SPE-192031-MS

A Novel Nanosilica-Based Solution for Enhancing Mechanical and

Rheological Properties of Oil Well Cement

R. Qalandari and A. Aghajanpour, Curtin University Malaysia; S. Khatibi, University of North Dakota

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Asia Pacific Oil & Gas Conference and Exhibition held in Brisbane, Australia, 23–25 October 2018.

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Abstract
The main purposes of employing cement in oil wells are to isolate the zones within formations, secure
casing from axial loading and corrosion and improve wellbore integrity. There are plenty of nanomaterials
represented in the literature which were introduced to cement in order to advance the strength and
rheological properties of cement slurry. The objective of this study is to propose a novel nanomaterial
which can upgrade the mechanical and rheological properties of cement. The smaller the size of Nano-
particles, the higher surface area and hence higher efficiency they possess to advance particular properties
of the support material. Bio-templating has been offered as an approach to reduce the size of utilized
nanoparticles. In this study, Nanosilica particles were synthesized and functionalized using modified sol-gel
method. Bio-templating was then implemented through crosslinking of the procured Nanosilica with soluble
egg protein using glutaraldehyde. In order to investigate the effect of bio-templated Nanosilica on cement
slurry, synthesized Nanosilica was added to cement and rheological and mechanical experiments were
conducted. To validate the performed bio-templating, ATR-FTIR spectrum was acquired which confirmed
successful crosslinking between the functionalized Nanosilica and SEP. Furthermore, experimental tests
were conducted to evaluate the effect of bio-templated Nanosilica on mechanical and rheological properties
of neat cement. The results were then compared to inclusion of commercial Nanosilica in cement.
Through the rheological studies, it was found that the modified Nanosilica has acted as dispersant in
cementitious system by decreasing the plastic viscosity of cement and maintaining the density. It was also
obtained that novel bio-templated Nanosilica has significantly increased uniaxial compressive strength of
cementitious system by 16.59% upon addition of only 0.25 wt.%. It was due to its pozzolanic reaction
in cement and its pore filling effect where the porosity of cementitious system was decreased. The
proposed synthesized Nanosilica demonstrates superior results than commercial Nanosilica which shows
its remarkable efficiency in cement strength reinforcement and rheological properties improvement. The
research study has successfully proposed a novel method to utilize biomaterial waste in the process of
synthesizing Nanosilica particles which is not only environmental friendly but also yields in phenomenal
rheological and mechanical properties of Class G cement.
2 SPE-192031-MS

Nanoparticle Surface area (m2/g) Size (nm) Purity (%) Author

CNT 40-300 40-80 >95 (Xu et al., 2015)

Nano Alumina N/A 27-43 99.5 (Barbhuiya et al., 2014)
nano-iron(III)oxide 50.51 10-20 N/A (Heikal, 2016)

Introduction
Even though Class-G cement is one of the most popular and widely used cement in oil and gas industry, there
are problems associated with durability, wait on time (WOC) and tensile strength of cement. Researcher
seek to propose new methods of improving strength of class G cement. Recently, nanomaterials have caught
enormous amount of attention for property enhancement of cement. Zolotarev et al. (2013) has summarized
application of nanomaterials in cement with reasons including a) Nano-size particles contains high surface
area which escalates the reactivity b) considering C-S-H gel being 10nm in size, nanomaterials are able to
fill existing voids between grain which leads to densified cementitious system c) given that nanoparticles
are well dispersed these plays crystallization role which promotes hydration process of cement that reduces
the cost in industry as WOC would be decreased.
For the improving the performance of cement pastes and increasing the durability and compressive
strength of cement, effects of different nanomaterials has been investigated such as nano-alumina, carbon
nanotubes and nano-iron (III) oxide (Fe2O3). Nano-Alumina has considerable effect on setting time of
cement paste. Addition of nano-Alumina in cement facilitates rapid hydration by speeding up hydration of
tricalcium aluminate (C3A) (Wengui et al., 2017). Moreover, nano-alumina has resulted in denser cement
matrix microstructurally acting as pore filler owing to its nano size. Scanning Electron Microscopy (SEM)
studies confirms denser microstructural properties of nano-alumina cement in 7 days. However, compressive
strength of nano-alumina cement matrix was not appreciable compared to nanosilica cement. Barbhuiya et al
(2014) found that 2 wt% and 4 wt% addition of nano-alumina in cement paste does not increase compressive
strength in 7 days. Conversely, Behfarnia & Salemi (2013) reported that 3 wt% of nanoalumina in cement
has increased compressive strength by 8% in 28 days while similar amount of nanosilica by weight of cement
resulted in 16.67% increase in compressive strength. Therefore, it was concluded that nano-alumina does
not impact compressive strength at early stages and an insignificant increase in compressive strength was
observed in later stages compared to nanosilica cement. Carbon nanotube (CNT) is another nanoparticle
that is used in cement paste for enhancing mechanical and flexural properties. CNT has smaller volume and
size comparted to nanosilica and nano-alumina (Norhasri et al., 2017). Therefore, it shows to be effective in
filling existing voids amongst hydration products due to its smaller size. Studies has shown that addition of
CNT with 1% by weight of cement, resulted in denser microstructure and higher compressive strength (Xu
et al., 2015). However, for enhancing mechanical and electrical properties of cement using CNT, it requires
incorporation of silica fumes in cementitious system to enhance mechanical and electrical properties of
cement matrix.
Amongst all the nano-sized particles, nanosilica has an outstanding effect to cement composites.
Nanosilica enhances strength of cement, refines porestructure, used as acceleration additive to decrease wait
on time (WOC), slumps rate of calcium leaching and increases durability of cement. Moreover, nanosilica
based cementitious material are environmentally friendly and sustainable which is of high value at the
current era. In order to understand the physics behind improvement of mentioned properties (strength,
decrease in WOC, calcium leaching etc.) it is essential to comprehend the evolution of microstructure and
hydration of cementitious system.
For a durable cement, various parameters such as permeability, water absorption, capillary absorption and
water permeability are improved than conventional cementitious system. Nanosilica had a positive impact
on water absorption, capillary absorption and permeability of concrete (Naji Givi et al., 2011; Tadayon
SPE-192031-MS 3

