WO2020019070A1 - Compositions à base de ciment et procédés de fabrication associés - Google Patents

Compositions à base de ciment et procédés de fabrication associés Download PDF

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Publication number
WO2020019070A1
WO2020019070A1 PCT/CA2019/051014 CA2019051014W WO2020019070A1 WO 2020019070 A1 WO2020019070 A1 WO 2020019070A1 CA 2019051014 W CA2019051014 W CA 2019051014W WO 2020019070 A1 WO2020019070 A1 WO 2020019070A1
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Prior art keywords
cement
water
slurry
nanoparticle precursor
precursor
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PCT/CA2019/051014
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English (en)
Inventor
Maen HUSEIN
Ahmed MEHAIRI
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Trican Well Service Ltd
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Publication of WO2020019070A1 publication Critical patent/WO2020019070A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/005—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing gelatineous or gel forming binders, e.g. gelatineous Al(OH)3, sol-gel binders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00008—Obtaining or using nanotechnology related materials

Definitions

  • This present invention relates generally to cement compositions. More particularly, the present invention relates to the in situ formation of nanoparticles during the preparation of cement slurries. More particularly, the present invention relates to the formation of cement matrices having nanoparticles dispersed therein where the cement matrices are formed from cement slurries having nanoparticles formed in situ during the preparation of said cement slurries.
  • Nanotechnology is the field of researching, synthesizing and using materials at the nanoscale level, i.e., 1-100 nm.
  • Nanoparticles can be classified as zero-dimensional (0D; having all its dimensions within the nano-domain), one-dimensional (1D; having two of its dimensions in the nano-domain) and two-dimensional (2D; having only one of its dimensions in the nanodomain).
  • Spherical NPs are examples of 0D NPs
  • carbon nanotubes (CNTs) are examples of 1D NPs
  • graphene is an example of 2D NPs.
  • 0D, 1D and 2D nanomaterials have unique properties such as high specific surface area, mechanical strength and high chemical reactivity. These properties make such nanomaterials suitable for various applications including well cementing operations in the oil and gas industry.
  • Well cementing is a vital process that requires introducing a cement slurry to the annular space between the wellbore and a casing (steel pipe inserted inside the well after drilling) by pumping the cement slurry down the casing and circulating it up the annulus (the space between the casing and the formation). The cement slurry then sets and hardens to form a cement sheath between the wellbore and the casing.
  • Cementing is one of the most crucial operations as it ensures complete zonal isolation, protection of ground water, and structural integrity of the wellbore.
  • the performance of the cement sheath may be affected by several factors such as gas migration, quality of the cement slurry, subsequent drilling and completion activities, high pressure fluid injection and formation movement. These factors may lead to well integrity issues or even wellbore failures, which result in costly remediation operations, production interruptions and environmental issues.
  • the long-term productivity of a well is highly dependent on the quality and durability of the cement sheath.
  • Nanoscale Si0 2 also referred to as nano-SiO
  • HVFA high volume fly ash
  • Nanoscale Ti0 2 (also referred to as “nano-Ti0 2 ”) has been shown to increase early-age hydration of Portland cement as well as compressive and flexural strengths. Moreover, nanoscale Ti0 2 -containing cement also displays self-cleaning characteristics and higher abrasion resistance than that of nanoscale Si0 2 . Nanoscale Zr0 2 (also referred to as“nano-Zr0 2 ”), through pore filling and bridging, improves compressive strength and the microstructure of the cement while decreasing its permeability and porosity. Nanoscale CaCC> 3 shortens the induction period for tricalcium silicates (C 3 S) hydration and improves various mechanical properties such as hardened property, impact resistance, flexural strength, low permeability to liquid water and sound absorption.
  • C 3 S tricalcium silicates
  • Carbon nanofibers (CNFs) and nanotubes (CNTs) have been found to increase the tensile strength of the cement sheath. Both have also been found to increase the modulus of elasticity and compressive strength. The high interaction between CNTs and cement hydrates enables CNTs to work as a bridge across the cracks/voids, which help with load transfer.
  • CNTs, CNFs and FeoCF NPs have been shown to modify the electrical resistance of concrete, especially under load, and contribute to what is known as self-sensing concrete.
  • Nano-clay composites have demonstrated the ability to increase resistance to chloride penetration, reduce permeability and shrinkage of the cement and increase its mechanical properties.
  • NPs can assist in the process of cement hydration due to their ability to act as nuclei for cement hydrates such as nano-smectite.
  • NP addition has also enabled the incorporation of higher percentage by-products into a cement slurry, without compromising the qualities of the resulting cement sheath. This is very attractive from an environmental point of view, since it entails less reliance on cement and beneficial use of waste products.
  • Other areas of investigation for NP-containing cement have included: low water adsorption, water proofing, antimicrobial activity, high Young’s modulus, blast heat resistance, high flexibility, corrosion resistance, and freeze/thaw resistance.
  • NPs can be added to a cement slurry in the form of an aqueous dispersion/slurry or in the form of a solid powder.
  • the performance of the cement sheath is highly dependent on its microstructure which is influenced by the nanomaterials added to the starting cement slurry. Proper dispersion of the nanomaterials in the cement slurry prevents the formation of weak zones inside the cement sheath. Weak zones, which can compromise the integrity of the cement sheath, typically arise from agglomeration of the NPs.
  • AI 2 O 3 NPs added to cement mortar at relatively low concentrations have been shown to increase the modulus of elasticity. Nevertheless, aggregation of the AI 2 O 3 NPs at higher concentrations significantly decreased the modulus of elasticity of the cement mortar.
  • NP addition involves two major steps, breaking down agglomerates of NPs to yield individual NPs, followed by stabilizing the individual NPs to prevent their re-agglomeration.
  • NP de- agglomeration and stabilization can be accomplished through one or a combination of mechanical, physical and/or chemical methods.
  • Mechanical methods pertain to imparting energy to the slurry by means of, for example, high shear mixing, mechanical stirring, ultrasonication and ball milling.
  • Physical methods include modifying the surface of the NPs by, for example, organic admixtures, surfactants and/or polymers by utilizing electrostatic and/or steric repulsion to prevent re-agglomeration of the NPs.
  • Chemical methods of dispersing and/or preventing the NPs from re- agglomeration include anchoring functional groups onto the surface by means of chemical reactions to enhance the hydrophilicity of the NPS, making them easier to disperse in an aqueous environment. While there are numerous methods to make commercial/prefabricated NPs suitable for use in cement slurries, the application of these methods adds considerable cost, time and labor to a well cementing operation and may require major modifications to the equipment and practices currently in use.
  • FIG. 1 is a graph illustrating the compressive strength (Megapascals, MPa), measured using an Ultrasonic Cement Analyzer (UCA), over time (hours, h) of cement matrices formed from cement slurries: nano-CaS0 4 slurry prepared by Ml (NRi , i, A), nano- CaC0 3 slurries prepared by Ml (NP 3 ⁇ 4i , B) and M2 (NP 2,2 , C), nano-Fe(OH) 3 slurries prepared by Ml (NP 3,I , D), M2 (NP 3 2 , E) and M3 (NP 3 3 , F), Class G Portland cement slurry (CS, G), NaCl-containing Class G slurry (CSi H), NaN0 3 -containing Class G slurry (CS 2 , 1), Fe(N0 3 ) 3 -containing Class G slurry (CS 3 , J) and NaOH-containing Class G slurry (CS 4 ).
