FIELD OF INVENTION
This invention relates to a polyamino-functionalized
nanoparticles based composition as hardener for particulate consolidation
and method relating thereto. Specifically, the present invention relates to a
5 treatment composition and methods for stabilizing portions of a
subterranean formation, including portions of a subterranean formation
comprising unconsolidated particulates.
BACKGROUND TECHNICAL INFORMATION
Treatment fluids can be used in a variety of
10 subterranean treatment operations. As used herein, the terms "treat,"
"treatment," "treating," and grammatical equivalents thereof refer to any
subterranean operation that uses a fluid in conjunction with achieving a
desired function andlor for a desired purpose. Use of these terms does not
imply , any particular action by the treatment fluid. Illustrative treatment
15 operations can include, for example, fracturing operations, gravel packing
operations, consolidation operations, and the like.
Hydrocarbon-producing wells are often stimulated by
hydraulic fracturing treatments. Hydraulic fracturing operations generally
involve pumping a fracturing fluid into a well bore that penetrates a
20 subterranean formation at a sufficient hydraulic pressure to create or
enhance one or more cracks, or "fractures," in the subterranean formation.
"Enhancing" one or more fractures in a subterranean forhation, as that term
is used herein, is defined to include the extension or enlargement of one or
more natural or previously created fractures in the subterranean formation.
25 The fracturing fluid may comprise particulates, often referred to, as
"proppant" particulates, that are deposited in the fractures. The proppant
particulates function, inter alia, to prevent the fractures from fully closing
upon the release of hydraulic pressure, forming conductive channels through
which fluids may flow to the well bore.
30 . . Hydrocarbon-producing wells also may undergo
gravel packing treatments, inter alia, to reduce the migration of
unconsolidated formation particulates into the well bore. In gravel-packing
treatments, a treatment fluid suspends particulates (commonly referred to as
"gravel" particulates) to be deposited in a desired area in a well bore, e.g.,
near unconsolidated or weakly consolidated formation zones, to form a
gravel pack to enhance sand control. ' The gravel can optionally be coated
5 with a resin or consolidating agent. One common type of gravel-packing
operation involves placing a sand co'ntrol screen in the well bore and
packing the annulus between the screen and the well bore with the gravel
particulates of a specific size designed to prevent the passage of formation
sand. The gravel particulates act, inter alia, to prevent the formation
10' particulates from occluding the screen or migrating with the produced
hydrocarbons, and the screen acts, inter alia, to prevent the particulates from
entering the production tubing. Once the gravel pack is substantially in
place, the viscosity of the treatment fluid may be reduced to allow it to be
recovered.
15 In some situations, fracturing and gravel-packing treatments
are combined into a single treatment (commonly referred to as "frac pack"
operations). In such "frac pack" operations, the treatments are generally
completed with a gravel pack screen assembly in place with the hydraulic
fracturing treatment 6eing pumped through the annular space between the
20 casing and screen. In this situation, the hydraulic fracturing treatment ends
in a screen-out condition, creating an annular gravel pack between the
screen and casing. In other cases, the fracturing treatment may be
performed prior to installing the screen ,and placing a gravel pack.
Occasionally, sand, formation fines, gravel, proppant, and/or
25 other unconsolidated particulates placed in the subterranean formation
during a fracturing, gravel or frac pack operation may migrate out
I of the subterranean formation into a well bore and/or may be produced with
the oil, gas; water, and/or other fluids produced by the well. The presence
of such particulates in produced fluids is undesirable in that the particulates
30 may abrade pumping and other producing equipment and/or reduce the
production of desired fluids from the well. Moreover, particulates that have
migrated into a well bore (e.g., inside the casing and/or perforations in a
cased hole), among other things, may clog portions of the well bore,
hindering the production of desired fluids from the well. The term
"unconsolidated particulates," and derivatives thereof is defined herein to
include loose particulates and particulates bonded with insufficient bond
strength to withstand the forces created by the production of fluids through
5 the formation. Unconsolidated particulates may comprise, among other
things, sand, .gravel, fines and/or proppant particulates in the subterranean
formation.
There are several known techniques used to control
particulate migration, some of which may involve the use of consolidating
10 agents. The term "consolidating agent" as used herein includes 'any
compound .that is capable of minimizing particulate migration in a
subterranean formation and/or modifying the stress-activated reactivity of
subterranean fracture faces and other surfaces in subterranean formations.
One technique that may be used to control particulate migration involves
15 coating proppant particulates with a consolidating agent to facilitate their
consolidation within the formation and to prevent their subsequent flowback
through the conductive channels in the subterranean formation.
Another method used to control particulate migration involves consolidating .
unconsolidated portions of subterranean zones into relatively stable
20 permeable masses by applying a consolidating agent to an unconsolidated
portion of the subterranean formation. One example of this method is
applying a resin to a portion of the zone, followed by a spacer fluid and then
a hardening agent.
BRIEF DESCRIPTION OF THE DRAWINGS
25 These drawings illustrate certain aspects of some of the
embodiments of the present disclosure, and should not be used to limit or
define the claims.
Figure 1 is a schematic illustration of a first representative
polyamino-functionalized nanoparticle having linear amino-functionalized
30 polymers according to certain embodiments of the present disclosure.
Figure 2 is a schematic illustration of a second representative
polyamino-functionalized nanoparticle having branched, polyaminofunctionalized
polymers according to certain embodiments of the present
disclosure.
Figure 3 is a graph depicting curves of storage modulus vs. .
temperature of epoxy resin compositions cured with (A) a conventional
5 hardening agent; (B) a representative hardening agent comprising
polyamino-functionalized nanoparticles at a weight percentage of 15% of
the cured composition; (C) a representative hardening agent comprising
polyarnino-functionalized nanoparticles at a weight percentage of 20% of
the cured composition; and (D) a representative hardening agent comprising
10 polyamino-functionalized nanoparticles at a weight percentage of 30% of
the cured composition, according to certain embodiments of the present
disclosure.
While embodiments of this disclosure have been depicted,
such embodiments do not imply a limitation on the disclosure, and no such
15 limitation should be inferred. The subject matter disclosed is capable of
considerable modification, alteration, and equivalents in form and function,
as will occur to those skilled in the pertinent art and having the benefit of
this disclosure. The depicted and described embodiments of this disclosure
are examples only, and not exhaustive of the scope of the disclosure.
20 DESCRIPTION OF INVENTION w.r.t. DRAWINGS
The present discl'osure relates to systems and methods for
stabilizing portions of a subterranean formation, including portions of a
subterranean formation comprising unconsolidated particulates, using
polyamino-functionalized nanoparticles.
