SPE-191577-MS

Big Problem-Small Solution: Nanotechnology-Based Sealing Fluid

Larry Todd, Matthew Cleveland, and Kevin Docherty, Schlumberger; James Reid, Oxy Oil & Gas, posthumously;
Kenneth Cowan and Christopher Yohe, Oxy Oil & Gas

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the 2018 SPE Annual Technical Conference and Exhibition held in Dallas, Texas, 24-26 September 2018.

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
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Abstract
A nanotechnology-based sealing fluid was developed to solve compromised integrity in pathways too small,
smaller than 120 μm, for conventional methods such as cement squeezes. Well integrity and environmental
stewardship are at the forefront of our industry's relation with the public as oil and gas fields continue to
encroach toward urban centers and the places we live and work. This push towards improved well integrity
and a growing number of mature wells requires new and novel technologies and materials to achieve our
goals.
The nanotechnology-based sealing fluid is capable of penetrating small gaps, as small as 20 μm, and seals
through a reaction from either set cement or brine in the leak path. Candidate wells were selected based
on very low injectivity rates that conventional remediation techniques could not tackle. Six candidate wells
were selected, and of them, two were selected to cure a leaking gas microannulus causing sustained casing
pressure and four were selected to cure a pinhole leak in the casing to pass the Texas Railroad Commission
H-5 pressure test. For the pinhole leak, the nanosealant was placed across the leak point, and pressure was
applied at surface continually until leakoff was minimized. The leaking gas microannulus was squeezed
from surface until the leakoff was eliminated.
The nanotechnology-based sealing fluid was successful in each case. For the leaking microannulus wells,
hesitation squeeze schedules were applied, and both leaks were sealed with a projected penetration greater
than 500 ft. These wells were then tested with light detection and ranging (LIDAR) to ensure no gas leaks
were occurring at surface after the treatment. For the candidates selected with casing leaks, all passed the
regulatory Texas Railroad Commission H-5 pressure test and were put back into service. Three of the wells
resulted in a final pressure drop of 0 psi/min based on the hesitation squeezes, and the other one well resulted
in a pressure bleedoff reduction more than 25 times the original bleedoff rate.
The activation mechanism based on contact with annular materials is a significant breakthrough in
squeeze operations because it removes all complexity from the fluid design, which historically required
extensive laboratory testing. It also removes time-based boundaries on placement, and ultimately, it
eliminates or reduces the drillout time compared to conventional or resin applications. Conventional
remedial placement techniques can be used with the sealant, thus further simplifying the job execution.
This combination of simplified execution techniques and the lack of necessary laboratory testing and well
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condition input allows for a quick fit-for-purpose implementation as problems arise, which saves both time
and money.

Introduction
Since drilling in the US started in the 1800s, more than two million wells have not been permanently
abandoned (US Environmental Protection Agency 2017). As these wells age, remediation and abandonment
become common activities in the life cycle of the wells. A few of the many challenges that emerge during
this cycle in a well's life are annular sustained casing pressure and pinholes in the casing.
Many wells are known to have annular casing pressure, also known as sustained casing pressure or
pressure between casing strings. Abandonment of these wells in the future will pose challenges, as it did in
a series of recent wells abandoned in Colorado. After completing plug and abandonment operations on two
wells, both were found to have continued gas leaks. Reentry was performed to establish the source of the
leak, and a low injectivity of 15 psi/min was achieved, a value low enough to prevent the use of conventional
or microfine cement to remediate the wells.
The second example of challenges faced due to aging wells is the generation of pinhole leaks in the casing.
In Texas, injection and disposal wells are required to demonstrate mechanical integrity at least every 5 years
if not more often per the Texas Railroad Commission (TRRC) H-5 test. The test consists of a stabilized
pressure test between 200 psig and 500 psig for 30 or 60 min (TRRC 2016). Wells that fail the pressure test
may have a small pressure leakoff that is a result of very small leaks in the casing that are low enough to
prevent the use of conventional cement to remediate the leak.
Over the years, Portland base cement has been the option of choice for the majority of oil and gas well
remediation treatments. The conventional Portland cement solution for remedial cementing has thus far been
mostly successful. However, as the industry ages, additional challenges are created, as seen in the scenario
mentioned above. The challenge of sealing pathways too small, smaller than 120 μm, for conventional
methods with Portland cement required additional technologies to be developed. Other well remediation
scenarios require sealing small path ways as well.