  • FIG. 2 is a graph illustrating the compressive strength (MPa), as measured using 1) an Ultrasonic Cement Analyzer (UCA) and 2) a Destructive Test, of cement matrices formed from cement slurries: Class G Portland cement (CS), NaCl-containing Class G slurry (CS1), nano-CaSCri slurry prepared by method Ml (NPu). and nano-CaC0 3 slurry prepared by method Ml (NP 3 ⁇ 4i ) formed in accordance with various aspects of the present disclosure; and [0013] FIG.
  • MPa compressive strength
  • 3 is a graph illustrating the reproducibility of 3 replicates expressed as +/- 1 standard deviation (dashed curves) from the average of nano-Fe(OH) 3 slurries prepared by Ml (NP 3 I , A), M2 (NP 3,3 ⁇ 4 B) and M3 (NP 3 3 , C) and cured at 25°C; compared to Class G slurry (CS, D).
  • FIG. 4 is a graph illustrating the reproducibility of 3 replicates expressed as +/- 1 standard deviation (dashed curves) from the average of nano-Fe(OH) 3 slurries prepared by Ml (NP 3,I , A), M2 (NP 3 2, B) and M3 (NP 3 3 , C) and cured at 80°C; compared to Class G slurry (CS, D).
  • FIG. 5 is a graph illustrating the compressive strength (MPa), measured using an Ultrasonic Cement Analyzer (UCA), over time (h) of cement matrices formed from cement slurries: nano-Fe(OH) 3 slurries prepared by Ml (NP 3J . A), M2 (NP 3 2 . B) and M3 (NP 3 3 , C), Class G slurry (CS, D), commercial nano-Si0 2 -containing Class G slurry (NP 4 , E), commercial nano-Fe 2 0 3 -containing Class G slurry (NP 5 . F) formed in accordance with various aspects of the present disclosure;
  • Ml NP 3J . A
  • M2 NP 3 2 . B
  • M3 NP 3 3 , C
  • Class G slurry CS, D
  • commercial nano-Si0 2 -containing Class G slurry NP 4 , E
  • commercial nano-Fe 2 0 3 -containing Class G slurry NP
  • FIG. 6 is a graph illustrating sedimentation type III experiments for different in situ NPs prepared using Ml, and commercial NPs used in this study at 25°C with specific beaker dimensions (600 ml, OD: 88 mm, height: 122 mm): CaS0 4 (NPi), CaC0 3 (NP 2 ), Fe(OH) 3 (NP 3 ), Si0 2 (NP 4 ) and commercial Fe 2 0 3 (NP5);
  • FIG. 7 is a graph illustrating the compressive strength (MPa), measured using an Ultrasonic Cement Analyzer (UCA), over time (h) of cement matrices formed from cement slurries: nano-CaC0 3 slurry prepared by Ml (NP 3 ⁇ 4i , A), nano-Fe(OH) 3 slurry prepared by M3 (NP 3 3 , B), nano-CaC0 3 slurry prepared by Ml including 0.7% BWOC dispersant (NP 2.i +CFR 12.
  • MPa compressive strength
  • UCA Ultrasonic Cement Analyzer
  • FIG. 8 is a graph illustrating the compressive strength (MPa), measured using an Ultrasonic Cement Analyzer (UCA), over time (h) of cement matrices formed from cement slurries: a slurry with 0.225% nano-Fe(OH) 3 prepared by Ml (NP 3 . A), a slurry with 0.550% nano-Fe(OH) 3 prepared by Ml (NP 3 . B), a slurry with 1.000% nano-Fe(OH) 3 prepared by Ml (NP 3,I , C), and a Class G slurry (CS, D);
  • MPa compressive strength
  • UCA Ultrasonic Cement Analyzer
  • FIG. 9 is a graph illustrating the compressive strength (MPa), measured using an Ultrasonic Cement Analyzer (UCA), over time (h) of cement matrices formed from cement slurries: a slurry with 0.225% nano-Fe(OH) 3 prepared by M2 (NP 3 2 . A), a slurry with 0.550% nano-Fe(OH) 3 prepared by M2 (NP 3 2 . B), a slurry with 1.000% nano-Fe(OH) 3 prepared by M2 (NP 3 2 , C), and a Class G slurry (CS, D);
  • MPa compressive strength
  • UCA Ultrasonic Cement Analyzer
  • FIG. 10 is a graph illustrating the compressive strength (MPa), measured using an Ultrasonic Cement Analyzer (UCA), over time (h) of cement matrices formed from cement slurries: a slurry with 0.225% nano-Fe(OH) 3 prepared by M3 (NP 3 3 , A), a slurry with 0.550% nano-Fe(OH) 3 prepared by M3 (NP 3 3 , B), a slurry with 1.000% nano-Fe(OH) 3 prepared by M3 (NP 3 3 , C), and a Class G slurry (CS, D);
  • MPa compressive strength
  • UCA Ultrasonic Cement Analyzer
  • FIG. 11 shows, for a cement matrix formed from CS slurry, an energy dispersive X- ray (EDX) image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and a scanning electron microscopy (SEM) image (bottom);
  • EDX energy dispersive X- ray
  • SEM scanning electron microscopy
  • FIG. 12 shows, for a cement matrix formed from NP 3 , I slurry, an EDX image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and an SEM image (bottom);
  • FIG. 13 shows, for a cement matrix formed from NP 3 , 2 slurry, an EDX image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and an SEM image (bottom);
  • FIG. 14 is a graph comparing the porosity of cured cement matrices formed from a Class G slurry (CS), a nano-Fe(OH) 3 slurry prepared by Ml (NP 3,I ), a nano-Fe(OH) 3 slurry prepared by M2 (NP 3 2 ) and a nano-Fe(OH) 3 slurry prepared by M3 (NP 3 3 );
  • FIG. 15 is a graph comparing the permeability of cured cement matrices formed from a Class G slurry (CS), a nano-Fe(OH) 3 slurry prepared by Ml (NP 3,I ) and a nano- Fe(OH) 3 slurry prepared by M2 (NP 3 2 ) and a nano-Fe(OH) 3 slurry prepared by M3 (NP 3 3 );
  • FIG. 16 is a graph illustrating triaxial compressive stress test results for a cement matrix formed from a Class G slurry (CS);
  • FIG. 17 is a graph illustrating triaxial compressive stress test results for a cement matrix formed from a nano-Fe(OH) 3 slurry prepared by Ml (NP 3,I );
  • FIG. 18 is a graph illustrating triaxial compressive stress test results for a cement matrix formed from a nano-Fe(OH) 3 slurry prepared by M2 (NP 3 2 ).
  • the phrase“at least one of’ when combined with a list of items means a single item from the list or any combination of items in the list.
  • the phrase“at least one of A, B and C,” means“at least one from the group A, B, C, or any combination of A, B and C.”
  • the phrase requires one or more, and not necessarily not all, of the listed items.
  • NPs nanoparticles
  • NP-based cements have been widely studied as discussed generally above, the in situ preparation of NPs during the formation of cement slurries has not been considered in the art.
  • the inventors of the present application have found that in situ preparation of NPs solves at least two major problems associated with industry scale applications of NPs in cement slurries.
