WO2014116457A1 - Matériaux à mémoire de forme à tg variable pour dispositifs de forage de puits - Google Patents

Matériaux à mémoire de forme à tg variable pour dispositifs de forage de puits Download PDF

Info

Publication number
WO2014116457A1
WO2014116457A1 PCT/US2014/011300 US2014011300W WO2014116457A1 WO 2014116457 A1 WO2014116457 A1 WO 2014116457A1 US 2014011300 W US2014011300 W US 2014011300W WO 2014116457 A1 WO2014116457 A1 WO 2014116457A1
Authority
WO
WIPO (PCT)
Prior art keywords
shape
memory material
memory
geometric position
onset
Prior art date
Application number
PCT/US2014/011300
Other languages
English (en)
Inventor
Nicholas Carrejo
Michael H. Johnson
Original Assignee
Baker Hughes Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US13/750,468 external-priority patent/US9068437B2/en
Application filed by Baker Hughes Incorporated filed Critical Baker Hughes Incorporated
Priority to GB1514785.3A priority Critical patent/GB2526026B/en
Priority to CA2897777A priority patent/CA2897777C/fr
Priority to AU2014209715A priority patent/AU2014209715B2/en
Publication of WO2014116457A1 publication Critical patent/WO2014116457A1/fr
Priority to NO20150877A priority patent/NO20150877A1/en

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/12—Packers; Plugs
    • E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means

