Egyptian Journal of Petroleum 27 (2018) 1265–1273

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Full Length Article

Vipulanandan models to predict the electrical resistivity, rheological

properties and compressive stress-strain behavior of oil well cement
modified with silica nanoparticles
Ahmed S. Mohammed
Department of Engineering, The American University of Iraq, Kurdistan Region, Sulaimani, Iraq

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

Article history: In this study, the effect of silica nanoparticles (NS) and temperature on the rheological properties with
Received 2 March 2018 ultimate shear stress and weight loss of the oil well cement (class H) modified with NS were investigated.
Revised 3 June 2018 The NS content was varied up to 1% by the weight of the cement. The total weight loss at 800 °C for the oil
Accepted 5 July 2018
well cement decreased from 6.10% to 1.05%, a 83% reduction when the cement was mixed with 1% of NS.
Available online 23 July 2018
The results also showed that 1% of NS increased the rheological properties of the cement slurry. The NS
modification increased the yield stress (so) and by 5% to 65% based on the NS content and the tempera-
Keywords:
ture of the cement slurry. The addition of 0.5% and 1% NanoSiO2 increased the initial electrical resistivity
Electrical resistivity
Nanosilica (NS)
of the cement by 17% and 35% respectively. The shear thinning behavior of the cement slurry with and
Temperature without NS has been quantified using the Vipulanandan rheological model and compared with the
Rheological properties Herschel-Bulkley model. Based on the Vipulanandan rheological model the maximum shear stress pro-
Shear stress limit duced by the cement slurry modified with 0% and 1% of NS at the temperature of 25 °C were 148 Pa
Modeling and 179 Pa respectively hence an increase of 21% in the ultimate shear stress due to the addition of
NS. The addition of 1% of NS increased the compressive strength of the cement by 14% and 42% after
1 day and 28 days of curing respectively. Effects of NS content and the temperature on the model param-
eters have been quantified using a nonlinear model (NLM). The NLM quantified the effect of NS treatment
on all the model parameters.
Ó 2018 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction critical issues in good construction to ensure wellbore integrity

In the petroleum industry, cement has been used in oil well
operations. Cement is typically utilized to fill the annular space
between the casing and rock formation by displacing the drilling
fluid. Also cement will support the casing and protect it against
corrosion and impact loading, restrict the movement of fluids
between formations, and isolate productive and nonproductive
zones. Oil well cement is used under different conditions of expo-
sures compared to the cement used in the conventional construc-
tion industry. The strength of oil well cement usually depends on
factors such as time and conditions of curing, environmental con-
ditions, slurry design and use of additives and any additional treat-
ments to the cement. One of the important additive that has been
used in cement is silica, which has been used in a certain amount
to mitigate the strength degradation [1–3]. Preventing the loss of
fluids to the formations and proper well cementing have become
Peer review under responsibility of Egyptian Petroleum Research Institute.
E-mail address: ahmed.salih@auis.edu.krd
because of varying downhole conditions [4–8]. With the advance-
ment of nanotechnology, polymer science, and engineering, several
of these materials can be a key to solving some of the problems
encountered in oil and gas well cementing [7,9–15]. One of which
is the use of nanotechnology and hence, nanomaterials which are
beneficial for their large surface area, high aspect ratio, small size,
low density and interesting physical and chemical properties. Sev-
eral reasons nanoparticles have had such a strong influence on the
mechanical properties of cementitious materials become the
nanoparticles have a high surface area, providing high chemical
reactivity [8,16,17]. Based on the results of compressive strength
tests, it is expected that NS behaves not only as a filler to improve
cement microstructure, but also as a promoter of pozzolanic reac-
tion. In addition, it can be considered as an agent for improving the
microstructure of the cement paste. Therefore, it is effective to add
NS particles to cement mixtures for introducing higher perfor-
mance to concrete. In addition, adding NS decreased the amount
of lubricating water available in the mixture [1]. Because of the
nanoparticles extremely small size, nanoparticles are preferred to

https://doi.org/10.1016/j.ejpe.2018.07.001
1110-0621/Ó 2018 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1266 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273