25 The subterranean formations treated using the methods and
compositions of the present disclosure may be any subterranean formation
wherein unconsolidated particulates reside in the formation. These
unconsolidated particulates may comprise, among other things, sand, gravel,
fines andlor proppant particulates within the open space of one or more
30 fractures in the subterranean formation (e.g., unconsolidated particulates
that form a proppant pack or gravel pack within the formation). Using the
consolidation fluids and methods of the present disclosure, the
unconsolidated particulates with the formation may be prophylactically or
remedially treated to consolidate the particulates into a cohesive,
consolidated, yet permeable pack and minimize or reduce their production
with production fluids.
5 As generally embodied herein, the present disclosure
provides treatment fluids comprising a base liquid and polyaminofunctionalized
nanoparticles, and methods of treating therewith a
subterranean formation or a portion of a subterranean formation. The
polyamino-functionalized nanoparticles can together constitute a hardening
10 agent or a component thereof, and can in certain embodiments be crosslinkable
with a hardenable resin to form a consolidating agent for
consolidation of particulates in a subterranean formation.
The presently disclosed treatment fluids may be suitable for
use in all operations involving the application of a consolidating agent
15 comprising a hardening agent to a portion of a subterranean formation.
Accordingly, as embodied herein, the treatment fluid can be, for example
and without limitation, one or more of a fracturing fluid, a consolidating
fluid, a gravel pack fluid, a sealing fluid, a workover fluid, andlor a
remediation fluid. The term "hardening agent" as used herein will refer to a
20 composition that effects the hardening of a resin composition by any means
or mech&sm. The term "resin" as used herein refers to any of numerous
known polymerized synthetics or chemically modified natural resins
including thermoplastic materials and thermosetting materials. In certain
embodiments of the present disclosure, one or more hardening agents
25 comprising polyamino-functionalized nanoparticles can cross-link with one
or more hardenable resins in situ to form a consolidating agent. The
consolidating agent in turn can enhance the contact between the individual
particulates within the formation, helping to bring about the consolidation of
the particulates into a cohesive and permeable mass.
30 The treatment fluids of the present disclosure generally
comprise a base fluid and a hardening agent comprising polyaminofunctionalized
nanoparticles as disclosed. By way of example, and not
limitation, the polyamino-functionalized nanoparticles can comprise
"ePG ODLH-H X 7 - Q L . - % O B 5 1 7 1 4 2 - -
- 6 -
inorganic nanoparticles onto the surfaces of which polymers having terminal
amino functionalities are grafted.. The polymers can be linear or branched,
and can be extensively branched (i.e., hyper-branched) in certain
embodiments to provide a high ratio of reactive amino functionalities per
5 nanoparticle. The density of surface modification and the extent of polymer
branching can be selected or modified as 'desired to alter the density of
cross-linking and the' resulting physical properties, including thermal
stability and glass transition temperature, of the cross-linked resin
compositions. Additionally, and as described herein, the terminal amino
10 functionalities can be modified or protected to modifl curing time and
temperature as desired.
In certain embodiments, the disclosed hardening additives
can be thermally curable at elevated temperatures within the range of
temperatures encountered downhole in situ within a subterranean formation.
15 As generally embodied herein, the polyamino-functionalized nanoparticles
and the hardenable resin composition can react under suitable conditions as
desired and as specified herein-to cross-link with one another to consolidate
a portion of a subterranean formation. A person of ordinary skill in the art,
with the benefit of this disclosure, will be able to select an appropriate
20 hardening agent comprising polyamino-functionalized nanoparticles suitable
for use with a selected subterranean formation treatment or operation.
Without limiting the disclosure to any particular theoj or
mechanism, it is believed that the high density of reactive functional groups
achievable on the polyamino-functionalized nanoparticles and the ability of
25 the polyamino-functionalized nanoparticles to cross-link in multiple
directions and in three dimensions permits incorporation of the polyaminofunctionalized
nanoparticles into highly adhesive resin polymer networks.
Accordingly, among the many potential advantages to the methods and
compositions of the present disclosure, only some of which are alluded to
30 herein, the methods, compositions, and systems of the present disclosure
may provide strongly adherent consolidating agents having high mechanical
bonding strength and thermal integrity. In certain embodiments, .the
disclosed consolidating agents can exhibit significantly higher thermal
stability and glass transition temperature than consolidating agents
containing conventional amino hardening agents, and can permit reduced
treatment fluid loading of resins and hardening additives relative to
treatment fluids containing conventional hardening additives.
5 Reference will now be made to certain representative and
non-limiting embodiments of polyamino-hctionalized ' nanoparticles
according to the present disclosure. As depicted at FIG. 1 and FIG. 2, a
representative polyamino-functionalized nanoparticle as embodied herein
generally comprises a nanoparticle core having one or more amino- or
10 polyamino-terminated polymers bound on its surface. Accordingly, as used
herein, the term "polyamino-functionalized nanoparticle" will generally
refer to a particulate composition of matter having a diameter, or, if nonspherical,
a maximum diameter or length of less than about 1 pm and having
at least one amino- or polyamino-terminated polymer on its surface.
15 The nanoparticle cores can be composed of any suitable
material having a maximum diameter or length of less than 1 pm. By way
of example and not limitation, the nanoparticle core can be composed of an
inorganic material, such as a ceramic material. suitable inorganic materials
according to the present disclosure 'include, by way of example and not
20 limitation, nanoparticles of silica (SO2), alumina (A1203), iron oxide (Fe304
and Fe203), nickel oxide (NiO), zinc oxide (OZn), magnesium oxide
(MgO), boron nitride (BN), and aluminum nitride (AlN). In alternative
embodiments, the nanoparticle core can be composed of carbon, such as
graphitic carbon nanoparticles and carbon black nanoparticles.
25 Accordingly, the maximum diameter or length of the nanoparticle cores can
be between about 1 nm and about 1 pm, or between about 10 nm and about
500 nm. The average maximum diameter or length of the nanoparticles can
be less than about 1 pm, such as between about 10 nm to about 500 nm, or
about 50 nm to about 500 nm, or about 100 nm to about 500 nm, or about
30 200 nm to about 500 nm, or 10 nrn to about 100 nm, or about 10 nm to
about 200 nm.
