IPTC-19600-MS

Unconventional Nanotechnology-Based Tracers for Drilling and Completion

Applications

Sankaran Murugesan, Radhika Suresh, Devesh Agrawal, Qusai Darugar, and Valery Khabashesku, Baker Hughes

Copyright 2020, International Petroleum Technology Conference

This paper was prepared for presentation at the International Petroleum Technology Conference held in Dhahran, Saudi Arabia, 13 – 15 January 2020.

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Abstract
Tracer technology is a very efficient diagnostic tool in the oil and gas industry to obtain valuable information
about reservoirs. The interpretation of tracers that have traversed the reservoir reveals characteristics
such as inter-well connections, heterogeneities, and water movements that can be used to improve
hydrocarbon recovery efforts. A strong need exists for tracers that can withstand increasingly harsh reservoir
conditions such as high pressure, high temperature, high salinity and sour environments. Recent progress
in nanotechnology and developments in nanoparticle synthesis and engineering bring possibilities for
tracer applications. This paper discusses a unique approach towards unconventional properties shown by
nanoparticle tracers.

Introduction
Reservoir tracer technologies have been employed for more than five decades for conventional reservoir
analysis, especially to understand water and gas flooding. The tracers are mainly based on radioactive
materials and water-soluble chemicals (fluorescent dyes). Recent developments in horizontal drilling and
hydraulic fracturing require more information about the reservoir, especially the effectiveness of the
fractures and productivity of each individual stage. Obtaining this information has generated a huge demand
for tracer technology. Commonly used radioactive tracers have become more restricted throughout the
world due to the associated radiation hazards. Fluorescent dyes and inorganic ions do not pose such
hazards. Nevertheless, dyes experience decomposition at reservoir temperatures and inorganic ions require
long detection times. Recent advances in nanotechnology, like synthesis and chemical modification of
nanomaterials, created a new technology platform for innovative oilfield applications. The enhanced
diffusion-driving forces through the high surface area of nanomaterials make corrosion and erosion-
resistant coatings, reduced-wear elastomer seals and abrasion-resistant carbon-carbon composites promising
uses for enhanced oil recovery (Negin et al., 2016). In addition, nanomaterial coatings alter reservoir
wettability by reducing the interfacial tension; (Ogolo et al., 2012); Hendraningrat et al., 2013).Similarly,
nanoparticles can be used for tracer applications due to their unconventional properties: they are inert, non-
volatile, chemically stable, non-reactive, and non-fractionating. Nanoparticles can be functionalized with
2 IPTC-19600-MS

hydrophilic/hydrophobic groups that forms a stable dispersion in water/oil. Stabilizing the nanoparticles in
high-temperature and high-salinity media has become a significant focus for exploration and production.
However, some earlier efforts were focused on stabilizing the nanoparticles with zwitterionic polymers
through covalent functionalization. (Kanj et al., 2011; Carlos et al., 2016). Further, nanoparticles can be
chemically modified so they can be pumped with each stage of multistage fracturing applications and
monitored with flowback or production fluid on the surface. Fluid analysis can determine the location
or zone of production and potentially assign percentages to each stage. This paper presents the unique
methodology used to synthesize and functionalize nanoparticles to exploit three fundamental principles of
photoluminescence in complex systems for tracer applications. (1) bringing "fluorescence" properties in
carbon-based materials by tuning its size and heteroatom substitution; (2) using fluorescence resonance
energy transfer (FRET) in a confined environment to overcome the limitation of donor and acceptor (FRET
can be used to generate a multiple color tracers by choosing appropriate donor and acceptor with a tuned
synthesis procedure); (3) exploring "upconversion" with selective doping of rare-earth in an oxide or
fluoride matrix for tracer applications. Upconversion uses low-energy excitation (near IR) and emits high
energy in the visible region, helping to eliminate overlapping signals of organic molecules containments
and background signals.