be used in oil and gas well design as their abrasive forces are neg-
ligible with less kinetic energy impact. In addition to all advantage
of using nanoparticles in mud design, it is safer than conventional
mud from the point of environmental view. In consideration of
nanoparticles with many novel properties and a significant
improvement on some properties of cement mixed with nanopar-
ticles [18,19].
The application of nanosilica in cement is to improve the char-
acteristics of the plastic and hardened material. Micro and nano-
scaled silica particles have a filler effect by filling up the voids
between the cement grains. With the right composition, the higher
packing density results in a lower water demand of the mixture
and it also contributes to strength enhancement due to the reduced
capillary porosity. Beside this physical effect as obtained by addi-
tion, nanosilica and since the NS has a pozzolanic reactivity it leads
to the increase in compressive, tensile and flexural strengths [20].
Electrical resistivity measurement has been applied by many
researchers on concrete and cement applications [21–24]. Electri-
cal response characteristics measurement has appropriate sensitiv-
ity in monitoring the characteristics of cementitious materials
[21,25]. The electrical resistivity of cement is affected by a number
of factors such as pore structure (continuity and tortuosity), pore
solution composition, cementitious content, water-to-cement
ratio, moisture content, and temperature [26].
The objectives of this study are:

1. Investigate the effect of the nanosilica (NS) on the rheological

properties of the oil well cement slurry at different temperature
conditions.
2. Quantify the shear stress-shear strain rate relationship of
cement slurry modified with varying amounts of NS at different
temperature using the Vipulanandan rheological model and
compare it to the Herschel-Bulkley model.
3. Investigate the relationship between the shear stress limit of
the cement slurry and the NS and temperature.
4. Investigate and quantify the changes in the electrical resistivity
during the curing time of the NanoSiO2 modified cement.
5. Investigate the effect of the NS on the compressive strength of
the cement at different curing time.
2. Materials and methods
2.1. Oil well cement
Commercially available oil well cement (Class H cement) was
modified with NS used in this study. The chemical composition
of the cement has been identified using X-ray diffraction as shown
in Fig. 1(a).
Fig. 1. XRD pattern of: (a) Oil well cement (b) Oil well cement + 1% NS.
NanoSiO2 was added to the cement in the mixer with the mix-
ing intervals of 20 s at 4000 rpm [7]. Cement, water, and NanoSiO2
were mixed at the speed of 4000 rpm for 3 min and 35 s at the
speed of 1200 rpm. The two wires were placed in the mold and
the vertical distances between any two wires were the same.
Embedment depth of the conductive wire was 1 in. For setting time
monitoring and compressive stress tests, cylinders with the diam-
eter of 50 mm (2 in.) and a height of 100 mm (4 in.) were prepared.
For quick results monitoring, a two-probe method was selected
[7,8]. During the initial stages of setting, API resistivity meters
were used to determine the curing cement resistivity and using
Eq. (1). The calibration parameter K was obtained with time [7].
In order to have consistent result, at least three specimens were
prepared for each type of mix.

2.2. Silica nanoparticles (NS) 2.4. XRD analysis

Silica nanoparticles (NS) with the grain size of 30 nm (DLS) and
bulk density varied from 0.926 to 1.158 g/mL at 25 °C and surface
area 175–225 m2/g (BET), 99.8% trace metals basis were purchased
from Aldrich, USA and used for this study.
2.3. Sample mixture
In this study, oil well cement (Class H) with the water-to-
cement ratio of 0.38 was used. The samples were prepared accord-
ing to the API standards. Three series of oil well cement slurries
were prepared with varying amounts of NS up to 1% (by the weight
of the cement). At least three samples were tested under each con-
dition. Three series of cement slurries were prepared with
NanoSiO2 up to 1% (by the weight of the cement) and tested up
to 28 days of curing.
An X-ray diffraction (XRD) analyses were performed in order to
determine the chemical composition of cement at 25 °C. The pow-
der (
2 g) was placed in an acrylic sample holder (3 mm) depth.
The samples were analyzed by using parallel beam optics with
CuKa radiation at 40 kV and 30 mA. The samples were scanned
for reflections (2h) from 0° to 90° in steps of 0.02° and a 2 s count
time per step [27,28].
2.5. Thermogravimetric analysis (TGA)
Thermogravimetric analysis curves, mass loss (TGA) and its
derivative (DTG) were quantified using a Setaram TGA 500 appara-
tus at a heating rate of 10 °C/min for a mass sample of about 20 mg.
The sample was loaded in a platinum pan (¾ full). This was fol-
lowed by the introduction of N2 gas into the TGA compartment
 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273
for 5 min to purge the likely oxygen in the environment of the sys-
tem. After the purging, the sample was heated in the N2 atmo-
sphere from room temperature to the maximum of 800 °C. The
weight loss percentage and temperature relationships were
obtained for the samples. In this study, the (TGA) and (DTG) curves
were obtained for cement, NS and cement modified with 1% of NS
after 7 days of curing.
2.6. Density
The density of cement slurry with and without NS was mea-
sured immediately after mixing using the standard mud balance
cup.
2.7. Rheological properties
The rheology tests were performed by utilizing a rotational vis-
cometer at the different temperature up to 85 °C at rpms ranging
from 0.3 to 600 rpm and related shear stresses were recorded.
The viscometer was calibrated using several standard solutions.
The rheological properties of the cement slurry modified with
varying amount of NS up to 1% by the weight of cement were
measured.
2.8. Electrical resistivity
(i) Digital resistivity meter
An API resistivity meter measured the resistivity of fluids,
slurries, and semi-solids with resistivities in the range of
0.01–400 O-m. The electrical resistivity device was calibrated
using standard solutions of sodium chloride (NaCl).
The electrical resistivity of the slurries was measured using an
API standard resistivity meter. To minimize the contact resistances,
the resistance was measured at 300 kHz using the two-wire
method. Each specimen was calibrated to obtain the electrical
resistivity (q) from the measured electrical resistance (R) based
on the Eq. (1) [6,7].