Definitions

  • the present invention relates to devices used in oil and gas wellbores employing shape-memory materials that remain in an altered geometric state during run-in; once the devices are in place downhole and are exposed to a given temperature at a given amount of time, the devices attempt to return to their original geometric position prior to alteration.
  • Shape-memory materials are smart materials that have the ability to return from a deformed state (temporary shape) to their original (permanent) shape induced by an external stimulus or trigger (e.g. temperature change). In addition to temperature change, the shape memory effect of these materials may also be triggered by an electric or magnetic field, light or a change in pH.
  • Shape-memory polymers cover a wide property range from stable to biodegradable, from soft to hard, and from elastic to rigid, depending on the structural units that constitute the SMP. SMPs include thermoplastic and thermoset (covalently cross-linked) polymeric materials. SMPs are known to be able to store multiple shapes in memory.
  • Dynamic Mechanical Analysis DMA
  • DMTA dynamic mechanical thermal analysis
  • dynamic thermomechanical analysis is a technique used to study and characterize SMP materials. It is most useful for observing the viscoelastic nature of these polymers.
  • the sample deforms under a load. From this, the stiffness of the sample may be determined, and the sample modulus may be calculated.
  • the time lag is reported as a phase lag, which is an angle.
  • the damping is called tan delta, as it is reported as the tangent of the phase lag.
  • Viscoelastic materials such as shape-memory polymers typically exist in two distinct states. They exhibit the properties of a glass (high modulus) and those of a rubber (low modulus). By scanning the temperature during a DMA experiment this change of state, the transition from the glass state to the rubber state, may be characterized. It should be noted again that shaped memory may be altered by an external stimulus other than temperature change.
  • the storage modulus ⁇ ' (elastic response) and loss modulus ⁇ " (viscous response) of a polymer as a function of temperature are shown in FIG. 1.
  • the nature of the transition state of the shaped memory polymer affects material's shape recovery behavior and can be descriptive of the polymer's shape recovery.
  • the Glass State is depicted as a change in storage modulus in response to change in temperature which yields a line of constant slope.
  • the Transition State begins when a slope change occurs in the storage modulus as the temperature is increased. This is referred to as the T g Onset which in FIG. 1 is approximately 90°C.
  • the T g Onset is also the point where shape recovery can begin.
  • T g for a shape-memory polymer described by FIG. 1 is defined as the peak of the loss modulus, which in FIG. 1 is approximately 1 10°C. If the slope's change of the storage modulus were represented by a vertical line of undefined slope, the material shape recovery would occur at a specific temperature and transition immediately from the glassy state to the rubber state. Generally, the more gradual the slope change of the storage modulus in the transition state, the greater the range of temperatures which exhibit characteristics of both the glass and rubber states. The transition state is the area of interest for the SMP material's shape recovery characteristics. It should also be evident that shape recovery would occur more slowly if stimulus temperature is closer the T g Onset temperature and shape recovery would be more rapid as the stimulus temperature approached or exceeded the T g .
  • One method of making use of the unique behavior of shape- memory polymers is via temperature response described above.
  • An example is seen in FIG. 2.
  • the finished molded part 100 of shape-memory polymer has a defined T g and T g Onset. This may be considered an original geometric position of the shape-memory material.
  • the part is then heated close to the T g of the polymer. Force is applied to the finished part to reshape the part into a different configuration or shape 100". This may be considered an altered geometric position of the shape-memory material.
  • the reshaped part 100" is then cooled below the shape-memory polymer's T g Onset and the force removed.
  • the finished part 100" will now retain the new shape until the temperature of the part is raised to the T g Onset at which point shape recovery will begin and the part will attempt to return to its original shape 100" or if constrained, the part will conform to the new constrained shape 100".
  • This shape 100" may be considered the shape-memory material's recovered geometric position.
  • U.S. Pat. No. 7,318,481 assigned to Baker Hughes Incorporated disclosed a self-conforming expandable screen which comprises a thermosetting open cell shape-memory polymeric foam.
  • the foam material composition is formulated to achieve the desired transition temperature slightly below the anticipated downhole temperature at the depth at which the assembly will be used. This causes the conforming foam to expand at the temperature found at the desired depth.
  • a wellbore filtration device involving at least two shape-memory materials.
  • the device includes a first shape-memory material which is a cross-linked polymer having a first crosslinking ratio, where the first shape-memory material has a position of altered geometry and where the original geometry is recoverable, where the shape-memory material is maintained in the altered geometry at a temperature below a first onset glass transition temperature, and where the shape-memory material expands from its altered geometric position to its original geometric position when it is heated to a temperature above the first onset glass transition temperature.
  • the device includes a second shape-memory material that comprises a cross-linked polymer having a second crosslinking ratio, where the second shape-memory material has an altered geometric shape and an original geometric shape where the shape-memory material is maintained in the altered geometric shape at a temperature below a second onset glass transition temperature.
  • the second onset glass transition temperature is different than the first onset glass transition temperature, and the shape- memory material recovers from its altered geometric shape to its original geometric shape when it is heated to a temperature above the second onset glass transition temperature.
  • the polymers and crosslinkers of the first and second shape memory materials may be the same or different.
  • the onset glass transition temperatures may be the same for the two shaped memory materials.
  • the slope change during the transition state from glass state to rubber state may vary. This would allow the altered geometric shapes of the two shaped memory materials to recover their respective original geometric shape but at differing recovery rates.
  • the method includes placing in any order or simultaneously, a first shape-memory material and a second shape-memory material on a billet, each in a respective original geometric position.
  • the first shape-memory material has a first onset glass transition temperature and a first slope change during a first transition state from a first glass state to a first rubber state.
  • the first shape-memory material comprises a cross-linked polymer having a first crosslinking ratio.
  • the second shape- memory material has a second onset glass transition temperature and a second slope change during a second transition state from a second glass state to a second rubber state.
  • the second shape-memory material comprises a cross-linked polymer having a second crosslinking ratio different from the first crosslinking ratio.
  • the method further involves altering the original geometric positions of the first and second shape-memory materials at a temperature above both the first and second onset T g to change the original geometric positions of the first and second shape-memory materials respectively. Further the method includes lowering the temperature of the first and second shape- memory materials to a temperature below the first and second onset T g s, respectively, where the first and second shape-memory materials each maintain their respective altered geometric positions.
