JournalofFood Engineering 25 (1995) 397-408

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Rheological Characterization of Mayonnaise. Part I:

Slippage at Different Oil and Xanthan Gum
Concentrations
L. Ma & G. V. Barbosa-Cinovas
Department

of Biological Systems Engineering, Washington State University, Pullman,

WA 99164-6120, USA
(Accepted 3 March 1994)

ABSTRACT
Two series of mayonnaise samples were prepared and used as model
mayonnaise to study the slip phenomenon during shear measurements.
The slip phenomenon,
which is due to the non-homogenous stress field
and/or directfluid-geometry surface interactions, was examined by setting
different gaps in a parallel disk rheometer, The magnitude of the slip
velocity was greatly affected by the oil concentration and/or xanthan gum
concentration as well as the applied shear stress during the shear
measurement. The true shear rate could be corrected with measured
apparent shear rate using a simple model, but the applied shear stress was
limited due to the weak structure of the mayonnaise sample and
measuring range limits of plate-plate geometry.

INTRODUCTION
is a semi-solid, oil-in-water
(O/W ) emulsion that contains egg yolk,
salt, vinegar, thickening agents, and flavoring materials (Dickinson & Stainsby,
1982). Hydrocolloid or gums are often used for emulsion stabilization, control
of pourability, cling improvement, and suspension of solid or spice particles in
mayonnaise products. The commonly used gums are xanthan gum, propylene
glycol alginate, and guar gum (Sanderson, 1981; Yilmazer et al., 1991).
Mayonnaise is formulated to develop characteristics such as mouthfeel and
spreadability which are considered desirable by the consumer. Any changes in
the product after manufacture, due to instability when stored prior to sale and
consumption, may have negative effects on the consumers attitude towards the
product. Due to the commercial importance of mayonnaise, many investigations
397
Mayonnaise

398

L. Ma, G. K Barbosa-Canovas

have been conducted on the stability and rheological properties of the product
(Kiosseoglou & Sherman, 19830).
The rheological properties tested so far include viscoelastic properties such
as compliance in the creep experiment (Kiosseoglou & Sherman, 1983a, 6;
Yilmazer et al., 1991), elastic modulus and loss modulus in the oscillatory
experiment (Elliot & Ganz, 1977; Mufioz & Sherman, 1990), and flow index (n)
and consistency index (K) in flow tests (Barbosa-Canovas
& Peleg, 1983;
Paredes et al., 1988, 1989). Herschel-Bulkley,
Casson, and power law models
have been used to model the flow properties of mayonnaise and salad dressing
(Bistany & Kokini, 1983; Paredes et&., 1988, 1989).
Slippage is often associated with rheological measurements of gels, concentrated suspensions, and emulsions at high stresses (Yoshimura & Prudhomme,
1988). The slippage analyses at the wall in Couette and capillary geometry were
reported by Mooney (1931). Princen (1985) and Yoshimura and Prudhomme
(1988) studied the slip phenomena of O/W emulsion in plate-plate geometry
and considered the small thickness of the boundary layer as a discontinuity at
the wall in the velocity field across the gap. Yoshimura and Prudhomme (1988)
proposed a modified approach to Mooneys method to analyze slip velocity by
concentric cylinder geometry and parallel disk geometry based on the discontinuity assumption. Later, Kiljanski (1989) proposed another modified method
to study the slip effect by concentric cylinder geometry.
Wall slip in polymers has been extensively studied (Bartos & Holomek, 197 1;
Cohen & Metzner, 1985; Ramamurthy, 1986; Magnin & Piau, 1990), whereas
in foods only a few reports have dealt with this topic. The shear rate deviation of
apple sauce due to slip at the wall was studied by Kokini and Plutchok (1987) in
a capillary viscometer. Qiu and Rao (1989, 1990) and Grikshtas and Rao
( 1993) studied the slip phenomena of apple sauce and tomato ketchup using
concentric cylinder geometry and concluded that slip velocity increased with
applied stress using both Kiljanskis (1989) and Mooneys (1931) methods.
However, the slippage effect of mayonnaise in the rheological measurements
using the plate-plate rheometer has not been reported yet. The objectives of the
present work are to: (1) examine the slip effect in mayonnaise during shear
measurements
with a parallel disk geometry
using Yoshimura
and
Prudhommes method ( 1988); and (2) determine the effect of oil and xanthan
gum concentrations on the slip velocity for mayonnaise samples.

MATERIALS

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
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.