L
R¼q ¼ qK
A
where L is the distance between the wires, A is the cross-sectional
area through which the current is flowing, and L/A is called the
nominal geometry factor. Hence, L/A in Eq. (1) was replaced by an
experimentally determined calibration factor (K), by measuring
the bulk resistance (R) and the resistivity (q) of the material at
the same time [29].
2.9. Compressive strength test (ASTM C 39)
The cylindrical specimen with the diameter of 2 in. and a height of
4 in. (50 mm Dia. * 100 mm Height) were capped and tested at a pre-
determined controlled displacement rate. Compression tests were
performed on cement samples after 1 day and 28 days of curing using
a hydraulic compression testing machine. Commercially available 10
mm resistance strain gages were used for strain measurement.
3. Rheological model
The rheological models used for predicting the shear thinning
behavior of cement slurry are as follows:
(i) Herschel-Bulkley model (1926)
The Herschel-Bulkley model (Eq. (2)) defines a fluid with three
parameters and can be represented mathematically as follows:
1267
s ¼ so1 þ k  ðc_ Þn ð2Þ
where s, s01, c_ k and n represent the shear stress, yield stress, shear
strain rate, correction parameter and flow behavior index respec-
tively. For s < s01 the material remains rigid. The model assumes
that below the yield stress (s01), the slurry behaves as a rigid solid,
similar to the Bingham plastic model. For s > s0 the material flows
as a Power law fluid. The exponent n describes the shear thinning
and shear thickening behavior. Slurries are considered as shear
thinning when n < 1 and shear thickening when n > 1. A fluid
becomes shear thinning when the apparent viscosity decreases with
the increase in shear strain rate.
From the Eq. (2)
when c_ ! 1 ) smax: ¼ 1
Hence Herschel-Bulkley model doesn’t satisfy the upper limit con-
dition for the shear stress limit
(ii) Vipulanandan rheological model (2014)
Based on the inspection of the test data the Vipulanandan rhe-
ological relationship (Eq. (5)) was used to predict the cement
behavior [26–28].
Hence the conditions are as follows:
s ¼ so when c_ ¼ 0 ð3Þ
c_ ! 1 ) s ¼ smax ð4Þ
c_
s  so2 ¼ ð5Þ
CðNS; TÞ þ DðNS; TÞ  c_
where: s: shear stress (Pa); so2: yield stress (Pa); C (NS, T) (Pas)1
and D (NS, T) (Pa)1: are model parameters and c_ : shear strain rate
(s1).
1
also; when : c_ ! 1 ) smax : ¼ so2 þ ð6Þ
D
Hence this model has a limit on the maximum shear stress (smax)
the cement slurry will produce or tolerate at the relatively high rate
ð1Þ of shear strains.
(iii) Vipulanandan p-q curing model
Based on experimental results, model proposed by [29–35] was
modified and used to predict the electrical resistivity of cement dur-
ing hydration up to 28 days of curing. Also the Eq. (7) can be used to
predict the electrical conductivity of the cement modified with NS
as shown in Fig. 6. The curing model is defined as follows [7]:
0   1