  • the first shape-memory material and the second shape-memory material are further different by a parameter where the first onset glass transition temperature is different from the second onset glass transition temperature and/or the first slope change is different from the second slope change.
  • a wellbore device with a variable onset glass transition temperature within a single molded part involves mixing a first isocyanate portion (comprising an isocyanate) with a first polyol portion (comprising a polyol) in a first ratio of polyol to isocyanate to form a first polyurethane material having a first onset glass transition temperature.
  • the method also involves mixing a second isocyanate portion (comprising an isocyanate, which may be the same as or different from the isocyanate in the first isocyanate portion) with a second polyol portion (comprising a polyol, which may be the same as or different from the polyol in the first polyol portion) in a second ratio to form a second material having a second onset glass transition temperature.
  • the first onset T g and the second onset T g may be different from one another.
  • a first slope change of the first polyurethane material is different from a second slope change of the second polyurethane material.
  • the method additionally involves altering the geometric shape of the first and second shaped memory materials at a temperature above both the first and second onset T g s to change the first and second original geometric shape to a first and second altered geometric shape, respectively. Further, the method involves lowering the temperature of the respective altered geometric shapes of the first and second materials to a temperature below the first and second onset T g s where the first and second materials each maintain their respective altered geometric shape.
  • the method may include securing a downhole tool to a string of perforated tubing.
  • the downhole tool may involve a filtration device including a first shape- memory material, where the first shape-memory material (e.g. a polyurethane) has an altered geometric shape for run-in position and an original geometric shape recoverable at a predetermined wellbore position.
  • the first shape- memory material is maintained in the run-in geometry below a first onset glass transition temperature of the first shape-memory porous material.
  • the device may also include a second shape-memory material, which may also be a polyurethane.
  • the second shape-memory material also has an altered geometric shape for run-in and an original geometric shape recoverable at a predetermined position in the wellbore.
  • the second shape-memory material is maintained in the run-in geometric shape below a second onset glass transition temperature of the second shape-memory material.
  • the first onset glass transition temperature T g is different from the second onset glass transition temperature T g .
  • the method additionally includes running the downhole tool in a wellbore, as well as expanding the first shape-memory material from its run-in geometric shape to its original geometric shape for instance when the material is heated beyond its onset T g .
  • the second shape-memory material may be separately recovered at a separate onset T g different from the onset T g of the first shape-memory material, at a different time.
  • the first and second shape-memory materials are not polyurethane, but are instead other crosslinked polymers, where the crosslinking ratio for each shape-memory material (first and second, or more, if present) is different one from the other.
  • FIG. 1 is a graph of storage modulus ⁇ ' (elastic response) (left vertical axis) and modulus ⁇ " (viscous response) as a function of temperature for a shape memory polymers illustrating the change in each modulus as the polymer is heated from the Glass State through the Transition State to the Rubber State;
  • FIG. 2 is a photograph of a finished shape-memory polymer part before it is heated close to the T g of the polymer and force is applied to reshape it to a different configuration or shape and then cooled below the polymer's onset T g , and finally when the part is heated to the onset T g at which point recovery will begin and the part returns to at or near its original shape;
  • FIG. 3 is a schematic, cross-section view of a device which bears two shape-memory materials having different onset T g s in concentric, layered configuration in their altered geometry, run-in thicknesses or volumes;
  • FIG. 4 is a schematic, cross-section view of the device of FIG. 3 where the outer shape-memory material has been permitted to recover or deploy so that it reaches part-way to the inner wall surface of the wellbore;
  • FIG. 5 is a schematic, cross-section view of the device of FIG. 4 where the inner shape-memory material has also been permitted to recover or deploy so that it firmly engages and fits to the inner wall surface of the wellbore;
  • FIG. 6 is a schematic, cross-section view of an alternate embodiment of a device which bears two shape-memory materials having different onset T g s in a side-by-side configuration along at least a portion of the length of the device in their altered geometric states, run-in thicknesses or volumes;
  • FIG. 7 is a schematic, cross-section view of the alternate embodiment of a device of FIG. 6 where one of the shape-memory materials has been permitted to recover or deploy so that it firmly engages and fits to the inner wall surface of the wellbore;
  • FIG. 8 is a schematic, cross-section view of the alternate embodiment of a device of FIG. 7 where the other of the shape-memory materials has been permitted to recover or deploy so that it firmly engages and fits to the inner wall surface of the wellbore.
  • Figures 3 through 8 are simply schematic illustrations which are not to scale and that the relative sizes and proportions of different elements may be exaggerated for clarity or emphasis.
  • wellbore devices such as those used in filtration, wellbore isolation, production control, lifecycle management, well- bore construction and the like may be improved by including at least two different shape-memory materials that are run into the wellbore in altered geometric positions or shapes where the shape-memory materials change to their respective original geometric positions or shapes at different T g s and/or different slope changes (the slope change in the respective transition state from a glass state to a rubber state).
  • the shape-memory material is made in one non-limiting embodiment from one or more polyol, such as, but not limited to, a polycarbonate polyol and at least one isocyanate, including, but not necessarily limited to, a modified diphenylmethane diisocyanate (MDI), as well as other additives including, but not necessarily limited to, blowing agents, molecular cross linkers, chain extenders, surfactants, colorants and catalysts.
  • polyol such as, but not limited to, a polycarbonate polyol and at least one isocyanate, including, but not necessarily limited to, a modified diphenylmethane diisocyanate (MDI), as well as other additives including, but not necessarily limited to, blowing agents, molecular cross linkers, chain extenders, surfactants, colorants and catalysts.
  • MDI modified diphenylmethane diisocyanate
  • the shape-memory materials may be made using cross-linked polymers, where the degree of crosslinking is different for the various shape-memory materials.
  • the crosslinking is a bond that links one polymer chain to another. They can be covalent bonds or ionic bonds. Polymer chains can refer to synthetic polymers or natural polymers (such as proteins). When the term "cross-linking" is used in the synthetic polymer science field, it usually refers to the use of cross-links to promote a difference in the polymers' physical properties.
  • Cross-linking refers to the linking of polymer chains, the extent of crosslinking and specificities of the crosslinking agents vary.
  • polymer chains When polymer chains are linked together by cross-links, they lose some of their ability to move as individual polymer chains. For example, a liquid polymer (where the chains are freely flowing) can be turned into a “solid” or “gel” by cross-linking the chains together.