Fluorescence by carbon nanoparticles

Carbon nanoparticle-based tracers can be another option due to their inherent properties; they are inert, non-
volatile, chemically stable, non-reactive, and non-fractionating. Further, these tracers can be functionalized
with hydrophilic/hydrophobic groups to form a stable dispersion in water/oil. These carbon nanoparticles
exhibit strong fluorescence properties that can be tuned appropriately. Recently, much attention has been
given to carbon quantum dots (CQDs) due to their outstanding fluorescence properties and their application
towards chemical sensing and bio-imaging (Haitao et al., (2012). In most cases, CQDs outperform
traditional semiconductor-based metal chalcogenide (CdS, CdSe and PbS, etc.) quantum dots. CQDs
properties have been improved by doping with heteroatoms (nitrogen, phosphorus and boron) or by
introducing surface functional groups. Fig. 1 shows the possibility of tuning the emission properties of
CQD by different doping through its energy levels. The electrochemical method seems to be more energy
efficient with significant capability for tuning the properties of synthesized CQDs. Here, we discuss one-
pot electrochemical synthesis through electro-carbonization of low molecular weight chemical precursors
and the ability to dope CQDs for tracer applications.

Figure 1—Schematic representation of the semiconductor property of carbon quantum dots having
fluorescence emission and modulation by suitable doping for different emissions with the same excitation
IPTC-19600-MS 3

Fluorescence resonance energy transfer (FRET) in a confined environment

The Förster resonance energy transfer or fluorescence resonance energy transfer (FRET) phenomena was
used to obtain multiple tracers with a single excitation process. In FRET, a donor chromophore in its
electronic excited state may transfer energy to an acceptor chromophore through non-radiative dipole–
dipole coupling (Stryer and Haugland 1967; Valeur and Berberan-Santos, 2012). This coulombic dipole-
dipole interaction requires a spectral overlap between the donor emission and an acceptor's absorption. The
energy transfer rate from the donor to the acceptor depends on the sixth power of the distance.

The rate constant kET of FRET:

Where τD is the lifetime of the donor in the absence of acceptor and R0 is a constant for the donor-acceptor
pair – Förster radius.
FRET occurs at distances of a few nm and only if the donor and acceptor are physically linked. Some
earlier work described the incorporation of a dye or chromophores into the silica matrix to enhance the
brightness and quantum efficiency (Ow et al., 2005; Liang et al., 2013). FRET within a silica matrix has been
utilized by using different organic molecules and different chromophores to understand the mechanism of
the charge-transfer process and enhanced quantum efficiency (Wang et al., 2006; Xu et al., 2010; Dhir and
Datta, 2016). Overall, for silica nanoparticles the distance between the donor and acceptor is not necessary
to generate multiple colors. The presence of a silica layer over the dye molecules plays an important role in
transferring the energy between the donor and acceptor. If the donor molecules are excited with a particular
wavelength, the generated energy excites different concentrations of the acceptor. By tuning the composition
and concentration of the acceptor and using the energy transfer from the donor molecules, multiple colors
of tracers are generated. Fig. 2 Shows the possibility of changing donors and acceptors to get different
emissions, and the possibility of oil-dispersible tracers with the functionalization process. The dielectric
component plays an important role in the fluorescence energy-transfer process by enhancing its quantum
efficiency. In addition, the dielectric silica system increases the lifetime of the system.

Figure 2—Schematic representation of the scientific phenomena of multicolor silica particles generated by donors and
acceptors in a constrained environment with the possibility of functionalization to make the particles dispersible in oil
4 IPTC-19600-MS

Upconversion nanoparticles
Upconversion nanoparticles can be alternate luminescent tracers that use low energy to excite and yield
high-energy emissions. This approach helps overcome the interference of organic molecules, enabling use of
these nanoparticles as tracers for production and well monitoring. Upconversion nanoparticles can tune the
wavelength of emission. They also have possibility of surface chemistry modification, no photobleaching,
no auto-fluorescence, non-toxic properties and excellent lightfastness. Upconversion nanoparticles are
generally rare earth oxides or fluorides with doping. Lanthanide-doped nanoparticles can be excited with
near-infrared light, and they are optimal for reducing an autofluorescence of crude oil due to hydrocarbons.
Lanthanide-doped nanoparticles are more often represented by fluorides such as NaYF4, NaGdF4, LiYF4,
YF3, CaF2 or oxides such as Gd2O3 doped with certain amounts of lanthanide ions (Wang et al., 2011).
Generally, lanthanide ions used in photon upconversion are pairs of erbium-ytterbium (Er3+, Yb3+) for
green and red emission or thulium-ytterbium (Tm3+, Yb3+) for near-ultraviolet, blue and red light emission
(Wilhelm, 2017). The potential for tuning the emission signatures by altering the sensitizer or activator in
the matrix is shown in Fig. 3.