 tþto
1 1 B B t minþto C
¼ C ð7Þ
q qmin @    q1p1þp1 A
q1 þ ð1  p1  q1 Þ  tminþt þ p1  tminþt
tþt o tþt o
o o
where:q electrical resistivity (O-m); qmin: minimum electrical
resistivity (O-m); tmin: time corresponding minimum electrical
resistivity (qmin) as shown in Fig. 4; p1 ¼ ðAt þ BÞ, to; A, B, and q1
are model parameters; and t: time (minutes). As summarized in
Table 4, model parameters to and B were sensitive to the NanoSiO2
content and curing time. But parameter A was not influenced by the
NanoSiO2 content.
Addition of 1% of NanoSiO2 to the cement increased the mini-
mum resistivity (qmin) and the minimum time (tmin) by 31% and
23% respectively as shown in Fig. 5. Also, additions of 0.5% and
1% of NanoSiO2 to the cement increased the electrical resistivity
(q24) of the cement by 7% and 22% respectively as shown in Table 1.
The parameters tmin and qmin can be used as quality control indices
and were related to the NanoSiO2 content as follows:
1268 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273
Fig. 2. Thermogravimetric analysis (TGA) result on oil well cement and NS and a
mixture (a) TGA and (b) DTG.
Fig. 3. TGA results for oil well cement and NanoSiO2 (NS).
t min ¼ 23  ðNanoSiO2 ð%ÞÞ þ 99 R2 ¼ 0:99
qmin ¼ 0:85 þ 0:26  ðNanoSiO2 ð%ÞÞ R2 ¼ 0:98
(iv) Nonlinear model parameters (NLM)
The model parameters of cement slurry modified with NS was
influenced by the temperature condition (T (°C)) and nanosilica
content (NS (%)). It is being proposed to relate the model parame-
ters to the independent variables (temperature and NS content)
using a nonlinear power relationship as proposed by [30]. The
effects temperature (T (°C)) and NS content (%) of the cement slurry
were separated as follows:
Model parameter ðso1 ; k; n; so2 ; A and BÞ
¼ a  ðTÞb þ c  ðTÞd  ðNSÞe
Fig. 4. Typical bulk resistivity development with curing time.
ð8Þ Fig. 5. Bulk electrical resistivity development of cement with various amount of
NanoSiO2: (a) 1 day and (b) 28 days.
ð9Þ
where a, b, c, d and e are NLM parameters (Table 5).
3.1. Compressive strength test (ASTM C 39)
The cylindrical specimen with the diameter of 2 in. and a height
of 4 in. (50 mm Dia. * 100 mm height) was capped (sulfur capping)
and tested at a predetermined controlled displacement rate. Com-
pression tests were performed on cement samples after 1 day and
28 days of curing using a hydraulic compression testing machine.
Also 10 mm in length stain gages with initial resistance of 120 O
ð10Þ were used to measure the axial strain.
 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273
Fig. 6. Electrical conductivity development of cement with various amount of
NanoSiO2: (a) 1 day and (b) 28 days.
4. Results and discussion
4.1. XRD
In this study commercially available Class H oil well cement
was used. A typical XRD pattern of Class H cement is shown in
Fig. 1(a). The major constituents in the cement included tricalcium
silicate (Ca3SiO5), dicalcium silicate (Ca2SiO4), calcium aluminofer-
rite (Ca2FeAlO5), calcium sulfate (CaSO4), quartz (SiO2) and magne-
sium sulfate (MgSO4). Addition of 1% NS modified the cement
composition with the formation of magnesium silicate sulfate
(Mg5 (SiO4)2SO4) (2h peaks at 51.58° and 56.50°) and quartz
(SiO2) (2h peaks at 23.55°, 36.90° and 62.50°) as shown in Fig. 1
(b). Hence some of the changes observed in the cement modified
with NS behavior could have been due to the changes in the min-
eralogy of cement.
4.2. TGA analysis
The thermogravimetric analysis (TGA) and differential
thermogravimetric (DTG) results were obtained for the oil well
cement, silica nanoparticle (NS) and cement modified with 1% NS
after 7 days of curing. Four characteristic endothermic effects were
Table 1
Bulk resistivity parameters for cement with NanoSiO2 content.
NanoSiO2 (%) Initial resistivity, qo (X-m)
0 1.03 ± 0.02
0.5 1.20 ± 0.03
1 1.39 ± 0.03
1269
Table 2
Effect of NS on the density of cement samples.
NS (%) Density (ppg)
0% 16.48
0.5% 16.50
1% 16.54
observed as shown in Fig. 2. The initial effect, in the temperature
range from 25 °C to 120 °C was due to evaporation of surface
adsorbed water because samples adsorbed water from air during
its curing at room temperature. The second endothermic effect
was in temperature range from 120 °C to 400 °C, is attributed to
the dehydration of C-S-H and calcium aluminoferrite. Below
120 °C, free water (interlamellar water not linked to the exchange-
able cation and water between cement particles); between 120 °C
and 400 °C, water linked to the exchangeable cation of the smectite
interlamellar space. The heating rate used in these tests was
10 °C/min which does not allow equilibrium of weight loss at
105 °C (standard temperature for determining free water), as
shown in Fig. 2(b). Total weight loss for cement between 25 °C
and 120 °C was 0.56% and for NS was 1.33% and it decreased to
0.07% when the cement modified with 1% NS as shown in Fig. 3.
The NS treatment strongly modified the free water dehydration
(25–120 °C). When the temperature changed from 120 °C to 400
°C, the weight loss of the cement increased to 0.66% but the weight
of the NS increased by 126% as shown in Fig. 3. The peak temper-
ature between 400 °C and 600 °C, indicates the decomposition of
Ca(OH)2 formed during hydration. For temperature range between
400 °C and 600 °C, the total weight loss for cement was 1.44% and
for NS was 0.85%. When the temperature changed from 600 °C to
800 °C, the weight loss for cement increased to 3.44% and 5.13%
for the NS. The weight loss of the oil well cement modified with
1% NS after 7 days of curing was 1.05% a 83% reduction in the tem-
peratures range of 600–800 °C as shown in Fig. 3. Finally, an
endothermic at 800 °C indicates the decarbonation of calcium
carbonate in the hydrated compound. It also indicatives of NS
interacted with the cement particles.
4.3. Density
The average density of the cement slurry was 1.948 ppg. Adding
0.5% and 1% NS slightly increased the density of the cement by 0.1%
and 0.4%, respectively as summarized in Table 2.
5. Rheological properties
Rheology of the oil well cement slurries formulated at different
temperature (T) up to 85 °C, and varying the amount of NS up to 1%
was studied. Yield stress (so) and shear stress limit (smax) were
measured according to API RP 10-B (see Table 3).
6. Constitutive rheological models
Shear stress-shear strain rate relationships were predicted
using the Vipulanandan rheological model and compared with
Herschel-Bulkley model as shown in Fig. 7.
qmin tmin q24h
(X-m) (min) (X-m)
0.85 ± 0.02 99 ± 5 3.90 ± 0.04
0.95 ± 0.05 110 ± 7 4.16 ± 0.01
1.11 ± 0.03 122 ± 4 4.76 ± 0.03
1270 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273

