ABSTRACT
The flow and viscoelastic properties of mayonnaise at diflerent oil and
xanthan gum concentrations (75-85X and 05-I.!% (w/w), respectively)
were investigated in the rotational and oscillatory mode using a
plate-plate rheometer. Yield stress, which was determined using a static
method, and steady measurements were corrected to account for slippage.
The corrected flow curves were fitted with the Herschel-Bulkley model,
and it was found that the flow index (n), consistency index (K), and yield
stress were greatly aflected by the oil and xanthan gum concentrations.
Viscoelastic properties of mayonnaise were characterized using small
amplitude oscillate y shear, and it was observed that mayonnaise
exhibited weak gel-like properties. The gel strength depends on the oil and
xanthan gum concentrations. The magnitude of elastic modulus and
complex viscosity increased with the increase of oil or xanthan gum
concentrations.
INTRODUCTION
Mayonnaise is an oil-in-water (O/W ) emulsion prepared from vegetable oil, egg
yolk, acidified ingredients, citric acid and/or maleic acid, and optional ingredients, i.e. salt, nutritive sweetener, stabilizer, thickener and crystallization
inhibitor (Code of Federal Regulations, 1986). Due to the commercial importance of mayonnaise, the rheological characteristics of mayonnaise have been
extensively studied. The flow properties (consistency index, K; flow behavior
index, n; and yield stress, to) of mayonnaise have been studied by Elliott and
Ganz (1977), Figoni and Shoemaker (1983), Kiosseoglou and Sherman
(1983a), Paredes et al. (1988, 1989), Yilmazer et al. (1991), and Yilmazer and
Kokini ( 1992). Several rheological equations, such as the power law, the Casson
model, and the Herschel-Bulkley
model, have been used to describe the stress
409
410
L. Ma, G. I/ Barbosa-C&ovas
AND METHODS
Materials
Vegetable oil (Wesson Vegetable Oil, Hunt-Wesson, Inc., Fullerton, CA) and
fresh grade A brown eggs were purchased from local supermarkets. The eggs
411
were broken, and the yolks were separated from the albumen. The vitelline
membranes were then punctured, and the liquid yolk collected. A 20% (w/w)
acetic acid was prepared from analytical grade glacial acetic acid (99.5%
minimum concentration). Sodium chloride and sucrose were analytical grade
reagents. Pure food grade xanthan gum was obtained from Sanofi BioIndustries, Waukesga, WI.
Mayonnaise
preparation
Rheological measurements
were performed
with a rheometer
(PhysicaRheolab@ MC20/UM, Physica USA Inc., Spring, TX) using both controlled
Formulation
of Mayonnaise
TABLE 1
Preparation at Different Oil Concentrations
02 concentration (w/w)
Oil k)
Water (g)
20% Acetic acid (g)
Egg yolk (g)
Sugar (g)
Salt (8)
75%
80%
85%
1.50
32.4
2.0
12.0
3.10
050
160
22.4
2.0
12.0
3.10
0.50
170
12.4
2.0
12.0
3.10
0.50
412
L. Mu, G. I/ Barbosa-Ckovas
TABLE 2
Formulation of Mayonnaise Preparation at Different Xanthan Gum Concentrations
Xanthan gum concentration (w/w)
1.00
100
81.4
2.0
12.0
3.10
0.50
2.00
100
80.4
2.0
12.0
3.10
0.50
3.00
100
79.4
2.0
12.0
3.10
0.50
H, l/aR, - HzYaR,
H, -4
where yaR, is the apparent shear rate at a gap distance of H,; jaR, is the apparent
shear rate at a gap distance of H,; H,, Hz are the gap distance between the upper
disk and bottom disk; and yR is the corrected shear rate.
The yield stress was determined from the corrected flow curves using the
static method - the stress initiate flow (Steffe, 1992; DeKee et al., 1986; Buscall
et al., 1987; James et al., 1987). With the measured yield stress, the flow
parameters (consistency index, K and flow index, n) were determined using the
Herschel-Bulkley model:
t= q+Kj
(2)
413
where r is the stress (Pa), r,, is the yield stress (Pa); K is the consistency index
(Pas); IZis the flow index; and j is the shear rate (s- ).
