Journal of Molecular Liquids 276 (2019) 417–430

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Experimental investigation and rheological behaviors of water-based

drilling mud contained starch-ZnO nanofluids through response
surface methodology
Limo Salehnezhad a, Amir Heydari a,⁎, Moslem Fattahi b
a
Chemical Engineering Group, Faculty of Engineering, University of Mohaghegh Ardabili, Ardabil, Iran
b
Chemical Engineering Department, Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The study of rheological properties is one of the essential aspects in designing drilling mud and its performance in
Received 9 August 2018 operational conditions. The adding nanoparticles and natural polymers such as starch in drilling mud is the one
Received in revised form 14 November 2018 way for modifying rheological properties. In this research, rheological behavior of a water-based drilling mud
Accepted 27 November 2018
containing starch and ZnO nanoparticles were investigated and optimized. The rheological parameters were
Available online 29 November 2018
modeled by means of power law and Bingham-plastic models, then they were analyzed using ANOVA. Initially
Keywords:
ZnO nanoparticles were synthesized and characterized using scanning electron microscopy (SEM), X-ray diffrac-
Water-based drilling mud tion (XRD) and Energy-dispersive X-ray spectroscopy (EDS). Experiments were arranged based upon the central
Rheological behavior composite design (CCD) and results were analyzed using response surface methodology (RSM). Experimental
Response surface methodology variables (starch percentage, percentage of nanoparticles and ultrasonic time) were studied at five levels and
Starch 17 experiments were obtained with three times repetitions in the center point. The obtained regression equa-
ZnO nanoparticles tions for the responses were the quadratic mathematical models. The main and interacting effects between var-
iables were studied using the analysis of variance and 3D plots. The results revealed that, the rheological
parameters were more influenced by the nanoparticles amount. The optimized values of starch, nanoparticle
and ultrasonic time variables were obtained equal to 0.82% (wt.), 0.2% (wt.) and 65.0 (min), respectively.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction replacement of biodegradable and environmentally friendly addi-

Drilling is a determinant process for recovering important under-
ground material and drilling muds are the key for achieving this inten-
tion [1]. Historically, application was the first goal in using drilling fluids,
it was used as a means of transporting and removing rubbles from the
front of drilling bit. But now, various performances in its construction
is considered such as suspending of cuttings and preventing from settle
them, cooling drilling pipes and bit, reducing friction between forma-
tion and drilling equipment, stabilizing wellbore and avoiding forma-
tion collapse [2,3].
The cost of drilling mud is often one of the largest investment
costs in drilling an oil well. In order to minimize expenses and ensure
an efficient drilling program, drilling mud properties should be
maintained continuously in operation [4,5]. These muds are a system
which are made of several materials, that play a special role in it [6].
Additives are used in order to improve the quality and performance
of drilling muds, creating surface and underground pollution in land-
fills and the environment [7]. Therefore, identification and
⁎ Corresponding author.
E-mail address: heydari@uma.ac.ir (A. Heydari).
tives is essential. The natural biodegradable polymers such as:
xanthan gum, guar gum, starch, and cellulose are the best drilling
mud additives in the drilling industry, because they are non-toxic
and they lack environmental problems [8]. On the other hand, acces-
sibility with low cost is regarded as its favor [9,10]. Thermal degrada-
tion of polymers is the most important problem in using them [11].
Thermal breakdown of the drilling mud will increase the viscosity
and fluid loss [12]. In order to solve this problem, nanomaterials
with high thermal stability are utilized. The purpose of utilizing
nanomaterial in drilling mud is to reduce the overall mud's cost by
decreasing consumption of solids and chemical materials in drilling
mud as well as improving its properties and efficiency [7,13].
Rheology is the study of deformation and flow of matter that,
evaluating the behavior of drilling fluid in solving problems can be
considered as one of its main applications, including hole cleaning
and hole erosion, suspension of cuttings, hydraulic calculations,
and drilling mud treatment [14,15]. In drilling operations, rheologi-
cal properties refer to the relationship between shear stress and
shear rate in drilling mud [16]. Amanullah et al. studied the rheolog-
ical properties and filtration of various nano-based drilling fluids.
Comparison of rheological profiles and gel strength behavior showed

https://doi.org/10.1016/j.molliq.2018.11.142
0167-7322/© 2018 Elsevier B.V. All rights reserved.
418 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430

Table 1 experiments and optimization of experimental conditions [23,24].