Table 3
Model parameters for electrical resistivity of cement with NanoSiO2 content.

NanoSiO2 (%) Curing time qmin tmin q1 to A B RMSE R2

(day) (Om) (min) (min) (1/Om)
0 1 0.85 ± 0.04 99 ± 5 0.69 ± 0.02 60 ± 5 0.0001 2.38 ± 0.5 0.034 0.99
1 1.11 ± 0.05 122 ± 4 0.51 ± 0.04 65 ± 4 0.0001 1.45 ± 0.6 0.020 0.99
0 28 0.85 ± 0.04 99 ± 5 3.62 ± 0.04 116 ± 6 0.0001 13.3 ± 0.3 0.050 0.99
1 1.11 ± 0.05 122 ± 4 25.3 ± 0.02 125 ± 6 0.0001 18.3 ± 0.6 0.166 0.90

summarized in Table 4. The root mean square of error (RMSE)

varied from 6.12 Pa to 6.61 Pa as summarized in Table 4. The yield
stresses (so1) for the cement slurry without NS at the temperature
of 25 °C and 85 °C were 20.8 Pa and 39.8 Pa respectively, a 91%
increase. The model parameter k for the cement slurry without
NS at the temperature of 25 °C and 85 °C were 10.94 Pasn and
48.33 Pasn increased with increasing temperature. The model
parameter n for the cement slurry decreased by 24% with increas-
ing the temperature from 25 °C to 85 °C as summarized in Table 4.

(b) NS = 1%

The relationship between shear stress with shear strain rate for
the cement slurry modified with 1% of NS (by dry weight of the
cement) at different temperatures varied from 25 °C to 85 °C was
modeled using the Herschel-Bulkley model (Eq. (2)). The coeffi-
cient of determination (R2) was 0.99 as summarized in Table 4.
The root mean square of error (RMSE) varied from 6.36 Pa to
7.55 Pa as summarized in Table 4. The yield stresses (so1) for the
cement slurry modified with 1% of NS at the temperature of
25 °C and 85 °C were 31.3 Pa and 50 Pa respectively, a 60%
increase. The model parameter k for cement slurry modified with
1% NS at the temperature of 25 °C and 85 °C were 49.76 Pasn
and 63.19 Pasn respectively, a 27% reduction. The model parame-
ter n for the modified cement slurry increased by 12% with increas-
ing the temperature from 25 °C to 85 °C as summarized in Table 4.

