International Journal of Food Properties

ISSN: 1094-2912 (Print) 1532-2386 (Online) Journal homepage: https://www.tandfonline.com/loi/ljfp20

Modeling Time-Independent Rheological Behavior

of Pistachio Butter

M. Taghizadeh & S.M.A. Razavi

To cite this article: M. Taghizadeh & S.M.A. Razavi (2009) Modeling Time-Independent
Rheological Behavior of Pistachio Butter, International Journal of Food Properties, 12:2, 331-340,
DOI: 10.1080/10942910701772048

To link to this article: https://doi.org/10.1080/10942910701772048

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International Journal of Food Properties, 12: 331–340, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1094-2912 print / 1532-2386 online
DOI: 10.1080/10942910701772048

MODELING TIME-INDEPENDENT RHEOLOGICAL

BEHAVIOR OF PISTACHIO BUTTER

M. Taghizadeh and S.M.A. Razavi

Department of Food Science and Technology, Ferdowsi University Mashhad
(FUM), Mashhad, Iran

Pistachio butter is a semi-solid paste, which is produced from ground and roasted pistachio
kernels. In this study, the flow curves and effect of different levels of emulsifier (Lecithin
and Mono-diglyceride) were assessed at different temperatures. It was found that pistachio
butter behaved as a non-Newtonian pseudo-plastic fluid with yield stress value. Seven
models were used to describe time-independent flow behavior of all samples. To evaluate
the ability of these models to predict rheological characteristics of pistachio butter, three
statistical parameters namely; R2, RMSE, and MRDM were used and finally Herschel-Bulkley
model was found to be the most appropriate to fit the flow curves of pistachio butter. The
effect of temperature on the apparent viscosity followed an Arrhenius relationship. Also,
the optimized sample consisting of 1% from both types of emulsifying mixtures (0.5%
lecithin and 0.5% mono-diglyceride) was found the most consistent one.

Keywords: Pistachio butter, Rheology, Pseudo-plastic, Yield stress, Modeling.

INTRODUCTION
Pistachio butter, a semi-solid paste, is made from ground and roasted pistachio
kernels with adding some proper flavorants and sweeteners. Because of the presence of
high amount of unsaturated oil in such a product, it is also necessary to use proper amount
of emulsifying and anti-oxidation agents in its formulation.[1] Pistachio butter is of high
nutritive value; for it is rich in lipids, proteins, carbohydrates, and vitamins and can be
used in different food products such as cookies, ice creams, and cakes.[1]
There is a number of published works on the rheological properties of semi-solid
pastes such as tomato paste,[2] mustard paste,[3] peanut butter,[4] and sesame butter.[5] Abu-
Jdayil et al.[6] investigated rheological characteristics of milled sesame (tehineh) and it was
found that tehineh behaved as a non-Newtonian pseudo-plastic foodstuff. Also, the power
law model was found to be the most appropriate to fit the flow curves of tehineh. However,
the rheological properties of pistachio butter, to the best of our knowledge, were not exam-
ined. A study regarding the chemical composition and sensory characteristics of pistachio
butter was carried out by Shaker et al.[1] They found that to achieve the most emulsion sta-
bility, the best type of emulsifying agent is a combination of mono-diglyceride and lecithin.

Received 17 December 2006; accepted 27 October 2007.

Address correspondence to S.M.A. Razavi, Department of Food Science and Technology, Ferdows,
University of Mashhad (FUM), Mashad PO Box 91775–1163, Iran. E-mail: s.razavi@um.ac.ir

331
332 TAGHIZADEH AND RAZAVI

Generally, an understanding of rheological properties of food materials has a direct effect

on the optimization of processing stages such as production, handling, storage, and final
quality.[7] The objectives of this work were: (i) to investigate the rheological properties of
pistachio butter; (ii) to determine the best time-independent model to fit the flow curves of
pistachio butter; (iii) to analyze the effect of different levels of emulsifying agents (mono-
diglyceride and lecithin at five levels) on the rheological characteristics of pistachio butter;
and (iv) to study the temperature dependency of pistachio butter in the range of 25–65°C.