et al., 2010; Mao-hua Zhang & Li, 2011). Permeability of cement was drastically reduced because of
nanosilica addition; it was due to densification of particles existing in the mixture. Furthermore, variation of
pore structure in a cement can influence permeability and ion migration. Composite cement had decreased
porosity with the addition of 4% nanosilica by weight of cement (Bwoc), it was observed that the porosity of
cement was reduced at an appreciable level (Mao-hua Zhang & Li, 2011). Water absorption is another factor
for a durable cement which was greatly reduced by addition of nanosilica (M.H. Zhang et al., 2012). Rapid
chloride penetration test revealed that nanosilica included cement was more resistant to chloride penetration
than the controlled sample. With increasing the amount of nanosilica content (i.e. 6% Bwoc) bulk porosity
were remarkably reduced in overall cementitious system (Said et al., 2012).
Commercial production of nanomaterials such as nanosilica requires high amount of energy that
emits greenhouse gases. With stringent environmental regulations researchers seek greener procedures
to synthesize nanomaterials. Nano-product produced from biomaterial is nontoxic, cost effective and
exhibits high quality. According to Zhang (2015) annual consumption of egg has been reported up to
1012 whereas eggshell is regarded as biomaterial that end up being discarded as poultry waste. Recently
eggshell membrane has been used as absorbent in environmental engineering and as a template for synthesis
of nanoparticles. Although successful synthesis of gold and silver nanoparticles has been reported but
nanosilica particles are yet to be produced using eggshell membrane. Hence, this study investigates the
synthesis of nanosilica using eggshell membrane and its effect in Class G cement.

Experiment
All steps from eggshell membrane extraction to its inclusion in cement is demonstrated in Figure 1. The
entire process for experiments conducted in this study has also been shown in Figure 2. Firstly, eggshell
membrane was detached from raw egg using vinegar. Afterwards, obtained eggshell membrane has been
characterized using various characterization tests including; morphological analysis of eggshell membrane
and their level of water uptake. Nanosilica particles were then synthesized by modified Stöber method
using reagents such as; trimethoxysilane, ammonium hydroxide, ethanol and polyvinyl alcohol. The ratio of
ethanol to ammonium hydroxide has been varied throughout the synthesis process to investigate their effect
on size and shape of synthesized Nanosilica particles. In the next step, glutaraldehyde was used to crosslink
the ammonium with silica nanoparticles. The bond that was created by glutaraldehyde between ammonium
and silica nanoparticles were covalent bonds that could be further used to crosslink soluble egg protein with
silica nanoparticles. Then produced amino-functionalized silica nanoparticles were modified with polyvinyl
alcohol (PLA) through dispersion in PLA solution the using magnetic stirrer and ultra-sonication probe.
Bio-templating was then implemented through crosslinking of the procured Nanosilica with soluble egg
protein using glutaraldehyde. To validate the performed bio-templating, ATR-FTIR spectrum was acquired
which confirmed successful crosslinking between the functionalized Nanosilica and SEP, Figure 3. ATR-
FTIR spectrum in Figure 3 shows that virgin PLA contains carbonyl group recording wavelength of 1750
cm-1. Next it shows single bonds of C-H showing peaks at 1086 and 1181 cm-1. The crosslinking of soluble
egg protein on PLA has been confirmed by the additional peaks of 1656 and 1561 cm-1 on modified PLA.
Each of these peaks corresponds to amide I and amide II bands which are characteristics of soluble egg
protein based on the spectrums obtained from ATR-FTIR. It shows that a new layer of soluble egg protein
has been formed on the top of PLA membrane. The results obtained in this section matches with the results
that obtained by Lu et al. (2008). Lastly, Poly lactic acid membrane was burnt under 900 Degree Celsius to
obtain the pure Nanosilica. In order to investigate the effect of bio-templated Nanosilica on cement slurry,
synthesized Nanosilica was then added to class G cement and rheological and mechanical experiments were
conducted.
4 SPE-192031-MS