Limitations of Current Solutions

Currently there are numerous solutions for remediating wells to allow an adequate seal. However,
when addressing sealing pathways that are smaller than 120 μm this requires additional alternatives to
conventional cementing techniques and fewer solutions are available. Fig. 1 shows a summary of the squeeze
materials available as quantified by the "injectivity factor" described by Cowan (2007). As the pressure
increases for a given flow rate or as the flow rate decreases for a given pressure, the injectivity factor
increases, thus indicating smaller particle systems are required to seal the leak path. The focus of this paper
is addressing applications in the rightmost column of Fig. 1, injectivity factors greater than 6,000. The
current options for sealing small leaks are microcement systems, resins, and casing patches. All have their
own operating envelope with limitations.
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Figure 1—Injectivity factor calculation and summary of current squeeze sealant availability application range.

Optimized microcement blends can reliably penetrate gaps down to 120 μm (Schlumberger 2010). The
setting time of cement blends are fixed by temperature and formulation, which also adds a limit to cementing
options.
Nanosealants are alternatives to in-situ polymerization technologies (resins/monomers) for sealing
pathways smaller than120 μm. Nanosealants have been validated to enter and effectively seal pathways as
small as 20 μm; further testing is required to extend this range to a lower value. Some in-situ polymerization
technologies utilizing low-viscosity monomers can enter and seal pathways as small as 2 μm. Specialized
knowledge of chemistry and experience with formulating resin or monomer sealants is necessary for
proper selection and design of in-situ polymerization technologies. Epoxy resins are among the most
common solids-free sealants used for well repair, but many commercial products have high viscosity, which
makes them difficult to place in small pathways. Additionally, resins, monomers, and catalysts for in-situ
polymerization technologies typically have Category 2 or higher Global Harmonized System (GHS) ratings
for health, environmental, and/or physical hazards, adding additional risks to those involved in the execution
of the treatment. Nanosealants eliminate most of the specialized expertise in design and testing associated
with in-situ polymerization technologies or cements.
Casing patches or scab liners are an appropriate solution to recover the integrity of casing with holes
in them; however, there are also limitations. Casing patches work well for short distances that have casing
integrity above and below the damaged casing, but there is a reduction in diameter that must be acceptable
for future operations of the well. Casing patches cannot be run in wells with restrictions that cannot be
removed. Casing patches cannot seal annular leak paths (micro-annuli/small channels) that may be the cause
of sustained casing pressure.
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Nanosealant Based Sealing Fluid

A nanosealant-based sealing fluid was developed to target cracks/micro-annuli smaller than120 μm as
the limitations to the currently available solutions warrant an additional option. The sealing fluid directly
addresses some of the limitations of the other alternatives available. First, the solution is a low-viscosity
nanoparticle fluid, which allows it to penetrate gaps smaller than 120 μm with the ability to work in gaps
up to 1,000 μm, providing an overlap with microcement. The penetration was validated by injecting cement
into slots of known dimensions, as shown in Fig. 2. The sealant was pumped into the slot with a volume
equal to 500 channel volumes with a pressure of 12 psi, reiterating the ease of injection. After the fluid was
pumped into the channel, it was allowed to cure at room temperature for 18 hours and the pressure was able
to build to greater than 1,000 psi/ft.

Figure 2—Cement slot (49-mm long, 9-mm wide, 60-μm thick) used for penetration validation.