MATERIALS AND METHODS

Sample Preparation
All samples studied in this research, were supplied from Pistachio Research Institute of
Iran. The approximate composition (w/w%) of provided pistachio butter samples was as fol-
lows: Grounded and roasted pistachio kernels 84%, sweeteners such as sugar 10%, moisture
content 3%, salt 1–2%, and emulsifying agents 0–2%. There were five types of samples, which
were different in emulsifier’s level. To facilitate the measurements, we named them as follows:
• Type 1: without any emulsifier.
• Type 2: contains 0.5% of lecithin and mono-diglyceride.
• Type 3: contains 1% of lecithin and mono-diglyceride.
• Type 4: contains 1.5% of lecithin and mono-diglyceride.
• Type 5: contains 2% of lecithin and mono-diglyceride.
It has to be mentioned that according to previous study, which was done on chemical and
sensory evaluation of pistachio butter, it was found that pistachio butter type 3 has the
most emulsion stability and the most homogenous texture.[1]

Rheological Measurements
Rheological properties of pistachio butter were measured with a Bohlin Visco 88
viscometer (Bohlin instrument, UK) equipped with a bob and cup geometry (bob length:
60 mm; bob diameter: 14 mm; gap width: 1 mm) and a heating circulator (Julabo, Model
F12-MC, Julabo Labortechnik, Germany). It should be pointed out that no surface slip was
observed in this viscometer system. The software Bohlin v06.32 was used to generate
shear stress-shear rate data. The flow curves of pistachio butter were measured at four
temperature levels of 25.0, 45.0, and 65.0°C by increasing the shear rate from 14 s−1 to
300 s−1. The period of experiment was about 4 min, and the values of the shear rate and
shear stress were recorded every 15 seconds.

Modeling Time-Independent Behavior

In the flow curves measurements, the shear stress, t, was measured as a function of
shear rate, g& . Then the apparent viscosity, ha, can be calculated using the equation:

t = h a g& (1)

The flow curves of pistachio butter samples were modeled by following famous equations
(7, 8):
 RHEOLOGICAL BEHAVIOR OF PISTACHIO BUTTER 333

1. Ostwald–de Waele (or Power-law):

t = k g& n (2)

where, k is the consistency index (Pa.sn) and n is flow behavior index.

2. Herschel – Bulkley

t − t0 = kh (g& )nh (3)

where t0 is the yield stress, kh is the consistency index for Herschel-Bulkley model, and nh
is flow behavior index for this model.
3. Casson:

t 0.5 = koc + kc (g& )0.5 (4)

0.5 0.5
where, k0c and kc are the intercept and slope of plot of (g& ) versus (t ) , respectively.
4. Bingham:

t − t0 = h ′g& (5)

where, h ′ is called the Bingham plastic viscosity.

5. Vocadlo:

nv
⎛ 1 ⎞
t = ⎜ t0 nv + kv g& ⎟ (6)
⎝ ⎠

where, kv is the consistency index for Vocadlo model, and nv is flow behavior index for
this model.
6. Mizrahi and Berk:

t = t0 + kmc (g& )n (7)

where, kmc is the consistency index for this model.

7. O’foli :

t n1 = t0n2 + h ∞ (g& )n2 (8)

where n1 and n2 are the model constants and h ∞ is the infinite viscosity.
334 TAGHIZADEH AND RAZAVI

Temperature Dependency
As consistency index (k) was highly dependent on heating temperature, the Arrhe-
nius type relationship was used to describe the influence of temperature on apparent vis-
cosity of pistachio butter as follow:

⎛E ⎞
h a = h ∞ exp ⎜ a ⎟ (12)
⎝ RT ⎠

where, ha is the apparent viscosity at a specific shear rate, h∞ is viscosity at infinite shear
rate, Ea is the activation energy of flow (kJ/mole), R is the gas constant (kJ/mole K), and T
is absolute temperature (K). The apparent viscosity data of samples were first measured at
three different shear rates (52, 155, and 297s−1), then the logarithm of the apparent viscos-
ity was plotted versus the reciprocal of absolute temperature (according to Eq. 13) in order
to estimate the Arrhenius model parameters, Ea and h∞, for each sample at a specific
temperature:

Ea
ln h a = ln h ∞ + (13)
RT

Statistical Analysis
To select the best model describing time-independent rheological properties of pis-
tachio butter samples, three regression parameters including R2, RMSE, and E% were
determined for the seven aforementioned rheological models. For statistical analysis,
Excel (Microsoft Office, Package 2003) and Slidewrite (Computer package version 2.0)
softwares were used to fit the data.

