Journal of Petroleum Science and Engineering 184 (2020) 106292

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Journal of Petroleum Science and Engineering

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Nanocellulose for oil and gas field drilling and cementing applications T
a,∗ a
Jothibasu Ramasamy , Md Amanullah
a
Drilling technology Division, EXPEC Advanced Research Center, Saudi Aramco, Saudi Arabia

A B S T R A C T

Global energy demand has been in an increasing trend over the last decades and it will continue to be in the same trend in the years to come. In order to match the
demand, the oil and gas drilling industry has been drilling deeper, long horizontal, extended reach multi-lateral wells to tap deeper reservoirs and to maximize
reservoir contact. Existing hydrocarbon reservoirs are getting depleted. Exploration of new hydrocarbon reserves are mostly found in challenging environment and
drilling operation in these fields are associated with high pressure and high temperature regime. The conventional drilling fluid typically consists of biopolymers such
as cellulose, starch and xanthan gum. These biopolymers are used as viscosifiers, fluid-loss control additives and suspending agents. When subjected under high
pressure and high temperature environment drilling, these additives will degrade and deteriorate. Nanomaterials such as nanocellulose exhibit excellent thermal and
physiochemical properties due to their well-ordered crystalline structure. These type of property enhancements are necessary to design a high performance water
based drilling fluid systems. An acid-digestion process of regular cellulose will remove the amorphous form and retain the nano-sized crystalline part of cellulose.
Further processing and chemical modification of crystalline nanocellulose can lead to a range of nano-based products such as polyanionic cellulose, hydroxyethyl
cellulose, carboxymethyl cellulose, etc. for various oil and gas field drilling applications. In this paper, we tried to capture the recent research and development efforts
around nanocellulose for oil and gas industry drilling applications. This review also includes techno-economic analysis of nanocellulose and the viability for oil and
gas industry applications.

1. Introduction
The global energy consumption has been in the rising trend over
two decades. Exploration activities of hydrocarbon resources in the low
risk geological environments have become a rare phenomenon. New oil
and gas fields discovered are mostly associated with high pressure and
high temperature zones (Matthew, 2009). Oil based drilling fluid is an
option to drill in the HPHT environment. Because it shows superior
properties than water based mud such as thermal stability, better lu-
bricity, low formation damage, thin mudcake, resistance against mi-
croorganisms, etc. However, due to the health, safety and environment
issues associated with oil based mud, the environmental agencies en-
forced restrictions for the use of oil based mud and guidelines for the
proper treatment for drill solids before disposal. This process takes
additional time and cost for the operator making it a less favored choice
(Amanullah et al., 2016). Synthetic mud will also be stable under these
conditions and is relatively non-toxic, but economically not favorable
due to the cost. Therefore, there is a need for a high performance water
based mud system with additives with enhanced thermal and physio-
chemical property. The emergence of nanotechnology over the last
decade has made tremendous advancements in science and engineering
research and opened a lot of avenue for new areas. Nanotechnology
demonstrated that nanomaterials have superior chemical, physical,
thermal and tribological properties than the corresponding macro and
micro materials (Amanullah and Ramasamy, 2014). Hence, the appli-
cation of nanomaterials is very vital in designing a high performance
water based drilling fluid for HPHT drilling applications.
A number of industries such as electrical, electronics, communica-
tions, biomedical, coating, etc. (Saidur et al., 2011) have already em-
braced nanotechnology very well and made significant breakthrough
technologies over the past ten years. Cellulose based products has been
a part of drilling fluid additives ever since drilling started mainly due to
its availability, ease of handling and its bio-degradable nature. Al-
though, cellulosic polymers provide impressive fluid properties such as
fluid loss control and rheology, the thermal stability is a fundamental
shortcoming due to hydrolysis, oxidation and cleavage at elevated
temperatures. Limited salt tolerance and poor dispersibility in water are
other disadvantages. Several synthetic polymers have been made to
overcome the above mentioned limitations. However, synthetic poly-
mers do not possess some of the key properties of biopolymers such as
excellent shear-thinning rheology. Therefore, a modification or a pro-
cess to make high performance cellulose materials that are able to
withstand the harsh conditions is a welcoming sign as this already
fulfils the criteria of being eco-friendly. This highlights that the devel-
opment of cellulosic nanomaterials for oil and gas field applications can
provide a highly viable source of additives to overcome the technical
challenges of current and future drilling and production operations in
extreme operating conditions. Nanocellulose exhibits excellent

∗
Corresponding author.
E-mail address: jothibasu.ramasamy@aramco.com (J. Ramasamy).