Viscoelastic measurements
were also performed
using the plate-plate
rheometer (@= 50 mm) (Physica-Rheolab@ MC20/UM Physica USA Inc.,
Spring, TX). The gap between plates was 1.0 and 1.5 mm. All experiments were
carried out at 20 f O*lC.
For comparison,
two standard fluids with different viscosities (fluid
HTlOOOOO and fluid 30000; Brookfield
Engineering
Laboratory,
Inc..
Stoughton, MA) were used to calibrate the instrument under different gaps (1.0
and 15 mm) and different geometries (plate-plate geometry and cone-plate
geometry) in order to exclude the possibility of instrument artifacts. The results
from the calibration tests proved that the viscoelastic estimate had a margin of
error of roughly 5% or less.
of mayonnaise
The flow curves of the model mayonnaise measured at two different gaps are
presented in Figs 1 and 2. Differences in the flow curves measured at two
different gaps indicate the existence of slippage in the shear measurements
(Yoshimura & Prudhomme, 1988). The corrected flow curves of the mayonnaise samples with different oil and xanthan concentrations using eqn (1) are
also presented in Figs 1 and 2.
The yield stress was determined by a static method - stress to initiate flow
(DeKee et al., 1986; Buscall et al., 1987; James et uf., 1987; Steffe, 1992) -based
on the corrected flow curves in Figs 1 and 2. It was noted that the yield stress
determined from measured curves was smaller than the yield stress determined
from corrected curves (Figs 1 and 2). At a very small shear stress, the mavonnaise sample between the gap behaved as a solid body due to the three-dimensional network structures (Princen, 1985; Rahalkar, 1992); thus, no apparent
flow was observed. When shear stress was increased to a certain magnitude
which was less than the true yield value of the bulk sample, an apparent flow was
observed. This observed flow was due to deformation in the boundary layer
(slip layer), since the bulk mayonnaise still behaved as a solid and did not flow at
the stress below the true yield value. When the stress was greater than the true
yield stress of the bulk sample in the gap, all of the sample, including the
boundary layer in the gap, was deformed and flowed. Therefore, the yield stress
determined from the measured flow curves would be smaller than that
determined from the corrected flow curves. The yield stress determined from
the measured flow curves was called apparent stress, t, and the yield stress
determined from corrected flow curves was called true yield stress, tO) or yield
stress, r,). The comparisons of apparent yield stress and the true yield stress of
mayonnaise with different oil and xanthan gum concentrations are presented in
Table 3.
The yield stress for the mayonnaise ranged from 23 to 235 Pa and increased
with the oil concentrations
(Table 3). A more compact three-dimensional
network was formed between the egg protein molecules and absorbed droplets
414
L. Ma, G. I/ Barbosa-Canovas
,
2mo
30.M)
40.00
50.00
60.00
200
250
300
(0)
50
100
150
(b)
0.00
50.00
Cc)
Fig. 1. Actual flow curve of mayonnaise calculated by means of eqn (1). Also shown
are the flow curves measured at two different gaps. (a) 75% oil concentration; (b) 80% oil
concentration; (c) 85% oil concentration. 1.0 mm gap; -A1.5 mm gap;
corrected.
41s
0.00
10.00
20.00
30.00
4C.CCI 50.M3
60.00
70.00
8O.M)
90.C0
(0)
8.W
0.00
50.00
15clm
lM3.00
203.00
250.M)
10.00
8.00
8
:
6
6.00
,i,,,,,
0.00
50.00
100.00
1w.m
mm0
250.00
3cKl.00
350.00
4OO.M)
Fig. 2. Actual flow curve of mayonnaise calculated by means of eqn (1). Also shown
are the flow curves measured at two different gaps. (a) 50% oil and 0.5% xanthan gum
concentration; (b) 50% oil and 1.0% xanthan gum concentration; (c) 50% oil and 15%
1.0 mm gap; -Axanthan gum concentration.