  • the NPs are prepared from their water-soluble precursors, reducing the cost for cement slurry preparation.
  • cement slurry is defined as a semiliquid mixture having cement particles suspended in water.
  • the relative amounts of cement powder and water used to form a cement slurry is not particularly limiting and can be changed depending on various factors such as application (such as well cementing, road paving, building of vertical and/or weight bearing structures, etc.) and/or environmental considerations (such as temperature, pressure, surrounding atmospheric composition, presence of contaminants, etc.).
  • the slurry can be relatively thin (that is, have a relatively low viscosity). In some instances, the slurry can be in the form of a thick paste or mortar.
  • cement matrix means a hardened or cured cement formed from a cement slurry.
  • in situ nanoparticle preparation can be accomplished by first dissolving nanoparticle precursors in an amount of water to be added to a dry cement powder to make a cement slurry.
  • nanoparticles will be prepared from two precursors.
  • one or more than two nanoparticle precursors can be used.
  • Each precursor can be dissolved in a certain volume of water.
  • the volumes of water, each containing a single precursor dissolved therein, can then be combined and mixed.
  • dry cement powder can be added to the combined mixture, which, depending upon the reaction rate of the two NP precursors, may contain freshly precipitated NPs therein.
  • a sufficient amount of dry cement is added to result in a cement slurry upon mixing/blending.
  • starting amounts of dry cement powder and water are each split into a number of equal portions, established by weight and/or volume.
  • a plurality of NP precursor-cement slurries is then prepared by dissolving a distinct nanoparticle precursor in each water portion followed by the addition of a corresponding portion of dry cement powder.
  • the plurality of NP precursor-cement slurries is then combined and the distinct NP precursors, now in a single slurry, react to form NPs.
  • the number of equal portions into which the dry cement and the water are split will equal the number of nanoparticle precursors used.
  • each nanoparticle precursor is then added to a corresponding portion of water to form a precursor solution A and a precursor solution B.
  • a portion of dry cement powder is added to each precursor solution to form a NP precursor-cement slurry A and a NP precursor-cement slurry B.
  • the NP precursor-cement slurry A and the NP precursor-cement slurry B are then mixed together and the nanoparticles (“AB”) are formed in situ in the combined slurry.
  • starting amounts of dry cement powder and water are each split into a number of unequal portions, established by weight and/or volume.
  • the ratio of the two portions can range from about 5:95 to about 49:51.
  • the dry cement powder is split into two portions, the ratio of the two portions can range from about 5:95 to about 49:51.
  • a plurality of NP precursor-cement slurries are then prepared by dissolving a distinct nanoparticle precursor in each water portion followed by the addition of a corresponding portion of dry cement powder. The plurality of NP precursor-cement slurries is then combined and the distinct NP precursors, now in a single slurry, react to form NPs.
  • the number of unequal portions into which the dry cement and the water are split will equal the number of nanoparticle precursors used. For example, if two NP precursors are used for the in situ preparation of nanoparticles, the dry cement powder and water will be split into two unequal portions.
  • precursor A and “precursor B” each nanoparticle precursor is then added to a corresponding portion of water to form a precursor solution A and a precursor solution B.
  • a portion of dry cement powder is added to each precursor solution to form a NP precursor-cement slurry A and a NP precursor-cement slurry B.
  • the NP precursor-cement slurry A and the NP precursor-cement slurry B are then mixed together and the nanoparticles (“AB”) are formed in situ in the combined slurry.
  • NP solid precursors are mixed into a dry cement powder to form a NP precursors-cement powder.
  • the NP precursors-cement powder is then mixed in an appropriate amount of water to form a NP precursors-cement slurry.
  • the NP precursors- cement slurry is subjected to continued mixing/blending to convert the NP precursors into NPs and form a NP-cement slurry.
  • NP solid precursors and dry cement powder are mixed into water in sequential steps.
  • precursor A can first be mixed in the water to form a precursor A solution.
  • an amount of dry cement powder can be added and mixed to form a precursor A-cement slurry.
  • Precursor B can then be mixed into the precursor A-cement slurry to form an initial precursor A/B-cement slurry.
  • another amount of dry cement powder can be added to and mixed with the initial precursor A/B-cement slurry to form a final precursor A/B-cement slurry.
  • NPs formed in accordance with various aspects of the present disclosure can have diameters ranging from about 1 nanometer (nm) to about 6 micrometers (pm).
  • the difference between the five approaches of NP preparation is the nucleation step. While the first approach allows for nucleation to take place within the aqueous solution prior to mixing the cement powder, the second through fifth approaches ensure that both nucleation and growth occur within a cement slurry. In the second through fifth approaches, however, the rate of nucleation and growth within a cement slurry may vary. A comparison between the approaches allows evaluation of the role of NP nucleation versus growth. In addition, the use of different approaches to prepare NPs of different types provides alternative routes in case of a failure.
  • the amount of each precursor in each volume of water will be stoichiometric.
  • a first NP precursor can have 1 molar equivalent of Fe 3+ ions and a second NP precursor can have 3 molar equivalents of OH ions.
  • a first NP precursor can have 1 molar equivalent of Ca 2+ and a second NP precursor can have 1 molar equivalent of C0 3 2 ions.
  • one of the precursors can be in excess relative to the other precursor.
  • an amount of dry cement powder will be added such that the cement slurry has a water to cement powder ratio ranging from about 0.1: 1 to about 1 : 1 by weight, alternatively from about 0.2: 1 to about 0.8: 1, alternatively from about 0.3: 1 to about 0.6: 1, alternatively from about 0.3: 1 to about 0.5: 1, and alternatively from about 0.4: 1 to about 0.5: 1.
  • the cement slurry can be formed such that it has a NP precursors to cement powder ratio ranging from about 0.01 :99.91 to about 20:80 by weight, alternatively from about 0.05:99.95 to about 15:85, alternatively from about 0.1 :99.9 to about 10:90, alternatively from about 0.15:99.85 to about 5:95, alternatively from about 0.2:99.8 to about 2.5:97.5, alternatively from about 0.35:99.65 to about 1.25:98.75, alternatively from about 0.4:99.6 to about 1 :99, alternatively from about 0.45:99.55 to about 0.8:99.2, alternatively from about 0.5:99.5 to about 0.8:99.2, and alternatively from about 0.55:99.45 to about 0.75:99.25 by weight.
  • a NP precursors to cement powder ratio ranging from about 0.01 :99.91 to about 20:80 by weight, alternatively from about 0.05:99.95 to about 15:85, alternatively from about 0.1 :99
  • the cement slurry can be formed such that it has a NP to cement powder ratio ranging from about 0.01 :99.91 to about 20:80, alternatively from about 0.05:99.95 to about 15:85, alternatively from about 0.1 :99.9 to about 10:90, alternatively from about 0.15:99.85 to about 5:95, alternatively from about 0.2:99.8 to about 2.5:97.5, alternatively from about 0.35:99.65 to about 1.25:98.75, alternatively from about 0.4:99.6 to about 1 :99, alternatively from about 0.45:99.55 to about 0.8:99.2, alternatively from about 0.5:99.5 to about 0.8:99.2, and alternatively from about 0.55:99.45 to about 0.75:99.25.
  • NPs can be formed in situ by a double displacement reaction scheme as follows: where AY (s) is the resulting NP.