Experimental range and levels of independent variables.
Variables Unit Coded variables Variable levels
−2 −1
Starch (wt%) A 0.2 0.4
Nanoparticles (wt%) B 0.2 0.4
Ultrasonic time (min) C 15 30
that these fluids have the same viscosity and gel strength after prep-
aration and different time periods, so that rheological stability has
been achieved in the long time. Besides, bentonite and nano-based
fluids showed a higher yield point than only bentonite-based fluids.
The higher yield point causes a better suspension of drilling rubbles,
as a result, the efficiency of cleaning fluid increases in the well [17].
Nasser et al. investigated the effects of pressure and temperature
on the viscosity and filtration of bentonite drilling fluids containing
a mixture of graphite and silicon nanoparticles. Investigating the vis-
cosity curves in terms of speed at different temperatures indicated
that viscosity in nano-based fluids increased, viscosity decreased
with an increase in temperature and shear rate as well. As a result,
it can be used in deep wells with high temperature and high pressure
[4]. William et al. examined the effects of CuO and ZnO nanofluids in
xanthan gum on the thermal, electrical and rheology of water-based
drilling fluids. It was observed that, thermal and electrical conductiv-
ity were enhanced by increasing the concentration of nanoparticles.
Nano-particles stabilized the nanofluids at high temperatures and
prevented the drilling mud from heating, thus the rheological prop-
erties almost remained constant. In their study, the Herschel-Bulkley
model was the best fitted model with experimental data [18,19].
Sadeghalvaad and Sabbaghi were investigated the effect of the
TiO2/polyacrylamide nanocomposite on rheological properties and
filtration of water-based drilling fluid. Rheological properties includ-
ing the plastic viscosity, yield point and consistency index were en-
hanced by increasing the nanocomposite concentration; on the
other hand, the flow behavior index was reduced, so shear thinning
was enhanced. According to R2 values, the power law model was a
more appropriate model to be fitted with data [1].
Investigating the variation of the basic rheological parameters
has led to the choice of a suitable model for each of the drilling
mud samples [20]. Different models reinforced the scientific concep-
tion of the flow in drilling mud [21,22]. Reviewing of these models
provided a mathematical explanation of the flow in drilling muds
[14]. The response surface methodology (RSM) is one of the mathe-
matical methods for describing rheological parameters. RSM is the
collection of mathematical and statistical techniques in making
models and studying the effect of process parameters on designing
Nam et al. reviewed the ecologically benign nanofluid micro-
drilling process. In their study, the optimization of paraffin oil-
0 +1 +2
based fluid and edible oil-based fluid was done based on RSM and ge-
netic algorithm (GA). The optimal values of process parameters were
0.6 0.8 1
obtained for minimizing drilling torques and thrust forces as well as
0.6 0.8 1
45 60 75 maximizing material removal rate. The results showed that the drill
diameter had the greatest impact on the responses [25]. Nee et al. in-
vestigated the lightweight biopolymer of xanthan and starch in a
water-based drilling fluid using RSM. Based on the analysis of vari-
ance results and quadratic mathematical models, in optimal condi-
tions, errors were b1.0, standard deviation was b0.5 and the
accuracy was N98.5% [26].
In order to investigate and improve the behavior of drilling fluid
in various stresses well, the different rheological models are re-
quired. Models are implemented part to part in all system [14].
Therefore, using a model alone is not appropriate for studying the
rheological properties of mud in different stresses and well condi-
tions. According to our studies, there has been no report on modeling
of the rheological parameters of drilling muds using the RSM so far.
In the current study, the parameters of two customary models are in-
vestigated in order to examine the rheological properties of drilling
muds using RSM method in the designing experiments, which is
based on central composite design (CCD). The variations of the re-
sponses were investigated compared to the independent variables
namely starch percentage, percentage of nanoparticles and ultra-
sonic time. Then, parameters optimization was performed with the
aim of achieving optimal rheological properties in well conditions.
2. Materials and methods
2.1. Materials
Zinc sulfate heptahydrate (ZnSO4·7H2O) and sodium hydroxide
(NaOH) were purchased from Merck chemical company and were
used in synthesis of zinc oxide (ZnO) nanoparticles. Ethanol 97% was
used in order to wash nanoparticles. Bentonite (with specific area of
338.69 m2/g, and specific gravity of 1.61 and cation exchange capacity
of 75.13 meq/100 g) and pre-gelatinized starch were supplied by
Kimia Pars Shayankar and Glucosan companies from Iran, respectively.
Deionized water was used for preparation of suspensions.
2.2. Synthesis of ZnO nanoparticles
First, 24.6 mmol of ZnSO4·7H2O was dissolved in 250 mL deionized
water under stirring at 80 °C. Simultaneously, the solution of NaOH in a
molar ratio of 1:2 was added slowly. The solution was stirred slowly for

Table 2
Central composite design of experimental and observed responses.

Run Starch (wt%) Nanoparticles (wt%) Ultrasonic (min) K (mPa·s) n (dimensionless) YP (mPa) PV (mPa·s)

1 0.4 0.8 30 34.33 0.51 50.32 3.93

2 1 0.6 45 45.56 0.50 55.51 4.09
3 0.6 1 45 43.71 0.48 61.34 4.51
4 0.4 0.4 60 35.50 0.63 35.30 3.11
5 0.8 0.4 30 22.45 0.60 40.42 3.27
6 0.6 0.6 15 30.78 0.54 42.71 3.83
7 0.8 0.4 60 26.25 0.59 41.45 3.22
8 0.6 0.2 45 12.95 0.67 25.43 2.43
9 0.4 0.8 60 34.01 0.50 52.69 3.65
10 0.4 0.4 30 12.94 0.61 22.18 3.01
11 0.8 0.8 30 41.23 0.61 43.39 4.12
12 0.2 0.6 45 35.39 0.49 43.28 3.34
13 0.6 0.6 75 43.49 0.49 57.03 3.98
14 0.8 0.8 60 34.18 0.51 48.70 4.15
15 0.6 0.6 45 12.90 0.68 23.41 2.99
16 0.6 0.6 45 11.61 0.70 20.70 2.93
17 0.6 0.6 45 11.60 0.70 22.02 3.04
 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430 419

Fig. 1. SEM images of (a) synthesized ZnO nanoparticles and (b) bentonite.

30 min at 80 °C and a milky white solution was obtained. After the reaction sodium sulfate (NaSO4). Then, the obtained precipitate was dried at room
process was completed, suspension washed with ethanol 97% and deion- temperature for 24 h. The resulting powder was calcined in an electrical
ized water for several times in order to remove the by-products including oven at 700 °C for 4 h in order to remove all impurities [27,28].