https://doi.org/10.1016/j.petrol.2019.106292
Received 17 July 2018; Received in revised form 16 July 2019; Accepted 17 July 2019
Available online 18 July 2019
0920-4105/ © 2019 Elsevier B.V. All rights reserved.
J. Ramasamy and M. Amanullah
properties as compared to larger cellulosic polymers. This is due to the
distinctive morphologies and other characteristics such as specific
surface area, reactive hydroxyl groups on the surface, low coefficient of
thermal expansion, high strength and modulus as well as gas perme-
ability. The ordered structure of the nanocellulose provides excellent
thermal and chemical stability compared to conventional cellulose. The
surface hydroxyl groups make them easily dispersed in water and
providing fluids with shear-thinning rheology and thixotropy even at
low concentrations. The other advantage of having reactive surface
hydroxyl groups is that further functionalization and modifications can
be performed on nanocellulose (Lee et al., 2014). Besides providing
enhanced thermal stability, the nanocellulose can provide additional
benefits such as good fluid loss control, low friction and hence better
rate of penetration, thin filter cake, therefore minimizing the chances of
getting differential stuck, etc. Nano based drilling fluids has received a
lot of attention in the recent years (Vryzas and Kelessidis, 2017). This
review article aims to capture some of the recent developments of na-
nocellulose and their application in drilling and cementing operations.
2. Nanocellulose
Cellulose is a polysaccharide consisting of several D-glucose units
linked together as shown in Fig. 1. Properties such as toughness, water
insolubility, and fibrous nature play a vital role in the functional
properties of cellulose and cellulose based materials. Cellulose fibers
and their derivatives constitute one of the most abundant renewable
bio-polymer resources available on earth (Siqueira et al., 2010) with
estimated annual production of around 10 bn tons (Habibi et al., 2010).
Cellulose is obtained from plants and woods. It is also synthesized by
algae, tunicate and bacteria (Rebouillat and Pla, 2013). Products based
on cellulose have been used in numerous industries including paper,
food, cosmetics, pharmaceutical as well as in oil and gas industry for
various applications. In the process of petroleum exploration and ex-
ploitation, cellulose based products such as carboxymethyl cellulose
(CMC) and polyanoinic cellulose (PAC) constitute an important part of
oilfield chemicals used frequently in drilling, cementing and fracturing
fluids (Hughes et al., 1993). Under extreme drilling conditions these
additives show limited performance due to inadequate physical,
thermal, chemical and tribological stability (Thomas, 1982).
Important characteristics of cellulose such as biodegradability, op-
tical, physical and mechanical properties could be greatly improved by
converting to nanocellulose (Lee et al., 2014). Many of the benefits of
nanocellulose are attributed to sustainability, abundance, mechanical
properties such as large surface to volume ratio, high tensile strength
and stiffness, high flexibility, and good electrical and thermal properties
(Deepa et al., 2011). Improved physical and chemical properties, such
as high surface area (~250 m2/g), high tensile strength (7500 MPa),
high stiffness (Young's modulus up to 140 GPa), and an abundance of
surface hydroxyl groups also make these class of cellulose very attrac-
tive for several applications including biomedical engineering, waste
water treatment, energy and electronics sector, etc. (Grishkewich et al.,
2017). Most typical dimensions of nanocellulose are in the range from 5
to 20 nm width and up to 2000 nm in length. The fibrils are isolated
from any cellulose although the most common source of nanocellulose
includes wood-based fibers. Appearance of nanocellulose is a snow
white solid as shown in Fig. 2.
Fig. 1. Structure of cellulose.
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Journal of Petroleum Science and Engineering 184 (2020) 106292
Fig. 2. Nanocellulose (source: Wikipedia).
2.1. Preparation method
Wood is the ideal raw material for cellulose production due to its
availability and high cellulose content (Brinchi et al., 2013). Depending
on the preparation method different types of nanocellulose can be
produced such as cellulose nanofibers (CNF), cellulose nanocrystals
(CNC) and bacterial cellulose (BC) with different properties and di-
mensions. BC is produced by micro-organisms with dimensions ranging
from 6 to 50 nm width and several micro meters in length (Moon et al.,
2011; Dufresne, 2012). Mechanical treatment of cellulose results in CNF
which contains both crystalline and amorphous regions having 5–60 nm
width and 500 nm to 100 μm in length (Moon et al., 2011; Klemm et al.,
2011; George and Montemagno, 2017). Mechanical treatment to gen-
erate CNF includes high-pressure, high temperature and high velocity
impact homogenization of cellulose. During the mechanical treatment,
cellulose is subjected to high shear resulting in transverse cleavage
along longitudinal axis of microfibrillar structure of cellulose. As a re-
sult, microfibrillated cellulose are extracted. Repeating the process will
enable the degree of defibrillation required. Mechanical treatment fol-
lowed by chemical treatment would yield even finer cellulose nanofi-
bers with even finer diameters. Acid hydrolysis has been the preferred
process for generating highly crystalline, rigid nanocrystalline cellulose
(CNC). The dimensions of CNC are in the range of 3–5 nm width and
