (proteln: 6.54-6.33% and 6.68-6.53% and fat: 1.85-1.78% and 2.072.00%. for Brands 1 & Il. respectively). Molsture content of test samples generally

ranged from 82.1-82.3% for Brand 1 and 82.1-83.0% for Brand Il durtng the pertod of
InvestigaUon. Most of the changes that took place during the storage occurred

ln

the

first twelve days of storage. Slmtlar obselVaUon was reported prev10usly by Jordono et
al. (1988) and Saljl and Ismail (1983). at hlgher storage temperatures.
Analysis of variance of ail the above constltuents except moisture showed that
they were very slgnificanUy influenced durtng the storage for both brands (p<O.O 1). The
values for molsture was slgnificant for Brand II. due to the lower value obselVed on day
0: the changes ln molsture wlth reference Brand 1 were non-slgnificant.

CONCLUSIONS

The data presented ln thls paper indlcates small. but slgnlficant

change~

!:

chemical composiUon durtng the relatlvely low temperature storage of 2C. The
influence of these changes on the rheologtcal behavtor was generally small and mosUy
non-stgniflcant. The 2C storage temperature therefore appears to be a good choice to
malntrun the structural qualiUes of yogurt samples durtng marketing.

-..

.'~

115

CIlAPTER IX

REFERENCES

Agriculture Canada 1988. Datry Market Revtew 1987. Agriculture Canada Development
Branch, Ottawa, ON.
Anantheswaran, RC. and Rao, MA. 1985. Heat transfer to mode! non-Newton1an l1quid
foods in cans durtng EOE rotation. J. Food Eng. 4:1.
Almon. 1977. The Influence of the Cooling Rate in the Qualtty of Stirred Yogurt.
Publication No. 225, Dantsh Dairy Research Institute, Hlllerod, Denmark.
AOAC. 1980. "Official Methods of Analysts", llth ed. Association of Official AnalyUcal
Chemtsts, Washington, OC.
Ayebo, AD. and Shahant, K.M. 1980. Role of cultured da1Iy products in the d!et. Cult.
Datry Prod. J. 15(4):21.
Bahrs, W. 1971. Question of eataract fonnation due to yogurt consumpUon.
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Barbosa Canovas, G.V. and Peleg, M. 1983. Flow parameters of selected commercial
semi-liquid food products. J. Texture Studies. 14:213.
Bantes, H.A and Walters, K. 1985. The yteld stress myth? Rheol. Acta. 24:323.
Becker, T. and Puhan, Z. 1989. Effect of dtlTerent processes to lncrease the mtlk soUds
non-fat content on the rheologtcal properttes of yogurt. MJ1ehwtssenschaft.
44(10):626.
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