Fig. 2. EDS analysis of synthesized ZnO nanoparticles.

420 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430

Fig. 3. XRD pattern of (a) synthesized ZnO nanoparticles, (b) standard ZnO corresponding to JCPDS card No. 36-1451 [51,52] and (c) bentonite.

2.3. The preparation of the water-based drilling mud
Due to the predominant role of surface forces in nanoparticles, the
particles in nanofluids were agglomerated once the mechanically agita-
tion is stopped. Using chemicals, polymers and surfactants with high
shielding around the nanoparticles can minimize attractive surface
forces and provide adequate stability in nanofluid. The surfactant addi-
tive is very costly and using any non-environmentally friendly nano-
stabilizing additive will have poor industrial acceptance, due to increas-
ing concern about environment. Hence, using an economically and envi-
ronmentally friendly additive is necessary [17,29]. In their study, pre-
gelatinized starch polymer was used as a viscosifier and stabilizer of
nanoparticles in the system. Interaction of clay minerals and polymers
and also the effect of additives on rheological properties are considered
as major concerns in the oil industry. Therefore, bentonite is used as
common additive clay in water-based muds and the role of starch,
metal nanoparticles and ultrasonic treatment on the properties of
these muds were investigated. The base fluid was prepared by dissolv-
ing various amounts of starch in 100 mL distillated water. Then, the syn-
thetic nanoparticles were added and agitated with magnetic stirrer in
fluid for 10 min. The suspension was sonicated in different length
time so that, a smooth solution was obtained. After that, 3 g bentonite
was added to the suspension and was stirred strongly with magnetic
stirrer for 20 min.
2.4. Characterization
The morphologies and microstructures of the bentonite and synthe-
sized ZnO were characterized using a field emission scanning electron
microscope (SEM, FEI NOVA Nano SEM 230). The approximate sizes of
 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430 421

Table 3
Sequential model for sum of squares and model for summarized statistic which were tested for responses.

Source Sum of squares df Mean square F value p-Value R2 Adj. R2 Pred. R2

Prob N F

Consistency index (K)

Mean 14,059.04 1 14,059.04
Linear 901.87 3 300.62 2.53 0.1026 0.3687 0.2230 0.0471
2FI 229.23 3 76.41 0.58 0.6407 0.4624 0.1399 0.1135
Quadratic 1267.16 3 422.39 61.79 b0.0001 0.9804 0.9553 0.8477
Cubic 45.15 4 11.29 12.51 0.0325 0.9989 0.9941 0.8595
Residual 2.71 3 0.90
Total 16,505.16 17 970.89

Flow behavior index (n)

Mean 5.66 1 5.66
Linear 0.032 3 0.011 1.96 0.1692 0.3119 0.1531 −0.0284
2FI 6.800E−003 3 2.267E−003 0.36 0.7848 0.3786 0.0058 0.0328
Quadratic 0.062 3 0.021 119.09 b0.0001 0.9881 0.9727 0.9217
Cubic 9.500E−004 4 2.375E−004 2.66 0.2234 0.9974 0.9860 0.9931
Residual 2.674E−004 3 8.913E−005
Total 5.76 17 0.34

Yield point (YP)

Mean 27,672.43 1 27,672.43
Linear 1266.25 3 422.08 3.40 0.0506 0.4394 0.3100 0.1905
2FI 171.55 3 57.18 0.40 0.7588 0.4989 0.1982 0.1893
Quadratic 1384.00 3 461.33 53.67 b0.0001 0.9791 0.9523 0.8454
Cubic 54.83 4 13.71 7.69 0.0627 0.9981 0.9901 0.8727
Residual 5.34 3 1.78
Total 30,554.40 17 1797.32

Plastic viscosity (PV)

Mean 208.95 1 208.95
Linear 3.83 3 1.28 12.04 0.0005 0.7354 0.6743 0.6042
2FI 0.027 3 9.083E−003 0.067 0.9761 0.7406 0.5850 0.5253
Quadratic 1.23 3 0.41 24.11 0.0005 0.9771 0.9477 0.8208
Cubic 0.11 4 0.027 6.58 0.0768 0.9977 0.9875 0.7448
Residual 0.012 3 4.067E−003
Total 214.16 17 12.60

nanoparticles on the SEM images were determined using Photoshop
CS6 software (Adobe, San Jose, CA). Elements in the sample were iden-
tified through the EDS analysis of the X-ray signal interpretation. The
dried powder sample was used for X-ray diffraction (XRD) analysis.
The XRD patterns were obtained using the Bruker D8-Advance instru-
ment with Cu Kα radiation (40 kV, 30 mA) with the scattering angles be-
tween 10° and 80° in the increments of 1°.
2.5. Rheological measurements
The rheological properties of the samples were measured according
to Power-law and Bingham- plastic models (MCR301 rheometer,
Austria). Measurements were carried out under environmental condi-
tions (temperature of 25 °C and pressure of 1 atm). Power-law is a
two-parameter model that relates the shear stresses to shear rate in a
nonlinear manner. In this model, the yield stress is not considered and
its relation is expressed as:
τ ¼ K ðγ Þn
where, K, n and γ are referred as the consistency index (dyn Sn/cm2),
flow behavior index (dimensionless) and shear rate (1/s), respectively.
Bingham-plastic is a two-parameter model that expresses the direct re-
lationship between shear rate and shear stress. In this model, the yield
stress is considered and its relation is expressed as:
τ ¼ YP þ PV ðγ Þ
from these two models are simple and various stresses which were ap-
plied to the fluid can be investigated using these two models. Typically,
Bingham-plastic and power-law models are preferred at higher and
lower shear rates, respectively. Bingham-plastic is used commonly for
the flow in the drill pipe and power-law is applied over the annulus
[14,20,30].
2.6. Experimental design
In this study, the experimental design and analysis of responses
were done using Design Expert software (Version 7.0.0, Stat-Ease, Inc.,
Minneapolis, MN). In this design, the RSM was applied based on the
CCD in order to achieve the mathematical relation between variables
and responses and describing the interactions between variables. Inde-
pendent variables (percentage of starch, percentage of nanoparticles
and ultrasonic time) were investigated in five levels with three replica-
tions in the center domain. Each independent variable was coded at five
levels between +2, +1, 0, −1 and −2 in which the details are shown in
ð1Þ Table 1. The experimental conditions and obtained responses are pre-
sented in Table 2.
The performance of the process was evaluated by analyzing the re-
sponses (Y), which depend on the input factors x1, x2, …, xk, and the re-
lationship between the response and the input process parameters is
described by:
Y ¼ f ðx1 ; x2 …xk Þ þ e ð3Þ
ð2Þ