RESULTS AND DISCUSSION

Flow Curves
Fig. 1 shows the typical flow curves of pistachio butter samples, obtained at 25°C,
45°C, and 65°C. The results showed that the shear stress-shear rate relationship is non-
linear, indicating that all pistachio butter samples behave as non-Newtonian fluid,
pseudoplastic type. Also, the presence of an intercept value exhibited that all samples have
a value of yield stress. Abu-Jdayil et al.[6] plotted shear stress-shear rate data of milled
sesame and suggested that all samples exhibited pseudo-plastic behavior without yield
stress value.

Selection of the Best Model

Table 1 shows the three regression parameters obtained for the seven rheological
models used in this study. It can be found that the Mizrahi & Berk and O’foli models were
generally the poorest, while the Herschel–Bulkley model was the more suitable than the
others. In addition, it can be observed that although Bingham model has fairly proper
 RHEOLOGICAL BEHAVIOR OF PISTACHIO BUTTER 335

1600

1400

1200
Shear Stress (Pa)

1000
25°C
800 45°C
65°C
600

400

200

0
0 50 100 150 200 250 300 350
Shear Rate (1/s)

Figure 1 Typical flow curves of pistachio butter at 25°C, 45°C, and 65°C.

values of R2, but two other parameters (RMSE and %E) show that this model is not suit-
able at all. So, it can be concluded that R2 is not always a suitable statistical parameter for
estimation of the models’ ability. Rheological parameters of pistachio butter samples
described by Herschel–Bulkley model, at 25, 45, and 65°C are given in Table 2. Determi-
nation coefficient (R2) for the model ranged from 0.952 to 0.999 showing adequate fit for
flow curves. Memnune et al.[12] studied the rheological behaviour of carob pekmez and the
Herschel-Bulkley model was found to be the best to describe the rheological property with
the coefficient of determination higher than 0.998.
Sample 1 at 45 and 65°C presented a negative value of yield stress, with no
physical meaning, showing that Herschel-Bulkley model was not suitable in this situ-
ation. Thus, and regarding to table1, the power law and Vocadlo models were more
suitable to describe the rheological behavior of these samples. At 25°C, consistency
indices calculated by Herschel-Bulkley model ranged from 8.972 to 64.658 Pa sn
showing the high effect of emulsifying agents on the structural characteristics of
pistachio butter samples. Also, there was a significant difference among the flow
behavior index of all samples, being the type 3 the most pseudoplastic (n = 0.517). At
25°C, flow behavior indices ranged from 0.517 to 0.792, indicating that all samples
presented pseudoplasticity.
Consistency indices at 45°C ranged from 3.338 to 19.051 Pa sn, showing loss of
consistency after temperature increase. Flow behavior indices at 45°C and 65°C were
from 0.401 to 0.806 and 0.320 to 1.317, respectively. So, samples 2, 3, and 4 at 65°C
showed dilatant behavior as a result of structural change due to increasing temperature. At
65°C, consistency indices ranged from 0.116 to 13.517 Pa sn as being expected.
Comparing flow behavior indices, we found that there is no significant difference between
data. However, consistency indices decreased with increasing temperature excepting
type5 at 45°C.
 Table 1 The regression parameters of the models.