6.1.1. Parameter so1

Based on the nonlinear model parameter a (Eq. (10)), the tem-
perature had the highest effect on increasing the yield stress com-
pared to parameters n and k. NLM parameter c indicated that the
addition of NS had the second highest effect on increasing the yield
stress compared to parameter k and n as summarized in Table 5.

6.1.2. Parameter k
Based on the nonlinear model parameter a (Eq. (10)), the tem-
perature had the second highest effect on parameter k compared
to yield stress and parameter n. NLM parameter c indicated that
addition of NS had the highest effect on increasing the parameter
k compared to the yield stress and parameter n as summarized
in Table 5.

Fig. 7. Predicted and measured shear stress - shear strain rate relationship for
cement slurries with different temperature (a) NS = 0%; (b) NS = 0.5%; and
(c) NS = 1%
6.1. Herschel-Bulkley model
(a) NS = 0%
The shear thinning behavior of oil well cement slurry without
NS at different temperatures varied from 25 °C to 85 °C was mod-
eled using the Herschel-Bulkley model (Eq. (2)) up to a shear strain
rate of 1021.4 s1. The coefficient of determination (R2) was 0.99 as
6.1.3. Parameter n
Based on the nonlinear model parameter a (Eq. (10)), the tem-
perature had the lowest effect on parameter n compared to yield
stress and parameter k. Based on the NLM parameter c, the addi-
tion of NS had the second lowest effect on increasing the parame-
ter n as summarized in Table 5.
6.2. Vipulanandan rheological model
(a) NS = 0%
The shear thinning behavior for the oil well cement slurry with-
out NS at different temperatures varied from 25 °C to 85 °C was
modeled using the Vipulanandan rheological model (Eq. (5)). The
 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273 1271

Table 4
Herschel-Bulkley and Vipulanandan Rheological model parameters for NS modified oil well cement.

Herschel–Bulkley Model (1926) (Eq. (2)) Vipulanandan Rheological Model (2014) (Eq. (5))
NS T so1 k n RMSE R 2
so2 C D RMSE R2 smax.
(%) (°C) (Pa) (Pasn) (Pa) (Pa) (Pas1) (Pa)1 (Pa) (Pa)
0 25 20.8 10.94 0.366 6.61 0.99 22.6 1.62 0.007 5.59 0.98 148
85 39.8 48.33 0.280 6.12 0.99 42.5 0.60 0.003 6.00 0.99 349
0.5 25 26.3 21.95 0.297 4.88 0.99 29.1 1.22 0.006 4.80 0.99 159
85 45.4 60.20 0.292 7.68 0.99 43.7 0.38 0.003 12.91 0.98 389
1 25 31.3 49.76 0.238 6.36 0.99 36.5 0.58 0.004 8.02 0.98 179
85 50.0 63.19 0.266 7.55 0.99 45.6 0.36 0.003 11.02 0.99 400

Table 5
Nonlinear model parameters for nanosilica (NS) modified oil well cement.

Model parameters a b c d e No. of data R2 RMSE

Eq. (2) so1 (Pa) 5.0 0.11 4.1 0.44 0.02 6 0.90 2.75
k (Pasn) 7.0 0.01 26.0 0.01 0.70 6 0.82 5.20
n 0.03 0.65 0.10 0.018 0.18 6 0.88 0.06
Eq. (5) so2 (Pa) 5.0 0.40 0.001 0.003 0.78 6 0.92 1.78
C (Pas1) 0.01 0.003 0.50 0.41 0.01 6 0.80 1.3
D (Pa)1 0.005 0.05 0.003 0.003 0.03 6 0.80 0.006

coefficient of determination (R2) was ranged between 0.98 and

0.99 as summarized in Table 4. The root mean square of error
(RMSE) varied from 5.59 Pa to 6 Pa as summarized in Table 4.
The yield stresses (so2) for the cement slurry at the temperature
of 25 °C and 85 °C were 22.6 Pa and 42.5 Pa respectively, a 88%
increase. The model parameter C for cement slurry at the temper-
ature of 25 °C and 85 °C were 1.62 Pas1 and 0.60 Pas1 respec-
tively, a 63% reduction. The model parameter D for cement slurry
at the temperature of 25 °C and 85 °C were 0.007 P a1 and
0.003 P a1 respectively, a 57% reduction as summarized in Table 4.

