High efficiency radiation-induced triggering for set-on-command compositions and methods of use.

The modalities described herein refer to systems and methods that use bremsstrahlung radiation (from German, "braking") to facilitate solidification of a solidifiable composition.

Natural resources such as oil and gas located in an underground formation can be recovered by drilling a well to the underground formation, commonly while a drilling fluid is circulated in the well. After the well has been drilled, a tube string (for example, a casing pipe) can be placed in the well. The drilling fluid is generally circulated in a downward direction through the inside of the tube and in an upward direction through the ring between the outside of the tube and the walls of the well, although other methodologies are known in the art.

Hydraulic cement compositions are commonly used in the drilling, completion and repair of oil and gas wells. For example, <Λ XX is used.

«♦” f'x

Χί · X _ki hydraulic cement compositions in primary cementing operations by means of which the pipe strips such as the casing pipe and the casing pipe cut into the wells are cemented. When performing primary cementation, a hydraulic cement composition is pumped into the annular space between the walls of a well and the outer surfaces of a tube string arranged there to harden. After the cement is placed inside the well, a period of time is needed for the cement to cure and obtain sufficient mechanical strength to resume drilling operations. This downtime is often referred to as "waiting for cement setting" or WOC. The WOC time varies from a few hours to several days, depending on the difficulty and criticality of the cement work in question. It is desired to reduce the WOC time, so that the equipment can start the drilling operation again and thus reduce the total time and cost of the operations. If operations resume before the cement achieves sufficient mechanical strength, the structural integrity of the cement can be compromised. As such, the systems are generally over-designed to have very long solidification (or thickening) times to ensure that the mixture remains fluid until all cementitious material is in place, which can result in an excess of WOC.

BRIEF DESCRIPTION OF THE FIGURES

The following figures are included to illustrate certain aspects of the modalities described herein and should not be viewed as exclusive modalities. The subject matter described may be subject to modifications, alterations, combinations and considerable equivalents in terms of form and function, as will occur to those skilled in the art with the benefit of the present description.

<td>The</td><td>Figure</td><td> 1</td><td>illustrates a</td><td>side view</td><td>from</td><td>cut</td>

<td colspan="2">cross section of a</td><td colspan="2">water well.</td><td></td><td></td><td></td>

<td>The</td><td>Figure</td><td> 2</td><td>provides</td><td>an illustration</td><td>from</td><td>cut</td>

transverse of a system for producing bremsstrahlung photons at the bottom of the well according to at least some modalities described herein.

Figure 3 provides a cross-sectional illustration of a system for producing bremsstrahlung photons at the bottom of the well in accordance with at least some modalities described herein.

DETAILED DESCRIPTION

The modalities described herein refer to systems and methods that use bremsstrahlung radiation to facilitate solidification of a solidifiable composition.

The systems and methods described herein use bremsstrahlung photons to solidify solidifiable compositions (eg, resins, cements, solidifiable sludges, circulation loss fluids, forming fluids and combinations thereof). As used herein, the term "solidify" refers to an increase in the mechanical strength of a solidifiable composition (for example, in the form of fluid or suspension) sufficient to obtain a desired result, such as restricting the movement of an element or prevent the flow of fluids or the transfer of pressure through a fluid. In some cases, it can be said that a cement is solidified when it can restrict the movement of a tube or prevent the flow of fluids or the transfer of pressure, regardless of whether the cement was vulcanized forming a completely solid composition. In some cases, it can be said that a fluid or suspension is solidified when it has thickened to a sufficient level that achieves the desired result, such as the isolation of a particular area or the restriction of fluid flow or pressure transfer, without matter if it reached its final consistency.

The use of bremsstrahlung photons can be advantageous in well environments because the production of bremsstrahlung photons can be performed more efficiently than the production of other ionizing particles such as neutrons and protons. Therefore, the amount of energy per particle needed to produce bremsstrahlung photons of adequate penetration capacity is smaller, which minimizes power requirements and heat dissipation. Also, since bremsstrahlung photons are produced from the deceleration of electrons, a precursor fuel such as deuterium or tritium is not necessary. In addition, it is possible to easily achieve high intensities of bremsstrahlung photons (10¹⁴ of photons per second) compared to other ionizing radiation. For example, it is difficult to produce even 10¹² of deuterium / tritium neutrons per second without producing challenging heat loads.

In some embodiments, a solidifiable composition may include solidification accelerators and solidification retarders that can be released, activated or deactivated ♦ 'ν *.

- &lt;Λ ** '&gt; * *. ♦ *' WW 1 ”* by command using radiation with bremsstrahlung photons. When the solidifiable compositions and the bremsstrahlung radiation described herein are used in cementing operations in underground formations, these can advantageously reduce the WOC time, thereby reducing the cost associated with the cementation operation.

Unless otherwise specified, all numbers that express quantities of ingredients, properties such as molecular weight, reaction conditions and others used herein and in the associated claims should be understood as modified in all cases by the term "approximately." Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and appended claims are approximations that may vary according to the desired properties that are intended to be obtained by means of the modalities described herein. At a minimum and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in the light of the amount of significant figures indicated and through the application of common rounding techniques. It should be noted that when "approximately" is used at the beginning of a numerical list, "approximately" modifies each number in the numerical list. In addition, in some numerical lists of intervals, some lower limits listed may be higher than some upper limits listed. One skilled in the art will recognize that the selected subset will require the selection of an upper limit that exceeds the selected lower limit.

Figure 1 provides a cross-sectional illustration of a system suitable for performing a cementing operation at the bottom of the well. A surface lining pipe 4, which has a wellhead 6 attached, is installed in well 2. A casing pipe 8 suspended from the head of the well 6, extends through the well 2 and ends with an open end (or alternatively includes circulation ports in the walls of the casing pipe 8 (not shown)). A ring 10 is defined between the casing 8 and the well 2. A flow line of the ring 12 communicates fluidly with the ring 10 through the well head 6 and / or surface liner pipe 4 and includes a ring valve 14. A flow line 16 communicates fluidly with the inner diameter of the casing pipe 8 through the well head 6 and includes a casing pipe valve 18.

A solidifiable composition can be pumped through the casing 8 and circulated upwardly in the ring 10 while the returns of the fluid from the ring 10 are taken out of the flow line of the ring 12, in a typical flow direction . Alternatively, a solidifiable composition can be pumped into the ring 10 from the flow line of the ring 12 while fluid returns are taken from the inside diameter of the casing 8 through the flow line 16. By therefore, the fluid flows through the well 2 in a direction of reverse circulation.