where, YP and PV are referred as the yield point (dyn/cm2) and the plas- where, f is the real response function which its format is unknown and e
tic viscosity (P), respectively. The flow equations which are obtained is the error which describes the differentiation.
422 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430

Table 4
ANOVA and significance of regression coefficients in model.

Source Sum of squares df Mean square F value p-Value

Prob N F

Consistency index (K)

Model 2398.26 9 266.47 38.98 b0.0001 Significant
A-Starch 47.85 1 47.85 7.00 0.0331
B-Nanoparticles 730.76 1 730.76 106.89 b0.0001
C-Ultrasonic 123.27 1 123.27 18.03 0.0038
AB 5.80 1 5.80 0.85 0.3878
AC 81.22 1 81.22 11.88 0.0107
BC 142.21 1 142.21 20.80 0.0026
A^2 986.40 1 986.40 144.29 b0.0001
B^2 325.61 1 325.61 47.63 0.0002
C^2 769.08 1 769.08 112.50 b0.0001
Residual 47.85 7 6.84
Lack-of-fit 46.74 5 9.35 16.72 0.0574 Not significant
Pure error 1.12 2 0.56
Cor total 2446.12 16
Std. dev. 2.61 R2 0.9804
Mean 28.76 Adj. R2 0.9553
C.V. % 9.09 Pred. R2 0.8477
PRESS 372.44 Adeq. precision 16.097

Flow behavior index (n)

Model 0.10 9 0.011 64.36 b0.0001 Significant
A-Starch 4.000E−004 1 4.000E−004 2.30 0.1732
B-Nanoparticles 0.029 1 0.029 166.18 b0.0001
C-Ultrasonic 2.500E−003 1 2.500E−003 14.38 0.0068
AB 3.200E−003 1 3.200E−003 18.40 0.0036
AC 1.800E−003 1 1.800E−003 10.35 0.0147
BC 1.800E−003 1 1.800E−003 10.35 0.0147
A^2 0.048 1 0.048 273.60 b0.0001
B^2 0.017 1 0.017 97.35 b0.0001
C^2 0.038 1 0.038 221.18 b0.0001
Residual 1.217E−003 7 1.739E−004
Lack-of-fit 9.507E−004 5 1.901E−004 1.43 0.4610 Not significant
Pure error 2.667E−004 2 1.333E−004
Cor total 0.10 16
Std. dev. 0.013 R2 0.9881
Mean 0.58 Adj. R2 0.9727
C.V. % 2.29 Pred. R2 0.9217
PRESS 7.979E−003 Adeq. precision 20.590

Yield point (YP)

Model 2821.80 9 313.53 36.48 b0.0001 Significant
A-Starch 89.92 1 89.92 10.46 0.0144
B-Nanoparticles 1017.13 1 1017.13 118.33 b0.0001
C-Ultrasonic 159.20 1 159.20 18.52 0.0036
AB 155.85 1 155.85 18.13 0.0038
AC 10.47 1 10.47 1.22 0.3063
BC 5.23 1 5.23 0.61 0.4608
A^2 912.91 1 912.91 106.21 b0.0001
B^2 557.06 1 557.06 64.81 b0.0001
C^2 944.77 1 944.77 109.91 b0.0001
Residual 60.17 7 8.60
Lack-of-fit 56.50 5 11.30 6.15 0.1457 Not significant
Pure error 3.67 2 1.84
Cor total 2881.97 16
Std. dev. 2.93 R2 0.9791
Mean 40.35 Adj. R2 0.9523
C.V. % 7.27 Pred. R2 0.8454
PRESS 445.48 Adeq. precision 16.921

Plastic viscosity (PV)

Model 5.09 9 0.57 33.21 b0.0001 Significant
A-Starch 0.41 1 0.41 24.04 0.0017
B-Nanoparticles 3.42 1 3.42 200.86 b0.0001
C-Ultrasonic 6.250E−004 1 6.250E−004 0.037 0.8536
AB 0.013 1 0.013 0.75 0.4148
AC 3.200E−003 1 3.200E−003 0.19 0.6778
BC 0.011 1 0.011 0.66 0.4432
A^2 0.65 1 0.65 38.38 0.0004
B^2 0.29 1 0.29 17.06 0.0044
C^2 1.04 1 1.04 60.79 0.0001
Residual 0.12 7 0.017
Lack-of-fit 0.11 5 0.023 7.46 0.1223 Not significant
Pure error 6.067E−003 2 3.033E−003
 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430 423