Figure 3—Schematic representation showing the scientific phenomena of upconversion nanoparticles

facilitated by suitable doping change in emission wavelength at a single excitation of 980 nm

This paper discusses the brief synthesis protocol and surface modification to alter the emission properties.
The adsorption behavior of these nanoparticles was studied in API brine and crude oil emulsion made with
API brine and surfactant through static and dynamic experimental conditions at 70°C. Further, the particles
were studied in a flow-through rock conditions to find their transport behavior by using a low-permeable
rock and sand pack setup.

Experimental Section
Nanoparticle synthesis and surface modification
Carbon Quantum Dots (CQDs). CQDs were synthesized using electrochemical redox reaction as
described in earlier publications (Murugesan et al., 2016, 2017). In summary, electrochemical reactions
were performed in a two-compartment cell that was separated by a sintered glass frit. The electrolyte
used in both cells was low molecular weight chemical precursor. For doping different concentrations of
IPTC-19600-MS 5

heteroatoms present, low molecular weight chemical precursors were added. Different concentrations of
nitrogen-containing precursors were added to the system to synthesize nitrogen-doped CQDs.
Functionalized Silica nanoparticle Synthesis. Silica nanoparticles were prepared by a sol-gel process
using ammonia and water as catalysts by using the modified Stöber synthesis method (Stöber and Fink
1968; Xu et al., 2010). Detailed experimental procedure for synthesis of FRET-silica and functionalization
process are given in our earlier publication (Murugesan et al., 2017). Schematic representation of the overall
synthetic process and functionalization is shown in Fig. 4.

Figure 4—Schematic representation of synthesis of multicolor silica nanoparticles

and the functionalization process to generate oil-dispersible nanoparticles

To validate that FRET activity was taking place in the constrained environment of silica nanoparticles,
we compared two different silica particles into which donor-acceptor dyes were incorporated by adsorbing
the donor-acceptor dye complex onto pre-synthesized commercial silica nanoparticles, and by adsorbing the
donor-acceptor dye complex onto pre-synthesized powder nanoparticles. A brief description of the processes
is as follows.
Process 1: A pre-synthesized commercial silica nanoparticle colloidal solution (10 mL) of approximately
20 nm was dispersed in 100mL of ethanol and sonicated for 10 minutes to ensure complete dispersion of
the particles. To that dispersion was added 1mL of ethanol containing 1.2mg of Fluorescein isothiocyanate
(FITC) and 1mL of ethanol containing 0.15mg dichlorotris (1,10-phenanathroline) ruthenium(II) hydrate.
The dispersion was stirred and maintained at 40°C for 24 hours. After 24 hours, the reaction mixture was
centrifuged and the coated fluorescent nanoparticles were collected from the bottom of the centrifuge tube.
Process 2: A pre-synthesized commercial silica nanoparticles dry powder (0.1g) of approximately 20
nm was dispersed in 100mL of ethanol and sonicated for 10 minutes to ensure complete dispersion
of particles in ethanol. To that dispersion was added 1mL of ethanol containing 1.2mg of Fluorescein
isothiocyanate (FITC) and 1mL of ethanol containing 0.15 mg dichlorotris (1,10-phenanathroline)
ruthenium(II) hydrate, and the dispersion was maintained at 40°C for 24hours. After 24, the reaction
mixture was centrifuged and the coated fluorescent nanoparticles were collected from the bottom of the
centrifuge tube. Silica nanoparticles (FRET-Silica) obtained from processes 1 and 2 were compared with
silica nanoparticles synthesized by incorporating donor-acceptor dyes systematically separated by thin silica
coating (Murugesan et al., 2017).
6 IPTC-19600-MS

Surface modification of upconversion nanoparticles. Upconversion tracers consist of a NaYF4 matrix with
Yb doping as sensitizers, and Er and Tm as activators, to tune their emission wavelengths. Here, we used
NaYF4 with Yb and Er doping for a green emission tracer (T1) and Yb with Tm for a red emission tracer (T2).
Generally, these nanoparticles are synthesized in oleic acid/oleylamine mixture at approximately 300°C
(Wang et al., 2011; Stefan Wilhelm, 2017). These synthesized particles have functional groups such as oleic
acid that makes them soluble in oil due to their hydrophobic behavior. To make these particles dispersible
in water, they must undergo functionalization. The functional groups present can be easily exchanged or
modified by different chemical functional groups. Exchange reaction is most commonly used for surface
modification (Murugesan et al., 2018). Here, we have adopted an exchange reaction with citrate molecules
(Fig. 5).