Additional slot widths were tested, demonstrating that gaps as small as 20-μm were penetrated and
sealable. The limitation from qualifying smaller gaps was control of the gap width below 20 μm. The
improvement in penetration of the nanosealant when compared to microcement is an estimated 1,000 times
based on the particle size. Typical microcement systems have less than 5% of the particles greater than 12
μm.
Second, the nanosealant solution is a single component, which reduces the complexity of fluid
formulation significantly from cementing and resin alternatives and which also reduces the opportunity for
formulation errors due to improper design basis, improper design, or changes in execution versus plan. The
single-component solution eliminates extensive laboratory testing requirements before treatment that come
with cement or resin cements. This also simplifies the on-location deployment as the only concentration
measurement needed is the volume to be pumped into the well.
The material activates only upon contact with divalent ions, which includes set cement. This allows
unlimited deployment time until the material is activated when it contacts divalent ions in the leak
path. This unlimited working time greatly reduces placement risks and enables deployment with more
exotic techniques than can be used for cement systems or resins, such as casedhole dynamics tester and
extended placement dump bailers through coiled tubing or with wireline allowing for low-volume precision
placements. Due to the activation mechanism of the nanosealant, the material is self-diverting, as shown
in Fig. 3. The nanosealant initially is injected into the wider gap or path of least resistance, as shown in
2 in the top right. Then, due to the reaction mechanism, the initial path is plugged as shown in 3 in the
bottom right. Then, the path of least resistance becomes the narrower gap, and the nanosealant injects into
the narrower gap in 4 in the bottom left.
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Figure 3—Nanosealant self-diverting. 1) Top left, injection begins. 2) Top right, injection into path of least resistance or larger
annular gap. 3) Bottom right, larger gap becomes sealed. 4) Bottom left, nanosealant self-diverts to penetrate new path.

An additional benefit is the low health, safety, and the environment (HSE) footprint from enabling safer
operations compared to resin solutions. Additionally, cleanup of equipment can be done with water in
contrast to the solvents that are often required to clean up resin systems.
Drilling out material and placement of tools after a squeeze treatment takes time and can increase
risk of casing damage in older wells or wells with casing corrosion or damage. In some cases, cement
treatments can be drilled out early when compressive strength is low to minimize time and potential
damage to the well. Resins and monomers typically cannot be drilled out early based on their setting and
hardening characteristics. Additionally, the ductility of some resins can make drilling out epoxy resins more
challenging than cements.
A simple qualitative demonstration of the drillability of the nanosealant as compared to a composite
resin, with comparable properties to high compressive strength cement, is shown in Fig. 4. The nanosealant
was much easier to penetrate and drilled within 15 sec. The composite resin was not penetrated after a 52-
sec duration.
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Figure 4—Drillability comparison of nanosealant to composite resin

shows that the drillout of the nano-sealant is qualitatively easier.

Case Histories
Two applications for the nanosealant were tested with positive results. An operator in the Permian basin in
Texas had four injector wells with casing leaks that utilized the sealant to pass the TRRC H-5. An operator in
Colorado had two wells that required remediation after abandoning the wells due to an indication of surface
gas after well abandonment. Both applications had wells with projected gaps smaller than 120 μm.
First, we review the case for the Texas wells. The wells were injector wells that failed to pass the TRRC
H-5 well integrity test, thus requiring either remediation to pass the test or abandonment. The well integrity
test required the wells to have a stabilized pressure within 10% of the 500-psi test pressure, and then maintain
a stabilized pressure for the 30-min test. The leaks in the casing were estimated to be 10 to 100 μm based on
the low injectivity. The casing inner diameter could not be reduced, which eliminated the option to utilize
a casing patch or a scab liner option. Other sealant options that had been tried resulted in a failure rate of
approximately 50% per the operator. Resin options posed challenges with drillout because the ductility of
the resin resulted in long flexible cuttings that plugged bottomhole assemblies and surface equipment while
drilling out. These challenges made the nanosealant option attractive for these wells.
The wells treated were 5 ½-in. or 7-in. casing strings with 20 to 233 ft of pinholes starting from 500 ft
to 4,885 ft. On all four of the wells, a low-pressure bleedoff rate was recorded. The initial bleedoff rates
varied from 1.38 psi/min to 146 psi/min. An example wellbore schematic of a well is shown in Fig. 5.
SPE-191577-MS 7

Figure 5—Sample wellbore schematic with pinhole leaks treated with nanosealant.