  • AY (s) is the resulting NP.
  • the AX and BY compositions are not particularly limiting. The only requirement of the AX and BY compositions are that they be soluble in water and, upon reacting form an insoluble nanoparticle AY.
  • Nanoparticles which can be formed in situ via a double displacement reaction include, but are not limited to, Ag 2 C0 3 , Ag 2 S0 4 , Ag 2 Cr 2 0 7 , Ag 3 P0 4 , Ag 2 S, AgBr, AgCl, Agl, Al 2 0 3 , Al(OH) 3 , Al 2 (Cr 2 0 7 ) 3 , AlP0 4 , BaC0 3 , BaCr0 4 , BaF 2 , BaS0 4 , CaF, CaS0 4 , CaC0 3 , CaC 2 0 4 , Ca 3 (P0 4 ) 2 , CaCr 2 0 7 , Cr(OH) 3 , Cr 2 (S0 4 ) 3 , CrP0 4 , Cu(OH) 2 , Cu 3 (P0 4 ) 2 , CuC0 3 , CuCr 2 0 7 , Fe(OH) 2 , Fe(OH) 3 , Fe 2 (Cr 2 0 7 ) 3
  • AX and BY compositions, and amounts of each to be used in cement slurries may be guided by general solubility rules for ionic compounds and solubility product constants.
  • numerous other insoluble NPs containing metals such as lead, mercury, cadmium, cobalt, palladium, platinum, gold, molybdenum, tungsten, bismuth, indium, actinides, zirconium, tungsten, actinides and lanthanides may be prepared using double displacement reactions, if desirable.
  • AX water soluble metal-containing salt where A is the metal and BY is water soluble compound containing an anionic Y species which when ionically bound to the metal A to form AY, while the anion X and cation B react to form a water soluble compound BX.
  • NPs can be formed using a double displacement reaction scheme, the present invention is not limited thereto.
  • NPs containing a single metal such as iron, nickel, copper, silver, gold, titanium and aluminum, can be formed by reacting a corresponding water soluble metal-containing salt with a suitable reducing agent.
  • metal oxide nanoparticles can be fabricated in situ from a water-soluble metal- containing salt, a base and/or an oxidizing agent.
  • metal or metalloid oxide nanoparticles can be fabricated in situ, from a water-soluble metal-containing salt and either an acid or a base, via a hydrolysis and condensation reaction mechanism.
  • Metal/metalloid oxide nanoparticles which can be formed in situ in accordance with various aspects of the present disclosure include, but are not limited to, Al 2 0 3 , Si0 2 , Sc 2 0 3 , Ti0 2 , V 2 Os, Cr 2 0 3 , MnO, Mn0 2 , MgO, iron oxides with their various crystal structures (e.g., FeO, Fe 2 0 3 , Fe 3 0 4 ), CuO, Cu 2 0, ZnO, Zr0 2 , SnO, Sn0 2 , Sb 2 0 3 , Bi 2 0 3 , and W0 3 .
  • the water used to form a cement slurry is freshwater. In some instances, the water used to form a cement slurry is purified water. In some instances, the water used to form a cement slurry is de-ionized water. In some instances, the water used to form a cement slurry is seawater. In some instances, the water used to form a cement slurry is brine. In some instances, the water used to form a cement slurry is brackish water.
  • a NP dispersion aid can be added to enhance the dispersion of the NPs within the cement slurry.
  • the dispersion aid can be added to the water prior to addition of the NP precursors.
  • the dispersion aid can be added to the water at the same time as addition of the NP precursors.
  • the dispersion aid can be added to the water after addition of the NP precursors and prior to addition of the dry cement powder.
  • the dispersion aid can be added to the water after addition of the NP precursors and at the same time as addition of the dry cement powder.
  • the dispersion aid can be added to the water after addition of the NP precursors and after addition of the dry cement powder.
  • the dispersion aid can be added as the NPs are forming. In some instances, the dispersion aid can be added after the NPs are formed. In some instances, the dispersion aid can be a component of the dry cement powder. In some instances, cement slurries according to the present disclosure can have between about 0.01 and about 5.0 % by weight of cement (BWOC) of the dispersion aid.
  • BWOC cement
  • cement slurries according to the present disclosure can have between about 0.05 and about 4.5 % BWOC, alternatively between about 0.1 and about 4 % BWOC, alternatively between about 0.2 and about 3 % BWOC, alternatively between about 0.3 and about 2 % BWOC, alternatively between about 0.4 and about 1 % BWOC, alternatively between about 0.5 and about 0.9 % BWOC, alternatively between about 0.6 and about 0.8 % BWOC, and alternatively about 0.7 % BWOC of the dispersion aid.
  • the NP dispersion aid can have any structure which reduces agglomeration of the NPs and aids in dispersing the NPs within the water and/or cement slurry.
  • aNP dispersion aid can have the following general structure:
  • X is an NP binding group; Z is hydrophilic functional group; and Y is a linking group.
  • X can be any polar functional group capable of coordinating to the surface of a NP such as, for example, a carboxylic acid, an alcohol, an amine, a thiol, a phosphine, and a phosphine oxide.
  • X can be any polar functional group that is hydrophilic, providing compatibility with the water phase of the cement slurry.
  • Z can be a functional group such as for example, a carboxylic acid, an alcohol, an amine, a thiol, a phosphine, and a phosphine oxide.
  • the linking group Y is not particularly limiting.
  • the Y group can be a linear or branched, saturated or unsaturated, carbon chain having between 2 and 24 carbons.
  • the linking group Y can be a linear or branched, saturated or unsaturated, mono- or polyester carbon chain having between 2 and 24 carbons and at least one oxygen.
  • the linking group Y can be a linear or branched, saturated or unsaturated, mono- or polyamine carbon chain having between 2 and 24 carbons and between at least one nitrogen.
  • the linking group Y can be a linear or branched, saturated or unsaturated, mono- or polysulfide carbon chain having between 2 and 24 carbons and between at least one sulfur.
  • the dispersion aid can have the following general structure: X-Y
  • X is an NP binding group and Y is a hydrophilic polymer, copolymer, terpolymer, or block copolymer.
  • X can be any polar functional group capable of coordinating to the surface of a NP such as, for example, a carboxylic acid, an alcohol, an amine, a thiol, a phosphine, and a phosphine oxide.
  • Y can be a hydrophilic polymer such as, for example, a polyethylene glycol (PEG), a polyethylene oxide (PEO), a poly(acrylic acid), a poly(methacrylic acid), a poly(2-ethyl acrylic acid) (PEAAc), a poly(2-propylacrylic acid), a polyKYY-diethylaminoethyl methacrylate) (PDEAEMA), a polyvinyl pyrrolidone (PVP), a polyacrylamide, a poly (vinyl alcohol) (PVOH), a poly carboxylic acid, a polycarboxylate salt, a polycarboxylate ether and a polysaccharide.
  • PEG polyethylene glycol
  • PEO polyethylene oxide
  • PEO poly(acrylic acid)
  • PEAAc poly(methacrylic acid)
  • PEAAc poly(2-propylacrylic acid)
  • PDEAEMA polyKYY-diethylaminoethyl
  • the dispersion aid can be provided by CFR-12 (Trican Well Service Ltd., Calgary, Alberta, Canada).