Figure 5—Schematic representation of surface modification of nanoparticles with citrate to make tracers water dispersible

Preparation stable oil in water emulsion

A stable crude oil emulsion was prepared by mixing 2mL of surfactant with 100mL of API brine. Then
500 microliters of oil was added and sonicated (2 hours) in a sonication bath to produce an oil-in-water
emulsion. API brine was prepared by dissolving 200 g of sodium chloride and 50 g of calcium chloride
dihydrate in de-ionized water (2.25L).

Nanoparticle characterization
Nanoparticles were analyzed by scanning electron microscopy (SEM) using a field emission scanning
electron microscope – JEOL JSM-7800. Fluorescence measurements were obtained using Horiba Jobin
Yvon Fluorolog 3 spectrofluorometer equipped with a single grating monochromator and a photomultiplier
tube detector having an accuracy of 0.5 nm. For lifetime measurements, NanoLEDs were used to generate
a pulsed light source. For upconversion experiments, the instrument was modified with a light source from
a 980-nm 2-Watt CW laser.
Time-resolved fluorescence measurements were performed to obtain information about the fluorescence
lifetime (FLT). Fig. 6 shows schematic representation of FLT measurement with use of a pulsed excitation
light source and a single photon detection module with pulsed detection. This makes FLT an absolute
measure that is independent of concentration, whereas the steady state gives only an average and relative
presentation. Steady-state and time-resolved measurements help to elucidate the complex fluorescence
signatures. The FLT of the system was measured by exciting with very short pulses (a d-pulse) at t = 0 and
measuring the decay of florescence intensity. This experiment was done by using time-correlated single-
photon counting (TCSPC).
IPTC-19600-MS 7

Figure 6—Schematic representation of fluorescence lifetime (FLT)

measurement system with time-correlated single-photon counting (TCSPC).

In ideal conditions, a single-exponential decay of fluorescence intensity (excited by a d-pulse at t = 0)

is given by the relationship

while the measured fluorescence decay is a convolution of the real decay with the response of the detection.

The instrument response function, iREF, is typically measured as a response of the instrument to a scattered
excitation pulse. Usually, from the measured data the parameters of I(t), (i.e., the lifetime t) are obtained
by nonlinear fitting combined with the deconvolution procedure. DAS V 6.1 was used for this analysis to
fit the data.
Particle-size measurements were conducted on a Malvern Zetasizer Nano instrument (using a dynamic
light scattering (DLS) technique also referred as Quasi-Elastic Light Scattering (QELS). The disposable
plastic cuvette containing the dispersion sample was placed in the sample chamber of the instrument. In
the dispersion, particles move randomly due to the Brownian motion, causing the laser light to scatter at
different intensities. In-built algorithms in the instrument analyze the intensity fluctuations and determine
the velocity of the Brownian motion, particle size and distribution using the Stokes-Einstein equation.
Absorption measurements were collected on a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer. API
brine solution stability was studied by mixing 1 wt. % of dots and kept in static mode for 30 days at 80°C.
After the static test, the fluorescence activity of the samples was studied.

Flow testing procedure

Flow experiments were performed to study the transport of carbon dots through the Berea sandstone cores
at 80°C. Carbon dots were injected at constant concentration and elutant samples were collected at regular
interval and analyzed on UV-Vis. Before the experiment, the core was thoroughly cleaned in running de-
ionized water and dried in the oven at 100°C to evaporate the water until the weight of the dried cores
stopped changing. Dried cores were CT scanned to visualize core internals and make sure they were free of
any cracks and defects. The conceptual representation of the experiment is shown in Fig. 7. For measurement
of the unknown concentration, a calibration curve is prepared from the UV absorbance measured at 274 nm.
8 IPTC-19600-MS