The treatments were pumped through a 2 3/8-in. or 2 7/8-in. tubing string and balanced. A sample
pumping schedule can be found in Table 1.

Table 1—Nanosealant pumping schedule example.

Fluid/Step Volume (bbl) Rate (bpm) Density (ppg)

Fresh Water 15.0 2-4 bpm 8.3

Wiper Ball – – –

Sealant 15.0 2-4 bpm 10.0

Wiper Ball – – –

Fresh Water 1.6 2-4 bpm 8.3

After balancing the fluids, the tubing string was pulled above the nanosealant, and a circulation was
completed prior to commencing squeeze operations by shutting in the annulus around the tubing and
applying pump pressure down the tubing. The hesitation times varied from 3 to 24 hours. As mentioned
earlier, the initial bleedoff rates varied from 1.38 psi/min to 146 psi/min, and the final bleedoff rate for three
of the wells were 0 psi/min whereas well 1 in Fig. 6-Hesitation schedule of example well 1.Fig. 6 had a
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final bleedoff rate of 0.553 psi/min. The hesitation charts are below in Fig. 6 through Fig. 10Fig. 9. All four
of the treatments resulted in a successful TRRC H5 test. After waiting for the sealant to cure for greater
than 24 hours, the majority of the residual material left in the wellbore was circulated out of the well since
it did not react with divalent ions. The locations that the material had cured allowed for efficient drillout.
The mechanism of sealing does not come from particle bridging, but is due to the material activating after
contacting the divalent ions.

Figure 6—Hesitation schedule of example well 1.

Figure 7—Hesitation schedule of example well 2.

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Figure 8—Example hesitation schedule of example well 3.

Figure 9—Example hesitation schedule of example well 4.

Figure 10—Example comparison of the initial hesitation pressure to the final hesitation pressure.
The red line is the initial bleedoff pressure and the green line is the final squeeze bleedoff pressure.
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An example of the initial hesitation pressure compared to the final hesitation pressure is shown in Fig. 10.
In Colorado, two wells experienced annular pressure after traditional plug and abandonment operations
had been performed and were subsequently treated with nanosealant. In the first case, the well was section
milled to open access between the production and surface casing annulus. After establishing pressure
connection between the section mill and bradenhead, a nanosealant treatment through the bradenhead valve
established over 500 ft of penetration. Pressure loss during squeezing on this well dropped from 123 psi/
min to 3.4 psi/min during squeeze operations. Final surface casing pressure dropped to 0 psi with no gas as
measured by light detection and ranging (LIDAR) or fluids detectable at surface after the treatment. In the
second case, the well was also section milled, and the nanosealant treatment was pumped via the balance
plug method described previously in this paper. Pressure loss during squeezing on this well dropped from
330 psi/min to 1.9 psi min. Again, after placing the regulatory required surface cap, the well showed no
detectable levels of gasor fluids at surface and was successfully abandoned.

Conclusion
The application of the nanosealant to seal both pinhole casing leaks and an annular gas micro annulus with
low injectivity resulted in successfully meeting the requirements for the jobs. The wells in Texas were
returned to injection and remain on injection today. The wells in Colorado were successfully abandoned with
no gas readings at surface. The field applications confirmed the testing results, and demonstrated the benefits
of the nanosealant with the simplified one-component formulation, environmentally sensitive formulation,
high injectivity into gaps smaller than 120 μm, effective penetration, and ease of drillout. The nanosealant
is an effective tool in the toolbox for remediation and well abandonment applications that would otherwise
be difficult to treat.

Acknowledgments
The authors of this paper would like to thank the support received in the writing of this paper and particularly
the implementation of the nanotechnology-based sealing fluid. We would like to acknowledge the Oxy Oil
& Gas and Schlumberger management teams for always pushing us to achieve better results. Also, we would
like to acknowledge Dr. Simon James for his technical support in the development of the nanosealant. All
of us honor the memory and contributions of our friend James "Jamie" Reid for his dedication and service
to our industry. He is missed.

References
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MS.
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