399

Rheological characterization of mayonnaise. Part I

Mayonnaise preparation
The mayonnaise samples were prepared following procedures described by
Kiosseoglou and Sherman (1983b) and Gates (198 1).
A rotary mixer (Sunbeam Mixinaster, Milwaukee, WI) was used. Egg yolks,
sugar, and salt were introduced into a stainless steel bowl (diameter = 150 mm
and height = 120 mm). They were mixed together at speed 4 for 2 min. Onetwentieth of the oil was then slowly added. The mixer was then operated at
speed 3. One-tenth of an acetic acid-water solution was added towards the end
of the oil addition. The oil and acetic acid-water solution were added alternately
while the mixer was kept at speed 3. When all the oil and acetic acid-water
solutions were added, the mixer was set at speed 4 for 3 min. The mayonnaise
sample was transferred to a 250 ml beaker, sealed with parafilm, and stored on
the reagent shelf (cu. 2 1C) overnight.
In order to study the effect of oil and xanthan gum concentrations on the
properties of mayonnaise, two series of samples were prepared. Tables 1 and 2
list the mayonnaise formulation with different oil and xanthan concentrations.
One series of mayonnaise samples was prepared with different oil concentrations, but the other ingredients (salt, sugar, and acetic acid) were kept constant,

Formulation

of Mayonnaise

TABLE 1
Preparation at Different Oil Concentrations
Oil concentration (w/w)

Oil (8)
Water (g)
20% Acetic acid (g)
Egg yolk (g)

Formulation

of Mayonnaise

150
32.4
2.0
12.0
3.10
050

160
224
2.0
12-o
3.10
0.50

170
12.4
2.0
12.0
3.10
050

TABLE 2
Preparation at Different Xanthan Gum Concentrations
Xanthan gum concentration (w/w)

Xanthan gum (g)

Oil (8)
Water (g)
20% Acetic acid (g)
Egg yolk (g)
Sugar (g)
Salt (8)

1.00
100
81.4
2.0
12.0
3.10
0x50

2.00
100
80.4
li.8
3.10
0.50

3.00
100
79.4
2.0
12.0
3.10
0.50

400

L. Ma, G. V. Barbosa-Cdnovas

and no xanthan gum was added. The second series of mayonnaise samples was
prepared with several xanthan gum concentrations, but the oil concentration
and other ingredients were kept constant.
Rheological measurements
Rheological measurements
were performed
with a rheometer
(PhysicaRheolab@ MC20/UM, Physica USA Inc., Spring, TX) using both controlled
shear rate and controlled shear stress with a plate-plate geometry of 50 mm
diameter. The measurements were conducted at two gap distances of 1.00 and
1.50 mm. Special care was taken to minimize the effect of the work softening
when the mayonnaise sample was initially loaded on the plate each time (Kokini
& Dickie, 1981). The mayonnaise sample was removed in one stroke from the
container (250 ml beaker) using a plastic spatula and was subsequently
deposited onto the plate. The sample filled up the whole gap by lowering the
upper plate down to the designed gap. The extra sample around the edge of the
plate was trimmed with the plastic spatula.
In this study, all samples were allowed to rest after loading to allow sample
relaxation and temperature equilibration. A preliminary test was conducted on
the effect of resting time (0, 1,3,5, lo,20 and 30 min) after loading the sample.
It was found that 5 min of resting was enough to get a reproducible result. The
data reported are the averages of three replicates.
two standard fluids with different viscosities (fluid
For comparison,
HT 100 000 and fluid 30 000; 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 viscosity estimate has a margin or
error of approximately 5% or less.
Based on the assumption that slip velocity is a function of stress only, the slip
velocity and the corrected shear rate were calculated by the following equations
(Yoshimura & Prudhomme, 198 8):

(1)

iR

YaR,

H2

l/aR,

(2)

HI--H,

where j&, is the apparent shear rate at a gap distance of H,; iaR2 is the apparent
shear rate at a gap distance of Hz; H,, H2 are the gap distances between the
upper disk and bottom disk; us is the slip velocity, and yR is the corrected shear
rate.