50–500 nm length (Habibi et al., 2010; Moon et al., 2011). Acid hy-
drolysis method of generating CNC will provide better control for the
given application and makes it easier to work with. Because cellulose
itself is not regular in shape contains amorphous and crystalline parts as
shown in Fig. 3. Amorphous and crystalline region of cellulose exhibit
difference in kinetics and resistance toward acid hydrolysis (Isogai
et al., 2008). Amorphous fibers are more susceptible to acid attack as
compared to the crystalline regions of cellulose fibers. Therefore, acid
hydrolysis takes place on the disordered, irregular amorphous portion
of the cellulose leaving the more rigid and acid resistant rod-like na-
nocrystalline part intact. In order to avoid the degradation of rod-like
crystalline form, the hydrolysis process should be conducted under
controlled conditions.
After decades of research, an ideal condition for the production of
nanocellulose by acid hydrolysis has been standardized. The typical
procedure consists of treatment of native cellulose with strong acid
(65%) under controlled temperatures from room temperature to 70 °C
stirring at 200 rpm for a period of 30 min to 16 h depending on the
J. Ramasamy and M. Amanullah
Fig. 3. Representation of cellulose structure with crystalline and amorphous forms (Börjesson and Westman, 2015).
Fig. 4. Chemical derivatization of nanocellulose (a) shows the surface polymer chain after H2SO4 hydrolysis, (b) after HCl or HBr hydrolysis, (c) after H3PO4
hydrolysis, (d) after H2SO4 hydrolysis followed by a surface cationization, and (e) after a HCl/HBr hydrolysis followed by a TEMPO-oxidation (Börjesson and
Westman, 2015).
reaction temperature. The nature of acid (HCl or H2SO4) and the acid to
fiber ratio are also vital parameters. The suspension obtained after
hydrolysis is subsequently diluted with water and centrifuged. Any free
acids present are removed by dialysis with distilled water. The choice of
acid for hydrolysis has a direct impact on the dimensions, stability and
yield of the nanocellulose produced. For instance, the use of sulfuric
acid over hydrochloric acid will increase the surface charges (sulfates
groups) on the nanocellulose. These charged ester groups increase the
water dispersibility and lead to much more stable colloidal suspensions
in water than HCl (Bondeson et al., 2006) and other acids (Szczesna-
Antczak et al., 2012). However, the downside of having these ester
groups will adversely hamper the thermal stability and rheological
behavior (Habibi et al., 2010). The surface characteristics of nano-
cellulose will be defined based on the type of acid used for hydrolysis,
isolation process and further treatment. Functional groups such as
sulfate group, hydroxyl group, phosphate group, carboxylate and amine
functionalized nanocellulose could be developed by choosing appro-
priate hydrolysis procedure and isolation process as shown in Fig. 4
described by Börjesson and Westman (2015). Surface charges such as
neutral, cationic and anionic can also be generated by selecting ap-
propriate process.
Quaternary amine functionalized CNC could be prepared by the
procedure reported by Hauser and Tabba (2001) as shown in Fig. 5.
CNC slurry (50 g of 20 wt%) was treated with 2,3-epoxypropyl tri-
methyl ammonium chloride (5 g) and sodium hydroxide solution (50 wt
%). Ethanol (100 mL) was added to the reaction mixture and kept at
elevated temperature (50 °C) for 2 h. The quaternary amine functiona-
lized CNC was then washed with deionized water.
Oxidation of CNC could be performed using 2,2,6,6-
Tetramethylpiperidin-1-yl)oxyl (TEMPO) by the procedure reported by
Satio et al. (2006) as shown in Fig. 6. A mixture of TEMPO (16 mg) and
sodium bromide (0.1 g) were added to CNC (1 g). pH of the mixture was
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Journal of Petroleum Science and Engineering 184 (2020) 106292
maintained at 10 by slow addition of sodium hydroxide solution. So-
dium chlorate (3.5 mmol) was then added to the mixture while the pH
was maintained at 10. HCl was added to neutralize the mixture which
was then washed with deionized water.
Carboxymethylation of nanocellulose could be performed by the
procedure reported by (Heinze et al., 1994) as shown in Fig. 7. CNC was
washed with ethanol and dried under air flow. 2-propanol was added to
CNC and the mixture was allowed to stir. Sodium hydroxide (0.5 g/g of
CNC) was added to the mixture slowly. Chloroacetic acid was added to
the mixture dropwise and the mixture was heated to 55 °C for 3 h while
stirring. The reaction mixture was filtered and residue was dispersed in
methanol. Acetic acid was added to neutralize the mixture and filtered.
The residue was washed with methanol and dispersed in water. The
desired product carboxymethyl cellulose is dissolved in water. Un-
reacted cellulose polymer was removed from carboxymethyl nano-
cellulose by centrifugation.
Amphoteric water soluble nanocellulose could be prepared in si-
milar ways as the synthesis of carboxylated nanocellulose and qua-
ternary amine substituted nanocellulose (Warren et al., 2003) as shown
in Fig. 8.
2.2. Characteristic features
The characteristics features of nanocellulose are significantly dif-
ferent than the characteristics of bulk cellulose. The CNF and CNC
prepared by mechanical or chemical methods are exceptionally rigid,
has rod like shape with high surface area and also has higher thermal
stability and thus expected to perform better in extreme operating en-
vironments. The physical characteristics of these tiny cellulosic pro-