In an alternative method, a solidifiable composition can be placed inside well 2 and a sealed or filled tubular structure can be lowered into well 2 so that the solidifiable composition moves to the area of ​​ring 10, thus placing the solidifiable composition within the ring 10 without pumping the solidifiable composition in the ring 10. The above method can be called puddle cementation. In some cases, the solidifiable composition may be a drilling fluid placed or left inside the well after the drilling operations are completed.

In some embodiments, the solidifiable composition is subjected to a radiation dose from bremsstrahlung photons. The radiation of bremsstrahlung or simply bremsstrahlung, is an electromagnetic radiation (for example, of photons) produced by the deceleration or deformation of charged particles (for example, electrons) that pass through matter (for example, a high Z material), by example through interaction with the strong electric fields of atomic nuclei. Bremsstrahlung radiation produces a continuous spectrum of photon energy (that is, the resulting photons cover a full range of energy, from a maximum value down through lower values ​​to zero). When generating bremsstrahlung, some electrons that collide with a matter decelerate to zero kinetic energy by means of a single frontal collision with a nucleus and, therefore, all their motion energy is converted at once into photon radiation from maximum energy Other electrons of the same incident beam stop after being decelerated many times by positively charged nuclei. Each deformation and subsequent scattering of the electrons gives rise to a photon. The maximum energy of any original kinetic energy of the typically one electron in this is less than the maximum energy, bremsstrahlung photon is the charged particle of entry, modality.

Some modalities described herein may involve irradiation of a solidifiable composition with bremsstrahlung photons produced at the bottom of the well (for example, with an electron accelerator tool described herein) to facilitate solidification of the solidifiable composition. Bremsstrahlung induced curing is a rapid non-thermal process that uses very energetic electrons in controlled doses to produce photons that may be useful to facilitate solidification of a solidifiable composition (for example, for polymerization and crosslinking of polymeric materials).

Figure 2 provides a cross-sectional illustration of a system 100 for producing bremsstrahlung photons at the bottom of the well according to at least some modalities described herein. System 100 includes an electron accelerator tool 500 coupled to an electric cable 401 and placed in a well 300 that penetrates an underground formation 301. The electric cable

401 Can provide electric power transmission and communications between electron accelerator tool

500 and the surface of the well.

The power tool cable

401 It also supports the mass of the electron accelerator tool 500 during transit up and down the well 300.

The electron accelerator tool 500 comprises a housing

501 to contain at least some of the components of the 500 electron accelerator tool.

The electron accelerator tool 500 may include throttle electrical power components

561. The electric power components 561 may include devices for properly distributing the electric power from the tool electric cable 401 to the different components that use power through the electron accelerator tool 500.

The electron accelerator tool 500 may also include the cooling components 521, the cryogenic liquid with insulation) and the communication components 541. The communication components

541 they can include devices for communicating signals between the electron accelerator tool 500 and the surface of the well.

The electron acceleration components 581 that provide / produce accelerated electrons 601 (also known as high energy electrons) can also be included in the electron accelerator tool 500. In some embodiments, a linear acceleration system using the abundant linear space within a cladding pipe to amplify the voltage in order to produce the accelerated electrons 601. This system, which can be modified to have a long and narrow shape makes it suitable for utility at the bottom of the well. In some embodiments, the accelerator can use radio frequency ("RF") energy to produce the accelerated ions 601. The accelerator can be a linear accelerator or cyclotron. In some modalities, some or all of the following components can be used: a high voltage power supply, a magnetron or kiistron, a high voltage switching circuit for pulse, waveguide for RF transfer, cavities / acceleration structures, an electron gun, addressing / beam focusing components of electrons, an electron beam target, an electron beam dump, radiation shielding, pumps and plumbing, and the like. In some embodiments, Wakefield technology using laser pulses can be used to evacuate electrons from small volumes of a solid (e.g., crystals) to produce 601 accelerated electrons.

Devices comprising the electron acceleration components 581 may vary according to the method of electron acceleration implemented (eg, linear RF acceleration, cyclotron acceleration or wakefield acceleration). For example, electron acceleration components 581 may include lasers, capacitors, diodes and other devices for producing a plasma, RF-induced electromagnetic fields and the like. In addition, the electron accelerator tool 500, an electron acceleration component 581 or a portion thereof may have a characteristic radius suitable for use in the production of an electron beam.

In some embodiments, the accelerated electrons 601 may have an energy ranging from a lower limit of approximately 0.1 MeV, 0.5 MeV, 1 MeV, or 5 MeV to an upper limit of approximately 50 MeV, 40 MeV, 30 MeV , 20 'Λ

MeV, or 10 MeV, where the energy of electrons can range between any lower limit and any upper limit and comprises any subset between them. In some modalities, the maximum intensity of the electron used to produce bremsstrahlung photons may be above 10¹⁴ of electrons per second (for example, up to about 6.25 x 10¹⁶ of electrons per second).

At least one of the electron acceleration components 581 may include an electron beam port 591, where the accelerated electrons are ejected from the electron acceleration component 581 and placed on a path to collide with a target 701 that converts the electrons accelerated 601 in bremsstrahlung 801 photons. In some embodiments, the target 701 may be a converting material (for example, a high Z material having an atomic amount of 70 and above) within the housing 501. Examples of converting materials may include, but are not limited to, tungsten. , tantalum, rhenium, osmium, platinum, thorium, uranium, neptunium,

<td>lead, mercury,</td><td>thallium, gold, iridium, iron, aluminum, tin</td>

<td>and the like, and</td><td>any combination of these, including</td>

<td>alloys that</td><td>They understand the above. In some</td>

modalities, the target 701 may have a thickness ranging from a lower limit of approximately 1 iran, 2 mm, 5 mm or 10 mm to an upper limit of approximately 100 mm, 50 mm, 25 mm, 10 mm or 5 mm, where The thickness of the lens can range from any lower limit to any upper limit and comprises any subset between them.

In some embodiments, it may be desirable to create a path for the accelerated electrons 601 where they collide with the target 701 at angles that are perpendicular to the coating pipe 302 when feasible. This path can minimize the path length of the bremsstrahlung 801 photons through the casing 302 and to the solidifiable 303. As such, the position of the electron beam port 591 and / or the target 701 can, in some embodiments, be positioned at least substantially parallel to the radial plane of the electron accelerator tool 500 and the coating pipe 302 (not shown ). In some embodiments, the electron accelerator tool 500 may include an electron beam scanning device 621 (for example, an electromagnet) to manipulate the path of the accelerated electrons 601 to start from straight lines. In some embodiments, permanent magnets can be used to manipulate the path of electrons either stationary or driven by a small motor. In other embodiments, the electron accelerator tool 500 may precede the use of the scanning device 621 and instead align the target 701 with the electron beam port 591 or increase the size of the target 701.