(b) NS = 1%

Using the Vipulanandan rheological model (Eq. (5)), the rela-

tionship between shear stress with shear strain rate for the cement
slurry modified with 1% of NS (by dry weight of the cement) at dif-
ferent temperatures varied from 25 °C to 85 °C was modeled. The
coefficients of determination (R2) was varied between 0.98 and
0.99. The root mean square of error (RMSE) varied from 8.02 Pa
to 11.02 Pa as summarized in Table 4. The yield stresses (so2) for
the cement slurry modified with 1% of NS at the temperature of
25 °C and 85 °C were 36.5 Pa and 45.6 Pa respectively, a 25%
increase as shown in Fig. 8(a). The model parameter C for cement
slurry modified with 1% NS at the temperature of 25 °C and 85 °C
were 0.58 Pas1 and 0.36 Pas1 respectively, a 34% decrease. The
model parameter D for cement slurry modified with 1% NS at the
temperature of 25 °C and 85 °C were 0.004 P a1 and 0.003 P a1
respectively, a 25% reduction.

6.2.1. Parameter so2

Based on the nonlinear model parameter a (Eq. (10)), the tem- Fig. 8. Variation of shear stresses with different NS content predicted the
perature had the highest effect on increasing the yield stress com- Vipulanandan rheological model (a) Yield stress and (b) Shear stress limit.

pared to parameters C and D. NLM parameter c indicated that

addition of NS had the lowest effect on increasing the yield stress
compared to parameters C and D as summarized in Table 5.
6.2.2. Parameter C
Based on the nonlinear model parameter a (Eq. (10)), the tem-
perature had the second highest effect on this parameter compared
to parameters so2 and B. NLM parameter c indicated that addition
of NS had the highest effect for increasing the parameter C com-
pared to the yield stress and parameter D as summarized in
Table 5.
6.2.3. Parameter D
Based on the nonlinear model parameter a (Eq. (10)), the tem-
perature had second least effect on this parameter. NLM parameter
c indicated that addition of NS had the lowest effect on reducing
the parameter D compared to the yield stress as summarized in
Table 5.
6.2.4. Shear stress limit (smax)
Based on Eq. (6) the Vipulanandan rheological model has a limit
on the maximum shear stress the slurry will produce at relatively
1272 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273

Table 6
Compressive stress-strain model parameters for NanoSiO2 modified cement.

NS (%) Curing time rf ef Ei po qo RMSE R2

(day) (MPa) (%) (GPa) (MPa)
0 1 10.9 ± 2 0.30 ± 0.02 10 0.034 ± 0.03 0.36 ± 0.02 0.128 0.99
28 19.3 ± 1 0.22 ± 0.02 13 0.160 ± 0.01 0.70 ± 0.03 0.110 0.99
0.5 1 11.6 ± 3 0.25 ± 0.02 11 0.061 ± 0.03 0.43 ± 0.02 0.095 0.99
28 22.3 ± 2 0.20 ± 0.02 19 0.092 ± 0.02 0.60 ± 0.02 0.085 0.99
1 1 12.4 ± 2 0.22 ± 0.02 11 0.094 ± 0.02 0.53 ± 0.03 0.244 0.99
28 27.5 ± 3 0.19 ± 0.02 25 0.100 ± 0.01 0.57 ± 0.01 0.150 0.99

high rate of shear strains. The smax for cement slurry without and
with 0.5% and 1% of NS at room temperature were 148 Pa, 159 Pa
and 179 Pa respectively as shown in Fig. 5. Increasing the temper-
ature of cement slurry without and with 0.5% and 1% of NS from 25
°C to 85 °C increased the maximum shear stress of cement slurry to
349 Pa, 389 Pa and 400 Pa respectively as shown in Fig. 8(b).
where: r is compressive stress; rf, ef are compressive strength and
corresponding strain (Table 6) and po, qo are model parameters
(Table 6). Model parameters po and qo increased with curing time
based on the NS content.
7.1. Curing time