The amino- or polyamino-terminated polymers can likewise
have any suitable composition. As depicted in FIG. 1, the polymers can be
aL'm nr -
~ P G - _ U _ ~ L M , P - P Z ' _ - O ~1. -7~ :~4~%~ -- --- - -
- 8 -
linear amino-functionalized polymers. In additional or alternative
embodiments, and as depicted in FIG. 2, the polymers can be branched
polyamines. Suitable linear amino-functionalized polymers include, for
1
example, amino-terminated C1-C6 alkanes. By way of example and not
5 limitation, the polyamino-terminated polymers can be selected from
polyethyleneimine ("PEI"), polypropyleneimine ("PPI"), polyamidoamine
("PAMAM"), polylysine, poly(dimethylaminoethy1 methacrylate)
("PDMAEMA"), and combinations thereof.
The polyamino-functionalized nanoparticles can be
10 ' synthesized by conventional methods. For example, silica nanoparticles can
be surface-modified by reaction with tetraethylorthosilicate to generate
reactive hydroxyl residues on the surface of the nanoparticles. Aminoterminated
polymers can subsequently be covalently bound to the surface of
the surface-modifed nanoparticles by reaction with an arninosilane, such as
15 3-aminopropyl-triethoxysilane, to yield the polyamino-functionalized
nanoparticles depicted schematically in FIG. 1. The resulting linear aminoterminated
polymers bound to the surface of the nanoparticles can be
modified as desired to generated branched or hyperbranched polyaminoterminated
polymers by conventional techniques known in the art. The
20 amino residues of the linear amino- or branched polyamino-terminated
polymers can subsequently be protected or modified, such as by reaction
with boron trifluoride, to increase cross-linking temperature .and/or crosslinking
time, as desired and as known in the art.
Each nanoparticle can comprise a plurality of amino-
25 terminated polymers. In certain embodiments, the amino-terminated
polymers can be chemically grafted onto the surface of the nanoparticles,
such as by surface modification of the nanoparticles and subsequent
covalent bonding of amino-terminated polymers or precursors thereof. In
certain embodiments, each nanoparticle includes comprise ten or more
30 amino-terminated polymers, or twenty or-more amino-terminated polymers,
or fifty or more amino-terminated polymers. The extent of polymer
branching of the polyamino-terminated polymers can be selected as desired,
with more extensive branching correlating with greater adhesive bonding
v W G -. F E ps a -2 5 17 142- -
-
strength and thermal stability after curing. In certain embodiments, the
polyarnino-terminated polymers (e.g., polyamines) can be "hyper-branched"
or "dendritic." In certain embodiments, each nanoparticle can comprise up
to 200 terminal amino functionalities, or up to 500 terminal amino
5 functionalities or more per polymer. The polyamino-terminated polymers
can have a molecular weight of at least 100 g/mol, or at least 500 g/mol, or
at least 5,000 g/mol, as desired.
In further embodiments in accordance with the present
disclosure, all or a portion of the amino 'terminal functional groups of the
10 polyamino-terminated polymers can be chemically modified or converted to
an alternative curing functionality. For example, and not by way of
limitation, the amino terminal functional groups of the amino terminal
can be modified to incorporate boron trifluoride (BF3) to form
terminal amine-BF3 complex 'groups. Consolidating agents of 'the present
15 disclosure containing such modified amino termini can e h b i t thermal
stability (i.e., retain cross-linking at elevated temperatures) at even greater
temperatures than the consolidating agents of the present disclosure
comprising unmodified polyamino-functional polymers. The inclusion of
alternative curing functionalities can also delay curing, which can in turn
20 beneficially ensure that curing occurs at suitable or desired locations
downhole.
In certain embodiments of the present, disclosure, the
consolidating agents comprising an polyamino-functionalized nanoparticle .
can have a curing temperature of at least about 120" F, or at least about 160"
25 F, or at least about 200" F. In additional or alternative embodiments, the
consolidating agents comprising an polyamino-functionalized nanoparticle
can have a glass transition temperature of at least about 120" F, or at least
about 160" F, or at least about 200" F. The curing temperature of the
consolidating agents can suitably be lower than the downhole temperature
30 of the subterranean formation or portion thereof into which they are
introduced, while the glass transition temperature of the consolidating
agents can suitably be greater than the downhole temperature of the
subterranean formation or portion thereof into which they are introduced..
T - h e n d b r v P - B -*a - a - m n 1 % &-Y-UL-U-~L-~-L-PPi z-~LL-- eLU d. %- P. B &:z - -
- 10-
Furthermore, in certain embodiments, the thermal stability andlor the glass
transition temperature of the consolidating agents comprising an polyamino-
I functionalized nanoparticle can depend on, and increase with, curing
temperature. Accordingly, hardening agents comprising an polyamino-
5 hctionalized nanoparticle of the present disclosure can be selected for their
I suitability for treatment of a subterranean formation based on, inter alia, the
downhole temperature of the subterranean formation. Additionally,
hardening agents of the present disclosure comprising an polyaminofunctionalized
nanoparticle can be suitable for a variety of downhole
10 conditions and operations.
The polyamino-functionalized nanoparticle hardening agents
of the present disclosure can be included in the treatment fluid in an amount
sufficient to at least partially harden a resin composition provided therewith
or via separate treatment fluid. In some embodiments of the present
15 disclosure, the polyamino-functionalized nanoparticle hardening agents are
included in the treatment fluid at a concentration of about 0.1% volume by
weight to about 20% volume by weight, or about 0.1% volume by weight to
about 5% volume by weight.
The polyarnino-functionalized nanoparticle hardening agents
20 of the present disclosure can cross-link upon curing with a hardenable resin
to form a consolidating agent comprising a polymerized resin network.
Hardenable resins suitable for use as an adhesive substance in the methods
of the present disclosure include all resins known in the art that are capable
of forming a hardened, consolidated mass. Many such resins are commonly
25 used in subterranean consolidation operations, and some suitable resins
include epoxy based resins, novolak resins, polyepoxide resins, phenolaldehyde
resins, urea-aldehyde resins, urethane resins, phenolic resins, furan
resins, furan/furfuryl alcohol resins, phenolic/latex resins, phenol
formaldehyde resins, polyester resins and hybrids and copolymers thereof,
30 polyurethane resins and hybrids and copolymers thereof, acrylate resins, and
mixtures thereof. Some suitable resins, such as epoxy resins, can be cured
with an internal catalyst or activator so that when pumped down hole, they
may be cured using only time and temperature. Other suitable resins, such
W- rn k s ~ 0 E-- ELmk lA Ba - 2-7 - QL. - hO 3. % 17 r 42.
- 11 -
as furan resins generally require a time-delayed catalyst or an external
catalyst to help activate the polymerization of the resins if the cure
temperature is low (i.e., less than 250" F.), but will cure under the effect of
time and temperature if the formation temperature is above about 250" F.,
5 preferably above about 300" F. It is within the ability of one skilled in the
art, with the benefit of this disclosure, to select a suitable resin for use in
embodiments of the present disclosure and to determine whether a catalyst
is required to trigger curing.