Figure 1—Process of eggshell membrane extraction to inclusion in cement

Figure 2—Flow chart illustrating the flow of experimental work conducted in this study.
SPE-192031-MS 5

Figure 3—ATR-FTIR of soluble egg protein, poly lactic acid and crosslinking of soluble egg protein with soluble egg protein.

Before rheological measurement, consistometer was used to condition the cement slurry at atmospheric
pressure based on API standard 10-B. Afterwards, cement slurry was transferred to viscometer cup and
the speeds were varied accordingly and recorded but readings for 600 rpm was not recorded because
measurements at 600 rpm would degrade cement properties and would lead to erroneous results (API, 2013).
In this experiment, samples were prepared for neat52 cement, commercial Nanosilica included cement and
in-house synthesized Nanosilica in cement. The water to cement ratio was maintained to be 0.44 and amount
of Nanosilica was fixed to 0.25 percent by weight of cement. To determine the compressive strength of
cement after curing for 24 hours in 50 degrees Celsius, universal testing machine was used. The reason that
samples were cured for 24 hours, was an attempt to simulating the real field condition as normally cement
would be allowed for 24 hours to set after pumping it downhole.

Result and discussion

Cement rheology tests
An essential part of cements’ characteristic is its rheological behavior through which pumping horse power
and frictional loss will be determined. Bingham model is one of the most common method for evaluating
rheological properties of cement. In this model, plastic viscosity and yield point are determined using a linear
plot of shear stress versus shear rate where the slope signifies the plastic viscosity of the cement while y-
intercept of the graph indicates yield point. These plots are shown in Figure 4 for neat52 cement, commercial
Nanosilica included cement and in-house synthesized Nanosilica in cement. The water to cement ratio was
maintained to be 0.44 and amount of Nanosilica was fixed to 0.25 percent by weight of cement.
6 SPE-192031-MS

Figure 4—Bingham rheological model: shear stress (lb. /100ft2) versus shear rate for a) neat cement, b) after adding
0.25 wt. % commercial Nanosilica to neat cement, c) after adding 0.25 wt. % synthesized Nanosilica to neat cement.

According to Bingham model, plastic viscosity has been determined as 132.1, 136.5, and 94.4 centipoise
for neat cement, cement enriched with 0.25 wt%. commercial Nanosilica, and cement enriched with 0.25
wt%. synthesized Nanosilica, respectively; while yield point of the samples were measured as 34.34, 32.31,
and 32.61 (lb./100ft2), respectively. These values were listed in Table 1 for comparison.
SPE-192031-MS 7

Table 1—Rheological measurements of different cement composites.

Plastic viscosity (cP) Yield point (lb/100 ft2) Density (ppg)

Neat cement 132.1 34.34 15.1

Commercial Nanosilica 136.5 32.31 14.9
in Cement
Synthesized Nanosilica 94.4 32.61 15.2
in cement