In some embodiments, the electron accelerator tool 500 can be transported through the well 300 or parts thereof in order to expose a solidifiable 303 placed between the coating pipe 302 and the well 300 to bremsstrahlung 801 photons.

One skilled in the art will recognize that other configurations of system 100 can be implemented without departing from the scope of the modalities described herein.

Figure 3 provides a cross-sectional illustration of a system 200 for producing bremsstrahlung photons at the bottom of the well according to at least some modalities described herein. Similar to the system 100 of Figure 1, the system 200 includes an electron accelerator tool 500 coupled to an electric cable 401. The electron accelerator tool 500 includes a housing 501, a cooling component 521, a communication component 541, an electrical power component 561, an electron acceleration component 581 and an electron beam port 591. However, in Figure 3, the electron beam port 591 is configured to be parallel to a coating pipe 302 placed in a well 300 that penetrates an underground formation 301.

In some embodiments, accelerated electrons 601 produced by means of electron acceleration components 581 can collide with housing 501 and can be converted into bremsstrahlung 801 photons. In some embodiments, the accelerated electrons 601 that pass through the housing 501 without being converted (not shown), can be converted into bremsstrahlung 801 photons by interaction with the drilling mud or the coating pipe 302 (not shown ).

The solidification rate for the solidifiable composition may depend on, among others, the dose of bremsstrahlung photons experienced by the solidifiable composition. In some embodiments, solidifiable compositions may be subjected to a dose of bremsstrahlung radiation ranging from a lower limit of approximately 1 gray, 10 gray or 100 gray to an upper limit of approximately 1 000 gray, 750 gray, 500 gray or 250 gray, where the radiation dose can range from any lower limit to any upper limit and comprises any subset between them.

The radiation dose of bremsstrahlung depends on the duration and intensity of the radiation exposure. The intensity of the bremsstrahlung photons depends, among others, on the properties of the electron beam used in the production of the bremsstrahlung photons. In some embodiments, the electron beam and, consequently, the bremsstrahlung photons can be generated continuously. In some embodiments, the electron beam and bremsstrahlung photons can be generated in pulses. In any case, the average current of the electron beam can range from a lower limit of approximately 10 microamps ("μΑ"), 50 μΑ, 100 μΑ or 500 μΑ to an upper limit of approximately 10 milliamps ("mA") 5 mA , or 1 mA, where the average current of the electron beam can range from any lower limit to any upper limit and comprises any subset between them.

In a pulsed electron beam, the average current depends on the characteristics of the pulses that include, in a non-taxable manner, the pulse width, the peak current and the repetition rate (i.e., pulses per second). One skilled in the art will recognize the appropriate values ​​for each of these suitable to produce an average current described herein.

Solidifiable compositions that can be solidified with the systems and methods described herein may include, but are not limited to, cements, sealants, solidifiable sludges, circulation loss fluids, forming fluids and combinations thereof).

Any cement suitable for use in underground applications may be suitable for use in the embodiments of the present invention. The cementitious compositions described herein generally include water and a cement component (for example, a hydraulic cement, which may include calcium, aluminum, silicon, oxygen and / or sulfur that solidifies and hardens by reaction with water). As used herein, the phrase "cementitious composition" encompasses pastes (or suspensions), mortars, grouts (eg, cement slurries from oil well), cast concrete and concrete compositions that include a hydraulic cement binder. The terms "paste", "mortar" and "concrete" are terms of the technique: "pastes" are mixtures composed of a hydratable (or hydraulic) cement binder (generally, but not exclusively, Portland cement, masonry cement, mortar cement and / or plaster and may also include limestone, hydrated lime, ashes, granulated furnace slag and silica dust or other materials commonly included in such cements) and water;

"mortars" are pastes that also include fine aggregates (eg sand) and "concretes" are mortars that also include ground or gravel). The cement compositions described herein can be formed by mixing the necessary amounts of certain materials (for example, a hydraulic cement, water and fine and / or coarse aggregate), as necessary to make a particular cementitious composition.

Examples of hydraulic cements may include, but are not limited to, Portland cements (for example, cements

Portland of classes A, C, G and H), pozzolana cements, gypsum cements, phosphate cements, high alumina cements, silicon cements, high alkalinity cements and combinations thereof. Cements that include shale, cement kiln powder or blast furnace slag may also be suitable for use in the modalities described herein. In certain modalities, the shale may include vitrified shale. In other specific embodiments, the shale may include raw shale (for example, uncooked shale) or a mixture of raw shale and vitrified shale.

In some embodiments, a cementitious composition described herein may include a polymerizable additive capable of undergoing polymerization when subjected to radiation. In some embodiments, the polymerizable additive may be present in an amount ranging from a lower limit of about 0.01%, 0.1%, 1% or 5% by weight of the cement composition to an upper limit of about 25 %, 15% or 10% by weight of the cement composition, where the amount of polymerizable additive may range between any lower limit and any upper limit and comprises any subset between them.

<img file="MX364246B_D0001.tif" />

Examples of the polymerizable additive may include, but are not limited to, alkenoxides, vinyl pyrrolidones, vinyl alcohols, acrylamides, vinyl methyl ethers, isobutylenes, fluoroelastomers, esters, tetrafluoroethylenes, acetals, propylene, ethylenes, methylpentenes, methyl fluorinated, methyl fluorinated and any derivative of these, and any combinations of these.

In some embodiments, a cementitious composition described herein may also include a crosslinking agent capable of crosslinking a polymer formed by the polymerization of the polymerizable additive. Examples of the cross-linking agent may include, but are not limited to, poly (ethylene glycol) diacrylates, poly (ethylene glycol) dimethacrylates, trimethylolpropane triacrylates (TMPTA), TMPTA ethoxylates, trimethylolpropane trimethacrylates, trimethylolpropanyl diacrylates, diacrylocyanocryptosylacrylates, diacrylates, trimethylsol , Ν-methylene bisacrylamides, hexanedioldivinyl ethers, triethylene glycol diacrylates, pentaerythritoltriacrylates, tripropylene glycol diacrylates, 1,3,5-triallyl-l, 3,5-triazine-2,4,6 (1H, 3H, 5H) -frionas, 2,4,6trialyloxy-1,3,5-triazines, bisphenol A alkoxylated diacrylates and similar, any derivative of these and any combination of these.

