SPE 155607

Use of Nanomaterials in Cementing Applications

Rahul Patil and Abhimanyu Deshpande, Halliburton
Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Oilfield Nanotechnology Conference held in Noordwijk, The Netherlands, 1214 June 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract
The two principal functions of oilwell cementing are to restrict fluid movement between zones within the formation and to
bond and support the casing. Apart from these, the cement sheath also protects casing from corroding, protects the casing
from shock loads when drilling deeper, and plugs lost circulation or thief zones. Once cement is placed in the wellbore, initial
setting occurs wherein development of compressive strength becomes more important for further drilling operations. Early
strength development is important to help ensure structural support to the casing and hydraulic and mechanical isolation of
downhole intervals. Delays in strength development cause significant amounts of lost time because of the need to wait on
cement (WOC). Typically, an accelerator is often used to enable early strength development in cement. It is desired that an
accelerator should improve overall compressive strength without causing excessive gelation.
Nanomaterials (being smaller in size and higher in surface area) are used in several fields, including catalysis, polymers,
electronics, and biomedicals. Because of a higher surface area, these materials can also be used in oilwell cementing to
accelerate the cement hydration process. Moreover, they are often required in small quantities. This paper documents a case
in which nanosilica was used in cement formulations to develop high early strength. Nanosilica also helps enhance final
compressive strength and helps control fluid loss. Using the correct quantity of nanosilica, it is possible to design cement
slurry with low rheology and good mechanical properties while controlling fluid loss.

Introduction
Nanotechnology continues to gain momentum in the areas of academics as well as applied research. Generally, material is
said to be a nanomaterial if one of its dimension is less than 100 nm (ISO/TS 80004-1). Because of the large increase in the
surface area to volume ratio, nanomaterials display different chemical and physical properties compared to their macro- or
micron-sized counterparts. For instance, opaque substances become transparent (copper) and inert materials become catalysts
(platinum). This enables niche application of nanomaterials. Nano composites are another class of materials, gaining wide
popularity because of their improved physico-chemical properties. Applications of nanocomposites are much more beneficial,
considering the improved properties (mechanical, chemical) of the prepared nanocomposites (Tjong 2006).
Development of high performance materials for construction is possible by unleashing the potential of nanotechnology.
Few literature reports are available mentioning use of nanomaterials in the concrete industry. For example, Campillo et al.
(2004) investigated the effect of nanoalumina in belite cement. They found that addition of nanoalumina enhances
mechanical properties to some extent. Li et al. (2004) reported use of nano-SiO
2
or nano-Fe
2
O
3
in cement mortar. Their
results showed improvement in compressive and flexural strength compared to plain cement mortar. Application of
nanomaterials to improve performance of the cement concrete is also described by Birgisson and Beatty (2007). Though
nanotechnology has shown its presence in other industries throughout a few decades, its application in the oil and gas
industry is still to be fully explored (Singh and Ahmed 2010). It has potential to provide solutions to some of the upstream
and downstream challenges the industry has faced for the past several years (Pourafshary et al. 2009).
Some of the examples of harnessing nanotechnology in drilling fluids (Singh and Ahmed 2010) (e.g., surfactant package
design (Zanten and Ezzat 2010) and spacer fluids (Maserati et al. 2010)) suggest that it can bring revolutionary changes to
additive development. To the best of the authors knowledge, however, so far, no report describing actual use of
nanomaterials with other additives to enhance properties of cement slurry systems for oilfield application has been
documented.
This paper demonstrates nanomaterials help improve properties of cement. It is always important to achieve early
compressive strength to reduce WOC and continue further drilling as quickly as possible. This becomes more evident with
cement systems with finer-sized elastomers embedded in the cement matrix. These finer-sized particles dispersed in water
2 SPE 155607
known as Latex are often used in cement systems to control fluid loss and help prevent gas migration. The incorporation of
such finer-sized particles hampers the development of strength. This problem was tackled by addition of nanosilica particles
to the cement system. In this paper, experimental findings depict how nanosilica enhances cement properties and aids
development of high early strength and higher compressive strength.

Experimental
All of the slurries were mixed and tested using current API standards and procedures. All of the dry additives were mixed
with cement, and the liquid additives with water. The amount of water was adjusted to obtain the required density. Additive
details and slurry density information are provided in Tables 2 and 3. All of the tests were conducted at 190F, unless
specified. Compressive strength measurements were taken at a pressure of 3,000 psi and thickening time tests were
performed at 11,000 psi. The Latex material used was a commercial product. The nanosilica dispersion (15 % active) was
procured from local vendor and particle size was found between 5 to 7 nm. This dispersion has a good stability and remains
stable for more than six months. The latex and nanosilica samples were mixed in different proportions and their mechanical
properties in particular compressive strength was monitored systematically. For fluid loss measurements, slurry was
conditioned at 190F for 20 min prior transferring slurry to fluid loss cell.

Results and Discussions
Table 1 shows the effect of nanosilica on the compressive strength. To show the real potential of nanoparticles, a comparison
was also made with micron-sized silica. It can be seen from Table 1 that by the addition of 0.2 gal/sk of nanosilica, the rate of
strength development increased from 172 to 460 psi/hr. The rate of strength development was calculated from the linear
portion of the compressive strength versus time graph. For this the portion of the graph, the time between the onset of the
strength development and the saturation of strength was taken into consideration. The composition without nanosilica is
referred as control. The ultimate strength of cement composition was found to be three times that of the control and control
plus microsilica. Compared to control, the rheological properties of the cement slurries with nanosilica are slightly higher;
however, the slurry remains pourable and pumpable.
It is important to mention that the particle size of Latex is approximately 150 nm, and size of nanosilica is approximately
6 nm. Normally, cement slurries contain different additives, and the particle sizes of cement also ranges in micron size;
therefore, the addition of small amounts of nanosilica should not impact mechanical properties drastically because, once
these particles are aggregated, they will not unleash their real potential. While mixing the slurry, the cement blend was added
to the fluid system containing nanosilica, Latex, and water. It is possible that the nanosilica particles were becomming
entangled with the Latex particles because they are also in nm size. This entanglement keeps nanosilica deaggregated and, as
a result, helps enhance early strength.
Oilwell cements contain primarily four main phases: C
3
A, C
4
AF, C
3
S, and C
2
S, along with gypsum and some alkali
sulphates and lime. Among the four measure species, C
3
A and C
4
AF control the rheology and gelation process of cement,
whereas C
3
S and C
2
S are mainly responsible for compressive strength development.