  • a synthetic polymer When a synthetic polymer is said to be cross linked, it usually means that the entire bulk of the polymer has been exposed to the cross-linking method. The resulting modification of mechanical properties depends strongly on the cross-link density. Low cross-link densities decrease the viscosities of polymer melts. Intermediate cross-link densities transform gummy polymers into materials that have elastomeric properties and potentially high strengths. Very high cross-link densities can cause materials to become very rigid or glassy, such as phenol-formaldehyde, epoxies, urethanes, and polyethylenes. Cross-links can be formed by chemical reactions that are initiated by heat, pressure, change in pH, or radiation.
  • cross-linking can also be induced in materials that are normally thermoplastic through exposure to a radiation source, such as electron beam exposure, gamma-radiation, or UV light.
  • a radiation source such as electron beam exposure, gamma-radiation, or UV light.
  • electron beam processing is used to cross-link polyethylene.
  • Other types of cross-linked polyethylene are made by addition of peroxide during extruding or by addition of a cross-linking agent such as vinylsilane and a catalyst during extruding and then performing a post-extrusion curing.
  • the chemical process of vulcanization, sulfur crosslinking is a type of cross-linking which changes the property of rubber to the hard, durable material.
  • Crosslinking accelerators such as 2-benzothiazolethiol or tetramethyl- thiuram disulfide contain a sulfur atom in the molecule that initiates the reaction of the sulfur chains with rubber. Accelerators increase the rate of cure by catalyzing the addition of sulfur chains to the rubber molecules.
  • thermoplastic elastomers rely on physical cross-links in their microstructure to achieve stability, and offer a much wider range of properties than conventional cross-linked elastomers.
  • the shape-memory polyurethane materials are capable of being geometrically altered, in one non-limiting embodiment compressed substantially, e.g., 20-30% of their original volume, at temperatures above their onset glass transition temperatures (T g ) at which the material becomes soft. While still being geometrically altered, the material may be cooled down well below its onset T g , or cooled down to room or ambient temperature, and it is able to remain in the altered geometric state even after the applied shape altering force is removed.
  • the shape-memory material When the material is heated near or above its onset T g , it is capable of recovery to its original geometric state or shape, or close to its original geometric position; a state or shape which may be called a recovered geometric position.
  • the shape-memory material possesses hibernated shape-memory that provides a shape to which the shape-memory material naturally takes after its manufacturing.
  • the compositions of the shape- memory materials are able to be formulated to achieve desired onset glass transition temperatures which are suitable for the downhole applications, where deployment can be controlled for temperatures below onset T g of devices at the depth at which the assembly will be used.
  • the shape-memory materials are polyurethanes
  • various ratios of polyol to isocyanate may be used to provide a polyurethane formulation having various onset T g s.
  • the polyurethane with different onset T g s may be geometrically altered and then run downhole.
  • the device When various target temperatures are reached, the device will then deploy at various rates allowing for soft, conformable deployments reinforced by hard, rigid, material. That is, the differing onset T g of different portions of the device not only affect the temperature at which that portion of the device will return to its original shape, but will also affect the hardness of the material and rates of deployment.
  • These various different onset T g s are also applicable for crosslinked polymers having different crosslinking ratios from each other.
  • polyurethane polymer or polyurethane foam is considered poor in thermal stability and hydrolysis resistance, especially when it is made from polyether or polyester. It has been previously discovered herein that the thermal stability and hydrolysis resistance are significantly improved when the polyurethane is made from polycarbonate polyols and MDI diisocyanates.
  • the compositions of polyurethane foam and the crosslinked polymer materials herein are able to be formulated to achieve different glass transition temperatures within the range from 60°C to 170°C, which is especially suitable to meet most downhole application temperature requirements. More details about these particular polyurethane foams or polyurethane elastomers may be found in U.S. Patent No. 7,926,565.
  • the shape-memory material is a polyurethane material that is extremely tough and strong and that is capable of being geometrically altered and returned to substantially its original geometric shape.
  • the T g of the shape-memory polyurethane foam ranges from about 40°C to about 200°C and it is geometrically altered by mechanical force at 40°C to 190°C. It will be appreciated that in the embodiment where two or more shape-memory materials are employed and each have a different T g from each other, all of the T g s will fall with the range of about 40°C to about 200°C, but they will be different from each other.
  • the material While still in geometrically altered state, the material may be cooled down to room temperature or some other temperature below the T g of each shape-memory material.
  • the shape-memory polyurethane is able to remain in the altered geometric state even after applied mechanical force is removed.
  • material When material is heated to above its onset T g , it is able to return to its original shape, or close to its original shape.
  • the time required for geometric shape recovery can vary from about 20 minutes to 40 hours or longer depending on the slope of the transition curves as the material moves from a glass state to a rubber state. If the material remains below the onset T g it remains in the geometrically altered state and does not change its shape.
  • shape-memory polyurethane when used as a downhole device, it is preferred that the device remains in an altered geometric state during run-in until it reaches the desired downhole location.
  • downhole tools traveling from surface to the desired downhole location take hours or days.
  • the devices made from the shape-memory material could start to recover.
  • delaying methods may or must be taking into consideration.
  • a polyvinyl alcohol) (PVA) film or other suitable film may be used to wrap or cover the outside surface of devices made from shape- memory material to prevent recovery during run-in. Once devices are in place downhole for a given amount of time at temperature, the PVA film is capable of being dissolved in the water, emulsions or other downhole fluids and, after such exposure, the shape-memory devices may recover to their original geometric shape or conform to the bore hole or other space.
  • the devices made from the shape-memory material may be coated with a thermally fluid-degradable rigid plastic such as polyester polyurethane plastic and polyester plastic.
  • thermally fluid-degradable plastic is meant any rigid solid polymer film, coating or covering that is degradable when it is subjected to a fluid, e.g. water or hydrocarbon or combination thereof and heat.
  • the covering is formulated to be degradable within a particular temperature range to meet the required application or down- hole temperature at the required period of time (e.g. hours or days) during run- in.
  • the thickness of delay covering and the type of degradable plastics or other materials may be selected to be able to keep devices of shape-memory material from recovery during run-in.
  • these degradable plastics decompose which allows the devices to recover their original geometric shape or conform to the inner wall of the bore hole or the casing.
  • the covering that inhibits or prevents the shape-memory material from returning to its original geometric position or being prematurely deployed may be removed by dissolving, e.g. in an aqueous or hydrocarbon fluid, or by thermal degradation or hydrolysis, with or without the application of heat, in another non-limiting example, destruction of the crosslinks between polymer chains of the material that makes up the covering.
  • the polyurethane material may be formed by combining two separate portions of chemical reactants and reacting them together. These two separate portions are referred to herein as the isocyanate portion and polyol portion.