--+1.5 mm gap; -corrected.
416
TABLE 3
Flow Parameters of Mayonnaise
Oil concentr$gn
Apparent
yield
t, (Pal
True yield
tcl (Pa)
K
(Pa.s-7
18
107
228
23
115
235
18.1
127.4
289.9
0.83
0.69
O-24
0.87
0.85
0.87
49
131
195
55
195
305
8.5
11.8
43.5
0.44
0,43
0.78
0.98
0.97
0.86
(w/w, %)
80
85
Xanthan gum concentration
(w/w, %)
0.5
1.0
1.5
(Zosel,
1982; Jaynes,
1985; Gladwell
structure
is responsible
et al.,
network
concentrations.
The yield stress increased with the increase in the xanthan gum concentrations (Table 3). Xanthan gum was reported to increase the stability of
mayonnaise and emulsion (Hibberd et al., 1987) as well as its structure by the
formation of aggregates of larger size (Yilmazer & Kokini, 1992). Thus, it was
expected that the yield stress would increase with the xanthan gum concentration. The yield stress of some commercial mayonnaises have been studied by
various methods (Elliott & Ganz, 1977; Dickie & Kokini, 1983; DeKee et al.,
1986; Campanella & Peleg, 1987~) and have a very wide range of yield magnitude, from 9 to 91 Pa (Steffe, 1992). This wide range of yield stress value in the
published data was due to differences in the methods as well as shear rate range
selected when extrapolating. The results in the present work, in general, were in
agreement with the published data with low oil or xanthan gum concentrations,
but the yield stress at higher oil or xanthan gum concentrations was greater than
the yield stress in the published data, because the key components (oil and
xanthan gum) varied widely in the model mayonnaise.
With the determined yield stress, the Herschel-Bulkley
model (eqn (2)) was
used to determine the flow properties (consistency index, K, and flow behavior
index, n) of model mayonnaise from the corrected flow curves. The magnitude
of consistency index (K) of the mayonnaise ranged from 18.1 to 289.9 Pa.s and
increased with oil concentrations
(Table 3), which was in agreement with
Gladwell et al. (1986). Similar results were observed with the concentration of
xanthan gum. That is, the magnitude of the consistency index of the mayonnaise
ranged from 8.5 to 435 Pa.s and increased with the xanthan gum concentration.
The flow index (n) of all model mayormaises were less than one (Table 3)
which indicated that they were pseudoplastic fluids (Paredes et al., 1989). The
flow behavior index ranged from 0.83 to 0.24 and decreased with the oil con-
417
centration (Table 3). The flow index was not significantly different between
xanthan gum concentration at 0.5 and 1.0% but was different at 1.5%. In general, the flow index for the model mayonnaise was in agreement with previous
reports (Dickie & Kokini, 1983; Steffe, 1992), since the flow index varied
widely from 0.13 to 0.9 1 for some commercial or model mayonnaise due to different methods (i.e. capillary viscometer, cone-plate viscometer, and/or concentric cylinder viscometer) and/or different shear rate range selected. In this study,
it was expected that the flow index would change with the oil and xanthan gum
concentrations,
since the variation of oil and xanthan gum concentrations
changed the levels of structure in mayonnaise (Yilmazer et af., 1991).
Viscoelastic
properties of mayonnaise
418
L. Ma, G. V Barbosa-CLinovas
5
8
1cKKl;
G (1 .Omm)
G(,,Omm)
-~i~T~~~~yYII~YbY4-S)
b
5
?J
~
-----__.
100:
10
0.1
10
G (1.5mm)
G (1.5mm)
102
Frequency (rod/s)
(0)
r
c
b
8
lcal
EDw
G(1 .Omm)
- - - - - __. G(,,Omm)
~.~~*~~~~Cee-*.*.
5
b
!