Type1 Type2 Type3 Type4 Type5

Model 25°C 45°C 65°C 25°C 45°C 65°C 25°C 45°C 65°C 25°C 45°C 65°C 25°C 45°C 65°C

Power law R2 0.996 0.988 0.975 0.996 0.990 0.905 0.993 0.981 0.950 0.993 0.945 0.800 0.991 0.952 0.977
RMSE 0.293 0.036 0.057 0.028 0.050 0.121 0.031 0.053 0.096 0.037 0.091 0.093 0.046 0.091 0.049
%E 22.340 3.264 5.058 2.914 5.600 11.564 3.175 5.470 9.585 4.045 7.425 8.276 5.455 9.142 3.579
Herschel-Bulkley R2 0.999 0.988 0.976 0.997 0.998 0.983 0.994 0.993 0.991 0.995 0.957 0.952 0.997 0.952 0.981
RMSE 0.014 0.036 0.055 0.026 0.020 0.044 0.028 0.025 0.037 0.033 0.078 0.044 0.023 0.090 0.045
%E 1.760 3.310 5.009 2.327 2.173 4.336 2.706 2.543 3.588 3.785 6.416 3.452 2.561 9.155 3.480
Casson R2 0.998 0.973 0.951 0.993 0.998 0.733 0.990 0.993 0.5 0.993 0.956 0.892 0.997 0.943 0.975
RMSE 0.018 0.060 0.168 0.043 0.021 67.172 0.038 0.028 — 0.038 0.079 0.067 0.024 0.099 0.051
%E 1.946 5.654 18.688 3.795 2.180 4323.469 3.496 2.547 — 4.437 6.418 5.943 2.651 10.339 4.503

336
Bingham R2 0.992 0.940 0.912 0.980 0.994 0.978 0.967 0.984 0.991 0.978 0.918 0.941 0.992 0.922 0.948
RMSE N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 0.302 N/A N/A N/A
%E N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A 19.899 N/A N/A N/A
Vocadlo R2 0.999 0.987 0.949 0.997 0.998 0.978 0.989 0.991 0.991 0.994 0.956 0.937 0.997 0.952 0.979
RMSE 0.016 0.039 0.072 0.028 2.130 0.977 0.104 0.028 0.039 0.037 0.079 0.050 0.024 0.090 0.047
%E 1.821 3.380 6.552 2.259 0.020 63.745 12.070 2.549 3.600 4.215 6.557 4.094 2.614 9.099 3.819
Mizrahi & Berk R2 0.509 0.504 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
RMSE 197.242 278.975 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
%E 9305.401 13815.85 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
O’foli R2 N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
RMSE N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A
%E N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A N/A

N/A = Not applicable.

 RHEOLOGICAL BEHAVIOR OF PISTACHIO BUTTER 337

Table 2 Rheological parameters of pistachio butter samples obtained by Herschel-Bulkley model at 25, 45, and
65°C.

Yield Value Consistency index Flow behavior

(s0, Pa) (k, Pa sn) index (n) R2

Sample 25°C 45°C 65°C 25°C 45°C 65°C 25°C 45°C 65°C 25°C 45°C 65°C

Type 1 107.957 −21.583 −91.212 17.135 13.562 10.426 0.752 0.401 0.320 0.999 0.988 0.976
Type 2 23.43 55.553 123.875 20.337 3.338 0.257 0.643 0.806 1.218 0.997 0.998 0.983
Type 3 141.658 111.460 45.206 64.658 7.075 0.338 0.517 0.732 1.034 0.994 0.993 0.991
Type 4 95.488 165.496 254.096 29.312 8.757 0.116 0.623 0.738 1.317 0.995 0.957 0.952
Type 5 110.532 15.518 79.813 8.972 19.051 13.517 0.792 0.514 0.489 0.997 0.952 0.981

Effect of Temperature
The logarithm of the apparent viscosity of pistachio butter samples versus the recipro-
cal of absolute temperature were shown at three different shear rates (52, 155, and 297s−1) in
Figs. 2–4. In the case of pistachio type 3, a straight line was obtained which confirms that
Arrhenius model fitted well with the experimental data and gave high R2 (0946-0983).
Also, these curves suggested that the most changes in apparent viscosity are belonged to
pistachio butter type 3, which shows the high effect of increasing temperature on the rheo-
logical characteristics of this sample.
The estimated values of Ea and h ∞ for each sample are given in Table 3. Regarding
to R2 values, it was shown that Arrhenius model was fitted reasonably well with experi-
mental data. For sample type 3, which was the optimized pistachio butter, the highest Ea
value was observed. Ea represents the activation energy of flow and it indicates a large
effect of temperature on viscosity.[8,11] In fact, temperature changes at a constant shear rate