  • the isocyanate portion may comprise a modified isocyanate (Ml) or a modified diphenylmethane diisocyanate (MDI) based monomeric diisocyanate or polyisocyanate.
  • the polyol portion may include, but not necessarily be limited to, a polyether, polyester or polycarbonate-based di- or multifunctional hydroxyl-ended prepolymer.
  • Water may be included as part of the polyol portion and may act as a blowing agent to provide a porous foam structure when carbon dioxide is generated from the reaction with the isocyanate and water when the isocyanate portion and the polyol portion are combined.
  • the isocyanate portion may contain modified MDI MONDUR PC sold by Bayer or MDI prepolymer LUPRA- NATE 5040 sold by BASF, and the polyol portion may contain (1 ) a poly(cyclo- aliphatic carbonate) polyol sold by Stahl USA under the commercial name PC- 1667; (2) a tri-functional hydroxyl cross linker trimethylolpropane (TMP) sold by Alfa Aesar; (3) an aromatic diamine chain extender dimethylthiotoluenediamine (DMTDA) sold by Albemarle under the commercial name ETHACURE 300; (4) a catalyst sold by Air Products under the commercial name POLYCAT 77; (5) a surfactant sold by Air Products under the commercial name DABCO DC198;
  • TMP tri-functional hydroxyl cross linker trimethylolpropane
  • DMTDA aromatic diamine chain extender dimethylthiotoluenediamine
  • the ratio between two separate portions of chemical reactants which are referred to herein as the isocyanate portion and polyol portion may, in one non-limiting embodiment, be chemically balanced close to 1 : 1 according to their respective equivalent weights.
  • the equivalent weight of the isocyanate portion is calculated from the percentage of NCO (isocyanate) content which is referred to herein as the modified MDI MONDUR PC and contains 25.8 % NCO by weight.
  • Other isocyanates such as MDI prepolymer LUPRANATE 5040 sold by BASF contains 26.3% NCO by weight are also acceptable.
  • the equivalent weight of the polyol portion is calculated by adding the equivalent weights of all reactive components together in the polyol portion, which includes polyol, e.g., PC-1667, water, molecular cross linker, e.g., TMP, and chain extender, e.g., DMTDA.
  • the glass transition temperature of the finished polyurethane foam may be adjustable via different combinations of isocyanate and polyol. In general, the more isocyanate portion, the higher the T g that is obtained.
  • the equivalent ratio of isocyanate portion to polyol portion ranges from 1.2: 1 to 1 : 1.2, alternatively from 1.1 to 1 to 1 to 1.1. When the one or more polyurethanes are used, in one non-restrictive versions, each polyurethane has a different ratio, but the ratio is within these ranges.
  • various ratios of polyol to isocyanate may be used to provide polyurethane polymers with variable T g s throughout the molded polymer part. This will allow the polymer molded to have unique properties, such as various sections of the downhole tool and/or wellbore device to undergo shaped memory influences as the temperatures change within the wellbore, such as heating up or cooling down.
  • the foam could be open cell foam for filtration, sand control or other application. After various target temperatures are experienced the screen or tool will then deploy at various rates allowing for soft conformable deployments (in a non-limiting embodiment, an outer layer or layers) reinforced by relatively harder, more rigid compacted foam (the inner layer or layers).
  • foam components include a chain extender, in one non- limiting embodiment, dimethylthiotoluenediamine (DMTDA) sold by Albemarle under the commercial name ETHACURE 300, which is a liquid aromatic diamine curative that provides enhanced high temperature properties.
  • chain extenders include but are not limited to 4,4'-methylene bis (2- chloroaniline), "MOCA”, sold by Chemtura under the commercial name VIBRACURE ® A 133 HS, and trimethylene glycol di-p-aminobenzoate, "MCDEA”, sold by Air Products under the commercial name VERSALINK 740M.
  • either amine-based or metal-based catalysts are included to achieve good properties of polyurethane foam materials.
  • Such catalysts are commercially available from companies such as Air Products.
  • Suitable catalysts that provide especially good properties of polyurethane foam materials include, but are not necessarily limited to, pentamethyldipropylenetriamine, an amine-based catalyst sold under the commercial name POLYCAT 77 by Air Products, and dibutyltindilaurate, a metal-based catalyst sold under the commercial name DABCO T-12 by Air Products.
  • a small amount of surfactant e.g., 0.5% of total weight, such as the surfactant sold under the commercial name DABCO DC-198 by Air Products and a small amount of cell opener, e.g., 0.5% of total weight, such as cell openers sold under the commercial names ORTEGOL 500, ORTEGOL 501 , TEGOSTAB B8935, TEGOSTAB B8871 , and TEGOSTAB B8934 by Degussa may be added into the formulations.
  • DABCO DC-198 is a silicone- based surfactant from Air Products.
  • Suitable surfactants include, but are not necessarily limited to, fluorosurfactants sold by DuPont under commercial names ZONYL 8857A and ZONYL FSO-100. Colorant may be added in the polyol portion to provide desired color in the finished products. Such colorants are commercially available from companies such as Milliken Chemical which sells suitable colorants under the commercial name REACT! NT.
  • the polyol portion including poly(cycloaliphatic carbonate) or other polyol and other additives such as cross linker, chain extender, surfactant, colorant, water, and catalyst is pre-heated to 90°C before being combined with the isocyanate portion.
  • the isocyanate portion is combined with the polyol portion and a reaction is immediately initiated and the mixture's viscosity increases rapidly.
  • the amount of polyol relative to isocyanate should be varied at least once, potentially numerous times, to give a varied polyurethane where different portions have different T g s.
  • the amount of isocyanate and polyol included in the mixture should be chemically balanced according to their equivalent weight and the desired T g s or range of glass transition temperatures. In one specific non-limiting embodiment, up to 5% more isocyanate by equivalent weight is combined with the polyol portion.
  • the ratio between isocyanate and polycarbonate polyol is about 1 : 1 by weight.
  • the polyol portion may be formed by 46.0 g of PC-1667 poly(cycloaliphatic carbonate) polycarbonate combined with 2.3 g of TMP cross-linker, 3.6 g of DMTDA chain extender, 0.9 g DABCO DC-198 surfactant, 0.4 g of ORTEGOL 501 , 0.1 g of REACTI NT Violet X80LT colorant, 0.01 g of POLYCAT 77 catalyst, and 0.7 g of water blowing agent to form the polyol portion.
  • the polyol portion is preheated to 90°C and mixed in a KITCHENAID ® type single blade mixer with 46.0 g of MDI MONDUR PC.
  • these formulations can be scaled-up to form larger volumes of this shape-memory material.
  • the mixture containing the isocyanate portion and the polyol portion may be mixed for about 10 seconds and then poured into a mold and the mold immediately closed by placing a top metal plate thereon. Due to the significant amount of pressure generated by foaming process, a C-clamp may be used to hold the top metal plate and mold together to prevent any leakage of mixture.
  • the polyurethane foam material including a mold and a C-clamp may be placed inside an oven and "post-cured" at a temperature of 1 10°C for approximately 8 hours so that the polyurethane foam material reaches its full strength. These times and temperatures are simply representative and should not be taken as limiting. After cooled down to room temperature, the polyurethane material is sufficiently cured such that the mold may be removed.
  • the polyurethane material is in its original, expanded shape having an original, or expanded, thickness.
  • the T g s of the polyurethane material are measured by Dynamic Mechanical Analysis (DMA) as 94.4°C from the peak of loss modulus, G".
  • the polyurethane material may be capable of being geometrically altered to at least 25% of original thickness or volume at temperature 125.0°C in a confining mold. While still in the altered geometric state, the material is cooled down to room temperature.
  • the shape-memory polyurethane is able to remain in the altered geometric state even after applied mechanical force is removed. When the material is heated to about 88°C, in one non-restrictive version, it is able to return to its original shape within 20 minutes.