401

Rheological characterization of mayonnaise. Part I

RESULTS AND DISCUSSION

The flow curves obtained from different gaps in the plate-plate rheometer
would be independent of gaps selected if there were no slippage (Yoshimura &
Prudhomme, 1988). The differences between flow curves at different gaps
presented in Fig. l(a)-(f) demonstrate that slippage existed among all mayonnaise samples tested. The slippage was due, most likely, to the formation of a
boundary layer (slip layer) (Mannheimer, 1972; Princen, 1985). The thickness
of the boundary is, in general, a few tens of nanometers (Princen, 1985). Thus,
the mayonnaise boundary layer thickness is so small compared to the gap
between plates (cu. 1-O mm) that wall slip can be considered a discontinuity in

0.00

2Q.M)

4c.cn

tmxl

la,

ml

300

Shea stress (Pa)

shear stress (Pa)

0.M)

lcnal

m.cxl

3oo.m

4m.00

shear stres3 (Pa)

d

I I

8.ca
1

10.00
1

.J

Fig. 1. Effect of gaps between plates on mayonnaise flow curves. (a) 75% oil concentration; (b) 80% oil concentration; (c) 85% oil concentration; (d) 50% oil and 05%
xanthan gum concentration; (e) 50% oil and 1*0S xanthan gum concentration; (f) 50%
oil and 1.5% xanthan gum concentration. l.Ommgap;---1.5mmgap.

L. Ma, G. T/.Barbosa-Crinovas

402

the velocity field. Therefore, the slip velocity can be defined as the difference
between the velocity of the plate and that of the fluid at the surface of the plate
(Yoshimura & Prudhomme, 1988). For narrow gaps, the diameter of the plate is
much bigger than the distance between the plates so that the shear stress is
nearly constant across the gap at any particular radial position (Yoshimura &
Prudhomme, 1988). These assumptions resulted in a linear velocity profile as
shown in Fig. 2. The slip velocity and corrected shear rate can be calculated
from eqns ( 1) and (2) (Yoshimura & Prudhomme, 1988).
The slip velocity for the mayonnaise samples with different oil concentrations
are presented in Fig. 3. For mayonnaise samples at 75% oil concentration (Fig.
3(a)), there was no slip until shear stress was increased to 18 Pa. Correspondingly, there was no apparent flow observed at the stress below 18 Pa (Fig.
l(a)). When the shear stress was greater than 18 Pa, apparent flow was observed.
Under the steady shear flow, the velocity gradients in the boundary layer were
different from the bulk. Thus, the shear rate registered at the upper plate (called
apparent shear rate) did not represent the shear rate of the bulk. The differences
between apparent shear rate measured at two gaps was used to calculate the slip
velocity using eqn (1). It was observed that the slip velocity increased with the
applied stress (Fig. 3(a)).
For mayonnaise samples at other oil concentrations (80 and 85%), similar
trends were observed even though the slip was not observed until the applied
shear increased to 107 and 228 Pa for 80 and 85% oil concentrations, respectively (Fig. 3(b) and (c)). These numerical differences on the flow initiation could
be due to the compact packing of the oil droplets at higher oil concentrations
and resulting in a mayonnaise of higher consistency (Jaynes, 1985). These
results also applied to other O/W emulsions (Gladwell ef al., 1986). As the oil
percentage decreases, as in reduced calorie mayonnaise, the mean distance
between the droplets is greater, and, for this reason, a lower consistency may be

I
1

Fig. 2. Parallel plate velocity field. The figure shows the velocity field at any particular
radius r. The wall slip velocity, us, is the same at each wall. Also shown are the actual
shear rate in the fluid, y, and the apparent shear rate, i,, (after Yoshimura &
Prudhomme, 1988).

Rheological characterization of mayonnaise. Part I

0.m

1o.ccl

20.00

30.00

40.03

5O.M)

403

60.00

Sheaf stress (Pa)

(0)

100

50

150

250

200

Shear stress (Pa)

(b)
1
0.50 y

2 0.40 .ii

0.30 --

ij 0.20 -I
>
p

0.10 -:
O.fxA--+0.00

iz/

%-WA=%
loO.M3

m.M3

~...,:...-i.,..:*...,
3cn.m
4co.cn

5cn.00

6Cxl.m

7cQ.00

Shear siress (Pa)

(cl

Fig. 3.

Effect

of mayonnaise oil concentration

concentration; (b) 80% oil concentration;

on the slip velocity. (a) 75% oil

(c) 85% oil concentration.

L. Ma, G. VTBarbosa-Ccinovas

404

40.03
Shear stress (Pa)

1.60 -~

-1

1.20

i
f

B 0.80 -1
5
>
g 0.40 --

i
J-

O.~-.1UmwwmwHa
0.00

.m.,
50.00

1OO.M)

150.00

..,
2ccm

25o.m

Shear stress (Pa)

W
2.00

0.00
0.00

5O.M)

lC0.00

150.00

2m.00

250.00

3cmm

350.00

Shea stress (Pa)

(cl
Fig. 4. Effect of mayonnaise xanthan gum concentration on the slip velocity. (a) 50%
oil and 0.5% xanthan gum concentration; (b) 50% oil and 1.0% xanthan gum concentration; (c) 50% oil and 1.5% xanthan gum concentration.