2.5
ln(apparent viscosity) at 52 s–1

2
type1
type2
(Pa.S)

1.5 type3
type4
type5
1

0.5

0
2.9 2.95 3 3.05 3.1 3.15 3.2 3.25 3.3 3.35 3.4
(1/T) × 1000 K–1

Figure 2 Apparent viscosity versus temperature data for pistachio butter at 52s−1.
338 TAGHIZADEH AND RAZAVI

2.5

2
ln(apparent viscosity) at 155 s–1

1.5

type1
1 type2
(Pa.s)

type3
0.5 type4
type5

–0.5

–1
2.9 3 3.1 3.2 3.3 3.4
(1/T) × 1000 K–1

Figure 3 Apparent viscosity versus temperature data for pistachio butter at 155s−1.

1.5
ln (apparent viscosity) at 300 s–1

1
type1
type2
(Pa.s)

0.5 type3
type4
type5
0

–0.5

–1
2.9 2.95 3 3.05 3.1 3.15 3.2 3.25 3.3 3.35 3.4
(1/T) × 1000 K–1

Figure 4 Apparent viscosity versus temperature data for pistachio butter at 297s−1.

have the most effect on pistachio butter typev3. This shows that with increasing the tem-
perature, the optimized mixture of emulsifying agent (type 3) lost its functionality and
therefore the structure breakdown, which is highly dependent on temperature, observed.
On the other hand, the pistachio butter type 5 had the lowest Ea values, indicating the least
temperature dependency. Simuang et al.[13] investigated the effect of temperature and fat
 RHEOLOGICAL BEHAVIOR OF PISTACHIO BUTTER 339

Table 3 Arrhenius’s model parameters for the effect of temperature on steady state apparent
viscosity at 52, 155, and 297 s−1.

Sample Shear rate (s−1) h∞ (Pa.s) Ea (kJ/mole) R2

Type1 52 1.50 × 10−1 10.274 0.807

155 4.38 × 10−2 12.119 0.688
297 2.89 × 10−3 18.328 0.866
Type2 52 2.41 × 10−5 30.591 0.999
155 3.02 × 10−6 34.874 0.999
297 1.94 × 10−6 35.386 0.999
Type3 52 9.69 × 10−9 52.489 0.946
155 1.21 × 10−8 50.330 0.976
297 1.93 × 10−8 48.279 0.983
Type4 52 8.13 × 10−2 11.058 0.566
155 7.37 × 10−3 15.720 0.940
297 2.72 × 10−3 17.596 0.983
Type5 52 3.79 × 10−1 6.607 0.375
155 3.15 × 10−2 11.693 0.839
297 1.43 × 10−2 13.062 0.769

content on the apparent viscosity of coconut milk samples. They suggested that an
increase in fat content decreases the effect of temperature on the changes of the apparent
viscosity. In other words, for the samples with high fat contents, low Ea values were
observed.

CONCLUSION
Pistachio butter is a semi-solid substance that behaves as non-Newtonian pseudo-
plastic with yield stress. To estimate the flow behavior of samples, the Herschel-Bulkley
model was found the best to fit the data among the seven models used in this study. It was
observed that rheological parameters obtained by Herschel-Bulkley model were highly
dependent on the levels of emulsifying agents used in the formulation. The pistachio
butter type 3 (containing 1% of Mono-diglyceride mixture and lecithin) was the most con-
sistent, coherent and uniform sample. The effects of temperature on the apparent viscosity
of pistachio butter were examined, and it was found that the Arrhenius relationship could
describe the effect of temperature on viscosity of pistachio butter.

ACKNOWLEDGMENTS
This project was supported by the Department of Food Science and Technology, Ferdowsi University
of Mashhad, Iran. Support from the Pistachio Research Institute of Iran is gratefully acknowledged,
as well.

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