2C
3
S + 6H C-S-H + 3 CH
2C
2
S + 4H C-S-H + CH

When C
3
S and C
2
S interact with water, they form C-S-H gel and CH (calcium hydroxide). The C-S-H gel acts as a binder
for cement, consolidates the cement matrix, and provides strength to cement. It might be possible that the addition of
nanosilica would accelerate the formation of C-S-H gel, thereby helping cement gain the strength earlier. Moreover, because
the fineness of silica particles, the particles are believed to fill the voids between the larger cement particles, resulting in a
dense, solid matrix, even before any chemical reaction between the cement particles occurs.

TABLE 1EFFECT OF NANOSILICA ON COMPRESSIVE STRENGTH
a

Latex
(gal/sk)
Silica
Retarder
(gal/sk)
UCA Strength
Time to 500 psi
(hr:min)
Rate of Strength Development
(psi/hr)
24-hr Strength
(psi)
1.5 0 0.05 23:05 172 690
1.5 Micron sized silica 0.05 21:45 160 610
1.5 Nanosilica 0.05 13:29 460 2203
a
Premium Class H cement, defoamer 0.05 gal/sk, stabilizer 0.2 gal/sk, dispersant 0.143 gal/sk, density 16.4 lbm/gal, Yield 1.1 ft
3
/sk.

Nanosilica has a synergetic effect with other additives and does not hamper their function. Tweaking the amount of
retarder allows the thickening time or pump time of the slurry to be designed, as per requirements, with improved mechanical
properties. To prove this, two different slurries were designed (Table 2) by varying the amount of set retarder and nanosilica
to have similar pumping time (one around 6 to 7 hr and other around 10 to 11 hr). In both the cases, it can be seen that
compositions having nanosilica developed high early strength and higher ultimate strength than the control slurry.

SPE 155607 3
TABLE 2EFFECT OF RETARDER CONCENTRATION ON THICKENING TIME AND STRENGTH DEVELOPMENT
a

Nanosilica
(gal/sk)
Retarder
(gal/sk)
Thickening Time
(hr/mn)
Rate of Building Compressive Strength
(psi/hr)
Ultimate Compressive Strength
(psi)
No silica
(Pure latex )
0.05 6:05 150 2000
0.2 0.1 7:24 220 2600
No silica
(Pure latex )
0.1 10:25 66 1100
0.2 0.15 10:36 140 2613
a
Premium Class H cement, defoamer 0.05 gal/sk, stabilizer 0.2 gal/sk, dispersant 0.143 gal/sk, density 16.4 lbm/gal, yield 1.1 ft
3
/sk

Table 3 depicts the effect of nanosilica on fluid loss. It can be seen, when used alone, it reduces the fluid loss. Also, when
used along with the traditional fluid-loss additive, it helps improve the fluid loss, further showing synergy with the fluid-loss
additive. This might be attributed to filling of small void places between larger cement particles.

TABLE 3FLUID LOSS RESPONSE WITH FLUID LOSS ADDITIVE
a

Latex
(gal/sk)
Nano Silica
(gal/sk)
Fluid Loss Additive
(% bwoc)
API Fluid Loss
(mL/30 min)
1.5 0 0 52
1.5 0.2 0 34
1.5 0 0.5 38
1.5 0.2 0.5 22
a
Premium Class H cement, defoamer 0.05 gal/sk, 0.2 gal/sk, dispersant 0.143 gal/sk, Density 16.4 lb/gal, Yield 1.1 ft
3
/sk

Table 4 shows the performance of nanosilica on variation of temperature. The effect on compressive strength was studied
by varying the temperature and keeping the amount of nanosilica constant. The study shows that nanosilica improves the
strength at all the temperatures, and that its performance does not change with the temperature. Note the slurry design for
330F is little different than the previously mentioned slurry compositions. Strength retrogation additives were added to this
design. The results at 80F indicate that nanosilica can also be used as an accelerator at low temperatures. The wide
temperature window makes this material unique for its application in variety of slurry designs and field conditions.

TABLE 4EFFECT OF TEMPERATURE ON THE COMPRESSIVE STRENGTH
Slurry
Temperature
(F)
Ultimate Compressive
Strength (psi)
Latex 80 Unset
Latex+ nanosilica 80 400
Latex 190 690
Latex + nanosilica 190 2203
Latex 330 2750
Latex + nanosilica 330 3356

Conclusions
The following conclusions are a result of this work.
Addition of nanosilica improves the mechanical properties, especially compressive strength, of the cement.
It improves early strength development, which allows drilling operations to resume quickly, thereby lowering
operational costs.
To a certain extent, nanosilica helps improve fluid loss.
It can be used at a wide range of temperatures, which provides flexibility to be used in different designs and
operating conditions.
Because of the synergetic effect, nanosilica with other cement additive compositions with required properties can be
designed easily.

References
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International Patent Application. PCT/US2007/073430.
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4 SPE 155607
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