As shown, in Table 1, density measurements have been performed on three different cement composites.
Density measurements is an important parameter that needs to be considered while designing cement for
a well. The density of cement signifies the amount of pressure that can be applied from the cement on the
formation. To prevent fluid loss into the formation it is essential design cement with higher density as it
needs to overcome the fracture pressure of formation. Once severe fluid loss takes place in the wellbore
it will lead to kick that might lead to blow out. Hence, it is important to measure the effect of Nanosilica
on density of cement. As it can be noticed in table 1 the density of composites that contains Nanosilica is
remains the same as neat cement and Nanosilica has minimum effect on density. It may be because amount
of Nanosilica that replaces cement is very small that cannot lead to changes in density of the cement.
Plastic viscosity is another important parameter in designing cement because this parameter will
determine the horse power of the pump which will be required in the field to pump the cement downhole.
Generally, plastic viscosity of neat cement would increase by addition of Nanosilica. Nanosilica is known
to be hydrophilic in nature and upon addition of it to cement it tends to absorb water and thickens the
cementitious system overall. Therefore, plastic viscosity of cement would increase. Similar trend has been
observed upon addition of commercial Nanosilica in cement where the reading for plastic viscosity has
jumped from 132.1 to 136.5 centipoise. However, when synthesized Nanosilica was added to the cement
it was observed that plastic viscosity of the cement has been decreased to 94.4 centipoise. This can be due
to the chemicals which were used during synthesis of Nanosilica that has altered the Plastic viscosity (cP)
Yield point (lb./100 ft2) Density (ppg) Neat cement 132.1 34.34 15.1 Commercial Nanosilica in Cement
136.5 32.31 14.9 Synthesized Nanosilica in Cement 94.4 32.61 15.256 charge of Nanosilica and it acts as
dispersant in the cementitious system. Dispersant agent are the agents which tends to release water which
leads to lower plastic viscosity (Hou et al., 2013). Obtaining lower plastic viscosity can be beneficial as
pump with lower horse power would be required in the field. This would further reduce the cost of cement
operation. Yield point of cement is defined as the initial force that is required to move cement. The yield
point of cement has been consistent throughout the three composites. There has been minor variation but
that is considered negligible.

Performance Testing-Cement uniaxial compressive strength

Uniaxial compressive strength is defined as the maximum stress that can be sustained by cement before
it fails. The results obtained from the compressive strength showed that uniaxial compressive strength
of neat cement has been increased upon addition of 0.25 wt. % of Nanosilica. It was also found that
synthesized Nanosilica has increased the compressive strength of neat cement by 16.59%. While the
percentage difference of commercial Nanosilica with neat cement is 29 percent. Strength comparison of
cement composites has been shown in Figure 5.
8 SPE-192031-MS

Figure 5—Comparison of uniaxial compressive strength of different cement composites.

Results shows that uniaxial compressive strength has been increased significantly (16.59%) by addition
of synthesized Nanosilica. However, the results show that compressive strength has been increased 7.1%
more than synthesized Nanosilica. The reason for this difference can be the pore filling effect of Nano-
particles. Nano particles tends to fill the void spaces in the cement system and increases the compressive
strength of it. The size of Nano particles plays key role in pore-filling effect as the smaller size of particles
the effective it is. The size of synthesized nanoparticles is measured to be 240 nm while the commercial
Nanosilica is as small as 15 nm. The same conclusion was made by Kontoleontos et al. (2012), who stated
that the finer additives such as nanomaterials would lead to a denser microstructure as the pores would pore
diameters would decrease resulting in lower porosity and higher compressive strength.

Conclusion
The research project has successfully proposed a novel method for synthesis of Nanosilica particles from
eggshell membrane and it has shown to be effective in increasing the compressive strength of class G
cement by addition of only 0.25 wt. % through the confirmation of studies such as ATR-FTIR, density
measurement and uniaxial compressive strength. Rheological and compressive strength comparison was
made between neat cement, synthesized Nanosilica in cement and commercial Nanosilica in cement.
Through the rheological studies, it was found that synthesized Nanosilica particles has acted as dispersant in
cementitious system by decreasing the plastic viscosity of cement and maintaining the density. Yield point
was reported as 32.61(lb. /100ft2) which was identical to cement composite containing commercialized
Nanosilica particles.59. Besides, synthesized Nanosilica has significantly increased uniaxial compressive
strength of cementitious system. By using universal testing machine, it was obtained that synthesized
Nanosilica has increased compressive strength of cement by 16.59%. It was due to the pozzolanic reaction
of in cement and pore filling effect where the porosity of cementitious system was decreased. With all being
said, it is confident to confirm that Nanosilica particles were synthesized that could effectively increase the
compressive strength of class G cement by 16.59% only with addition of 0.25 wt. %.

Recommendation
For future work, there is a need to further synthesis Nanosilica from proposed method to reduce particles
size and produce controllable shape and size of Nanosilica particle using polyol method as spherical shape
with finer size are highly compatible with class G cement. It can be done by varying parameters such as
ratio of tetraethyl orthosilicate to triethoxysilane, temperature and ratio of ammonia to water. In addition,
to investigate the behavior of Nanosilica added cement in subsurface condition, experimental studies can
be performed to study the compressive strength of Portland in CO2 rich environment.
SPE-192031-MS 9

Acknowledgement
This research was supported by Curtin University Malaysia. We thank our colleagues from Curtin University
Malaysia who provided insight and expertise that greatly assisted the research.

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