In some embodiments, a cementitious composition described herein may also include a solidification retarder that prolongs the solidification time of the cementitious composition. In some cases, these solidification retarders allow a cementitious composition to be pumped over long distances without the effect of premature solidification. In some embodiments, solidification retarders may be present in an amount ranging from a lower limit of about 0.01%, 0.1% or 1% by weight of the cement composition to an upper limit of about 10%, 5% or 1% by weight of the cement composition, where the amount of solidification retarders can range from any lower limit to any upper limit and comprises any subset between them.

Examples of solidification retarders may include, but are not limited to, phosphonic acid, phosphonic acid derivatives, lignosulfonates, salts, sugars, carbohydrate compounds, organic acids, carboxymethylated hydroxyethylated celluloses, copolymers and synthetic terpolymers including sulfonate and acid groups. carboxylic,

<img file="MX364246B_D0002.tif" />

borate compounds and the like, and any derivative thereof and any combination thereof. In some embodiments, solidification retarders may include phosphonic acid derivatives, such as those described in US Patent No. 4,676,832. Examples of suitable borate compounds may include, but are not limited to, sodium tetraborate and potassium pentaborate. Examples of suitable organic acids may include, but are not limited to, gluconic acid and tartaric acid.

In some embodiments, solidification retarders may include a retarder containing sensitizers (eg, a boron containing retarder), also known as sensitized retarder. In some embodiments, the sensitizer may comprise a material that has a strong radiation absorption property. In some embodiments, the sensitizer may be a scintillator material. In some embodiments, the sensitizer can be any material that increases the effectiveness of capturing the radiation of bremsstrahlung within the cementitious composition. In some embodiments, the sensitizer may be a boron containing retarder, also known as a boron retarder. Examples of erased retarders may include bordered versions of the solidification retarders described above (for example, an erased sugar, an erased carbohydrate, an erased glucose (for example, 3-o- (o-carborani-1-methyl) -D-glucose filed in U.S. Patent No. 5,466,679) and the like).

In some embodiments, a cementitious composition described herein may include a solidification accelerator. As used herein, the term "solidification accelerator" may include any component that reduces the solidification time of a solidifiable composition.

In some embodiments, solidification accelerators may be present in an amount ranging from a lower limit of about 0.1%, 1% or 5% by weight of the cement composition to any upper limit of about 20%, 15% or 10% by weight of the cement composition, where the amount of the solidification accelerators can vary from any lower limit to any upper limit and comprises any subset between them.

Examples of solidification accelerators may include, but are not limited to, alkali metal and alkaline earth metal salts (for example, calcium salts such as calcium format, calcium nitrate, calcium nitrite and calcium chloride), silicate salts, aluminates , amines (for example, triethanolamine) and the like, and any derivative thereof and any combination thereof.

In some embodiments, a cementitious composition described herein may include oxidation agents that degrade or otherwise deactivate the solidification retarder. In some embodiments, the oxidizing agents may be present in an amount ranging from a lower limit of about 0.1%, 1% or 5% by weight of the cement composition to an upper limit of about 20%, 15% or 10% by weight of the cement composition, where the amount of oxidizing agents may range from a lower limit to any upper limit and comprises any subset between them.

Examples of oxidizing agents may include, but are not limited to, alkaline earth peroxide and zinc salts, perfosphate, perborate, percarbonate; calcium peroxide, calcium perfosphate, calcium perborate, magnesium peroxide, magnesium perfosphate, zinc perfosphate ;

calcium hypochlorite, magnesium hypochlorite, chloramine T, trichloroisocyanuric acid, trichloromelamine, dichloroisocyanurate dihydrate, anhydrous dichloroisocyanurate, and the like, and any derivative thereof and any combination thereof.

In some embodiments, a solidifiable composition described herein may be a sealant (for example, a hardenable resin composition comprising a hardenable liquid resin and a hardening agent).

The selection of a suitable and liquid resin that can harden can be affected by the temperature of the underground formation into which the composition will be introduced. As an example, for underground formations having a static well bottom temperature ("BHST") ranging from about 60 ° F to about 250 ° F, two resins based on Two component epoxy comprising a hardenable resin component and a hardening agent component together with specific hardening agents. For underground formations that have a BHST ranging from about 300 ° F to about 600 ° F, a furan based resin may be preferred. For underground formations that have a BHST ranging from about 200 ° F to about 400 ° F, either a phenolic base resin or a high temperature epoxy-based resin and a component may be suitable. For underground formations having a BHST of at least about 175 ° F, a phenolic / phenolic / formaldehyde / furfuryl alcohol resin may also be suitable.

In some embodiments, liquid resins that can harden may be included in the hardenable resin compositions described herein in an amount ranging from a lower limit of about%, 30%,%, 50%, 60%, 70% or 75% by volume of the resin composition that can harden an upper limit of about%,% or 75% by volume of the resin composition that can be hardened, and where the amount can range from any lower limit to any upper limit and comprises any subset between them. The expert in the present description has the technique with the benefit of the ability to determine how much liquid resin that can harden may be necessary to achieve the desired results, which may depend, among others, on the composition of the liquid resin that can be hardened. , the composition of the hardening agent and the relative proportions thereof.

As used herein, the term "hardening agent" refers to any substance capable of transforming the liquid resin that can harden into a consolidated and hardened mass.

Examples of suitable hardening agents may include, but are not limited to, aliphatic amines, aliphatic tertiary amines, aromatic amines, cycloaliphatic amines, amines, heterocyclics, amidoamines, polyamides, polyethyl amines, polyether amines, polyoxyalkyleneamines, carboxylic acids, carboxylic anhydride, triethylenetetramine, ethylenediamine,

Ncocoalkyltrimethylene, isoforondiamine,

N-aminophenyl piperazine, imidazoline,

1,2-diaminocyclohexane, polyetheramine, diaminodiphenyl polyethyleneimines, diethyltholuenediamine, 4,4 'methane, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, polyazelaic polyanhydride, these anhydride and combinations of these. Examples of commercially available hardening agents may include, without limitation, ETHACURE®100 (75% -81% 3,5-diethyltoluene-2,4-diamine, 18% -20% 3,5- diethyl toluene-2,6-diamine and 0.5% -3% of dialkylated m-phenylenediamines, available from Albemarle Corp.) and JEFFAMINE®D-230 (a polyetheramine, available from Huntsman Corp.).