  • CFR-12 is a blend comprising about 15 wt% of a polycarboxylate ether (the active dispersion aid), 30 to less than 60 wt% of diatomaceous earth, 10 to less than 30 wt% aluminum oxide, 3 to less than 7 wt% boric acid, 3 to less than 7 wt% calcium oxide and 1 to less than 5 wt% ferric oxide)
  • Nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries using, for example, a dry cement powder manufactured according to the specifications of the American Society for Testing and Materials (an“ASTM cement”), dry cement powder manufactured to the specifications of the American Petroleum Institute (an“API cement”), a concrete (cement plus fine and course aggregates of sand, crushed stones, gravel and so on), gypsum (calcium sulfate dihydrate), fly ash, silica flour, silica fume, metakaolin, a microcement and any combination thereof.
  • ASTM cement dry cement powder manufactured according to the specifications of the American Society for Testing and Materials
  • an“API cement” dry cement powder manufactured to the specifications of the American Petroleum Institute
  • gypsum calcium sulfate dihydrate
  • fly ash silica flour
  • silica fume metakaolin
  • microcement any combination thereof.
  • compositions such as bentonite, calcium carbonate, glass (for example, glass spheres), ceramics (for example, ceramic spheres), a salt (for example, NaCl, CaCl . KC1), barite, hematite, and any combination thereof, can be added to cement slurries formed in accordance with various aspect of the present disclosure.
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an ASTM Type I (general purpose) portland cement, which characteristically has a fairly high tricalcium silicate (cement notation: C 3 S) content for good early strength development, for the construction of, for example, buildings, bridges, pavements, precast units, and other similar structures.
  • ASTM Type I general purpose
  • C 3 S tricalcium silicate
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an ASTM Type II (moderate sulfate resistance) portland cement, which characteristically has a low tricalcium aluminate ( ⁇ 8%; cement notation: C 3 A) content, for the construction of structures which will be exposed to soil or water containing sulfate ions.
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an ASTM Type III (high early strength) portland cement, for use in, for example rapid construction projects and cold weather concreting.
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an ASTM Type IV (low heat of hydration, i.e., slow reacting) portland cement, which characteristically has a low C 3 S ( ⁇ 50%) and C 3 A content, for the construction of massive structures such as dams.
  • ASTM Type IV low heat of hydration, i.e., slow reacting
  • portland cement which characteristically has a low C 3 S ( ⁇ 50%) and C 3 A content
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an ASTM Type V (high sulfate resistance) portland cement, which characteristically has a very low C 3 A ( ⁇ 5%) content, for the construction of structures which will be exposed to high levels of sulfate ions.
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an ASTM White portland cement, which characteristically has no tetracalcium aluminoferrite (cement notation: C 4 AF) and low MgO content for the construction of decorative structures or items.
  • ASTM White portland cement which characteristically has no tetracalcium aluminoferrite (cement notation: C 4 AF) and low MgO content for the construction of decorative structures or items.
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having an API class A portland cement (53% C 3 S, 24% dicalcium silicate (C 2 S), > 8+% C 3 A, 8% C 4 AF; Wagner Fineness of 1,500-1,900 cm 2 /g).
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having API class B portland cement (47% C 3 S, 32% C 2 S, ⁇ 5% C 3 A, 12% C 4 AF; Wagner Fineness of 1,500-1,900 cm 2 /g).
  • nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having API class C portland cement (58% C 3 S, 16% C 2 S, 8% C 3 A, 8% C 4 AF; Wagner Fineness of 2,000-2,800 cm 2 /g). In other instances, nanoparticles formed in accordance with various aspects of the present disclosure can be used in the preparation of cement slurries having API class G or H portland cement (50% C 3 S, 30% C 2 S, 5% C 3 A, 12% C 4 AF; Wagner Fineness of 1,400-1,700 cm 2 /g).
  • the mixing and blending of the cement slurry can be performed according to American Petroleum Institute (API) specifications.
  • API American Petroleum Institute
  • blending and mixing of the NP precursors, NPs and dry cement powder, and/or NP precursors and dry cement powder can be accomplished in any suitable manner.
  • mixing can be accomplished manually.
  • mixing can be accomplished with use of an apparatus such as a blender, a twin shaft mixer, a vertical axis mixer, a drum mixer, an in-transit mixer, a portable concrete mixer, and a self-loading mixer.
  • the precursors react to form nanoparticles.
  • mixing and blending can take place under ambient pressure and temperature.
  • mixing and blending can be performed at an elevated temperature.
  • mixing and blending can be performed at a temperature below ambient temperature and above the freezing point of water.
  • the slurry is conditioned (i.e. subjected to pressure and temperature) to simulate downhole conditions using a conditioning cell that provides continuous mixing and heats up the slurry to the required temperature (25 - 90)°C. Then, a series of tests is run on each sample to study the compressive strength, tensile strength, thickening time, fluid loss, rheology, free water, permeability and porosity as the cement slurry cures or hardens to form a resulting cement matrix.
  • cement matrices formed in accordance with various aspects of the present disclosure can have anywhere from about 0.05 to about 5 wt% of nanoparticles by weight of cement (BWOC).
  • BWOC is determined relative to the amount of dry cement powder used to make a corresponding cement slurry.
  • cement matrices formed in accordance with various aspects of the present disclosure can have anywhere from about 0.1 to about 4 wt%, alternatively from about 0.15 to about 3 wt%, alternatively from about 0.2 to about 2 wt%, alternatively from about 0.225 to about 1.75 wt%, alternatively from about 0.25 to about 1.5 wt%, alternatively from about 0.4 to about 1.4 wt%, alternatively from about 0.5 to about 1.3 wt%, alternatively from about 0.5 to about 1.2 wt%, alternatively from about 0.5 to about 1 wt% of nanoparticles BWOC.
  • the preparation of cement slurries resulting in cement matrices with about 0.66 wt% of NPs has been found particularly effective from an efficiency and raw materials input perspective.
  • Portland cement (mainly Class G) powder was used in the examples below to prepare the cement slurries as it is the most commonly employed in the oil and gas industry.
  • Water-soluble salts as shown in Table 1, were used as precursors to form the NPs as well as simulate the side products from the NP precipitation reactions (Rl) to (R4).
  • These NPs included CaS0 4 (NPi), CaC0 3 (NP 2 ) and Fe(OH) 3 (NP 3 ). All reactions were assumed to proceed to completion.
  • NP 3 ⁇ 4i refers to CaC0 3 NPs prepared by Ml.
  • CSi Class G cement
  • Cement slurries incorporating commercial nano-Si0 2 (average particle size ⁇ 7 nm) and nano-Fe 2 0 3 (average particle size ⁇ 50 nm) were also used in order to provide a comparison with the in situ prepared NPs.
  • the commercial Si0 2 and Fe 2 0 3 NPs were labeled as NP 4 and NP 5 . respectively.
  • Trican dispersant CFR-12 was added to some slurries to investigate the role of NP dispersion within the slurry.
  • NP impregnated-cement slurries were prepared using three methods.
  • a first method Ml
  • the volume of the water to be added to the cement i.e. 350 ml
  • the first NP precursor was dissolved in the first water portion to form a first NP precursor aqueous solution and the second NP precursor was dissolved in the second water portion to form a second NP precursor aqueous solution.