7. Compressive stress-strain modelling (i) 1 day: The compressive strengths (rf) of the cements with
0%, 0.5% and 1% of NS after 1 day of curing were 10.9 MPa, 11.6
Based on the experimental results, Vipulanandan p-q stress- MPa, and 12.4 MPa, representing a 6% and 14% increase due to
strain model [33,34] was used to predict the compressive stress- the addition of 0.5% and 1% of NS, respectively, as shown in
strain relationship for cement with and without NS and the rela- Fig. 9(a). Additional of 1% NS increased the initial modulus after
tionship is as follows: 1 day of curing from 10,100 MPa to 10,600 MPa, a 5% increase as
summarized in Table 6. The axial strain of the samples at failure
e
ef  rf varied between 0.22% and 0.3% as summarized in Table 6. The
r¼  ðpopþqo Þ ð11Þ
model parameters qo and po increased with NS content. The coeffi-
qo þ ð1  po  qo Þ ee þ p e o

f ef cients of determination (R2) were 0.99 as summarized in Table 6.

(ii) 28 days: The average compressive strength of cement modified
with 0%, 0.5% and 1% of NS after 28 days of curing were 19.3 MPa,
22.3 MPa, and 27.5 MPa, respectively, representing an 16% and a
42% increase due to the addition of 0.5% and 1% of NS, respectively,
as shown in Fig. 9(b). Additional of 1% NS increased the initial mod-
ulus after 28 days of curing from 12,500 MPa to 25,400 MPa, a
103% increase as summarized in Table 6. The axial strain of the
samples at failure varied between 0.19% and 0.22% as summarized
in Table 6. The model parameters qo and po decreased with NS con-
tent. The coefficients of determination (R2) were 0.99 as summa-
rized in Table 6.

8. Conclusions

Based on the experimental and analytical study on the cement

modified with silica nanoparticles (NS) up to 1%, the following con-
clusions are advanced:

1. Based on the XRD analyses, with the addition of 1% NS, changes

in cement mineralogy was observed and the new constituents
were magnesium silicate sulfate (Mg5 (SiO4)2SO4) (2h peaks at
51.58° and 56.50°) and quartz (SiO2) (2h peaks at 23.55°,
36.90° and 62.50°). Hence some of the changes observed in
the modified cement with NS behavior could have been due
to the changes in the cement mineralogy.
2. TGA analyses also showed a great reduction in the total weight
loss of the cement at 800 °C when it’s modified with 1% NS.
3. The Vipulanandan rheological model was effective in predicting
the shear stress-shear strain rate shear thinning behavior and
was better than Herschel-Bulkley model based on the coeffi-
cient of determination and root mean square of error (RMSE).
4. Resistivity was sensitive to the amount of NanoSiO2 used to
modify the cement. The amount of NanoSiO2 can be detected
based on the change in the initial resistivity. An addition of
Fig. 9. Stress- strain relationship of modified cement with curing time (a) 1 day and 1% NanoSiO2 increased the initial electrical resistivity (qo) of
(b) 28 days. cement by 35% and also increased the time to reach minimum
 A.S. Mohammed / Egyptian Journal of Petroleum 27 (2018) 1265–1273
resistivity by 31 min. Initial electrical resistivity can be used as
a good indicator for quality control. Vipulanandan p-q curing
model predicted the behavior very well.
5. The addition of NS up to 1% modified the yield stress, shear
thinning behavior, and ultimate shear stress limit of the cement
slurry. The amounts of changes in the properties were influ-
enced by the temperature and NS content in the cement slurry
and have been quantified using a nonlinear model.
6. The yield stress of cement slurry increased with increasing of
temperature and NS contents. Increasing the NS content in
the cement slurry from 0% to 1% increased the yield stress from
22.6 Pa to 36.5 Pa at room temperature using the Vipulanandan
rheological model.
7. Based on the Vipulanandan rheological model the maximum
shear stress produced by the 1% NS modified cement slurry at
room temperature increased from 148 Pa to 179 Pa, a 21%
increase.
8. The addition of 1% NS increased the compressive strength of the
oil well cement by 14% and 43% after 1 day and 28 days of cur-
ing respectively. Also the modulus of elasticity of the cement
increased with the additional of 1% NS. Vipulanandan p-q
stress-strain model predicted the behavior very well.
9. Using nonlinear relationship the model parameters were
related to the composition of the cement. A nonlinear model
was effective in identifying the contribution of each constituent
(temperature and NS content).
Acknowledgements
The author would like to thanks, Dr. Cumaraswamy Vipulanan-
dan (http://www.cive.uh.edu/faculty/vipulanandan) Director of
the Center for Innovative Grouting Materials and Technology (CIG-
MAT) at the University of Houston, Houston, Texas for the help
during the study work.
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