Table 4 (continued)

Source Sum of squares df Mean square F value p-Value

Prob N F

Cor total 5.21 16

Std. dev. 0.13 R2 0.9771
Mean 3.51 Adj. R2 0.9477
C.V. % 3.72 Pred. R2 0.8208
PRESS 0.93 Adeq. precision 18.479

Table 5 In order to investigate the behavior of the response surface, a nonlin-

Uncertainties analysis. ear regression method was used. The generalized response surface
Parameter Unit Comment model is:
Experimental measurements
Uncertainty in the weight measurement g ±0.004 X
k X
k k−1 X
X k
Uncertainty in the time measurement s ±0.01 Y ¼ b0 þ bi xi þ bii xi 2 þ bij xi x j þ e ð4Þ
i¼1 i¼1 i¼1 j¼1
Responses values
Total uncertainty for K Dimensionless ±1.17%
Total uncertainty for n Dimensionless ±1.47%
where, Y is the response; xi and xj are variables (i and j range from 1 to
Total uncertainty for YP Dimensionless ±0.76%
Total uncertainty for PV Dimensionless ±0.34% k); b0 is the model intercept coefficient; bj, bjj and bij are interaction co-
efficients of linear, quadratic and the second-order terms, respectively;

Fig. 4. Predicted versus actual plots of a) consistency index, b) flow behavior index, c) yield point, and d) plastic viscosity.
424 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430

k is the number of independent parameters (k = 3 in this study) and ei 3. Results and discussion
is the error [31–33].
3.1. Characterizations and properties of ZnO nanoparticle

2.7. Statistical and uncertainty analysis The morphology of the synthesized ZnO nanoparticles and bentonite
were investigated using SEM that was presented in Fig. 1. As shown in
The statistical analysis of experimental data was performed using Fig. 1(a), shapes of the nanoparticles were nearly spherical with a slight
multiple regressions and the quality of the polynomial model was aggregation. According to Fig. 1, the average particle size ranged from
expressed through least square method. The significance of the regres- 40 to 70 nm. In Fig. 2, the EDS patterns of the synthesized nanoparticles
sion coefficients on responses was evaluated using F test and p-value were presented and revealed that, synthesized ZnO nanoparticles were
(probability) with 95% confidence level. The fit quality of the models pure. As it was mentioned, the prepared ZnO nanoparticles were cal-
was investigated using coefficient of determination R2 and adjusted cined at 700 °C. The defects of the surface of ZnO nanoparticles were cre-
R2. The results were analyzed using the analysis of variance (ANOVA) ated at temperatures higher than 230 °C. This treatment will make the
and the regression coefficients were determined. In order to examine oxygen vacancy sites or defective sites more favorable to adsorb hy-
the system behavior, 3D surface plots were drawn and the interactions droxyl group than oxygen which makes the surface more hydrophilic.
of the variables were investigated. The simultaneous optimization for On the other hand, oxygen atom of water molecule may bind to un-
multiple responses was performed using the Derringer's desirability paired Zn ions on the ZnO surface coordinately which formed a thin
function method. Also, uncertainties in the experimental results were water layer on surface of ZnO [35]. The XRD technique has been used
performed using the method which was described by Holman [34] as for the determination of the crystallite structure, phase purity and com-
below: position of the particles. Fig. 3(a) shows the diffraction peaks in XRD
pattern of the synthesized ZnO nanoparticles. The obtained XRD was
in well agreement with the Joint Committee on Powder Diffraction
" 2  2  2 #1=2 Standards (JCPDS) Card No. 36-1451 (Fig. 3(b)). Based on the sharp
∂F ∂F ∂F
UF ¼ u1 þ u2 þ…þ un ð5Þ and narrow observed peak, nanoparticles had good crystallinity. The
∂z1 ∂z2 ∂zn
strongest peak was at 2θ = 36.4°., average size of the zinc oxide