ducts can be determined by commonly used techniques such as scan-
ning electron microscopy (SEM), transmission electron microscopy
(TEM) and/or atomic force microscopy (AFM) to determine particle size
J. Ramasamy and M. Amanullah
Fig. 5. Reaction scheme to get quaternary ammonium functionalized nanocellulose.
along with the particle size ranges and modality. Degree of crystallinity
of the nanocellulose could be measured using Wide angle X-ray dif-
fraction (WAXD). Besides renewable and biodegradable, other proper-
ties of nanocellulose are biocompatibility, high aspect ratio, high sur-
face area, high strength and modulus, dimensional stability, thermal
stability (stable up to 200 °C) and ease of chemical modifications to
enhance the functional capability. Nanocellulose has extremely good
properties such as light weight, very strong, non-toxic, gas imperme-
able, electrically conductive, high tensile strength and highly absor-
bent. Properties of CNC and CNF are provided in the below Table 1.
3. Oil field applications of nanocellulose
Many bio-polymers have been used in oil industry during different
stages of operation such as drilling, cementing and fracturing as fluid
loss control additive and viscosifying agent. These two properties of the
drilling mud govern most of the technical performances required for
safe and economic drilling operation. Poor maintenance of these
properties frequently leads to a lot of drilling problems such as fluid
invasion to the formation affecting production, deposition of thick
mudcake on the borehole wall which may lead to stuck pipe problem,
poor cutting carrying capacity which will lead to inefficient hole
cleaning, etc.
Fluid loss below the API recommended value is very important to
maintain the designed drilling fluid viscosity, near wellbore formation
stability, preventing damage in pay zone, etc. The spurt loss is the main
source of near wellbore formation damage. High performance spurt and
fluid loss additives are essential to minimize the scope of any spurt loss
especially while drilling the pay zone as particles in the mud filtrate will
block the pore throats leading to reduction in permeability of the pay
zone (Mungun, 1965). An investigation by Todd et al. shows that water
suspension even with 1–15 ppm particle concentration of less than 3 μm
size may cause serious damage to oil and gas reservoirs (Todd et al.,
1990). Additives that are capable to create a very low permeable
mudcake immediately after contacting the wellbore formations may
eliminate the near wellbore formation damage while drilling.
Stuck pipe is one of the major problems that is associated with the
performance of fluid loss additives used in the formulation of a drilling
mud. Analyses of field data indicate that frequency of stuck pipe pro-
blem is significantly higher for water-based muds than the oil-based
muds as the later have thick mudcake deposition (Chilingarian and
Fig. 6. Reaction scheme for TEMPO oxidation of nanocellulose.
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Journal of Petroleum Science and Engineering 184 (2020) 106292
Vorabutr, 1983). Hence, mud additives that ensure the deposition of a
very thin mudcake in the presence of a water-based mud will reduce the
frequency of pipe sticking problems in differential sticking prone
borehole environments. The pulling force required for freeing a stuck
pipe also increases with increasing mudcake thickness (Outmans,
1958). Isambourg et al. showed how the magnitude of pulling force that
is necessary to free a stuck pipe changes with a change in mudcake
thickness (Isambourg and Marti, 1999). As the wellbore integrity de-
pends on casing, placement of casing at the desired borehole location is
extremely crucial especially in deviated, horizontal and extended reach
wells due to the requirement of higher casing running load. A thin, low
friction and slippery mudcake is very important for these wells (Maidla,
1987). Also a thick, poorly packed mudcake can give a high torque and
drag in a long horizontal well compared to an ultrathin, well packed
mudcake and thus has the possibility to reduce the torque and drag
significantly.
3.1. Application of nanocellulose in drilling fluids
Several studies have been carried out in the recent past on the ap-
plication of nanocellulose in the drilling fluid to have low fluid loss and
thin mudcake. The effect of nano-sized carboxymethyl cellulose (CMC)
and polyanionic cellulose have been investigated by Saboori et al.
(2012) and Fereydouni et al. (2012) for the application as fluid loss
additives. The authors observed that a desirable reduction in the
amount of fluid loss and the mudcake thickness in the API fluid loss
experiments carried out by in-house developed nanocellulose materials.
Saboori and Sabbaghi (2017) have reported a detailed comparison
study on bulk CMC, nano-CMC and core-shell nano-CMC-polystyrene
composite. The average particle size of bulk CMC, nano-CMC and core-
shell nano-CMC-polystyrene composite was found to be 6 μm, 47 nm
and 80 nm, respectively. Drilling fluids have been prepared with each of
the three additives with loading starting from 1 g to 10 g. Rheological
properties such as plastic viscosity and yield point have been measured
for fluids with bulk CMC, nano-CMC and nano-CMC-polystyrene core
shell. The results are given the below Fig. 9. There is no major impact
on plastic viscosity by the different CMCs. Nano-CMC and nano-CMC-
polystyrene core-shell composite have less impact on the yield point
than the bulk CMC. This behavior can be attributed to the polymeric