The type and amount of the polyamino-functionalized
10 nanoparticle hardening agent and hardenable resin composition included in
a particular treatment fluid or method of the disclosure may depend upon,
among other factors, the composition and/or temperature of the subterranean
formation, the chemical composition of formations fluids, flow rate of fluids
present in the formation, the effective porosity and/or permeability of the
15 subterranean formation, pore throat size and distribution, and the like.
Furthermore, the concentration of the consolidating agent can be varied,
inter alia, to either enhance bridging to provide for a more rapid coating of
the consolidating agent or to minimize bridging to allow deeper penetration
into the subterranean formation. It is within the ability of one skilled in the
20 art, with the benefit of this disclosure, to determine the type and amount of
consolidating agent to include in the consolidating agent emulsions of the
present disclosure to achieve the desired results.
As noted, the hardening agent can be provided in the
treatment fluid in an amount to at least partially harden the resin. In
25 particular embodiments, the hardening agent may be present in the
consolidation fluid in a stoichiometric ratio with the resin. In those
embodiments in which the hardening agent comprises multiple polyaminoterminated
polymers per nanoparticle andlor highly branched polyaminoterminated
polymers having a high number of polyamino-terminal (or
30 chemically modified polyamino-terminal) functionalities, the molar ratio of
the polyamino-functionalized nanoparticles to the hardenable resin
composition can be significantly lower. Given a particular combination of
resin and hardening agent,' one of ordinary skill in the art will be able to
determine an appropriate amount of hardening agent to use in a particular
application. In those treatment fluids of the present disclosure comprising
both a hardenable resin and a hardening agent comprising polyaminofunctionalized
nanoparticles, the hardenable resin may be included in the
5 treatment fluid in an amount in the range of about 0.1% to about 20% by
weight of the treatment fluid. It is within the ability of one skilled in the art
with the benefit of this disclosure to determine how much of the hardenable
resin component may be needed to achieve the desired results. Factors that
may affect this decision include which type of hardenable resin component
1 0 and hardening agent comprising polyamino-functionalized nanoparticles are
used.
The treatment fluids used in the methods and systems of the
present disclosure may comprise any base fluid known in the art, including .
aqueous base fluids, non-aqueous base fluids, and any combinations thereof.
15 The term "base fluid" refers 'to'the major component of the fluid (as opposed
to components dissolved and/or suspended therein), and does not indicate
any particular condition or property of that fluids such as its mass, amount,
pH, etc. Aqueous fluids that may be suitable for use in the methods and '
systems of the present disclosure may comprise water from any source.
20 Such aqueous fluids may comprise fi-esh water, salt water (e.g., water
containing one or more salts dissolved therein), brine (e.g., saturated salt
water), seawater, or any combination thereof. In most embodiments of the
present disclosure, the aqueous fluids comprise one or more ionic species,
such as those formed by salts dissolved in water. For example, seawater
25 and/or produced water may comprise a variety of divalent cationic species
dissolved therein. In certain embodiments, the density of the aqueous fluid
can be adjusted, among other purposes, to provide additional particulate
transport and suspension in the. compositions of the present disclosure. In
certain.embodiments, the pH of the aqueous fluid may be adjusted (e.g., by
30 a buffer or other pH adjusting agent) to a specific level, which may depend
on, among other factors, the types of viscosifylng agents, acids, and other
additives included in the fluid. One of ordinary skill in the art, with the
benefit of this disclosure, will recognize when such density andlor pH
adjustments are appropriate. Examples of non-aqueous fluids that may be
suitable. for use in the methods and systems of the present disclosure
include, but are not limited to, oils, hydrocarbo'ns, organic liquids, and the
like. In certain embodiments, the treatment fluids may comprise a mixture
5 of one or more fluids andlor gases, including but not limited to emulsions,
foams, and the like. The base fluid may be present in the treatment fluid in
an amount in the range of about 20% to about 99.9% by weight or in'an
amount in the range of about 60% to about 99.9% by weight of the
consolidating agent emulsion composition. or in an amount in the range of
10 about 95% to about 99.9% by weight of the treatment fluid.
In certain embodiments, the treatment fluids used in the
methods and systems of the present disclosure optionally may comprise any
number of additional additives. Examples of such additional additives
include, .but are not limited to, salts, surfactants, acids, proppant particulates,
15 diverting agents, fluid loss control additives, gas, nitrogen, carbon dioxide,
surface modifying agents, tackifylng agents, foamers, corrosion inhibitors,
scale inhibitors, catalysts, clay control agents, biocides, fiiction reducers,
antifoam agents, bridging agents, flocculants, additional H2S scavengers,
C02 scavengers, oxygen scavengers, lubricants, additional viscosifiers,
20 breakers,. weighting agents, relative permeability modifiers, resins, wetting
agents, coating enhancement agents, filter cake removal agents, antifreeze
agents (e.g., ethylene glycol), and the like. In certain embodiments, one or
more of these additional additives (e.g., a crosslinking agent) may be added
to the treatment fluid andlor activated after the viscosifylng agent has been
25 at least partially hydrated in the fluid. A person slulled in the art, with the
benefit of this disclosure, will recognize the types of additives that may be
included in the fluids of the present disclosure for a particular application.
For example, in certain embodiments, a treatment fluid, such
as a consolidation fluid, may also include a surfactant, which facilitates the
30 coating of the resin onto the particulates. Examples of suitable surfactants
include, but are not limited to, alkyl phosphonate surfactants (e.g., a C12-C22
alkyl phosphonate surfactant), ethoxylated nonyl phenol phosphonate esters,
cationic surfactants, nonionic surfactants, and mixtures of one or more
cationic and nonionic surfactants. Generally, the surfactant is present in the
consolidation fluid in an amount sufficient to facilitate the wetting of the
proppant or other particulate matter being consolidation. In particular
embodiments, the surfactant may be present in the consolidation fluid in an
5 amount from about 0.1 % wlv to about 5%' wlv.
Likewise, in certain embodiments, the treatment fluid can
also comprise a silane coupling agent, which facilitates the adhesion of the
resin to the particulates. The optional silane coupling agent may be used,
among other things, to act as a mediator to help bond the resin to formation
10 particulates or proppant particulates. Examples of suitable silane coupling
, agents include, but are not limited to, N-P-(aminoethy1)-y-aminopropyl
trimethoxysilane, N-2-(aminoethy1)-3-aminopropyltrimethoxysilane, 3-
glycidoxyp~opyl-trimethoxysilane, and mixtures thereof. The silane
coupling agent may be included in the treatment fluid in an amount capable
15 of sufficiently bonding the resin to the particulate. In some embodiments' of
the present disclosure, the silane coupling agent used is included in a
treatment fluid in an amount from abbut 0.1% w/v to about 5% wlv.