Fig. 5. Normal plot of residual plot of a) consistency index, b) flow behavior index, c) yield point, and d) plastic viscosity.
 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430
Fig. 6. Response surface plots (3D) of consistency index (K) in terms of a) starch (wt%) vs. nanoparticles (wt%); b) starch (wt%) vs. ultrasonic (min); c) nanoparticles (wt%) vs. ultrasonic
(min).
nanoparticles was determined about 58 nm using Scherrer's equation
[33,36], which was in accordance with the SEM results.
3.2. Study of rheological parameters
First, the rheological properties of prepared samples were measured
and the obtained results were used in order to examine the fitness of the
results to the rheological parameters of the power-law and Bingham-
plastic conventional models using CFTool toolbox of Matlab (Ver.
2014b) software. Second, the obtained rheological parameters were an-
alyzed using RSM. These parameters (K, n, PV, and YP) were considered
as a response for RSM separately as a result, starch percentage, percent-
age of nanoparticles and ultrasonic time and their regression equations
were obtained. Third, the adequacy of the obtained quadratic models
was analyzed using analysis of variance (ANOVA) in order to investigate
the effect of selected variables (starch percentage, percentage of nano-
particles and ultrasonic time) and their interactions on responses (K,
n, PV, and YP). Finally, the system was optimized in order to achieve
the highest cleaning capacity in the well.
3.3. Mathematical models
The obtained data were fitted to various models (linear, interactive,
quadratic and cubic models) in order to find the best regression equations
[37]. The adequacy of models was compared in Table 3. According to
Table 3, for selecting the appropriate model for the responses, both R2
and p-value were considered. If the p-value is at a significant level, but
the value of R2 is not close to one, or vice versa, the model will not be suf-
ficient. Based upon the R2 and p-value of different models, the best statisti-
cally models for responses were second-order ones. In Table 3, the selected
models for each response were indicated through the bold manner type.
425
3.4. Models
The obtained data were fitted with different models in order to find
significant relationship between variables and responses as well as
selecting the best model according to the p-value and R2 parameters.
The best fitness was found with the second-order polynomial. The ob-
tained final equations in terms of actual factors are given below:
ConsistencyindexðK Þ ¼ 77:34−170:42A‐38:74B‐0:85C þ 21:28AB‐1:06AC
‐1:40BC þ 178:41A2 þ 102:50B2 þ 0:03C2
ð6Þ
FlowbehaviorindexðnÞ ¼ ‐0:36 þ 1:44A þ 0:60B þ 0:02C þ 0:50AB‐5  10−3 AC
‐5  10−3 BC‐1:24A2 ‐0:74B2 ‐1:99  10−4 C2
ð7Þ
YieldPo intðYP Þ ¼ þ97:39‐110:75A‐42:69B‐2:19C‐110:34AB‐0:38AC
ð8Þ
‐0:27BC þ 171:64A2 þ 134:07B2 þ 0:03C2
PlasticVis cosity ¼ þ6:15‐5:61A‐1:40B‐0:09C þ 1AB þ 6:67  10−3 AC
‐0:01BC þ 4:59A2 þ 3:06B2 þ 1:03  10−3 C2
ð9Þ
where, A is starch percentage, B is percentage of nanoparticle and C is ul-
trasonic time.
3.4.1. Evaluation of the models and uncertainty analysis
Analysis of variance (ANOVA) was applied in order to find the inter-
action between process variables and responses. Adequacy and compat-
ibility of the models were examined through ANOVA. Analysis of
variance for the responses was shown in Table 4. Results showed the
sufficiency of the models in establishing an appropriate relationship
426 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430
Fig. 7. Response surface plots (3D) of flow behavior index (n) in terms of (a) starch (wt%) vs. nanoparticles (wt%); b) starch (wt%) vs. ultrasonic (min); c) nanoparticles (wt%) vs. ultrasonic
(min).
between independent variables and responses. The significance of each
coefficient was checked based on the p-value, in order to understand in-
teractions between the process variables. The p-value which was lower
than 0.05 indicated that, the model coefficient was statistically signifi-
cant [38,39]. The values of R2 and adjusted R2 close to 1 are desirable
and necessary [40,41]. Regression coefficients and p-value for the
second-order polynomial equations were presented in the Table 4.
The R2 values for responses (consistency index (K), flow behavior
index (n), yield point (YP) and plastic viscosity (PV)) were close to
one and have a reasonable agreement with adjusted R2, which is desir-
able. The reproducibility of the model could be discussed based on the
coefficient of variance (CV) which is the ratio of the standard error of es-
timation to the mean value of the observed response. The CV for normal
model must be lower than 10% [38,42]. The CV for K, n, YP and PV, were
equal to 9.09, 2.27, 7.27 and 3.72, respectively. This parameter was de-
creased 10% in all models, thus in equations, predicted values for re-
sponses were close to the actual values.
The ANOVA results for the responses (K, n, YP and PV) showed the F-
value was equal to 38.98, 64.38, 36.48 and 33.21, respectively. As seen,
p-value for the nanoparticles percentages parameter was low (p b
0.0001), therefore F-value for that was larger compared to the others.
The “Adequate Precision” ratio of the models were equal to 16.097,
20.59, 16.92 and 18.48 that were N4. The obtained indicated adequate
signal was desired in supporting the fitness of the models [40,42].
Studying standard deviations of models showed that predicted values
were close to the actual values for the responses. In case of the replica-
tion for the central point, performing the lack-of-fit test is necessary in
order to study the significance of the repetitious error compared to de-
pendent error in model [40]. In the present study, lack-of-fit unto all
models was not significant. It was good and showed that the models
were appropriate to predict responses within the range of studied vari-
ables. Results of uncertainty analysis were showed in Table 5. It was ob-
tained that, all uncertainties were in an acceptable range.
3.4.2. Evaluation of models using diagnostic plots
Generally, it is momentous to confirm the selected model in order to
ensure that it gives a sufficient approximation to the actual values.
When the model is not satisfactory, continuation of research and opti-
mization of response surface gives poor results and is misleading [43].
To evaluate the models satisfactoriness the relationship between pre-
dicted and experimental values was used as diagnostic plots. In Fig. 4,
the obtained values for responses were compared to the predicted
values by the model. The suitable distribution of data points around
and close to a straight line, showed the ability of the models to predict
the response values. In addition, the data were analyzed in order to de-
termine the normality of the residuals. The residuals give the difference