In some embodiments, the hardening agent may comprise a mixture of hardening agents selected to impart particular qualities to the resin-based sealing composition. For example, in particular embodiments, the hardening agent may comprise a fast solidifying hardening agent and a slow solidifying hardening agent. As used herein, the terms "fast solidifying hardening agent" and "slow solidifying hardening agent" do not imply any specific rate at which the agents solidify a resin that can harden, instead, the Expressions merely indicate the relative rates at which the hardening agents initiate the hardening of the resin. Whether a particular hardening agent is considered fast hardening or slow hardening may depend on the other hardening agents with which it is used. In a particular embodiment, ETHACURE®100 can be used as a slow solidifying hardening agent together with JEFFAMINE®D-230 as a fast solidifying hardening agent. In some embodiments, it is possible to select the ratio of the fast solidifying hardening agent to the slow solidifying hardening agent to achieve a desired behavior of the liquid hardening agent component. For example, in some embodiments, the fast solidifying hardening agent may be in a ratio of about 1: 5 by volume with a slow solidifying hardening agent. With the benefit of the present description, one skilled in the art should be able to select the appropriate ratio of hardening agents for use in a particular application.

In some embodiments, the curing agent may be included in the resin compositions that can be cured in an amount sufficient to at least partially cure the liquid resin that can be cured. In some embodiments, the hardening agents may be included in the hardenable resin compositions described herein in an amount ranging from a lower limit of about 1%, 5%, 10%, 25% or 50% by volume of the liquid hardening agent to an upper limit of ^r 4*. - · * t · '' -4¹* '' - Chi ^k w "I *" approximately 100%, 75% or 50% by volume of the liquid hardening agent, and where the amount can range between any lower limit and any upper limit and comprises any subset between them.

In some embodiments, the resin compositions that can be hardened may further comprise at least one solvent (for example, an aqueous diluent or carrier fluid), a silencer coupling agent, an accelerator and any combination thereof.

In some embodiments, a solvent can be added to resin compositions that can be hardened to reduce their viscosity in order to facilitate handling, mixing and transfer. However, in particular embodiments, it may be desirable not to use said solvent for environmental and safety reasons. The person skilled in the art with the benefit of the present description has the ability to determine how much solvent may be necessary to achieve a suitable viscosity for the underground conditions of a particular application. Factors that may affect this decision include the geographical location of the well, the surrounding climatic conditions and the desired long-term stability of the resin-based closure that is the result of solidification of the resin compositions that can harden.

Generally, any solvent that is compatible with the liquid resin that can harden and that achieves the desired viscosity effect (eg, degree of hardening) may be suitable for use in the resin composition that can harden. Suitable solvents may include, but are not limited to, polyethylene glycol, butyl lactate, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dimethyl formamide, diethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, propylene carbonate, dylene -limonene, fatty acid methyl esters, reactive diluents and combinations thereof. The selection of a suitable solvent may depend on the compositions of the liquid resin that can harden, the concentration of the liquid resin that can harden and the composition of the hardening agent. With the benefit of this description, the person skilled in the art should be able to select a suitable solvent. In some embodiments, the solvent may be included in the resin compositions that can harden in an amount ranging from a lower limit of about 0.1%, 1% or 5% by weight of the resin

V liquid that can harden to an upper limit of approximately 50%, 40%, 30%, 20% or 10% by weight of the liquid resin that can harden, and where the amount can range between any lower limit and any upper limit and It comprises any subset between these. Optionally, the hardenable liquid resin component can be heated to reduce its viscosity, instead of or in addition to using a solvent.

In some embodiments, the hardenable resin compositions described herein may comprise an accelerator that accelerates (eg, by catalysis) the onset and duration of hardening of the resin compositions that can be hardened with respect to

<td colspan="2">the sealing composition a</td><td>i base</td><td>of resin.</td><td colspan="2">Accelerators</td>

<td>adequate</td><td>may include</td><td>, from</td><td>no mode</td><td>taxative,</td><td>acids</td>

<td>organic</td><td>and inorganic</td><td>how</td><td>the acid</td><td>maleic,</td><td>acid</td>

<td>fumaric,</td><td>bisulfate</td><td>sodium,</td><td colspan="2">hydrochloric acid,</td><td>acid</td>

hydrofluoric, acetic acid, formic acid, phosphoric acid, sulfonic acid, alkylbenzene sulfonic acids such as toluene sulfonic acid and dodecylbenzene sulfonic acid ("DDBSA"), phenols, tertiary amines (eg 2.4 , 6-tris (dimethylaminomethyl) phenol, benzyl dimethylamine and 1,4-diazabicyclo [2.2.2] octane), imidazole and its derivatives (for example, 2-ethyl, -4-methylimidazole, 2-methylimidazole, and 1- (2 -cyanoethyl) -2-ethyl-4-methylimidazole), Lewis acid catalysts (for example, aluminum chloride, boron trifluoride, boron trifluoride ether complexes, boron trifluoride alcohol complexes and boron trifluoride amine complexes) and the like, and any combination thereof.

Some modalities may involve introducing a solidifiable composition described herein into a well that penetrates an underground formation; placing the solidifiable composition in a part of the well, in a part of the underground formation or in both; subject the solidifiable composition to bremsstrahlung photons in a radiation dose of about 1 gray to about 1 000 grays and solidify the solidifiable composition therein. Some embodiments of insulating a well or a part of a well may include pumping a solidifiable composition containing a polymerizable additive into a well that penetrates an underground formation; subject the solidifiable composition to bremsstrahlung photons in a radiation dose of about 1 gray to about 1 000 grays and solidify the solidifiable composition therein.

Some embodiments may include preparing a cement composition comprising: hydraulic cement, a polymerizable additive and sufficient water to form a suspension; place the cement composition in the well and subject the cement composition to a radiation dose of about 1 gray to about 1 000 grays to activate the solidification of the cement composition. In some embodiments, additives such as a solidification retarder, a solidification accelerator, an oxidation agent or combinations thereof can be added to the cement mixture, each independently before or after water is added to the mixture. or during mixing.

In some embodiments, a solidifiable composition described herein may include a solidification retarder, a solidification accelerator and an oxidizing agent. In some embodiments, upon exposure to bremsstrahlung radiation, both the solidification accelerator and the oxidant may be released or otherwise activated. The simultaneous deactivation of the solidification retarder by means of the oxidant and the acceleration of the cement hydration by the solidification accelerator provides a fast solidification time.