In certain embodiments, a curing agent can be provided in
the treatment fluids to promote cross-linking of the polyamino- '
20 functionalized nanoparticles and a hardenable resin compound. By way of
example, the curing agent may be a phenolic compound, an mine
compound, an imide compound, an amide compound, a barbituric acid
derivative, a cyanuric acid derivative, a thio phenolic compound, or a
carboxylic acid compound. Suitable phenolic compounds include phenol,
25 cresol, resorcinol, o-cresol, m-cresol, p-cresol, chlorophenol, nitrophenol,
bromophenol, dinitrophenol, hydroquinone, pyrocatechol, pyrogallol,
hydroxyhydroquinone, 2-methoxyphenol, 2,5-dichlorophenol, 3-
acetoxyphenol, m-aminophenol, p-aminophenol, 4,4'-
dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 3,3'-
30 'dihydroxydiphenylpropane, ' 4,4'-dihydroxy diphenyl ether, 4,4'-
dihydroxydiphenylethane, 4,4'-dihydroxy diphenyl ketone, 2-allylphenol
and 2-allylcresol, derivatives thereof, and combinations thereof. Suitable
mine compounds include dialkyltoluenediamine, phenylenediamine,
@
1 .4 ?I - - 1.P 8 -B~EL_HIXLT:8-L:_B-Q % 5 1.7' . 9sl - --- - --- - --
- 15-
diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenyl sulfone
(such as 4,4'-diaminodiphenylsulfone), diaminodiphenyl sulfide,
aminophenylalkylaniline (such as 4-[(4-aminophenyl)methyl]aniline), an
aromatic mine compound comprising a halogen-substituted derivative or
5 an alkyl-substituted derivative of the compounds mentioned above, an
mine compound obtained by the reaction between aniline or an aniline
derivative and an aldehyde compound, and an amino phenol derivative
having both a hydroxyl group and an amino group in a molecule, and
combinations thereof.
10 In certain embodiments of the treatment fluids of the.present
disclosure which comprise a liquid hardenable resin compound, a solvent
can be added to the resin to reduce its viscosity for ease of haridling, mixing
and transferring; It is within the ability of one skilled in the art with the
benefit of this disclosure to determine if and how much solvent may be
15 needed to achieve a viscosity suitable to the subterranean conditions.
Factors that may affect this decision include geographic location of the well,
the surrounding weather conditions, and the desired long-term stability of
the consolidating agent emulsion. An alternate way to reduce the viscosity
of the hardenable resin is to heat it. Any solvent that is compatible with the
20 hardenable resin and achieves the desired viscosity effect may be suitable
for use in the liquid hardenable resin component. Suitable solvents may
include butyl lactate, dipropylene glycol methyl ether, dipropylene glycol
dimethyl ether, dimethyl formamide, diethyleneglycol methyl ether,
ethyleneglycol butyl ether, diethyleneglycol butyl ether, propylene . '
25 carbonate, methanol, butyl alcohol, d'limonene, fatty acid methyl esters, and
combinations thereof. Other suitable solvents may include aqueous
dissolvable solvents such as, methanol, isopropanol, butanol, glycol ether
solvents, and combinations thereof. Suitable glycol ether solvents include,
but are not limited to, diethylene glycol methyl ether, dipropylene glycol
30 methyl ether, 2-butoxy ethanol, ethers of a C2 to C6 dihydric alkanol
containing at least one C1 to C6 alkyl group, mono ethers of dihydric
alkanols, methoxypropanol, butoxyethanol, hexoxyethanol, and isomers
thereof. Selection of an appropriate solvent is dependent on the resin
IQ 0- D ELH L H-L-Q_F-E_Q1 5 2-7 Y; 4'2. -
- 16-
composition chosen and is within the ability of one skilled in the art with the
benefit of this disclosure.
In certain embodiments of the disclosed methods and
systems, flexibilizer additives may be used to provide flexibility to the cured
5 consolidating agents. Examples of suitable flexibilizer additives include, but
are not limited to, an organic ester, an oxygenated organic solvent, an
aromatic solvent, and combinations thereof. In certain embodiments,
flexibilizer additive can be an ether, such as dibutyl phthalate. Where used,
the flexibilizer additive may be included in the treatment fluid in an amount
10 in the range of from about 0.05% to about lo%, or in the range of from
about 20% to about 45% by weight of the hardenable resin.
The present disclosure in some embodiments provides
methods for using the treatment fluids to cany out a variety of subterranean
treatments, including but not limited to, hydraulic fracturing treatments,
15 gravel pack treatments, particulate consolidation and remediation
treatments, workover treatments, and combinations thereof (e.g., "frac pack
treatments).
In some embodiments, the treatment fluids of the present
disclosure may be used in treating a portion of a subterranean formation, for
20 example, in particulate consolidation treatments. In certain embodiments, a
treatment fluid may be introduced into a subterranean formation. In some
embodiments, the treatment fluid may be introduced into a well bore that
penetrates a subterranean formation.
In additional or alternative embodiments, the treatment fluids
25 may be used on a well bore having a screen or liner in place, wherein the
disclosed hardening additives are placed in the formation by injecting them
directly through the screen or liner. Also by way of example, the treatment
fluids may be used on a well bore having a gravel pack in place (with or
without a screen or liner in place), wherein the disclosed hardening additives
30 are placed in the formation by injecting them directly through the gravel
pack as a means to prevent damage due to formation fines migration or as a
remedial treatment to cure a sand production problem. In addition, the
treatment fluids may be used to help reduce proppant flowback from a
I P O -DEL&LLL--8_B- 2.01.5' 17 '.' 4.2 - - - - - - -- -- - --
- 17-
propped fracture by introducing the disclosed hardening additives into a
fracture so as to contact unconsolidated particulates (be they proppant or
formations fines) and a hardenable resin composition to consolidate the
unconsolidated particulates in place once the operation is complete.
5 In certain embodiments, after application of the treatment
fluid (and any pre-flush or post-flush fluids), the well may be shut in for a
period of time to allow the polyamino-functionalized nanoparticle hardening
agent and hardenable resin composition to cure. The amount of time
necessary for the polyamino-functionalized nanoparticle hardening agent
10 and hardenable resin composition to cure sufficiently may depend on
temperature andor the compositions of the hardening agent and resin. After
the polyamino-hctionalized nanoparticle hardening agent and hardenable
resin composition have sufficiently cured, the well may be returned to
production.