between the experimental values and the obtained values by the model,
and the smaller residuals values Indicating precision in model [44]. The
normal probability plots of the residuals were shown in Fig. 5. The data
points on this plot lied reasonably close to a straight line, therefore, it
could be concluded that, data was distributed normally.
3.5. Effect of process variables in responses
3.5.1. Effect of process variables on consistency index (K)
The consistency index (K) is depended on structure and stability of
gel [45]. According to Fig. 6(a), by increasing the weight percentage of
the starch, the concentration index reduced first and then increased.
 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430
Fig. 8. Response surface plots (3D) of flow yield point (YP) in terms of a) starch (wt%) vs. nanoparticles (wt%); b) starch (wt%) vs. ultrasonic (min); c) nanoparticles (wt%) vs. ultrasonic
(min).
By adding the starch, the interaction between starch and bentonite de-
creased the concentration index initially. The presence of bentonite par-
ticles disrupted the continuity of the polymer gel structure and reduced
the concentration index [45]. At higher percentages, the role of starch in
the system became more pronounced due to the enhancement of poly-
mer gel structures and the concentration index was increased conse-
quently. In the average percentages of starch, the amount of K had a
minimum amount due to instability in bentonite bonds and starch poly-
mer networks. The obtained results were in accordance with the Besün
and Peker's finding [45]. As shown in Fig. 6(a), the concentration index
increased by adding nanoparticles due to increased surface loads and
hydrogen bonds. Intermolecular hydrogen bonds were created by inter-
actions between hydrogen and oxygen atoms in suspension and influ-
enced the rheological behavior [46]. In adding higher weight
percentages of starch to nanoparticles, the concentration index in-
creased more due to interactions between starch and ZnO nanoparticles
which lead to structural changes in starch [46] and enhanced the stabil-
ity and cohesion of the polymeric network of starch. The aforemen-
tioned results were in accordance with the results which were found
by Mousazadeh et al. [46].
According to Fig. 6(b), in various percentages of starch, with the in-
crease in ultrasonic time, the concentration index reduced initially and
then increased. At low to medium time, interactions between the parti-
cles had a dominant role in the system, which these interactions inter-
feres the creation of stable structures in the system. However, in
polymeric solutions the energy which was generated by ultrasonic vi-
brations will break the polymer and the molecular weight declines
over time [47]. The lighter polymers created more stable polymer gel
so, concentration index increased at high ultrasonic times.
427
In Fig. 6(c) it was seen that, the concentration index increased by in-
creasing the percentage of nanoparticles and ultrasonic time. On the one
hand, the presence of nanoparticles caused the formation of hydroxyl
bonds and structural stability in the system as well as, the energy of ul-
trasonic waves prevents nanoparticles from agglomeration and en-
hances the active level of them.
3.5.2. Effect of process variables on flow behavior index (n)
According to flow behavior index, the fluids are classified into three
different types, including shear thinning for less (n b 1), Newtonian
fluids (n = 1) and shear thickening (n N 1) [1]. The flow behavior
index (n) depends on the ease with which the particles can change
their orientation [45]. The lower values of this index increase the viscos-
ity in the annular space and flatten the speed profile and improve the
cleaning efficiency of the well by drilling mud [18]. Therefore, the dril-
ling muds should have shear thinning behavior to clean the drill path
from the cuttings. The values of the n parameter in all experiments
showed the shear thinning behavior in muds.
According to Fig. 7(a) with the increase in the starch percentage, the
flow behavior index was increased on first and then, it was decreased.
This behavior could be explained by the swelling of the gels. At low con-
centrations, the gel particles will be completely swollen so, the molecu-
lar weight of the granule is higher and the shear thinning behavior is
less, but at higher concentrations the starch particles are compressed
and rigid, therefore its swelling power has reduced [48]. Therefore, the
granules are lighter and easier to change their orientation with stress.
By increasing the percentage of nanoparticles, the effect of bearing in-
creased lubrication, as a result, it has reduced the flow behavior index.
428 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430
Fig. 9. Response surface plots (3D) of flow plastic viscosity (PV) in terms of a) starch (wt%) vs. nanoparticles (wt%); b) starch (wt%) vs. ultrasonic (min); c) nanoparticles (wt%) vs.
ultrasonic (min).
The result was in accordance with the findings by Sadeghalvaad and
Sabbaghi [1].
As shown in Fig. 7(b), at different times of ultrasonic and various
percentages of starch, the fluid behavior index increased and then de-
creased. Initially, by applying ultrasonic waves the interaction between
starch molecules and bentonite in the suspension has increased the
fluid behavior index. However, as shown in Fig. 5(a), over time, the en-
ergy which was generated by ultrasonic waves will break the polymer
so the molecular weight declines [47]. Lower molecular weight poly-
mers changed directions more easily by applying stress thereby, it has
reduced the fluid behavior index.
According to Fig. 7(c), at different ultrasonic times by increasing
the nanoparticles percentage the flow behavior index decreased,
due to their lubrication effect in system. In addition, it was observed
that, in different percentages of nanoparticles, the interaction be-
tween particles increased the fluid behavior index. However, with
the increase of ultrasonic time, the energy of these waves causes
the particles to be dispersed in the system, thus it has decreased
the fluid behavior index.
3.5.3. Effect of process variables on yield point (YP)
The electrochemical forces between the particles will cause the ini-
tial resistance which is known as yield point. Yield point is depended
Table 6
The values of rheological parameters in optimal conditions.
Starch (wt%) Nanoparticles (wt%) Ultrasonic (min)
0.82 0.2 65.01
on the mud solids concentration and their ionic surrounding environ-
ment [3,49].
As shown in Fig. 8(a), at low percentage of nanoparticles by increas-
ing the starch percentage, the hydrogen bands in mud also increased. In
low percentage of starch, by increasing nanoparticles percentage, the