⁴ 'V *

<img file="MX364246B_D0003.tif" />

<img file="MX364246B_D0004.tif" />

The modalities described herein include:

A. a method that includes providing a solidifiable composition in a part of a well that penetrates an underground formation, in a part of the underground formation or both;

transport an electron accelerator tool along the well next to the solidifiable composition;

produce an electron beam in the electron accelerator tool with a trajectory that collides with a converter material, thus converting the electron beam into bremsstrahlung photons and irradiating the solidifiable composition with the bremsstrahlung photons.

B. a method that includes providing a composition

<td colspan="2">solidifiable in one part</td><td>of a well</td><td>what</td><td>penetrates a</td>

<td>training</td><td>underground in</td><td>a part</td><td>from</td><td>the formation</td>

<td>underground</td><td>or in both;</td><td>transport</td><td>a</td><td>tool</td>

<td>accelerator</td><td>from electrons to</td><td>along the</td><td>water well</td><td>next to the</td>

<td>composition</td><td>solidifiable;</td><td>produce a</td><td>make</td><td>of electrons</td>

pulsed on the electron accelerator tool with a trajectory that hits a converter material, thus converting the pulsed electron beam into bremsstrahlung photons, where the pulsed electron beam has an average current of approximately 10 microamps to approximately 10 milliamps; and irradiating the solidifiable composition with the bremsstrahlung photons; Y

C.

a method that includes providing a solidifiable composition in a part of a well that penetrates an underground formation, in a part of the underground formation or both;

transport an electron accelerator tool along the well next to the solidifiable composition;

produce an electron beam in the electron accelerator tool with a trajectory that collides with a converter material that is a part of an electron accelerator tool housing, thereby converting the electron beam into bremsstrahlung photons, where the electron beam it has an average current of about 10 microamps at about 10 milliamps; and irradiate the solidifiable composition with the bremsstrahlung photons.

Each of the modalities A, B and C may have one or more of the following additional elements in any combination (unless it has already been arranged): Element 1: the method that also includes the manipulation of the electron beam path with a device

<img file="MX364246B_D0005.tif" />

swept; Element 2: where the electron beam is continuous;

Element 3: where the electron beam is pulsed; Element 4: where the electron beam comprises electrons that have an energy of about 0.5 MeV to about 50 MeV; Element 5: where the electron beam has an average current of approximately 10 microamps to approximately 10 milliamps; Element 6: where the converter material comprises at least one of: tungsten, tantalum, rhenium, osmium, platinum, thorium, uranium, neptunium, lead, mercury, thallium, gold, iridium, and any combination thereof;

iron, aluminum, tin

Element 7: where the converter material comprises a material that has an atomic amount greater than 70; Element 8: where the converter material is a part of an electron accelerator tool housing; Element 9; where the converter material approximately mm to approximately cm; Element

10: where the converter material is a part of a casing pipe placed in the well and where the solidifiable composition is placed within a ring of the casing pipe and the well: Element 11: where the solidifiable composition is a cement; Element 12: where the solidifiable composition is a sealant; Element 13: where the solidifiable composition is at least one of: a solidifiable sludge, a circulation loss fluid, a forming fluid and any combination thereof; and Element 14: where the solidifiable composition comprises at least one of: a solidification accelerator, a solidification retarder, a polymerizable additive, an oxidizing agent and any combination thereof.

By way of non-taxative example, exemplary combinations applicable to A, B, C include:

Element 1 together with one of Elements 2-3; at least one of Elements 4-5 together with one of Elements 2-3; at least one of Elements 6-7 together with one of Elements 2-3 and optionally together with Element 1; Element 9 together with at least one of Elements 6-7; Element 9 together with one of Elements 2-3 and optionally together with Element 1; Element 8 or 10 together with any of the above; Element 8 or 10 together with at least one of Elements 1-7; Element 8 or 10 together with Element 9 and optionally together with at least one of Elements 1-7; one of Elements 11-14 along with any of the above; two or more of Elements 1114 together; and at least one of Elements 1-14 along with at least one of Elements 1-10.

The modalities described herein may also be useful or adapted for a cement or concrete other applications, including infrastructure and construction materials, where a rapid solidification time can be achieved with the polymer system.

Some specific examples include the rapid hardening of pre-molded units such as pipes, panels and beams, on-site molded structures for bridges, dams or roads, rapidly solidifying cement grout, increased cement adhesion, adding water-resistant properties to cement, concrete decorative, quick concrete repair, cement board production. Other advantages over concrete systems enhanced with typical polymers include the ability to use a wider variety of polymer species, including oligomers that are significantly less volatile, combustible and toxic, and the removal of initiators, which are also toxic to humans. and the environment.

To facilitate a better understanding of the modalities described herein, the following examples of preferred or representative modalities are provided. The following examples should not be understood as limiting or defining the scope of the modalities described herein.

EXAMPLES

Example 1: Cement suspension samples were prepared by mixing the following ingredients: 400 grams of a class H cement (Lafarge, Joppa IL), 160 grams of water (p / c = 0.40), 8.0% by weight solids (bwos) acrylamide, 0.42% bwos of N, N-methylene-bisacrylamide as crosslinker, 0.50% bwos of maltodextrin as solidification retarder, 0.50% bwos of HR®-25 as solidification retarder (a high temperature retarder available from Halliburton Energy Services, Inc.), 0.20% bwos of Diutan rubber as a rheology modifier and 0.10% bwos of SnC12 as an oxygen scavenger and 1.0% bwos of SYLOID® RAD 2105 silica gel (Grace Performance Chemicals, USA).

The suspension was mixed for 45 seconds in a Waring blade mixer according to the API mixing program. The suspension was divided into two samples. A sample was exposed for 20 seconds to bremsstrahlung radiation produced by focusing a 5-6 MeV electron beam of energy on a tungsten lens and placing the sample in a vial at the other end of the tungsten target and thus exposing the sample to the photons of bremsstrahlung. The other sample was not irradiated and remained as a control. The control sample remained fluid. The irradiated sample had been crosslinked and showed a behavior similar to that of the self-stable solid.

Example 2: A cement / sand suspension was prepared in a manner similar to that of Example 1, with the exception that 1% SYLOID RAD particles were not included and 200 grams of class H cement were replaced with 200 mesh sand for a 50:50 mixture of cement and silica flour.