chain length of CMCs as nano-CMC is expected to have shorter chain
length than the bulk CMC.
J. Ramasamy and M. Amanullah
Fig. 7. Reaction scheme for carboxylation of nanocellulose.
The effect of nano-sized CMC and CMC-core shell is very evident in
fluid loss behavior especially in the lower range of CMC concentration
(Fig. 10). As expected nano-CMC and CMC-core shell has shown better
fluid loss control property as compared to bulk-CMC due to their nano
size. Almost 20% reduction in fluid loss is observed for the addition of
1 g of bulk CMC and CMC-core shell composite. Difference in fluid loss
volume got smaller as the concentration of different CMCs increased in
fluid.
Hall et al. have reported the formulation of high performance water
based mud using cellulose nanofiber (CNF) and its derivatives (Hall
et al., 2017). They have measured various mud properties of drilling
fluids formulated using different nanocellulose derivatives such as un-
modified cellulose nanofiber (CNF-0), carboxymethylated cellulose
nanofiber (C–CNF) and TEMPO-oxidized cellulose nanofiber (TO-CNF)
and the cationic cellulose nanofiber with quaternary amine group (Cat-
CNF). It is worth mentioning that the positively charged quaternary
ammonium compounds are known to be very effective as shale in-
hibitors and clay stabilizers as well (Arvind 2009). Shale section of the
formation is usually drilled with highly inhibitive water based mud to
prevent shale from swelling and collapsing upon contact with water.
The cationic cellulose with quaternary ammonium compounds replace
small cations like Na+ and stabilize the shale by minimizing the water
invasion into shale layers and prevent it from swelling. The thermal
stability of unmodified cellulose nanofiber (CNF) was compared against
xanthan gum (XG), a very commonly used viscosifier in water based
drilling fluids by conducting dynamic aging at elevated temperature of
150 °C under 125 psi pressure. The rheological behavior of the muds is
shown in Fig. 11. It is very obvious that the rheological behavior of
fluid having CNF-0 does not alter significantly before and after dynamic
aging experiment. On the other hand, the effect of temperature is very
evident in the case of mud having xanthan gum as viscosifier. The high
thermal stability of the cellulose nanofiber keeps the fluid system intact
even at higher temperature as compared to xanthan gum which de-
grades after thermal treatment, as a result losing its ability as viscosi-
fier.
Another report by Li et al. (2015) described the application of cel-
lulose nanocrystals (CNC) as rheology modifier. CNC used in their study
has been obtained by sulfuric acid hydrolysis of microfibrillated cellu-
lose (MFC). The authors demonstrated the effectiveness of CNC in
bentonite water based mud with superior rheological properties, higher
Fig. 8. Amphoteric nanocellulose synthesis.
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Journal of Petroleum Science and Engineering 184 (2020) 106292
thermal stability, less fluid loss volume and thinner mudcake deposi-
tion. The bentonite mud containing CNC has enhanced rheological and
fluid loss properties than the bentonite mud having MFC. Moreover, the
addition of polyanionic cellulose to bentonite mud having CNC instilled
a synergy with CNC which reflected in further improvement in rheo-
logical and filtration control performance. The API fluid loss properties
have been improved for bentonite mud as the CNC concentration in-
creases as shown in Fig. 12. Fluid loss for the drilling mud with no CNC
is around 35 mL after 30 min. For the fluid with 1 wt% CNC the fluid
loss reduced to less than 20 mL, which is around 50% reduction in the
volume. Addition of CNC has also led to the formation of more compact
and uniform filter cake. This highlights the potential of application of
CNC in overcoming the current and future drilling challenges.
Monclin et al. (2015) have reported the superior performance of
CNF and CNC as thickeners as compared to sulfonated nanocellulose
and bentonite as thickening agents for water based drilling fluid.
Moreover, CNF and CNC used in their study showed excellent tolerance
to salts. This property is attributed to the presence of small number of
charged groups or absence of any charged groups on surfaces. The
authors also reported lignin coated hydrophobic CNC and CNF as
thickeners for oil based mud.
3.2. Application of nanocellulose in oil well cementing
Cementing the drilled section of the borehole is an important stage
of the operation. This is done to protect and support the casing, prevent
fluid and gas migration as well as seal off the abandoned hole. Failure
to have proper cementation could lead to serious consequences such as
Deepwater Horizon accident in offshore USA, which is one of the worst
oil disasters, causing a great amount of environmental pollution and
economic loss (McNutt et al., 2012). The problems associated with
conventional oil well cementing include low tensile strength and low
fracture toughness (Banthia and Nandakumar, 2003). Different tech-
niques and reinforcements have been introduced in oil well cementing
to improve the parameters of cementation process.
A number of additives have been incorporated into cement mixture
such as silica fume (Toutanji and El-Korchi, 1995), fly ash (Chaipanich
et al., 2010) and natural fiber (Savastano et al., 2009 and Chakraborty
et al., 2013) in order to enhance rheological and mechanical properties
of cement. By having hybrid mixture of steel and polypropylene fiber
J. Ramasamy and M. Amanullah Journal of Petroleum Science and Engineering 184 (2020) 106292