surface loads in suspension increased therefore, it enhanced the YP. In
the high and constant values of each of the variables (starch percentage
and nanoparticles) by increasing the percentage of another variable
from low to medium, interactions between the components reduced
the yield point. Then, from medium to high values, increasing the per-
centage of nanoparticles enhanced surface loads and increasing the
starch percentage enhanced the intermolecular hydrogen bonds there-
fore, it has increased the YP. As shown in the analysis of variance of the
model, the percentage of nanoparticles parameter had greater effect on
the YP.
In Fig. 8(b) it was seen that, by increasing each of the variables
(starch percentage and ultrasonic time) in the constant value of another
variable, the yield point was reduced first and then it was increased.
From low to medium value of variables, the interactions between the
components reduced the yield point. From medium to high value of var-
iables, an enhance in the percentage of starch increased the intermolec-
ular hydrogen bonds and the increase in ultrasonic time also led to the
breakdown of polymers as well as the increase in hydrogen bands, so
the yield point has increased.
K (mPa·s) n (dimensionless) YP (mPa) PV (mPa·s) (YP/PV) (mPa/mPa·s)
45.56 0.48 66.08 3.44 19.43
 L. Salehnezhad et al. / Journal of Molecular Liquids 276 (2019) 417–430
In Fig. 8(c), the interaction between the components in low to mod-
erate values (nanoparticles percentage and ultrasonic time) has re-
duced the yield point. In higher values, the increase in nanoparticles
leads to enhancing the charge on the surface and increasing ultrasonic
time that caused the homogenized nanoparticles in the system and in-
creased its active level, as a result, it was increased the yield point.
3.5.4. Effect of process variables on plastic viscosity (PV)
Plastic viscosity is resistance against flow due to mechanical frictions
which are caused by concentration, size and shape of solids as well as
viscosity of the fluid phase [49]. According to Fig. 9(a) and (c), by in-
creasing the nanoparticles percentage due to the increase in contact sur-
face and surface forces, the strong hydrogen bonds were formed with
other components in the system so has increased the plastic viscosity
(PV). As seen in Fig. 9(a) and (b), by increasing the starch percentage,
the interactions between the components has reduced the PV initially.
However, high starch percentage increased the intermolecular hydro-
gen bonds and polymeric strength thus it was enhanced the PV. By in-
creasing the ultrasonic time, due to increase in the interactions
between the components the viscosity has decreased initially, however
high ultrasonic times has caused breakdown of starch polymers and ho-
mogenization of nanoparticles in suspension (Fig. 9(b) and (c)),
resulting in an increase in the PV.
3.6. Optimization
In traditional mode, the optimization has been carried out by inves-
tigating the effect of one factor on a response while others parameters
were kept constant. It does not check the interactions effects amongst
the variables and it is regarded as the most important disadvantage in
this method, so multivariate statistic techniques have been used as
one of the most important aspects in the RSM. In this method, it opti-
mizes the levels of variables simultaneously, in order to achieve the
best system efficiency. The objective of optimizing is improving the effi-
ciency of system, process, or product for obtaining the maximum profit
or minimum cost [23,31].
The optimization was performed in order to find the proper effi-
ciency of the drilling mud in hole-cleaning. Investigating the role of rhe-
ological parameters on the efficiency of drilling mud showed that, by
reducing the flow behavior index (n) and increasing the consistency
index (K), the hole-cleaning capacity has improved due to the increase
in the effective annular viscosity and flattening of the annular velocity
profile [1,17,18]. On the other hand, suspending and carrying of cuttings
have achieved at higher YP and lower PV using drilling mud.
The ratio of (YP/PV) is often used as a scale of the shear-thinning
characteristic (reduction of viscosity by increasing the shear rate) and
its capacity in order to suspend and remove cuttings from the wellbore.
By increasing this ratio, the behavior of the shear-thinning mud will be
better [17,50]. Table 6 showed the optimized values of variables and re-
sponses. The simultaneous optimizations of responses were performed
using Derringer's desirability function method.
4. Conclusions
In this study, the optimization was conducted in the formulation of
the drilling mud based on RSM using the Derringer's desirability func-
tion method. The purpose was to improve the proper efficiency of the
drilling mud in hole-cleaning. The effects of starch percentage, percent-
age of nanoparticles and ultrasonic time on the rheological parameters
were investigated using the power-law and Bingham-plastic models,
they were analyzed using ANOVA and response surface plots (3D). It
was found that, percentage of ZnO nanoparticles was more influential
on rheological parameters. In addition, the interaction between vari-
ables in the system was significant statistically. Most interactions be-
tween the variables were found in their mean values. Forming the
strong intermolecular hydrogen bonds, breaking the polymer by
429
ultrasonic vibrations over time and increasing the surface loads which
is caused by the nanoparticles presence were most important factors
in interactions between the variables. In all responses, the results
were fitted to the quadratic mathematical model. The optimum values
for starch percentage, percentage of nanoparticles and ultrasonic
time variables were obtained about 0.82 (wt%), 0.2 (wt%) and
65.01 (min), respectively. The optimized mud has a consistency
index (K) about 45.56 (mPa·s), flow behavior index (n) about 0.48,
yield point (YP) about 66.08 (mPa), plastic viscosity (PV) about
3.44 (mPa·s) and shear-thinning characteristic (YP/PV) about
19.43 (mPa/mPa·s). Regarding the parameter of the flow behavior
index, that was less than one in all experiments it showed the
shear thinning behavior of mud. Considering the statistical results
which were obtained in this research, the predicted results were in
good agreement with the experimental results so it was confirmed
the adequacy of the models in data prediction.
Acknowledgements
The financial support of this work by University of Mohaghegh
Ardabili is acknowledged. Also, we would also like to extend our thanks
to the technicians of the research laboratory of chemical engineering
group, faculty of engineering, University of Mohaghegh Ardabili.
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