The suspension was mixed for 45 seconds in a Waring blade mixer according to the API mixing program. The suspension was divided into two samples. A sample was exposed for 30 seconds to bremsstrahlung radiation produced by focusing a 5-6 MeV electron beam of energy on a tungsten target and placing the sample in a vial at the other end of the tungsten target and thus exposing the sample to the photons of bremsstrahlung. The other sample was not irradiated and remained as a control. The control sample remained fluid. The irradiated sample had been crosslinked and showed a behavior similar to that of * ♦ *

Λ solid self-stable.

Example 3: Silica flour suspension samples were prepared by mixing the following ingredients: 400 grams of SSA-1 silica flour (Halliburton, Houston, Texas) 168 grams of water (p / c = 0.42), 0.18 % by weight of

<td>Ca (OH) 2 by</td><td>100 grams</td><td colspan="2">of water, 8.0%</td><td>in</td><td>solid weight</td>

<td>(bwos) of</td><td>acrylamide,</td><td> 0,42</td><td>% bwos</td><td>from</td><td>N, N-Methylene-bis-</td>

<td>acrylamide</td><td colspan="2">as crosslinker, 0,</td><td>, 20% bwos</td><td>from</td><td>Diutan rubber as</td>

<td>modifier</td><td>of rheology,</td><td> 0,10</td><td>% bwos of</td><td colspan="2">SnC12 as debugger</td>

<td>of oxygen</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">The suspension is</td><td>mixed</td><td>during</td><td> 45</td><td>seconds in a</td>

<td colspan="2">blade mixer</td><td>Waring</td><td>according to him</td><td colspan="2">mixing program</td>

API The suspension was divided into two samples. A sample was exposed for 30 seconds to bremsstrahlung radiation produced by focusing a 5-6 MeV electron beam of energy on a tungsten target and placing the sample in a vial at the other end of the tungsten target and thus exposing the sample to the photons of bremsstrahlung. The other sample was not irradiated and remained as a control. The control sample remained fluid. The irradiated sample had been crosslinked and showed a behavior similar to that of the self-stable solid.

The samples demonstrate that bremsstrahlung radiation can be used to solidify cement by irradiating a polymerizable additive sample included in the cement.

Example 4: Cement suspension samples were prepared by mixing the following ingredients: 800 grams of a class H cement, 320 grams of water, 8.0% by weight bwos of acrylamide, 0.42% bwos of N, N-methylene-bis-acrylamide as a crosslinker, 0.50% bwos of maltodextrin as a retarder of solidification, 0.50% bwos of HR-25 as solidification retarder 0.20% bwos of Diutan rubber as rheology modifier, 1.0% bwos of SnC12 as oxygen scavenger and 1.0% bwos of SYLOID® RAD 2105 .

The suspension was mixed for 45 seconds in a Waring blade mixer according to the API mixing program and divided into 1-inch x 2-inch plastic vials. The vials were subjected to bremsstrahlung radiation produced by concentrating the electron beam of approximately 5 MeV of energy and an average current of 75 μΑ (5 ps of pulse width, 0.05 A of peak current, and 300 pulses per second ( “Pps”) of service cycle) that passed through the tungsten target of various thicknesses * * ' ^!-¾ *

I »w« ί and a 1/2 inch thick carbon steel pipe. A dosimeter was attached to the cement vials to measure the radiation dose. Table 1 provides the dose rate (ie, dose divided by the exposure time) for the thickness of the tungsten target from 2 mm to 25 mm showing that as the thickness of the tungsten target increases the dose rate decreases.

Table 1

<td>Cumshot #</td><td>Tungsten Lens Thickness (mm)</td><td>Dose rate (cGy / sec)</td>

<td> 1</td><td> 0</td><td> 6593</td>

<td> 2</td><td> 2</td><td> 6690</td>

<td> 3</td><td> 3</td><td> 6669</td>

<td> 4</td><td> 3</td><td> 6535</td>

<td> 5</td><td> 5</td><td> 5059</td>

<td> 6</td><td> 25</td><td> 934</td>

<td> 7</td><td> 25</td><td> 925</td>

After being exposed to bremsstrahlung radiation, the samples were analyzed on (1) the side closest to the

<img file="MX364246B_D0006.tif" />

radiation and (2) the farthest side of the radiation to determine Shore hardness. Table 2 provides the results of Shore hardness.

Table 2

<td colspan="2">Thickness aim of</td><td rowspan="2">Time of exposition (seconds)</td><td rowspan="2">Shore hardness (side closest to radiation)</td><td rowspan="2">Shore hardness (side furthest from radiation)</td>

<td>tungsten</td><td>(mm)</td>

<td colspan="2"> 0</td><td> 3,3</td><td> 73</td><td> 47</td>

<td colspan="2"> 2</td><td> 3, 3</td><td> 79</td><td> 68</td>

<td colspan="2"> 2</td><td> 3,3</td><td> 79</td><td> 60</td>

<td colspan="2"> 3</td><td> 3,3</td><td> 79</td><td> 71</td>

<td colspan="2"> 3</td><td> 3,3</td><td> 75</td><td> 71</td>

<td colspan="2"> 3</td><td> 3, 3</td><td> 80</td><td> 67</td>

<td colspan="2"> 3</td><td> 3, 3</td><td> 75</td><td> 58</td>

<td colspan="2"> 5</td><td> 3,3</td><td> 72</td><td> 66</td>

<td colspan="2"> 10</td><td> 10</td><td> 79</td><td> 57</td>

<td colspan="2"> 25</td><td> 10</td><td> 77</td><td> 64</td>

<td colspan="2"> 25</td><td> 6, 6</td><td> ★</td><td> *</td>

It cannot be measured because it is not hardened / solidified.

<img file="MX364246B_D0007.tif" />

&gt;

This example demonstrates that while the dose rate may decrease with increasing thickness of the tungsten target, the exposure time can be adjusted to provide comparable solidification / hardening.

Example 5: Cement suspension samples were prepared by mixing the following ingredients: 800 grams of a class H cement, 320 grams of water, 8.0% by weight bwos of acrylamide, 0.42% bwos of N, N-methylene bis-acrylamide as crosslinker, 0.50% bwos of maltodextrin as solidification retarder, 0.50% bwos of HR-25 as solidification retarder 0.05% bwos of Diutan rubber as rheology modifier, 1.0% bwos of SnC12 as an oxygen scrubber and 1.0% bwos of SYLOID® RAD 2105.