Figure 7—Representation of flow experiment utilized for CQDs at 80°C

Flow testing of the mixture of the nanoparticle's dispersion in the crude oil in the API brine emulsion
was conducted on the sand pack flow setup. The experiment was conducted at the flow rate of 5 mL/min at
70°C. The 20/40 mesh gravel pack sand was filled and compressed in the flow cell to prepare a 4.4-in. tall
sand pack column. Initially, API brine at 5 mL/min flow rate was injected through the sand pack, followed
by the injection of the nanoparticle mixture in the emulsion at same flow rate through accumulator. DI water
was used to feed the injection pump that pushed the piston in the accumulator. This action then pushed an
equal amount of nanoparticle dispersion to the flow cell. Nanoparticle dispersion was injected in the flow
cell from the bottom, and samples were collected from top of the cell in the fraction collector at a regular
interval. Prior to the injection, nanoparticle dispersion used in the experiment was filtered through the 200-
nm PTFE filter. The sand pack setup and conceptual diagram is shown in Fig. 8.

Figure 8—Picture of sand pack experiment set up and the flow process in the experiment
IPTC-19600-MS 9

Results and discussion

Syntheses of CQDs occurred through electrochemical carbonization of low molecular weight chemical
precursors containing carbon, oxygen, and hydrogen. Nitrogen doping of CQDs are performed through
addition of low molecular weight nitrogen source to the electrochemical reaction. SEM images of carbon
dots (A. pure and B. nitrogen doped CQD) and fluorescence spectrum (C. pure CQD and D. doped CQD)
were shown in Fig. 9. SEM images of these synthesized particles shows a spherical morphology and particle
sizes between 10 and 20 nm. Presence of nitrogen shows strong blue coloration, whereas pure CQDs show
green coloration.

Figure 9—SEM images of electrochemically synthesized CQDs (A) and nitrogen-doped CQDs (B). CQD absorption
spectrum from UV-Vis and fluorescence excitation and emission spectrum by 480 and 355 nm (C) and Nitrogen-doped CQD
absorption spectrum from UV-Vis and fluorescence excitation and emission spectrum by 435 and 335 nm (D), respectively.

Synthesized silica nanoparticles were characterized by different spectroscopic techniques. The SEM
images of FRET-Silica particles have a spherical morphology and a particle size between 50 and 100 nm
(Fig. 10A). The normalized emission spectrum of all samples taken where synthesized silica nanoparticles
without dye show no emission spectrum [Fig. 10 B (a)], silica particles made with the addition of dye during
the synthesis show a sharp emission of approximately 520 nm [Fig. 10 B (b)], FRET-Silica shows a shift in
the emission due to the addition of acceptor electron energy levels [Fig. 10 B (c)]. The presence of acceptor
dye increases the intensity, and the observed peak shift produces the shift in the silica nanoparticle color,
which shows the multicolor property. The energy transfer from the dye-1 to dye-2 plays an important role
in the fluorescence enhancement mechanism in FRET silica nanoparticles. Traces d, e shown in Fig. 10 B
are the emission properties of silica produced by Process 1 and 2, respectively. Process 1 and 2 do not show
significant FRET effect at the same level of donor-acceptor dye complex added to the system. This further
confirms that controlled synthesis and constrained environment play an important role in the FRET activity.
Process 1 with colloidal silica nanoparticles enhances the signal relative to the dye-1 compared to dye-1
and dye-2 complex. This may be preferential adsorption of dye-1. In Process 2 the dye-1-dye-2 complex
is weakly adsorbed, showing weak FRET signals.
10 IPTC-19600-MS

Figure 10—A. SEM image of synthesized FRET silica nanoparticles and B. Normalized fluorescence
emission spectrum of all samples with an excitation at 365 nm. (a). As synthesized silica nanoparticles
without any dye, (b). With the addition of dye-1 to silica, (c). FRET-Silica, (d). Process-1, (e). Process-2

A photograph was taken in white light and UV-light to see the color difference with as synthesized
silica, dye-1 incorporated silica, and FRET silica with 22 μmols of dye-2. The photograph clearly projected
the color difference in UV light due to the fluorescence property of the molecules (donor and acceptors)
presence (Fig. 11).