  • the amounts of first and second NP precursors were stoichiometric.
  • the first and second NP precursor aqueous solutions were mixed together in a blender for 10 - 20 seconds (s).
  • the dry cement was then added to the freshly precipitated NPs and mixing commenced for another 96 s.
  • a second method M2
  • the cement and the water to be added to it were split into two equal masses.
  • a first NP precursor was added to a first water portion to form a first NP aqueous solution
  • the first amount of dry cement powder was then added to the first NP precursor aqueous solution and mixed for about 28 seconds (s) to form a first NP precursor cement slurry.
  • a second NP precursor was added to a second water portion to form a second NP aqueous solution
  • the second amount of dry cement powder was then added to the second NP precursor aqueous solution and mixed for about 28 seconds (s) to form a second NP precursor cement slurry.
  • first and second NP precursor cement slurries were mixed together for 56 s using a blender to form a NP-containing cement slurry upon reaction of the NP precursors.
  • the amounts of first and second NP precursors were stoichiometric.
  • a third method M3
  • stoichiometric amounts of first and second NP precursor salts were added directly to an amount of dry cement powder, followed by thoroughly mixing with a rod to ensure proper distribution of the first and second NP precursor salts within the dry cement powder to form a dry blend.
  • the dry blend was mixed with the water in a blender for 120 s to form a NP-containing cement slurry upon reaction of the NP precursors.
  • Another method (M4) involved mixing a first NP precursor aqueous solution with a first half of dry cement powder and mixing for 20 s. Then, adding a second NP precursor aqueous solution to the slurry and continue mixing for another 20 s, followed by the addition of the second half of the dry cement. The resultant slurry (now containing first and second NP precursors) was then mixed for 80 s.
  • the other control sample slurries (CS 1 CS 2 , CS 3 and CS 4 ) were prepared similar to CS with the exception of dissolving the salts in the water before mixing it with the cement.
  • Slurries containing CFR-12 involved the addition of CFR-12 to the dry cement instead of water. All slurries were then conditioned through continuous mixing at 25°C for 20 min.
  • Cyclic axial testing was conducted to determine the effect of compression cycles on the elastic properties of the cement sample.
  • a cylindrical sample (1 inch in diameter and 2 inches long) was prepared, cured for 2 days at 80°C and submerged in oil under 2.5 MPa of pressure in a triaxial rock testing machine. The sample was compressed until a certain strain value (0.2%) was reached and then the load was decreased so the sample could return to its original shape. Ten compression cycles were applied after which the sample was compressed until it failed. The peak in the compressive stress after these compression cycles was compared to the peak without any compression cycles to assess the impact of subsequent pressure cycles on the durability of the cement sheath.
  • Porosity and permeability test samples were prepared by pouring the cement slurry into a cylindrical mold and leaving it to cure for 2 days at 80°C. Then, porosity was calculated by making bulk and skeletal density measurements using a gas pycnometer, whereas permeability was determined by pulse decay method using helium.
  • NP characterization within the cement matrix was accomplished using scanning electron microscopy (SEM) equipped with energy dispersive X-ray (EDX).
  • SEM scanning electron microscopy
  • EDX energy dispersive X-ray
  • sedimentation experiments were carried out to provide details on particle settling following their preparation using Ml.
  • the precursor solutions were mixed together in a blender for 30 s to form the NPs before pouring them into a beaker (600 ml, OD: 88 mm, height: 122 mm) to observe the movement of the interface over time, per sedimentation type III protocol (S. Verma, B. Prasad, and I. M. Mishra, “Pretreatment of petrochemical wastewater by coagulation and flocculation and the sludge characteristics,” J. Hazard. Mater., vol. 178, no. 1-3, pp. 1055-1064, 2010).
  • FIG. 1 is a graphical display of the evolution of cement compressive strength over time for nano-CaS0 4 slurry prepared by Ml (NRi , i, A in FIG. 1), nano-CaC0 3 slurries prepared by Ml (NP 3 ⁇ 4i , B in FIG. 1) and M2 (NP 2 2 , C in FIG. 1), nano-Fe(OH) 3 slurries prepared by Ml (NP 3,I , D in FIG. 1), M2 (NP 3 2 , E in FIG. 1) and M3 (NP 3 3 , F in FIG. 1), Class G slurry (CS, G in FIG. 1), NaCl-containing Class G slurry (CSi, H in FIG.
  • the nano-CaS0 4 slurry prepared by Ml showed overall higher compressive strength than the Class G slurry (CS).
  • a slurry containing the same amount of NaCl side product from Rl (CSi in Table 1) displayed an even higher value of compressive strength than exhibited by NRi , i. Therefore, the use NPu appears ineffective.
  • a similar trend similar to NRi , i is observed with nano-CaC0 3 slurries prepared using Ml (NP 2,I ) and M2 (NP 22 ). This also indicates that the increase in the compressive strength for in situ prepared nano-CaC0 3 slurries was mainly due to the NaCl side product.
  • FIG. 1 also provides data for nano-Fe(OH) 3 prepared by the three different methods (NP 3 4, NP 3,2 and NP 3 3 ). These samples exhibit an increased compressive strength compared to class G control sample (CS) by 70 to 80% in the first 24 h. Control samples CS 2 and CSi could not achieve the compressive strength values obtained by NP 32 to NP 3 3 . Even though Fe(N0 3 ) 3 -containing class G slurry (CS 3 ) showed significant increase in compressive strength (around 44% increase in 6 days), the development of the compressive strength was much slower than that of the NP 3 slurries.
  • the high 6-day compressive strength of CS 3 slurry could result from the conversion of Fe(N0 3 ) 3 precursor to Fe(OH) 3 with hydroxide ions appearing from the cement hydration reaction.
  • Reproducibility of the results obtained by NP 3 I (A in FIGS. 3-4), NP 3 2 (B in FIGS. 3-4) and NP 3 3 (C in FIGS. 3-4) at 25°C and 80°C are shown in FIGS. 3 and 4, respectively, for three replicates and compared to Class G slurry (CS, D in FIGS. 3-4).
  • FIG. 5 is a graphical display of the evolution of compressive strength over time for nano-Fe(OH) 3 slurries prepared by Ml (NP 3 I , A in FIG. 5), M2 (NP 3 2 , B in FIG. 5) and M3 (NP 3 3 , C in FIG. 5), Class G slurry (CS, D in FIG. 5), commercial nano-Si0 2 -containing Class G slurry (NP 4 , E in FIG. 5) and commercial nano-Fe 2 0 3 -containing Class G slurry (NP 5 , F in FIG. 5).
  • Ml NP 3 I , A in FIG. 5
  • M2 NP 3 2 , B in FIG. 5
  • M3 NP 3 3 , C in FIG. 5
  • Class G slurry CS, D in FIG. 5
  • commercial nano-Si0 2 -containing Class G slurry NP 4 , E in FIG. 5
  • commercial nano-Fe 2 0 3 -containing Class G slurry NP
  • FIG. 6 is a graphical display of sedimentation type III experiments for different in situ prepared (using Ml) and commercial NPs used in this study at 25°C with specific beaker dimensions (600 ml, OD: 88 mm, height: 122 mm).
  • FIG. 7 is a graphical display of the evolution of compressive strength over time for nano- CaC0 3 slurry prepared by Ml (NR 3 ⁇ 4 i, A in FIG.