  • a first portion of polyurethane foam may be heated to about 88°C and thus return to its original shape and size at that temperature and a second portion of polyurethane foam may be heated to about 100°C for sufficient time to return to its original shape and size to complete the expansion of the screen, e.g. This is possible because the different portions of the foam have different
  • the ratio between isocyanate and polycarbonate polyol is about 1.5: 1 by weight.
  • the polyol portion may be formed by 34.1 g of PC-1667 poly(cycloali- phatic carbonate) polycarbonate combined with 2.3 g of TMP cross linker, 10.4 g of DMTDA chain extender, 0.8 g DABCO DC-198 surfactant, 0.4 g of ORTE- GOL 501 cell opener, 0.1 g of REACTINT Violet X80LT colorant, 0.01 g of POLYCAT 77 catalyst, and 0.7 g of water blowing agent to form the polyol portion.
  • the polyol portion is preheated to 90°C and mixed in a KITCHENAID ® type single blade mixer with 51.2 g of MDI MONDUR PC.
  • these formulations can be scaled-up to form larger volumes of this shape-memory material. Again, a change in the ratio of polyol to isocyanate will change the T g .
  • the mixture containing the isocyanate portion and the polyol portion may be mixed for about 10 seconds and then poured into a mold and the mold immediately closed by placing a top metal plate thereon. Due to the significant amount pressure generated by foaming process, a C-clamp or other device may be used to hold the top metal plate and mold together to prevent any leakage of mixture. After approximately 2 hours, the polyurethane foam material including a mold and a C-clamp may be transferred into an oven and "post-cured" at a temperature of 1 10°C for approximately 8 hours so that the polyurethane material reaches its full strength. After cooled down to room temperature, the polyurethane material is sufficiently cured such that the mold can be removed.
  • T g of this particular polyurethane material in this non-limiting example may be measured as 1 17.0°C by DMA from the peak of loss modulus, G".
  • the polyurethane having more isocyanate than polyol by weight results in higher glass transition temperature.
  • the polyurethane having less isocyanate than polyol by weight results in lower T g .
  • different glass transition temperatures of shape-memory polyurethane may be achieved.
  • Compositions of a shape-memory polyurethane material having a specific T g may be formulated based on actual downhole deployment/application temperature.
  • the T g s of a shape-memory polyurethane is designed to be about 20°C higher than actual downhole deployment/application temperatures.
  • the shape-memory polyure- thane in tubular shape may be altered under hydraulic pressure above glass transition temperature, and then cooled to a temperature well below the T g or room temperature while it is still under altering force. After the pressure is removed, the shape-memory polyurethane is able to remain at the new geometric state or shape.
  • the tubing string 20 having device 30 including shape-memory materials 32 and 40 is run-in wellbore 50, which is defined by wellbore casing 52, to the desired location.
  • Device 30 may include a billet which may be a cylinder of material with varying outer diameters (ranging from about 6 to about 12 inches (about 15 to about 30 cm)) and of different lengths (e.g. from about 4 to 5 feet (about 1.2 to about 1 .5 m) in height), which may be understood as a substrate upon which the polymer is placed.
  • first shape-memory material 32 has an altered, run-in, thickness 34.
  • Second shape-memory material 40 overlying first shape- memory material 32 and concentric therewith, has an altered, run-in thickness 36, which may be the same as or different from thickness 34. After a sufficient amount of time at a sufficient temperature at or above the onset T g of second shape-memory material 40, it expands from the run-in shape position (FIG. 3) to the recovered or set position (FIG. 4) having an expanded thickness.
  • first shape- memory material 32 expands from the run-in or altered position (FIG. 3) to the recovered or set position (FIG. 5) having an expanded thickness.
  • second shape-memory material 40 engages with inner wall surface 54 of wellbore casing 52.
  • the entire distance 38 from billet 30 of the device to inner wall surface 54 will be occupied by the device - the device being understood as the combined first shape-memory material 32 and second shape-memory material 40.
  • first and second shape- memory materials 32 and 40 may be reversed.
  • the relatively harder, more rigid material may be the inner one.
  • FIGS. 6-8 Shown in FIGS. 6-8 is another non-limiting embodiment where the first shape-memory material 32" and second shape-memory material 40" are oriented next to each other along at least a portion of the length of the billet 30 or in a side-by-side relationship. In one non-restrictive version, they are not touching each other, but may be separated.
  • the T g of second shape-memory material 40" is lower than the T g of first shape-memory material 32" and is subject to an effective temperature for a sufficient amount of time to cause it to recover or enlarge to the recovered or set position shown in FIG. 7. In this embodiment, its recovered or set position would be sufficient to substantially contact and engage inner wall surface 54 across the entire distance 38.
  • the filtration device may contain open cells of polymer material 32" that are much smaller than the open cells of polymer material 40" so that only fluids are passed through annulus 60 and no particles of appreciable size are permitted to pass through the smaller cells of the filtration device.
  • first shape-memory material 32 and second shape-memory material 40 may be arranged or configured in any number of designs.
  • the two or more shape memory materials having different T g s and/or different slope changes from each other may be mixed together in complex geometrical configurations.
  • a device "totally conforms" to the borehole what is meant is that the shape-memory material recovers or deploys to fill the available space up to the borehole wall.
  • the borehole wall will limit the final, recovered shape of the shape-memory material and in fact not permit it to expand to its original, geometric shape. In this way however, the recovered or deployed shape-memory material, will perform the desired function within the wellbore.
  • a wellbore device may comprise at least two shape-memory materials, at least a first shape memory material and at least a second shape memory material.
  • the first shape memory material may consist essentially of or consist of a cross-linked polymer having a first crosslinking ratio, where the first shape-memory material has an altered geometric position and an original geometric position, where the first shape- memory material is maintained in the altered geometric position at a temperature below a first onset glass transition temperature, and where the shape- memory material expands from its altered geometric position to its recovered geometric position when it is heated to a temperature above the first onset glass transition temperature, where the first shape-memory material has a first slope change during a first transition state from a first glass state to a first rubber state.
  • the second shape-memory material may consist of or consist essentially of a cross-linked polymer having a second crosslinking ratio different from the first crosslinking ratio, where the second shape-memory material has an altered geometric position and an original geometric position, where the shape-memory material is maintained in the altered geometric position at a temperature below a second onset glass transition temperature, and where the shape-memory material recovers from its altered geometric position to its recovered geometric position when it is heated to a temperature above the second onset glass transition temperature, where the second shape-memory material has a second slope change during a second transition state from a second glass state to a second rubber state.
  • the first shape-memory material and the second shape-memory material of the wellbore device are further different by one or both of the parameters: the first onset glass transition temperature is different from the second onset glass transition temperature or the first slope change is different from the second slope change.