Figure 11—Photograph of as-synthesized silica, dye-incorporated silica, FRET-Silica,

Process-1 silica and Process-2 silica nanoparticles exposed to visible light (A) and UV light (B)

The surface of silica is very versatile. It can be modified easily according to the medium in which it
will be used. Hydrophobic FRET silica particles were dispersed in mineral oil for fluorescence activity
measurements. Mineral oil was chosen as the model hydrophobic compound to show the feasibility of
the functionalized nanoparticles to disperse in oil. Functionalized silica nanoparticles showed very good
dispersion in oil. The spectra were generated by exciting the samples at 365-nm wavelength. The emission
spectrum of mineral oil and functionalized FRET silica in mineral oil is shown in [Fig. 12 (A)]. The
spectrum clearly shows the distinct peaks pertaining to the FRET. Generally, the mineral oil spectrum is
seen in the shorter wavelength region. By using functionalized FRET-silica in mineral oil, the emission
spectrum is clearly distinguishable with the tracers. The TCSPC FLT measurement of the dye and the dye-
IPTC-19600-MS 11

incorporated SiO2 and the FRET silica. The figure clearly shows that FRET silica has a higher FLT than
dye-1-incorporated silica and pure dye-1 [Fig. 12 (B)]. This enhanced lifetime is due to the charge transfer
from the donor to acceptor.

Figure 12—A. Emission spectrum of mineral oil (a) and FRET silica dispersed in mineral oil (b) by excitation at 365
nm and B. Time-correlated single-photon counting FLT measurements of pure dye-1, silica-dye-1 and FRET-silica.

The upconversion tracer nanoparticles morphology was characterized by scanning electron microscopy
(SEM). The SEM images of the surface modified upconversion nanoparticles tracer are shown in Fig. 13
A. From the analysis, the particle sizes are approximately 50 nm, with uniform size distribution. Fig 13.B
is a photograph of surface-modified nanoparticles by the ligand exchange process with citrate molecules in
DI water, API brine and crude oil in water emulsion.

Figure 13—A. SEM image of surface modified upconversion nanoparticles dried over the Si wafer chip
for imaging. These particles were imaged at a 10-mm working distance with 20 kV. B. photograph of the
stable dispersions formed by the tracer nanoparticles in DI water, API brine and crude oil in water emulsion.

The luminescence spectra of tracers in API brine-based crude oil in water emulsion taken individually
and in a mixture (Fig. 14). The spectra clearly show the peaks corresponding to a green emission from
T1 with a maximum wavelength of approximately 542 nm and approximately 800 nm for T2. These peak
features are maintained in the mixture of two tracers. For further analysis of the samples in the static and
flow experiments, peaks at 542 and 800 nm are used for T1 and T2, respectively. The calibration plot for
the individual tracers shows good R-square value (Fig. 14 B and C).
12 IPTC-19600-MS

Figure 14—A. Luminescence spectra of tracer in individual T1 and T2 form and a mixture of T1 and T2 in API brine
crude oil in water emulsion. B and C. Calibration plots of T1 at 542 nm and T2 at 800 nm showing good R square value.

Flow studies
Flow experiments of pure CQD in 1 wt. % NaCl solution was performed in low permeable cores at 80°C. Fig.
15 shows percentage of recovery of CQDs in the eluting samples with respect to the injected concentration
at any time. The breakthrough of CQDs occurred before one pore volume, which is due to smearing of the
concentration front in the core due to dispersion of CQDs. Due to the same reason, CQDs continue to come
into the elutant even when the injection of the same is stopped. The area under the curve represents the
amount of the CQDs injected and collected. The percentage recovery of CQDs is found to be 76% after
7.5 pore volume of CQDs injection.

Figure 15—Concentration profile of CQDs in a core-flood experiment with 1 wt. % NaCl at 80.C.