15 As stated above, the methods of the present disclosure may
be employed in any subterranean treatment where unconsolidated
particulates reside in the formation. These unconsolidated particulates may
comprise, among other things, sand, gravel, fines andor proppant
particulates within the open space of one or more fractures in the
20 subterranean formation (e.g., unconsolidated particulates that form a
proppant pack or gravel pack within the formation). Using the consolidation
fluids and methods of the present disclosure, the unconsolidated particulates
within the formation may be remedially treated to consolidate the
particulates into a cohesive, consolidated, yet permeable pack and minimize
25 or reduce their production with production fluids.
In some embodiments, the polyamino-functionalized
nanoparticle hardening agents of the present disclosure may be coated on
particulates to be used in a fracturing or gravel packing process like those
described above. The term "coated" implies no particular degree of
30 coverage or mechanism by which the consolidating agent becomes
incorporated with the particulates. The term includes, but is not limited to,
simple coating, adhesion, impregnation, etc. The resultant coated
particulates may be introduced as part of a fracturing or gravel packing
DEhHE l F - T ~ O2-0 x 5 17 142 - - - - -- -
- 18-
process, at any point during one of the methods described above. For
example, the coated particulates can be introduced towards the end of a
fracturing or gravel packing treatment so that the maximum economic
benefit can be obtained. ,
5 Tn accordance with the methods and compositions of this
aspect of the present disclosure, all or part of the particulates may be coated
(preferably on-the-fly) with a polyarnino-functionalized nanoparticle
hardening agents of the present disclosure and may then be suspended in a
fracturing fluid or used as part of a gravel packing process. The
10 consolidating agent emulsions are used to coat the consolidating agent on
dry particulates while the particulates are conveyed in a conveying and/or
mixing device. The amount of consolidating agent coated on the particulates
can be in the range of about 0.1% to about lo%, or about 1% to about .3%
wlv.
15 The term "on-the-flyyyis used herein to mean that a flowing
stream is continuously inh-oduced into another flowing stream so that the
streams are combined and mixed while continuing to flow as a single
stream. The coating of the dry particulates with the consolidating agent
emulsions and any mixing of the consolidating agent coated particulates
20 with a fracturing fluid or treatment fluid can all be performed on-the-fly.
However, as is well understood by those skilled in the art, such mixing can
also be accomplished by batch mixing or partial batch mixing.
A wide variety of particulate materials may be used in
accordance with this aspect of the present disclosure, including, but not
25 limited to, sand, bauxite, ceramic materials, glass materials, resin pre-coated
proppant (e.g., commercially available from Borden Chemicals and Santrol,
for example, both from Houston, Tex.), polymer materials, TEFLON
(tetrafluoroethylene) materials, nut shells, ground or crushed nut shells, seed
shells, ground or crushed seed shells, fruit pit pieces, ground or crushed fruit
30 pits, processed wood, composite particulates prepared from a binder with
filler particulate including silica, alumina, fumed carbon, carbon black,
graphite, mica, titanium dioxide, meta-silicate, calcium silicate, kaolin, talc,
zirconia, boron, fly ash, hollow glass microspheres, solid glass, and
HP8 -DELHL_LZ:QE- B Q 1 S 17'- $2 -- -
- 19-
mixtures thereof. The particulate material used may have a particle size in
the range of about 2 to about 400 mesh, U.S. Sieve Series. Preferably, 'the
particulate material is graded sand having a particle size in the range of
about 10 to about.70 mesh, U.S. Sieve Series. Preferred sand particle size
5 distribution ranges are one or more of 10-20 mesh, 20-40 mesh, 40-60 mesh
or 50-70 mesh; depending on the particle size and distribution of the
formation particulates to be screened out by the particulate materials. Other
particulates that may be suitable for use in subterranean applications also
may be useful.
10 Certain embodiments of the methods of this aspect of the
' present disclosure can generally include the steps of providing a, coating
composition comprising of an polyamino-functionalized nanoparticle
hardening agent and, optionally, a hardenable resin composition. The
coating further optionally can comprise on or more of a silane coupling
15 agent, a solvent for the hardenable resin composition, a hydrolyzable ester
breaker additive, and a surfactant to facilitate coating and coating flow. The
polyamino-functionalized nanoparticle hardening agent can be provided in a
suspension in a liquid canier fluid. Curing of the polyamino-functionalized
nanoparticle hardening agent ai~d a hardenable resin composition can be
20 promoted by elevated temperature and pressure in situ, such as in a fracture.
The hardening of the resin composition in situ can promote -the
consolidation of the resin coated particulates into a hard permeable pack
having sufficient compressive strength to prevent unconsolidated
particulates and formation sand from -flowing out of the fractures with
25 produced fluids.
To facilitate a better understanding of the present disclosure,
the. following examples of certain aspects ' of preferred embodiments are
given. The following examples are not the only examples that could be
given according to the present disclosure and are not intended to limit the
30 scope of the disclosure or claims. Figure 3 is a graph depicting adhesive
strength of epoxy resin compositions cured with representative hardening
agents comprising polyamino-functionalized nanoparticles according to
certain embodiments of the present disclosure, as well as an epoxy resin
composition cured by a conventional hardening agent.
EXAMPLES
Example 1 - Characterization of Representative Polyamino-
5 Fun ctionalized Nan oparn:cles
Representative hardening agents comprising polyaminofunctionalized
nanoparticles according to the present disclosure were
synthesized, and cured epoxy resin compositions comprising same were
tested.
10 Hyperbranched poly(amidoamine) ("PAMAM")-grafted
silica nanoparticles were synthesized according to known methods. Briefly,
commercial silica nanoparticles (Nippon Aerosil Company, Ltd., Japan)
were obtained and dried in vacuum at 1 10" C. The surfaces of the silica
nanoparticles were functionalized with amino groups. by reaction with y-
15 aminopropyltriethoxysilane. PAMAM was grafted onto the amino
functionalities by repeated addition of methyl acrylate followed by
amidation of terminal ester groups .with ethylenediamine (EDAJ. The
hyperbranched PAMAM-grafted silica nanoparticles so synthesized were
treated with boron trifluoride diethyl ether to generate hyperbranched
20 PAMAM-grafted silica nanoparticles having boron trifluoride (BF3)
complex groups ("hyperbranched PAMAM-BF3 nanoparticles"). The
hyperbranched PAMAM-BF3 nanoparticles. were mechanically mixed at a
weight ratio of 15%, 20%, or 30% with Bisphenol A epoxy resin (Araldite
AER 260, Asahi-Ciba, Japan) prior to curing at 160" C for 24 hours.