Table 1 bridging ability. Addition of CNF has been found to significantly delay
Properties of CNC and CNF (Bardet et al., 2015). the setting time and increase the degree of hydration (DOH)
Properties Nanocellulose (Onuaguluchi et al., 2014). It was proposed by the authors that the
delay in setting time is due to the presence of possible organic acids and
CNC CNF non-acidic products due to alkaline hydrolysis of cellulose. The internal
curing of CNF resulted in increased DOH. CNF produced from eu-
Morphology
Shape Rod-like Fibrilar calyptus pulp has been investigated for its mechanical, thermal and
Length (nm) 174 652 microstructural effects on Portland cement (Mejdoub et al., 2017). The
Thickness (nm) 8 8 optimum strength increase, which was found to be 0.3% due to high
Aspect Ratio 88 67 hydrophilic potentials, high reactivity and high specific surface area of
Physical Property
CNF. It was observed by Dai et al. (2015) that by adding 0.15% of CNF
Crystalline Index (%) 86 77
Surface Charge (μmol/g) 151 101 obtained from eucalyptus pulp to Type I cement paste of 0.50w/c, the
Zeta Potential (mV) −30 −18 compressive strength and flexural strength have been increased re-
Thermal Stability spectively by 20% and 15%. The property enhancements were attrib-
Onset T of thermal degradation 241 289
uted to the reactive hydroxyl groups that promote interaction between
CNF and cement.
Sun et al. studied the application of CNF as rheology modifierin oil
improved the resistance to nucleation and cracks growth (McNutt et al.,
well cement (Sun et al., 2016). It was observed that the shear stresses
2012). Nano-sized additives in cement slurry formulation are gaining
increased with the increase of the shear rate and loading level of CNF in
attention for improved cement properties. Due to the high surface area
the oil well cement matrix as expected. The yield stress and plastic
available in nano-sized materials, chemical reactions can be sig-
viscosity also follow the same trend.
nificantly improved and promote degree of hydration (Sanchez and
Modeling studies such as Bingham-Plastic model, Herschel-Bulkley
Sobolev, 2010). High aspect ratio and high strength moduli of elasticity
model, Volcano model, Vom Berg model also confirmed the increasing
ratio of nano-sized materials can be translated as nano-reinforcement in
trend of shear stress with increasing concentration of CNF in oil well
cementitious materials. Nanosilica has been shown to provide concrete
cement mixture although with different values of shear stress as each
mechanical properties improvement (Sobolev et al., 2009) and provide
model has its own type of data intake and processing methods as shown
impermeability (Ji, 2005) to set cement due to its small size and high
in Fig. 13. Degree of hydration is also in the increasing trend with in-
surface area. Moreover, the compressive strength was also reported to
creasing concentration of CNF as shown in Table 2.
increase by 10% and flexural strength by 25% upon addition of 0.25%
CNF is also exhibiting an important role in decreasing the porosity
of nanosilica (Sobolev et al., 2009). Carbon nanotube (CNT) reinforced
of oil well cement. Therefore the mechanical properties of interfacial
cement has also attracted lot of consideration as the CNTs bring the
transition zone can be improved in the oil well cement paste. The
changes of reinforcing mechanism from macro to nano level (Raki et al.,
composite consisting of CNF and oil well cement at very low con-
2010). CNTs are instrumental in reducing electrical resistivity and in-
centration of nanocellulose (0.04 wt%) still exhibited the best flexural
creasing the compressive strength and Young's moduli of cement (Li
strength value among all formulations even after aging in the air for an
et al., 2007). However the high-cost of CNTs makes it economically not
extended period of 382 days. This indicates stable material composition
favorable for cementing applications.
as shown in Fig. 14. The authors concluded that the CNF-reinforced oil
Nanocellulose has been gaining popularity having potential with
well cement as depicted in Fig. 15 exhibits better mechanical and
high volume production, low cost and abundant resources.
rheological properties compared with the original oil well cement due
Nanocellulose has been used in cementing process to improve proper-
to the enhancement of matrix material bonding, structural units and the
ties such as rheology, durability, degree of hydration, yield stress, shear
fabrics.
thinning, etc. making it a suitable candidate to increase cement sus-
Shenoy et al. (2017) reported application of nanocellulose in oil
tainability. The effect of CNF in mechanical properties of cement
well cementing to increase the compressive strength of the cement. The
composites have been reported by Ardanuy et al. (2012). The source of
authors have used nanocellulose in suspension with 7% concentration
CNF used in this study is sisal fibers and CNF was produced by me-
(NCS) and due to its viscous nature it cannot be used more than 5% that
chanical treatment. The CNF-cement composite was found to have 40%
is 0.35% nanocellulose in 4.65% water BWOC. Typical cement for-
increased flexural strength and having flexural modulus twice as com-
mulation used to prepare cement slurry is given in below Table 3.
pared to sisal fiber-cement composites. On the other hand, fracture
Compressive strength is a main property of cement helps to avoid
toughness of sisal fiber-cement composite is twice as CNF-cement
collision of the casing in well. Compressive strength is measured using
composite. This is because the nano-sized of CNF does not have crack