To study the flow behavior of the FRET-silica nanoparticles, 500 ppm of samples were used for sand
pack experiments. Generally, nanoparticles in the dispersion encounter more resistance compared to the
carrier phase when injected into a reservoir. Depending upon the nanoparticle affinity to reservoir rock,
neighboring nanoparticles, and the carrier phase, an obvious concern is that they might become blocked at
IPTC-19600-MS 13

the inlet and form filter cake or aggregates. Another concern is that the nanoparticles might aggregate and
block pores and pore throats. For these reasons, nanoparticles were tested in the sand pack without crude
oil to obtain an initial perception of their transport behavior in porous media.
The FRET-Silica dispersion samples at the inlet and outlet of the flow cell were collected and measured
on the Fluorolog for fluorescence emission spectrum. The fluorescence signal was detected in all the
outlet samples after FRET-Silica breakthrough, which confirmed that the FRET-Silica in the dispersion
successfully passed through the sand pack. Fig. 16 shows the fluorescence emission spectrum of the effluent
from the sand pack at different time intervals. Usually, it is expected that the concentration at the outlet
will closely reach the level of injected concentration at some point. However, the intensity of the peak in
the outlet samples was significantly lower compared to the injected concentration, even after the injection
of over twenty pore volumes of FRET-Silica nanoparticles through the sand pack. Visual observation of
the samples showed clear differences in their appearance, not only among inlet (Fig. 17(a), (b), (C)) and
outlet ((d), (e), (f)) samples, but even the inlet samples collected at the accumulator outlet at different times
(Figure (a) and (b)) look very different.

Figure 16—Fluorescence emission spectrum of the effluent from the sand pack at different time intervals

Figure 17—FRET- Silica Nanoparticle Dispersion. Sample collected at the flow cell inlet (a)
Initially (b) After 136 minutes; and sample collected at the flow cell outlet (c) After 36 minutes
(d) 60 minutes (e) 64 minutes; (f) Flow cell bottom drained at the end of the experiment.
14 IPTC-19600-MS

In this study, the goal was to verify the detection of the FRET-Silica in the flow cell outlet and to disregard
the effluent concentration so that the issues pertaining to any new FRET-Silica could be identified. The DLS
measurement for particle size distribution was performed. Visually, the initial FRET-Silica sample (Fig.
11(a)) looked very translucent, and precipitation of particles was observed. The DLS measurement showed
very wide particle size distribution from nanometer scale to several microns. Due to this precipitation of
particles in the accumulator, the accumulator outlet or flow cell inlet concentration decreased with time.
One way to avoid this precipitation could be to filter the bigger particles and only use smaller nanometer-
scale materials. The bigger particles that were initially in the dispersion and flowing from the accumulator
towards flow cell were blocked, possibly at the sand pack inlet and partly at the stainless steel screen in the
bottom and remaining at the sand pack face. Only the smaller particles were able to pass through the sand
pack, as confirmed by DLS measurements. Flow testing of the mixture of the upconversion nanoparticle's
dispersion in the crude oil in the API brine emulsion was conducted on the sand pack flow setup as shown
in Fig. 8.
The Eluting concentration plotted for tracer 1 and tracer 2, as detected on the Florolog, is shown in Fig.
18. For tracer 1, almost half of the injected concentration is adsorbed in the sand pack, and more than 80
percent of the tracer 2 seems to be adsorbed in the sand pack. Injected tracer concentration initially and after
two hours were found to be same, indicating very good stability of the tracers in the emulsion.

Figure 18—Eluting concentration in parts per billion (ppb) for the tracer 1 and tracer 2

Conclusions
The procedures successfully exploited unconventional properties of nanoparticles for tracer applications in
a simulated downhole environment. CQDs show approximately 76 percent recoverable in a low permeable
Berea sandstone core. Further surface modifications are needed to have good recovery rate. Multicolor silica
nanoparticles are generated through a FRET mechanism of donor and acceptor dye molecules. It is possible
to flow FRET-silica nanoparticles through the sand pack. Successful flow conditions depend on nanoparticle
size and dispersion in the solvent. Upconversion tracers were evaluated in an oil-in-water emulsion with
surface modification. The flow experiments with a mixture of these tracers in an emulsion demonstrated that
individual tracers in a mixture can be differentiated without any interference from crude oil. Overall, this
novel approach in our studies confirms that the development of tracers with nanoparticles is successful and
test results are promising. However, some challenges encountered in choosing the dispersion and controlling
the particle size distribution must be addressed. This approach of using unconventional nanoparticles
IPTC-19600-MS 15

can open new opportunities for in-situ monitoring of reservoir zonal communication and provide further
understanding for improving the enhanced oil recovery efforts and water flooding operations.

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