25 The thermal stability of the mixtures after curing was
analyzed by thermogravimetric analysis with a thermogravimetric analyzer
(Shimadzu TGA-50) in nitrogen at a temperature range between ambient
temperature and 600" C at a heating rate of 10" Clminute. The adhesive
strength of the mixtures between alumina plates was measuring wing an
30 Instron-type tensile machine (Shimadzu AGS-1OKNG) at a crosshead speed
of 0.2 mm/min at 25' C and 50% relative humidity. The dynamic
mechanical performance of the compositions was evaluated by known
techniques. The thermal stability, adhesive strength, and dynamic
mechanical performance of epoxy resin cured with a conventional hardener
(EDA) in the presence of untreated silica nanoparticles was also evaluated
for comparison.
The 10% weight loss temperature (indicative of the upper
5 range of heat tolerance) of the hyperbranched PAMAM-BF3 nanoparticles
cured with epoxy resin was 392" C, compared to 348" C for the epoxy resin
cured with EDA and untreated silica nanoparticles. The adhesive strength
of the cured hyperbranched PAMAM-BF3 nanoparticles compositions with
15%, 20%, and 30% hyperbranched PAMAM-BF3 nanoparticles and the
10 epoxy resin cured with EDA and untreated silica nanoparticles is shown in
Table 1, below. As shown, the hyperbranched PAMAM-BF3. nanoparticles
cured with epoxy resin exhibited greater adhesive strength than epoxy resin
cured with EDA, and the adhesive strength of the hyperbranched PAMAMBF3
nanoparticles cured with epoxy resin increased with increasing weight
15 percentage of the hardening agent.
Table 1 : Adhesive Strength of Cured Epoxy Consolidating Agents
The dynamic mechanical analysis curves of the cured
compositions is shown in FIG. 3. As shown, h e glass transition
temperature of the cured consolidating agents comprising hyperbranched
PAMAM-BF3 nanoparticles at weight percentages of 15% (B), 20% (C),
and 30% (D) was greater than that of the cured epoxy-EDA consolidating
agents (A), and increased with weight percentage of the hardening agent to
exceed 170" C for the cured compositions containing 30% by weight of
hyperbranched PAMAM-BF3 nanoparticles. The storage modulus of the
-
Hardening Agent
EDA .
hyperbranched PAMAM-BF3 (1 5% wlw)
hyperbranched PAMAM-BF3 (20% wlw)
hyperbranched PAMAM-BF3 (30 % wlw)
25 cured compositions of hyperbranched PAMAM-BF3 nanoparticles in the
rubbery regions and glass transition regions was slightly increased relative
to the storage modulus of the epoxy-EDA-nanoparticle compositions in the
Adhesive Strength After
Curing (MPa)
6.5
9
10
11
same regions of the curve.
HPO- DEL-KP- 1 7 -0.2- hQIf.5' 17 &E --- - - - - - - -- - - -- - - - - - ---
It was further observed that the glass transition temperature
of the cured compositions containing hyperbranched PAMAM-BF3
nanoparticles cured at 160' C was significantly higher than similar
compositions cured at 1 60° C.
5 Sand Control Devices
Certain embodiments of the methods and compositions
disclosed herein may directly or indirectly affect one or more components or
pieces of equipment associated with the preparation, delivery, recapture,
recycling, reuse, and/or disposal of the disclosed compositions. For
10 example, sand control devices may be used with the methods and systems of
the present disclosure. Such sand control devices are essentially filter
assemblies used to retain either formation solids or particulates such as
gravel that are placed into the subterranean formation. Suitable sand control
devices that may be used in the present disclosure include sand control
15 screens, liners, and combinations thereof. A sand control liner is generally a
well bore tubular in which slots (slotted liner) or holes (perforated liner)
have been made before the tubular is placed into the well bore. A, sand
control screen is generally a more flexible filter assembly that may be used
in conjunction with a liner or alone. As will be understood by one of
20 ordinary skill in the art, a wide range of sizes and screen configurations are
available to suit the characteristics (such as size, spherocity, etc.). of the
formation solids or particulates that are meant to be controlled by the
device. The sand control device, with or without added gravel, presents a
barrier to migrating sand fiom the formation while still permitting fluid
25 flow.
Any sand control screen or perforated liner known in the art
and suitable for the subterranean formation or portion thereof being treated
may be used in the embodiments of the present disclosure. One known type
of sand control screen commonly used in open hole completions where
30 gravel packing may not be feasible, is expandable sand control screens.
Typically, expandable sand control screens are designed to not only filter
particulate materials out of the formation fluids, but also provide radial
support to the formation to prevent the formation fiom collapsing into the
-5- m TPB' - 2 - LY-Q-DE-L,FLL B-L-ZU-L-- Lw.-UQ -L~ D. ~ Ia.L- - s - -- Qa Ln -- - -- -
-23-
well bore. Another open hole completion screen type known in the art is .a
stand alone screen. Typically, stand alone screens may be used when the
formation generally comprises a more uniform particle size distribution.
Still another known type of sand control screen is a telescoping screen
5 whereby hydraulic pressure is used to extend the telescoping screen radially
outwardly toward the well bore. This process requires providing fluid
pressure through .the entire work string that acts on the telescoping members
to shift the members fiom a partially extended position to a radially
extended position. Another type of suitable sand control screen includes a
10 base pipe having at least one opening in a sidewall portion thereof; a
swellable material layer disposed exteriorly of the base pipe and having at
least one opening corresponding to the at least one opening of the base pipe;
a telescoping perforation operably associated with the at least one opening
of the base pipe and at least partially disposed within the at least one
15 opening of the swellable material layer; and a filter medium disposed within
I
I the telescoping perforation. Still another suitable sand control device can
I emp1oy.a swellable packer activated screen that may provide stand off fiom
1
i the formation to allow filter-cake clean up.
I
I Placement of a sand control screen in a well can include the
1 20 step of packing an annulus surrounding the sand control screen with gravel,
I
I which can be retained by the screen. Accordingly, in certain embodiments
I of the methods disclosed herein, the treatment fluid is a a gravel packing
I
I fluid containing gravel for a gravel packing operation. Certain
I embodiments of the methods disclosed herein include the steps of providing
I 25 a sand control screen assembly disposed within a wellbore penetrating a !
I subterranean formation; and forming a gravel pack proximal to the sand
control screen assembly with a treatment fluid, wherein the treatment fluid
is a gravel packing fluid comprising gravel and a polyamino-functionalized
. nanoparticle hardening agent according to the present disclosure. In certain
30 embodiments, the polyamino-functionalized nanoparticle hardening agent or
a portion thereof can be provided in a coating on the surface of the gravel
particulates in the treatment fluid.