The suspension was mixed for 45 seconds in a Waring blade mixer according to the API mixing program and divided into 1-inch x 2-inch plastic vials. The vials were subjected to bremsstrahlung radiation produced by concentrating the electron beam of approximately 7.5 MeV of energy and a varied average current produced by changing the pulse width (0.1 peak current and 250 pps duty cycle ) that passed through a 3mm tungsten lens and a 1/2 inch thick carbon steel pipe. After being exposed to bremsstrahlung radiation, the samples were analyzed on (1) the side closest to the radiation and (2) the side farthest from the radiation to determine Shore hardness. Table 3 provides the results of Shore hardness.

Table 3

<td>Time of exposition (seconds)</td><td>Pulse width ()</td><td>Average current (pA)</td><td>Shore hardness (side closest to radiation)</td><td>Shore hardness (side furthest from radiation)</td>

<td> 3</td><td> 4</td><td> 100</td><td> 76</td><td> 47</td>

<td> 12</td><td> 1</td><td> 25</td><td> 90</td><td> 83</td>

<td> 12</td><td> 1</td><td> 25</td><td> 72</td><td> 69</td>

<td> 12</td><td> 1</td><td> 25</td><td> 87</td><td> 71</td>

<td> 6</td><td> 1</td><td> 25</td><td> 78</td><td> 58</td>

<td> 6</td><td> 1</td><td> 25</td><td> 75</td><td> 54</td>

The 12-second exposure and the pulse width of 1 ps compared to the 3-second exposure and pulse width of 4 ps have ¼ of the exposure time but 4 times the pulse width, so it is substantially the

<td>same dose of</td><td>radiation.</td><td>Without</td><td>embargo,</td><td>the</td><td>time of</td>

<td>more exposure</td><td>dragged on</td><td>It seems</td><td colspan="2">provide</td><td>A better</td>

<td colspan="2">hardening / solidification</td><td>of the</td><td>suspension</td><td>from</td><td>cement.</td>

Example 6: Cement suspension samples were prepared by mixing the following ingredients: 800 grams of a class H cement, 320 grams of water, 8.0% by weight bwos of acrylamide, 0.42% bwos of N, N-methylene bis-acrylamide as a crosslinker, 0.50% bwos of maltodextrin as a retarder of

<td>solidification,</td><td> 0,50</td><td>Q, O</td><td>bwos</td><td>from</td><td>HR-25</td><td>how</td><td>retarder</td><td>from</td>

<td>solidification</td><td> 0,05%</td><td colspan="2">bwos of</td><td>rubber</td><td>Diutan</td><td>how</td><td>modifier</td><td>from</td>

<td>rheology, 1.0%</td><td>bwos</td><td>from</td><td>SnCl₂</td><td>how</td><td colspan="2">debugger</td><td>oxygen and</td><td> 1,0</td>

% bwos of SYLOID® RAD 2105.

The suspension was mixed for 45 seconds in a Waring blade mixer according to the API mixing program and divided into 1-inch x 2-inch plastic vials. The vials were subjected to bremsstrahlung radiation produced by concentrating the electron beam of approximately 7.5 MeV of energy and a varied average current produced by changing the peak current (4 ps peak width and 250 pps duty cycle) which passed through a 3mm tungsten lens and a 1/2 inch thick carbon steel pipe. After being exposed to bremsstrahlung radiation, the samples were analyzed on (1) the side closest to the radiation and (2) the side farthest from the radiation to determine Shore hardness. Table 4 provides the results of Shore hardness.

Table 4

<td>Time of exposition (seconds)</td><td>Stream peak (A)</td><td>Average current (μΑ)</td><td>Shore hardness (side more close to radiation)</td><td>Shore hardness (side furthest from radiation)</td>

<td> 3</td><td> 0,10</td><td> 100</td><td> 76</td><td> 62</td>

<td> 3</td><td> 0,10</td><td> 100</td><td> 80</td><td> 63</td>

<td> 3</td><td> 0,10</td><td> 100</td><td> 76</td><td> 64</td>

<td> 3</td><td> 0,10</td><td> 100</td><td> 74</td><td> 64</td>

<td> 3</td><td> 0,10</td><td> 100</td><td> 73</td><td> 59</td>

<td> 2</td><td> 0,025</td><td> 25</td><td> 59</td><td> *</td>

<td> 4</td><td> 0,025</td><td> 25</td><td> 74</td><td> 54</td>

<td> 4</td><td> 0,025</td><td> 25</td><td> 75</td><td> 56</td>

<td> 6</td><td> 0,025</td><td> 25</td><td> 76</td><td> 59</td>

<td> 12</td><td> 0,025</td><td> 25</td><td> 88</td><td> 73</td>

* It cannot be measured because it is not hardened / solidified.

This example demonstrates that the average terms of the service cycle towards a larger total amount of pulses along with a lower peak current (ie, a lower average current) seem advantageous in bottomhole applications.

Therefore, the modalities described herein are well adapted to achieve the purposes and advantages that were mentioned as well as those inherent in them. The particular modalities disclosed above are exclusively illustrative, since the modalities described herein can be modified and practiced in different but equivalent ways evident to those skilled in the art who have the benefit of the instructions contained herein. Likewise, it is not intended to impose limitations on the construction or design details presented herein, apart from what is described in the claims below. Therefore, it is clear that the particular illustrative modalities described above may be altered, combined or modified and all such variations are considered within the scope and spirit of the modalities of the modalities herein. The modalities described illustratively herein can be properly implemented in the absence of any element that is not specifically described herein and / or any optional element described herein. While the compositions and methods are described in terms of "comprising", "containing", or "including" various components or steps, the compositions and methods may also "essentially consist of" or "consist of" several components and stages. All the numbers and intervals described above may vary to some extent. Whenever a numerical interval with a lower limit and an upper limit is described, any number and any interval included within the interval is specifically described. In particular, it should be understood that any range of values ​​(of the type "of approximately a to approximately b" or, equivalently, "of approximately aab" or, equivalently, "of approximately ab") described herein indicates each number and range within the broadest range of values. In addition, the terms used in the claims have their simple and common meaning, unless the patent holder clearly and explicitly defines otherwise. Likewise, indefinite articles "a" or "a", as used in the claims, are defined herein as one or more of one of the elements that they introduce. If there is any ♦ · * * conflict in the uses of a word or term in this specification and in one or more patents or other documents that are incorporated herein by reference, the definitions that are consistent 5 should be adopted with the present specification.

NEW OF THE INVENTION

Having described the present invention, it is considered as a novelty and, therefore, the content of the following is claimed as property:

CLAIMS