Fig. 3.
loo:
10
0.1
10
G(l.5mm)
G(l.5mm)
100
Frequency (rod/s)
,h\
The storage modulus and loss modulus vs frequency. (a) 85% oil concentration;
(b) 50% oil and 1.0% xanthan gum concentration.
higher oil concentrations than in lower oil concentrations (Jaynes, 1985). The
viscoelastic response of model mayonnaise had a very similar pattern (Fig.
4(d)-(f)) at all xanthan gum concentrations, which had less variation than that of
mayonnaise with different oil concentrations.
It is also noticed that the
magnitude of the maximum storage modulus G is of the order of lo4 Pa, so
these gels are very weak and break down easily under shear stress. The
magnitude of storage modulus, loss modulus G(w), is also dependent on the oil
and xanthan concentrations.
The comparison of storage modulus, G(w), for mayonnaise with different oil
and xanthan gum concentrations is presented in Fig. 5. Since the elastic modulus
419
..-_i
1'
01
hequency(rad/s)
IO
102
hequency (rod/s)
01
hequency (rod/s)
10
1Cn
hequency (rod/s)
f
loo00
a
5
IMX)
. . . ..mm.mmmm=mmm=~m=
AAAAAAAAAAAAAAAAAAAA
&y_____
0.1
10
hequency (rod/s)
103
01
__i_
10
co
tequency (rod/s)
420
L. Ma, G. K Barbosa-Crinovas
a
loo00
1ccO
a
8
75%oil
-)-
looi
-+-e
2-H
b
10
85%oil
._*_._*_.-._._.-.-.-.a-.-.-.-.-.-.-.-.
1
0.1
10
100
10
100
frequency (fad/s)
r
b
1
0.1
frequency (rod/s)
L
Fig. 5.
Effect of mayonnaise
gum concentration
on the storage
421
,I
_L-__c
01
10
75%oil
-----t-
80% oil
85%011
..>
1M)
frequency
~____
10
-.-
0.5% xanthan
-t-
1.O% xanthon
-*-
1 5% xanthan
103
frequency
Fig. 6.
Effect
of mayonnaise
oil and
xanthan
viscosity.
gum
concentration
on the complex
with xanthan concentrations over the entire experimental shear frequency range
(0.63-62.8 rad/s), due to the interaction between xanthan gum microgel and
emulsion droplets.
Loss factor, tan( 6) = G/G, is a dimensionless measure that compares the
amount of energy lost during a test cycle to the amount of energy stored during
this time (Darby, 1976; Ferry, 1980). The loss factor indicates whether elastic or
viscous properties predominate in a sample. The comparison of loss factor for
mayonnaise with different oil and xanthan gum concentrations is presented in
Fig. 7. The slope for 75% oil concentration is greater than that for 80%, while
the slope for 85% oil is near zero (flat). These differences might be due to the
different fine structures or three-dimensional networks formed by a two-phase
emulsion. The difference in loss factor could be considered an index to
distinguish the fine structure at different oil contents of mayonnaise. The quanti-
L. Ma, G. V. Barbosa-Ctinovas
422
a
10.00
-t-
80% oil -
85%oil
6
s
8
,o
1.oo
0.10
loO.M3
10.00
1.m
tequency
:;,,(I
0.5% xanthan
A 1.0% xanthan
,,~;::;:x;:~~:::~:~
0.10
,,,,
1o.cKl
1.00
1.5% xanthan
100.00
frequency
Fig. 7.
Effect of mayonnaise oil and xanthan gum concentration on the loss factor.
tative relation among loss factor, elastic modulus, loss modulus, and the network
structure of mayonnaise needs further investigation. However, the shape of the
curves are more or less similar, showing that all the mayonnaise samples at
different xanthan gum concentrations exhibit similar viscoelastic properties.
CONCLUSIONS
It was found that the flow properties determined from direct flow curve
measurements were significantly different from the corrected flow curves after
taking slippage into account. The correction of the flow curve was necessary to
determine the actual flow parameter of mayonnaise. The yield stress and
consistency index increased with oil and xanthan concentrations due to the
formation of a higher level of network structure; the flow behavior index varied
423
ACKNOWLEDGEMENT
This project
was partially
supported
by a Sigma Xi grant.
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