Rheological characterization of mayonnaise. Part I

405

expected (Muiioz & Sherman, 1990). Therefore, the stress required to deform
the mayonnaise sample at higher oil concentrations would be greater than at
lower oil concentrations.
The slip velocity was also determined using eqn (1) for mayonnaise in the
presence of xanthan gum ranging from 05 to 1*5%, while the oil concentration
was kept constant at 50%. For a mayonnaise sample at 05% xanthan gum
concentration, there was no slip until shear stress increased to 49 Pa (Fig. 4(a)),
and no apparent flow was observed at a shear stress below 49 Pa (Fig. l(d)).
When the shear stress was greater than 49 Pa, the slip velocity increased with
applied shear stress (Fig. 4(a)). For the mayonnaise samples at 1.0 and 15%

3o.Gu

20.00

4mxl

50.00

6mKl

Shear stress (Pa)

(0)

0.00

lM).CQ

150.00

2mcn

250.00

Shea stress (Pa)

Fig. 5. Corrected mayonnaise flow curve calculated by eqn (2). Also shown are flow
curves measured at two different gaps. (a) 75% oil concentration; (b) 50% oil and 1.0%
xanthan gum concentration.
---o-1.0 mm gap; -A1.5 mm gap; corrected.

406

L. Ma, G. K Barbosa-Cinovas

xanthan gum concentrations, similar trends were observed even though the slip
was not observed until the applied stress increased to 131 and 228 Pa, respectively. The higher the xanthan gum concentration, the higher stress required to
deform the mayonnaise sample because the levels of structure in mayonnaise
were formed at higher xanthan gum concentrations (Yilmazer et al., 1991). At
concentrations of 05% or below, the aggregates were formed by the association
of xanthan gum molecules in solution by hydrogen-bonding (Lim et al., 1984).
At a higher xanthan gum concentration, a viscoelastic structure was formed
(Hibberd et al., 1987) and the consistency of mayonnaise increased by the
formation of larger-sized aggregates at higher xanthan gum concentrations
(Yilmazer & Kokini, 1992). Therefore, the slippage occurred at a higher shear
stress range for a mayonnaise sample with a higher xanthan gum concentration
due to the differences in the network structure.
Apparent shear rate measured at two different gaps can be corrected into
actual shear rate by using eqn (2). Figure 5(a) and (b) demonstrate the corrected
shear rate for mayonnaise at 7.5% oil concentration and 1.0% xanthan gum
concentration. Note that at low shear stress, the actual shear rate in the mayonnaise was zero. Thus, the mayonniase was not flowing at all but slipping along
the walls and rotating as a solid. Figure 5(a) and (b) show that actual shear rate
was always smaller than the apparent shear rate measured at any gap. This
smaller actual shear rate can be seen in Fig. 2. The slip velocity was considered
the discontinuity at the surface of the plate; after exclusion of the slip velocity, it
is seen that the actual shear rate was always smaller than the apparent shear rate.
In addition, it is known that the plate-plate rheometer has been limited in the
low shear rate or shear stress measurements (Kokini & Plutchok, 1987). The
upper limit of shear rate or shear stress is dependent on the tested material, i.e.
for polymer the limit of shear rate can be up to 500 s-. For materials with a
weak structure such as mayonnaise the shear rate range should be less than
lo-15 s- l (Peleg, 1993). Beyond this range, structure breakdown and radial
migration would have a significant negative effect in the steady shear
measurement. In the case of higher shear rate or shear stress applied, eqn (2)
was no longer applicable due to measuring range limitations of plate-plate
geometry and/or destructive effects. Therefore, for a mayonnaise sample which
has a weak structure, application of eqn (2) is limited to low shear stress or shear
rate range when using plate-plate geometry.

CONCLUSIONS
Slippage was found in the shear flow measurement of mayonnaise samples with
different oil and/or xanthan gum concentrations. The extent of the slippage was
greatly affected by the composition, i.e. the higher the oil or xanthan gum
concentrations, the smaller the slippage. The slippage effect can be corrected,
and the actual shear rate under controlled shear stress can be determined by a
simple model (eqn (2)). Equation (2) for corrected shear rate works well for
plate-plate geometry at low shear stress, whereas at large shear stress, a concentric cylinder geometry should be used.

Rheologicul characterization of mayonnaise. Part I

407

ACKNOWLEDGEMENT
This project was partially supported by a Sigma Xi grant.

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