Fig. 9. Rheological properties comparison for different CMCs (Saboori and Sabbaghi, 2017).

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J. Ramasamy and M. Amanullah Journal of Petroleum Science and Engineering 184 (2020) 106292

Fig. 10. Fluid loss behavior of different CMCs (Saboori and Sabbaghi, 2017).

Fig. 13. Predicted yield stresses of CNF-OWC composite slurries from different
rheology models (Sun et al., 2016).

Table 2
Formulation and DOH of CNF-oil well cement composite (Sun et al., 2016).
Sample # Formulation Degree of hydration (%)

Oil well cement (OWC) Water CNF

CE-0 100 38 0 41.57

CE-1 100 38 0.04 45.04
CE-2 100 38 0.12 53.43
CE-3 100 38 0.20 59.7
CE-4 100 38 0.28 60.13

nanocrystals (CNC) in oil well cementing by preparing cementitious

Fig. 11. Viscosity profile of 0.5 wt% of suspension of CNF and XN before and
after aging at 150 °C and at 125 psi (Hall et al., 2017).
hydraulic compressing machine. Effect of increasing concentration of
NCS on compressive strength is shown in the below Fig. 16. Compres-
sive strength of cement is increased by increasing concentration of NCS.
Cement slurry with 5% loading of NCS has almost 50% improvement in
compressive strength than that of cement slurry with no NCS added.
Dousti et al. (2015) investigated the application of cellulose
slurry containing bentonite, CNC and oil well cement in water. Col-
loidal suspensions having bentonite and CNC were also prepared and
utilized to predict the behavior of cementitious slurry containing CNC.
It was observed that the addition of CNC to colloidal suspension in-
creases the viscosity and stability of suspension at low shear rates. On
the other hand, the conventional cellulose has thermal limitations and
degrades at elevated temperature which will have detrimental effect as
the fluid will fail to maintain its viscosity and suspending ability. The
authors also investigated the flowability analysis of cementitious slurry
using two methods namely Mini slump test and flow table analysis. The
mini slump test was done to understand the yield stress of different
cementitious systems and their flow behavior under gravity with no
external loading. It was observed, that CNC is more effective than the
bentonite when added to the conventional cement mixture consisting of

Fig. 12. API fluid loss behavior of bentonite mud with different nanocellulose concentrations (Li et al., 2015).