  • nano-Fe(OH) 3 slurry prepared by M3 (NP 3 , B in FIG. 7), nano-CaC0 3 slurry prepared by Ml including 0.7% BWOC dispersant (NP 2 i +CFRl2, C in FIG. 7), nano-Fe(OH) 3 slurry prepared by M3 including 0.7% BWOC dispersant (NP 3 3 +CFRl2, D in FIG. 7), Class G slurry (CS, E in FIG. 7) and Class G slurry including 0.7% BWOC dispersant (CS+CFR12, F in FIG. 7).
  • NP nano-Fe(OH) 3 slurry prepared by M3
  • NP 2 i +CFRl2, C in FIG. 7 nano-Fe(OH) 3 slurry prepared by M3 including 0.7% BWOC dispersant
  • NP 3 3 +CFRl2 nano-Fe(OH) 3 slurry prepared by M3 including 0.7% BWOC dispersant
  • CS Class G slurry
  • FIG. 8 shows the compressive strength of cement matrices formed from nano-Fe(OH) 3 slurries prepared using Ml and having 0.270% (A), 0.660% (B) and 1.200% (C) BWOC nano-Fe(OH) 3 ;
  • FIG. 8 also shows the compressive strength of a cement matrix formed from Class G slurry (CS, D) for reference.
  • FIG. 9 shows the compressive strength of cement matrices formed from nano- Fe(OH) 3 slurries prepared using M2 and having 0.270% (A), 0.660% (B) and 1.200% (C) BWOC nano-Fe(OH) 3 ;
  • FIG. 9 also shows the compressive strength of a cement matrix formed from Class G slurry (CS, D) for reference.
  • FIG. 10 shows the compressive strength of cement matrices formed from nano-Fe(OH) 3 slurries prepared using M3 and having 0.270% (A), 0.660% (B) and 1.200% (C) BWOC nano-Fe(OH) 3 ;
  • FIG. 10 also shows the compressive strength of a cement matrix formed from Class G slurry (CS, D) for reference.
  • FIGS. 8-10 confirm that, among the different contents tested in this study, 0.660% BWOC of NPs presents a good balance between the cost of NPs and product quality, regardless of in situ synthetic protocol.
  • FIG. 11 shows, for a cement matrix formed from CS slurry, an EDX image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and an SEM image (bottom).
  • FIG. 12 shows, for a cement matrix formed from NP 3 , I slurry, an EDX image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and an SEM image (bottom).
  • FIG. 11 shows, for a cement matrix formed from CS slurry, an EDX image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and an SEM image (bottom).
  • FIG. 13 shows, for a cement matrix formed from NP 3.2 slurry, an EDX image with bright regions indicative of aluminum (top left), an EDX image with bright regions indicative of iron (top right) and an SEM image (bottom). From the EDX results, it can be noticed that there is a correlation between the content of iron and aluminum in the nano-Fe(OH) 3 samples (NP 3 , I and NP 3 , 2 ). Such a correlation is not as strong in class G control sample (CS), where native iron exists. SEM was used to investigate the morphology of the samples in areas of overlap between iron and aluminum. As shown in the SEM images, the length of the aluminosilicate crystals in CS is larger than their length in the samples containing NP 3 and NP 3 2.
  • FIG. 14 is a graph displaying the porosity (%) of CS, NP 3,I , NP 3 2 , NP 3 3 , respectively, from left to right.
  • FIG. 15 is a graph displaying the permeability (mD) of CS, NP 3,I , NPs; . NP 3 3 , respectively, from left to right.
  • the Fe(OH) 3 NPs prepared in situ via Ml (NP 3,i ) exhibited porosity and permeability values 5% and 52% lower than the CS sample, respectively.
  • the Fe(OH) 3 NPs prepared in situ via M2 (NP 3 2 ) exhibited porosity and permeability values 7% and 10% lower than the CS sample, respectively.
  • the Fe(OH) 3 NPs prepared in situ via M3 (NP 3 3 ) exhibited porosity and permeability values 48% and 93% lower than the CS sample, respectively.
  • Triaxial compressive stress testing was conducted on three cement matrices.
  • the first matrix was formed from a nano-Fe(OH) 3 cement slurry formed according to Ml (NP 3 4).
  • the second matrix was formed from a nano-Fe(OH) 3 cement slurry formed according to M2 (NP 3 2 ).
  • the third matrix was prepared from a class G cement slurry (CS).
  • FIG. 16 shows CS suffered fatigue after 10 compression cycles (B) which caused it to fail before reaching its original maximum strain (A).
  • the NP 3 cement matrix resisted the cyclical compression (10 cycles, B) and maintained its original peak strain (A). Also as shown in FIG.
  • the NP 3.2 cement matrix resisted the cyclical compression (10 cycles, B) and maintained its original peak strain (A).
  • A peak strain
  • This disclosure teaches various methods for the large-scale synthesis and application of NPs in cement slurries for strengthening resultant cured cement matrices.
  • the cost of NPs and their state of dispersion have been addressed by in situ preparation of the particles from their inexpensive water-soluble precursors.
  • the effect of in situ prepared NPs on compressive strength, cyclical compressive stress, porosity and permeability was studied. While not limiting the scope of the invention in any way, the in situ preparation of Fe(OH) 3 NPs in cement slurries was found particularly effective. Slurries containing in situ Fe(OH) 3 NPs exhibited significant enhancement in compressive strength regardless of the synthesis method.
  • Fe(OH) 3 based slurries show higher resistance to cyclic compressive stress and reductions in porosity and permeability.
  • the effectiveness of Fe(OH) 3 based slurries can be attributed to the slower kinetics of growth/aggregation of the Fe(OH) 3 particles which allowed the Fe(OH) 3 NPs to remain suspended and well dispersed within the slurry without any dispersing agents.
  • In situ prepared Fe(OH) 3 NPs also affect the cement structure by hindering the growth of long cement crystals making the cement matrix more compact as well as through acting as a filler reducing porosity and permeability while providing support preventing the collapse of pore throats.
  • Statement 1 A composition of matter, the composition comprising a cement powder; a first nanoparticle precursor; and a second nanoparticle precursor.
  • Statement 2 A composition according to Statement 1, further comprising water.
  • Statement 3 A composition according to Statement 2, wherein the water is any one of freshwater, purified water, de-ionized water, seawater, brine, and brackish water.
  • Statement 4 A composition according to Statement 2 or 3, wherein the composition has a water to cement powder ratio ranging from about 0.1 : 1 to about 1 : 1 by weight.
  • Statement 5 A composition according to any one of Statements 1-4, further comprising a dispersion aid.
  • Statement 6 A composition according to any one of Statements 1-5, wherein the composition has a nanoparticle precursors to cement powder ratio ranging from about 0.01:99.91 to about 20:80 by weight.
  • Statement 7 A multi-component system for making a cement slurry, the system comprising a first aqueous solution comprising a first water soluble nanoparticle precursor; a second aqueous solution comprising a second water soluble nanoparticle precursor; and a cement powder.
  • Statement 8 A system according to Statement 7, wherein one or both of the first aqueous solution and the second aqueous solution further comprises a dispersion aid.
  • Statement 9 A system according to Statement 7 or 8, wherein the cement powder comprises a dispersion aid.