Landscapes

  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mining & Mineral Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Physics & Mathematics (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Semiconductor Memories (AREA)
  • Micromachines (AREA)
  • Networks Using Active Elements (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des dispositifs de forages de puits pour l'utilisation dans la filtration, l'isolation de forage de puits, la commande production, la gestion de cycle de vie et la construction de forage de puits. Lesdits dispositifs de forages de puits peuvent comprendre au moins des premier et second matériaux à mémoire de forme qui possèdent chacun une position géométrique modifiée et qui possèdent chacun une position géométrique d'origine. Chaque matériau à mémoire de forme peut être maintenu dans la position de pénétration géométrique modifiée à une température inférieure à la température de transition vitreuse (Tg), où les Tg et/ou les changements d'inclinaison respectifs des premier et second matériaux à mémoire de forme sont différents. Facultativement, les matériaux à mémoire de forme peuvent être des polymères réticulés, les polymères réticulés possédant des rapports de réticulation différents l'un de l'autre. Une fois que le dispositif de forage de puits est en place en fond de puits et les premier et second matériaux à mémoire de forme sont soumis à des températures supérieures à leurs Tg, les matériaux se déploieront jusqu'à des positions géométriques récupérées à ou proche de leurs positions géométriques d'origines pour réaliser leur filtration, isolation, commande ou autre fonction. Ces déploiements peuvent se produire à des instants ou des taux différents.
PCT/US2014/011300 2011-03-07 2014-01-13 Matériaux à mémoire de forme à tg variable pour dispositifs de forage de puits WO2014116457A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
GB1514785.3A GB2526026B (en) 2013-01-25 2014-01-13 Variable Tg shape memory materials for wellbore devices
CA2897777A CA2897777C (fr) 2013-01-25 2014-01-13 Materiaux a memoire de forme a tg variable pour dispositifs de forage de puits
AU2014209715A AU2014209715B2 (en) 2011-03-07 2014-01-13 Variable Tg shape memory materials for wellbore devices
NO20150877A NO20150877A1 (en) 2013-01-25 2015-07-06 Variable TG shape memory materials for wellbore devices