7
J. Ramasamy and M. Amanullah
Fig. 14. Flexural strength of CNF-OWC composites as a function of CNF loading
at three different curing times (Sun et al., 2016).
only water and cement in terms of changing the yield stress and the
flow behavior of the system. On the other hand, addition of both ben-
tonite and CNC to the cement slurry showed the most satisfactory re-
sult. Flow test results also indicated the superior performance of CNC.
The slurry without CNC could not resist the twenty five blows. On the
other hand, after the addition of CNC to the slurry, not only the dia-
meter got significantly lowered after two blows but also able to with-
stand the complete twenty five blows without failure. This demon-
strates that the yield strength of cementitious slurry with CNC is higher
than the slurry without nanocellulose.
Cao et al. (2015) have reported the several property enhancements
of CNC-cement composite by adding different concentrations of CNC
(0.04%, 0.1%, 0.2%, 0.5%, 1% and 1.5% in volume) to Type V cement
composite. The enhanced properties include DOH, flexural strength,
rheological properties and zeta potential. DOH% was found to increase
as concentration of CNC increases. Upon addition of 1.6 vol% of CNC,
the DOH has been increased to 66% as compared to the DOH of cement
without CNC (around 46%). Flexural strength on the other hand was
found to decrease as a function of CNC loading. This could be due to
agglomeration of CNC particles at higher loading. There needs to be an
effective dispersion of CNC particles in order to get property enhance-
ments. The same authors proposed effective ways of dispersing CNC by
ultrasonication of CNC-cement composite (Cao et al., 2016a). This re-
sulted to reduce CNC agglomeration and a critical concentration of CNC
(1.35 vol%) was found which was in agreement with theoretical value
of 1.38 vol% calculated from percolation model. After ultrasonication
Fig. 15. Nanocellulose-Oil well cement reinforcement (Sun et al., 2016).
8
Journal of Petroleum Science and Engineering 184 (2020) 106292
Table 3
Cement slurry formulation (Shenoy et al., 2017).
Materials Loading (%)
Class G Cement 100% 100% 100% 100%
NCS 0% 2% 4% 5%
Friction Reducer 0.3% 0.3% 0.3% 0.3%
Water 44.45% 42.69% 40.94% 40.05%
of CNC-cement composite, the flexural strength was increased by up to
50%. The effect of sonication on the modifications of microstructures of
cement paste was also reported (Cao et al., 2016b) using energy-dis-
persive X-ray. It was observed from X-ray analysis that CNC-cement
paste without sonication tends concentrate along the interfacial regions
between the cement particles and the paste. For sonicated samples, well
dispersion of CNC into the paste was observed.
4. Techno-economic analysis
Assis et al. (2017) has performed extensive techno-economic as-
sessment of cellulose nanocrystals as it presents wide range of oppor-
tunities for new product development. Techno-economic study will
provide insightful information for the efficient conversion process de-
sign, cost-saving efforts and reduce financial risks. The authors used
information from the USDA Forest Products Laboratory Pilot Plant and
literatures. Considered scenarios include variations related to Green-
field, co-location and acid recovery. Other factors such as operating
costs, capital investment, minimum product selling price (MPSP), fi-
nancial performance matrices are taken into account for each scenario.
The effect of drying and higher reaction yields for manufacturing of
CNC were also taken into account. Risk analysis indicates that 95%
probability of CNC production costs below USD 5900 per ton. MPSP is
also found to be USD 7200 per ton. Finally, the authors provided gui-
dance on process optimizations that can improve the economic benefits
of CNC manufacturing process.
By applying different manufacturing process to produce CNC, it was
found that in 2018 around 525 tons of CNC were produced as shown in
Table 4. Sulfuric acid hydrolysis is the primary process to produce CNC
in the world. Almost one ton of CNC produced per day using sulfuric
acid hydrolysis process. SO2 fractionation process also used to produce
considerable quantity of CNC.
In oil and gas industry, CNC and CNF are still mostly in research
phase for applications in drilling fluids, cementing and EOR domain.
Cost of CNC and CNF is much higher than regular cellulose based
products used currently in the industry. However, the desired fluid and
cement properties could be achieved by using very small quantity of
CNC/CNF as compared to the regular cellulosic products. Moreover,
shelf life of CNC and CNF is much higher than regular cellulose thereby
reducing disposal due to decomposition. Hence, companies would be
able to cut down their spending while using CNC/CNF in terms of
J. Ramasamy and M. Amanullah
Fig. 16. Compressive strength of cement with NCS (Shenoy et al., 2017).
Table 4
CNC production dry basis (tons per year).
Source: Nanocellulose: Producers, Products, and Applications, A
Guide for End Users, TAPPI, 2017. Updated, Biobased Markets,
Sept. 2018.
Process Capacity in tons
Sulfuric acid hydrolysis 338
Acid hydrolysis 5
SO2 fractionation 130
Enzymatic hydrolysis 50
Catalytic conversion 2 extremely challenging drilling and production environments. In: Abu Dhabi
reduced quantity, long shelf life, reduced logistics and labor. Therefore,
overall benefits of using CNC/CNF would reduce the gap in cost dif-
ference while providing excellent properties.
The current CNC production rate of around 525 tons in 2018 is not a
viable quantity to be able to routinely use for drilling and cementing
applications in oil and gas industry. Moreover, nanocellulose has been
already widely used in composites, paper, paints and food industry.
Therefore, out of the 525 tons produced in a year, the above mentioned
industries would take a huge share of produced quantity. As of now,
there is not enough production of CNC/CNF to meet oil and gas in-
dustry market demand. In 2016, nanocellulose global market size was
estimated to be more than USD 87.5 million. Its growth is estimated to
grow over 34% by 2024. Increase of production rate, in the years to
come as forecasted could bring down the cost significantly. Moreover,
its proven properties will accelerate the nanocellulose market in the oil
and gas industry during the forecast period making CNC/CNF as an
attractive product.
5. Recommendations
Nanocellulose has very good physical, mechanical and chemical
properties. Combining these properties with other characteristics such
as sustainability, bio-degradability and environment friendly nature
make nanocellulose the right choice for the application in oil and gas
industry especially in off-shore, deep water, extreme environment
drilling. The reports available in the literature clearly demonstrates that
the application of nanocellulose to impart good mud properties such as
viscous characteristics, enhanced fluid loss behavior and generation of
thin mudcake in drilling fluids. Nanocellulose has also been applied in
oil well cementing with good improvements of cement properties such
as yield stress and structural rigidity to withstand detrimental action of
any external forces. Also the rheological, mechanical and flexural
properties of the cement have also shown improvement with the ad-
dition of nanocellulose and thus demonstrate its suitability to overcome
current and future cement related drilling problems. More research
should be directed for the application as fluid loss control additives
with high thermal stability as the current high temperature fluid loss
control additives are mostly derived from synthetic polymers for water
based drilling fluids as well as for cementing. Investigation should be
made to carry out feasibility study on quaternary amine functionalized
9
Journal of Petroleum Science and Engineering 184 (2020) 106292
nanocellulose for its ability as shale inhibitor and for clay encapsula-
tion. Furthermore, efforts should be directed to use nanocellulose as
rheology modifier for water based drilling mud. In cementing, degree of
hydration could be significantly increased by the addition of nano-
cellulose. Effective dispersion of nanocellulose could be an issue and
will hamper the outcome. Therefore, it should be addressed as well. The
source is abundant in nature and the results of the preliminary ex-
amples are very promising that nanocellulose based products are indeed
a good candidate for drilling fluids and cementing applications al-
though it is the early stage of research. Full potential is yet to be studied
by conducting pioneering research to overcome technical as well as
environmental benefits.
Acknowledgement
The authors thank Timothy Eric Moellendick, the Chief
Technologist of Drilling Technology Team, EXPEC Advanced Research
Center of Saudi Aramco for the support and encouragement for this
publication.
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