Representative Embodiments
An embodiment of the present disclosure is a method
comprising: providing a treatment fluid comprising a base liquid and
polyamino-functionalized nanoparticles; and introducing the treatment fluid
5 into a portion of a subterranean formation. Another embodiment of the
present disclosure is a treatment fluid composition for treating a
subterranean formation, the treatment fluid composition comprising a base
liquid and polyarnino-functionalized nanoparticles. Another embodiment of
the present disclosure is a method comprising providing a sand control
10 screen assembly disposed within a wellbore penetrating a subterranean
formation; providing a treatment fluid comprising a base fluid, a plurality of
gravel particulates, and a hardening agent comprising polyaminofunctionalized
nanoparticles; and forming a gravel pack proximal to the
sand control screen assembly with the gravel packing treatment fluid.
15 Therefore, the present disclosure is well adapted to attain the
ends and advantages mentioned as well as those that are inherent therein.
The particular embodiments disclosed above are illustrative only, as the
present disclosure may be modified and practiced in diffeient but equivalent
manners apparent to those skilled in the art having the benefit of the
20 teachings herein. While numerous changes may be made by those skilled in
the art, such changes are encompassed within the spirit of the subject matter
defined by the appended claims. Furthermore, no limitations are intended to
the details of construction or design herein shown, other than as describedin
the claims below. It is therefore evident that the particular illustrative
25 embodiments disclosed above may be altered or modified and all such
variations are considered within the scope and spirit of the present
disclosure. In particular, every range of values (e.g., "from about a to about
b," or, equivalently, "from approximately a to b," or, equivalently, "from
approximately a-b") disclosed herein is to be understood as refemng to the
30 power set (the set of all subsets) of the respective range of values. The
terms in the claims have their plain, ordinary meaning unless otherwise
explicitly and clearly defined by the patentee.

WE CLAIM:
1 A method of treating subterranean formation comprising:
providing a treatment fluid comprising a base liquid and
polyamino-functionalized nanoparticles; and
5 introducing the treatment fluid into .a portion of a
subterranean formation.
2. A method as .claimed in claim 1, wherein the polyaminofunctionalized
nanoparticles comprise a nanoparticle core comprises at least
10 one material selected from the group consisting of: silica, alumina, iron I1
oxide, iron I11 oxide, nickel oxide, zinc oxide, magnesium oxide, boron
nitride, aluminum nitride, elemental carbon, and any combination thereof.
3. A method as claimed in claim 1, wherein the polyamino-
15. functionalized nanoparticles comprise one or more amino-terminated
polymers, at least one of the amino-terminated polymers selected from the
group consisting of: polyethyleneimine, polypropyleneimine,
polyamidoamine, polylysine, poly(dimethylaminoethy1 methacrylate), and
any combination thereof.
20
4. A method as claimed in claim 1 wherein the portion of the
subterranean formation comprises unconsolidated particulates, and the
method further comprises:
contacting the portion of the subterranean formation with a
25 hardenable resin composition; and
allowing the polyamino-functionalized nanoparticles to at
least partially cure the hardenable resin composition, whereby the cured
hardenable resin composition consolidates at least a portion of the
unconsolidated particulates in the.subterranean formation.
30
5. A method as claimed in claim 1, wherein the polyaminofunctionalized
nanoparticles are coated on particulates suspended in the
treatment fluid.
6. A method as claimed in claim 1, wherein the treatment fluid
further comprises a hardenable resin composition.
5 7. A treatment fluid composition for treating a subterranean
formation, the treatment fluid composition comprising a base liquid and
polyamino-functionalized nanoparticles.
8. A treatment fluid composition as claimed in claim 7, wherein
10 the polyamino-functionalized nanoparticles comprise a nanoparticle core
comprises at least one material selected from the group consisting of silica,
alumina, iron I1 oxide, iron I11 oxide, nickel oxide, zinc oxide, magnesium
oxide, boron nitride, aluminum nitride, elemental carbon, and and any
combination thereof.
15
9. A treatment fluid composition as claimed in claim 8, wherein
the polyamino-functionalized nanoparticles comprise one or more
polyamino-terminated polymers, at least one of the amino-terminated
polymers selected from the group consisting of polyethyleneimine,
20 polypropyleneimine, polyamidoamine, polylysine, poly(dimethylaminoethy1
methacrylate, and any combination thereof.
10. A treatment fluid composition as claimed in claim 8, wherein
the polyamino-terminated polymers comprise 200 terminal amino
25 functionalities or more per polymer.
I 11. A treatment fluid composition as claimed in claim 10,
wherein at least a portion of the polyamino-terminated polymers is modified
to include terminal boron trifluoride functionalities.
30
12. A treatment fluid composition as claimed in claim 8, wherein
the treatment fluid further comprises a hardenable resin composition.
13. A treatment fluid composition as claimed in claim 8, wherein
the treatment fluid further comprises particulates, and wherein at least a
portion of the polyamino-functionalized nanoparticles and the hardenable
resin composition are coated on the particulates.
5
14. A method comprising:
providing a sand control screen assembly disposed within a
wellbore penetrating a subterranean formation;
providing a treatment fluid comprising a base fluid, a
10 plurality of gravel particulates, and a hardening agent comprising
polyamino-functionalized nanoparticles; and
forming a gravel pack proximal to the sand control screen
assembly with the gravel packing treatment fluid.
15 1 5. A method as claimed in claim 14, wherein the treatment fluid
further comprises a hardenable resin composition.
16. A method as claimed in claim 15, wherein forming a gravel
pack comprises allowing the hardening agent comprising polyamino-
20 functionalized nanoparticles to at least partially consolidate the gravel pack.
17. A method as claimed in claim 16, allowing the hardening
agent comprising polyamino-functionalized nanoparticles to at least
partially consolidate the gravel pack comprises allowing the hardening agent
25 comprising polyamino-functionalized nanoparticles and hardenable resin
composition to cure.
18. A method as claimed in claim 17, wherein the treatment fluid .
does not comprise a catalyst to promote curing of the hardening agent
30 . comprising polyamino-functionalized nanoparticles and hardenable resin
composition.
19. A method as, claimed in claim 14, wherein the polyaminofhnctionalized
nanoparticles comprise a nanoparticle core composed of
silica and a plurality of branched polyamidoamine polymers.
20. A method as claimed in claim 14, wherein at least a portion
of the hardening agent comprising polyamino-functionalized nanoparticles
is provided in a coating on the surface of the gravel particulates.