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/750,468 2013-01-25
US13/750,468 US9068437B2 (en) 2010-03-26 2013-01-25 Variable Tg shape memory materials for wellbore devices

Publications (1)

Publication Number Publication Date
WO2014116457A1 true WO2014116457A1 (fr) 2014-07-31

Family

ID=51227948

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/011300 WO2014116457A1 (fr) 2011-03-07 2014-01-13 Matériaux à mémoire de forme à tg variable pour dispositifs de forage de puits

Country Status (5)

Country Link
AU (1) AU2014209715B2 (fr)
CA (1) CA2897777C (fr)
GB (1) GB2526026B (fr)
NO (1) NO20150877A1 (fr)
WO (1) WO2014116457A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018118014A1 (fr) * 2016-12-19 2018-06-28 Halliburton Energy Services, Inc. Utilisation de matériaux à mémoire de forme dans des liquides d'entretien de puits de forage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080296023A1 (en) * 2007-05-31 2008-12-04 Baker Hughes Incorporated Compositions containing shape-conforming materials and nanoparticles that absorb energy to heat the compositions
US20100089565A1 (en) * 2008-10-13 2010-04-15 Baker Hughes Incorporated Shape Memory Polyurethane Foam for Downhole Sand Control Filtration Devices
US20100132944A1 (en) * 2006-12-18 2010-06-03 Leiming Li Differential filters for removing water during oil production
US20100236794A1 (en) * 2007-09-28 2010-09-23 Ping Duan Downhole sealing devices having a shape-memory material and methods of manufacturing and using same
US20110232901A1 (en) * 2010-03-26 2011-09-29 Baker Hughes Incorporated VARIABLE Tg SHAPE MEMORY POLYURETHANE FOR WELLBORE DEVICES

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100132944A1 (en) * 2006-12-18 2010-06-03 Leiming Li Differential filters for removing water during oil production
US20080296023A1 (en) * 2007-05-31 2008-12-04 Baker Hughes Incorporated Compositions containing shape-conforming materials and nanoparticles that absorb energy to heat the compositions
US20100236794A1 (en) * 2007-09-28 2010-09-23 Ping Duan Downhole sealing devices having a shape-memory material and methods of manufacturing and using same
US20100089565A1 (en) * 2008-10-13 2010-04-15 Baker Hughes Incorporated Shape Memory Polyurethane Foam for Downhole Sand Control Filtration Devices
US20110232901A1 (en) * 2010-03-26 2011-09-29 Baker Hughes Incorporated VARIABLE Tg SHAPE MEMORY POLYURETHANE FOR WELLBORE DEVICES

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018118014A1 (fr) * 2016-12-19 2018-06-28 Halliburton Energy Services, Inc. Utilisation de matériaux à mémoire de forme dans des liquides d'entretien de puits de forage
GB2572260A (en) * 2016-12-19 2019-09-25 Halliburton Energy Services Inc Use of shape memory materials in wellbore servicing fluids
US10570330B2 (en) 2016-12-19 2020-02-25 Halliburton Energy Services, Inc. Use of shape memory materials in wellbore servicing fluids
GB2572260B (en) * 2016-12-19 2022-12-14 Halliburton Energy Services Inc Use of shape memory materials in wellbore servicing fluids

Also Published As

Publication number Publication date
NO20150877A1 (en) 2015-07-06
CA2897777C (fr) 2017-11-07
GB201514785D0 (en) 2015-10-07
GB2526026B (en) 2017-03-01
AU2014209715A1 (en) 2015-07-16
CA2897777A1 (fr) 2014-07-31
GB2526026A (en) 2015-11-11
AU2014209715B2 (en) 2017-04-13

Similar Documents

Publication Publication Date Title
US9441458B2 (en) Variable Tg shape memory polyurethane for wellbore devices
US9068437B2 (en) Variable Tg shape memory materials for wellbore devices
AU2009303675B2 (en) Shape memory polyurethane foam for downhole sand control filtration devices
US9090012B2 (en) Process for the preparation of conformable materials for downhole screens
WO2011133319A2 (fr) Prévention, actionnement et commande du déploiement de matériaux expansibles à base de mousse polymère à mémoire de forme
US20140332220A1 (en) Polyurethane activator-breaker fluid system
US8960314B2 (en) Shape memory seal assembly
US8696963B2 (en) Functionally graded swellable packers
US20120305238A1 (en) High Temperature Crosslinked Polysulfones Used for Downhole Devices
NO20210997A1 (en) Non-metallic compliant sand control screen
AU2014209715B2 (en) Variable Tg shape memory materials for wellbore devices
US20220025251A1 (en) Diverting agents for well stimulation
CA2897397C (fr) Prevention, actionnement et commande du deploiement de materiaux expansibles a base de mousse polymere a memoire de forme
CN114458171A (zh) 一种套管、井眼强化完井管柱和完井固井方法及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14743649

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2897777

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2014209715

Country of ref document: AU

Date of ref document: 20140113

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 1514785

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20140113

WWE Wipo information: entry into national phase

Ref document number: 1514785.3

Country of ref document: GB

122 Ep: pct application non-entry in european phase

Ref document number: 14743649

Country of ref document: EP

Kind code of ref document: A1