  • Statement 10 A system according to any one of Statements 7-9, wherein the system has a water to cement powder ratio ranging from about 0.1 : 1 to about 1 : 1 by weight.
  • Statement 11 A system according to any one of Statements 7-10, wherein the system has a nanoparticle precursors to cement powder ratio ranging from about 0.01 :99.91 to about 20:80 by weight.
  • Statement 12 A multi-component system for making a cement slurry, the system comprising an aqueous solution comprising a first water soluble nanoparticle precursor and a second water soluble nanoparticle precursor; and a cement powder.
  • Statement 13 A system according to Statement 12, wherein the aqueous solution further comprises a dispersion aid.
  • Statement 14 A system according to Statement 12 or 13, wherein the powder comprises a dispersion aid.
  • Statement 15 A system according to any one of Statements 12-14, wherein the system has a water to cement powder ratio ranging from about 0.1 : 1 to about 1 : 1 by weight.
  • Statement 16 A system according to any one of Statements 12-15, wherein the system has a nanoparticle precursors to cement powder ratio ranging from about 0.01 :99.91 to about 20:80 by weight.
  • Statement 17 A multi-component system for making a cement matrix, the system comprising: a first cement slurry comprising a first cement powder, a first nanoparticle precursor, and water; and a second cement slurry comprising a second cement powder, a second nanoparticle precursor, and water.
  • Statement 18 A system according to Statement 17, further comprising a dispersion aid in one or both of the first cement slurry and the second cement slurry.
  • Statement 19 A system according to Statement 17 or 18, wherein one or both of the first cement slurry and the second cement slurry has a water to cement powder ratio ranging from about 0.1 : 1 to about 1 : 1 by weight.
  • Statement 20 A system according to any one of Statements 17-19, wherein one or both of the first cement slurry and the second cement slurry has a nanoparticle precursors to cement powder ratio ranging from about 0.01 :99.91 to about 20:80 by weight.
  • Statement 21 A method of making a cement slurry, the method comprising adding a cement powder, a first nanoparticle precursor and a second nanoparticle precursor to water; and mixing the cement powder, the first nanoparticle precursor and the second nanoparticle precursor in the water to form a cement slurry.
  • Statement 22 A method according to Statement 21, wherein the water is any one of freshwater, purified water, de-ionized water, seawater, brine, and brackish water.
  • Statement 23 A method according to Statement 21 or 22, wherein the cement powder comprises a dispersion aid.
  • Statement 24 A method according to any one of Statements 21-23, further comprising adding a dispersion aid to the water.
  • Statement 25 A method according to any one of Statements 21-24, wherein adding the cement powder, the first nanoparticle precursor and the second nanoparticle precursor to water comprises adding the first nanoparticle precursor to a first amount of water to form a first nanoparticle precursor-containing aqueous solution; adding the second nanoparticle precursor to a second amount of water to form a second nanoparticle precursor-containing aqueous solution; combining the first nanoparticle precursor-containing aqueous solution and the second nanoparticle precursor-containing aqueous solution; and adding a cement powder to the combined first and second nanoparticle precursor-containing aqueous solutions.
  • Statement 26 A method according to any one of Statements 21-24, wherein adding the cement powder, the first nanoparticle precursor and the second nanoparticle precursor to water comprises adding the first nanoparticle precursor to a first amount of water to form a first nanoparticle precursor-containing aqueous solution; adding a first amount of the cement powder to the first nanoparticle precursor-containing aqueous solution to form a first nanoparticle precursor-containing cement slurry; adding the second nanoparticle precursor to a second amount of water to form a second nanoparticle precursor-containing aqueous solution; adding a second amount of the cement powder to the second nanoparticle precursor- containing aqueous solution to form a second nanoparticle precursor-containing cement slurry; and combining the first nanoparticle precursor-containing cement slurry and the second nanoparticle precursor-containing cement slurry.
  • Statement 27 A method according to Statement 26, wherein the first amount of water and the second amount of water are the same amount.
  • Statement 28 A method according to Statement 26 or 27, wherein a ratio of the first amount of water to the second amount of water ranges from about 5:95 to about 49:51.
  • Statement 29 A method according to any one of Statements 26-28, wherein the first amount of the cement powder and the second amount of the cement powder are the same amount.
  • Statement 30 A method according to any one of Statements 26-29, wherein a ratio of the first amount of the cement powder to the second amount of the cement powder ranges from about 5:95 to about 49:51.
  • Statement 31 A method according to any one of Statements 21-24, wherein adding the cement powder, the first nanoparticle precursor and the second nanoparticle precursor to water comprises mixing the cement powder, the first nanoparticle precursor and the second nanoparticle precursor to form a nanoparticle precursors-cement powder mixture; and adding the nanoparticle precursors-cement powder mixture to the water.
  • Statement 32 method according to any one of Statements 21-24, wherein adding the cement powder, the first nanoparticle precursor and the second nanoparticle precursor to water comprises adding a first nanoparticle precursor to water to form a first nanoparticle precursor-containing aqueous solution; adding a first amount of the cement powder to the first nanoparticle precursor-containing aqueous solution to form a first nanoparticle precursor-containing cement slurry; and adding a second nanoparticle precursor to the first nanoparticle precursor-containing cement slurry to form a nanoparticle precursors-containing cement slurry.
  • Statement 33 A method according to Statement 32, further comprising adding a second amount of the cement powder to the nanoparticle precursors-containing cement slurry.

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Abstract

L'application de nanotechnologie dans des opérations de cimentation de puits améliore les propriétés mécaniques du ciment. On obtient ainsi une meilleure isolation zonale et une meilleure protection de l'environnement. Des opérations de cimentation de puits ont préalablement utilisé des nanoparticules préfabriquées dans des coulis de ciment. On a toutefois remarqué que des particules préfabriquées présentent une dispersion incorrecte à l'intérieur d'une gaine de ciment obtenue, ce qui a un impact négatif sur ses propriétés mécaniques. La présente invention concerne la synthèse in situ des nanoparticules à l'intérieur d'un coulis de ciment tandis qu'il s'hydrate pour former une matrice de ciment qui a pris/durci. La préparation de nanoparticules in situ est une technologie de plateforme qui permet la préparation d'une grande variété de nanoparticules avec régulation de leur taille, de leur morphologie et de leur résultat en dispersion élevée. En plus de l'atténuation du problème de dispersion observé avec des nanoparticules préfabriquées, l'approche in situ pour la synthèse de nanoparticules décrite ici utilise des précurseurs peu coûteux, réduisant significativement le coût des nanoparticules et d'une opération globale de cimentation de puits.
PCT/CA2019/051014 2018-07-24 2019-07-23 Compositions à base de ciment et procédés de fabrication associés WO2020019070A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN113583642A (zh) * 2021-08-30 2021-11-02 卫辉市化工有限公司 油井水泥用改性纳米二氧化硅早强促凝剂、制备方法及其应用
CN114441573A (zh) * 2021-12-29 2022-05-06 广西科技大学 一种便于观测石墨烯调控水泥水化晶体形貌的新型扫描电镜试样制备方法
CN114441573B (zh) * 2021-12-29 2023-07-28 广西科技大学 一种便于观测石墨烯调控水泥水化晶体形貌的新型扫描电镜试样制备方法

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