 
                 Patent Grant
 Patent Grant
                     12352127
 12352127
                    Wellbores are drilled into the earth for a variety of purposes including accessing hydrocarbon bearing formations. A variety of downhole tools may be used within a wellbore in connection with accessing and extracting such hydrocarbons. Throughout the process, it may become necessary to isolate sections of the wellbore in order to create pressure zones. Downhole tools, such as frac plugs, bridge plugs, packers, and other suitable tools, may be used to isolate wellbore sections.
The aforementioned downhole tools are commonly run into the wellbore on a conveyance, such as a wireline, work string or production tubing. Such tools often have either an internal or external setting tool, which is used to set the downhole tool within the wellbore and hold the tool in place, and thus function as a wellbore anchor. The wellbore anchors typically include a plurality of slips, which extend outwards when actuated to engage and grip a casing within a wellbore or the open hole itself, and a sealing assembly, which can be made of rubber and extends outwards to seal off the flow of liquid around the downhole tool.
Reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
    
    
    
    
    
In the drawings and descriptions that follow, like parts are typically marked throughout the specification and drawings with the same reference numerals, respectively. The drawn figures are not necessarily, but may be, to scale. Certain features of the disclosure may be shown exaggerated in scale or in somewhat schematic form and some details of certain elements may not be shown in the interest of clarity and conciseness.
The present disclosure may be implemented in embodiments of different forms. Specific embodiments are described in detail and are shown in the drawings, with the understanding that the present disclosure is to be considered an exemplification of the principles of the disclosure, and is not intended to limit the disclosure to that illustrated and described herein. It is to be fully recognized that the different teachings of the embodiments discussed herein may be employed separately or in any suitable combination to produce desired results. Moreover, all statements herein reciting principles and aspects of the disclosure, as well as specific examples thereof, are intended to encompass equivalents thereof. Additionally, the term, “or,” as used herein, refers to a non-exclusive or, unless otherwise indicated.
Unless otherwise specified, use of the terms “connect,” “engage,” “couple,” “attach,” or any other like term describing an interaction between elements is not meant to limit the interaction to direct interaction between the elements and may also include indirect interaction between the elements described.
Unless otherwise specified, use of the terms “up,” “upper,” “upward,” “uphole,” “upstream,” or other like terms shall be construed as generally toward the surface of the well; likewise, use of the terms “down,” “lower,” “downward,” “downhole,” or other like terms shall be construed as generally toward the bottom, terminal end of a well, regardless of the wellbore orientation. Use of any one or more of the foregoing terms shall not be construed as denoting positions along a perfectly vertical or horizontal axis. Unless otherwise specified, use of the term “subterranean formation” shall be construed as encompassing both areas below exposed earth and areas below earth covered by water, such as ocean or fresh water.
Referring to 
The well system 100 illustrated in the embodiment of 
The well system 100 illustrated in 
The downhole tool assembly 180, in the illustrated embodiment, includes a downhole tool 185 and a wellbore anchor 190. The downhole tool 185 may comprise any downhole tool that could be positioned within a wellbore. Certain downhole tools that may find particular use in the well system 100 include, without limitation, sealing elements, sealing packers, elastomeric sealing packers, non-elastomeric sealing packers (e.g., including plastics such as PEEK, metal packers such as inflatable metal packers, as well as other related packers), liners, an entire lower completion, one or more tubing strings, one or more screens, one or more production sleeves, etc. The wellbore anchor 190 may comprise any wellbore anchor that could anchor the downhole tool 185 within a wellbore. In certain embodiments, the downhole tool 185 is deployed without the wellbore anchor 190, and in certain other embodiments the wellbore anchor 190 is deployed without the downhole tool 185.
In accordance with the disclosure, at least a portion of the downhole tool 185 or the wellbore anchor 190 may include expandable metal. In some embodiments, all or part of the downhole tool 185 or the wellbore anchor 190 may be fabricated using expandable metal configured to expand in response to hydrolysis. The expandable metal, in some embodiments, may be described as expanding to a cement like material. In other words, the expandable metal goes from metal to micron-scale particles and then these particles expand and lock together to, in essence, fix the downhole tool 185 or the wellbore anchor 190 in place. The reaction may, in certain embodiments, occur in less than 2 days in a reactive fluid and in downhole temperatures. Nevertheless, the time of reaction may vary depending on the reactive fluid, the expandable metal used, and the downhole temperature, as well as other aspects discussed further below.
In some embodiments the reactive fluid may be a brine solution such as may be produced during well completion activities, and in other embodiments, the reactive fluid may be one of the additional solutions discussed herein. The expandable metal, pre-expansion, is electrically conductive in certain embodiments. The expandable metal may be machined to any specific size/shape, extruded, formed, cast or other conventional ways to get the desired shape of a metal, as will be discussed in greater detail below. The expandable metal, pre-expansion, in certain embodiments has a yield strength greater than about 8,000 psi, e.g., 8,000 psi+/−50%. In other embodiments, the expandable metal is a slurry of expandable metal particles.
The hydrolysis of any metal can create a metal hydroxide. The formative properties of alkaline earth metals (Mg—Magnesium, Ca—Calcium, etc.) and transition metals (Zn—Zinc, Al—Aluminum, etc.) under hydrolysis reactions demonstrate structural characteristics that are favorable for use with the present disclosure. Hydration results in an increase in size from the hydration reaction and results in a metal hydroxide that can precipitate from the fluid.
The hydration reactions for magnesium is:
Mg+2H2O→Mg(OH)2+H2,
where Mg(OH)2 is also known as brucite. Another hydration reaction uses aluminum hydrolysis. The reaction forms a material known as Gibbsite, bayerite, and norstrandite, depending on form. The hydration reaction for aluminum is:
Al+3H2O→Al(OH)3+3/2H2.
Another hydration reactions uses calcium hydrolysis. The hydration reaction for calcium is:
Ca+2H2O→Ca(OH)2+H2,
Where Ca(OH)2 is known as portlandite and is a common hydrolysis product of Portland cement. Magnesium hydroxide and calcium hydroxide are considered to be relatively insoluble in water. Aluminum hydroxide can be considered an amphoteric hydroxide, which has solubility in strong acids or in strong bases.
In an embodiment, the expandable metal used can be a metal alloy. The metal alloy can be an alloy of the base metal with other elements in order to either adjust the strength of the metal alloy, to adjust the reaction time of the metal alloy, or to adjust the strength of the resulting metal hydroxide byproduct, among other adjustments. The metal alloy can be alloyed with elements that enhance the strength of the metal such as, but not limited to, Al—Aluminum, Zn—Zinc, Mn—Manganese, Zr—Zirconium, Y—Yttrium, Nd—Neodymium, Gd—Gadolinium, Ag—Silver, Ca—Calcium, Sn—Tin, and Re—Rhenium, Cu—Copper. In some embodiments, the alloy can be alloyed with a dopant that promotes corrosion, such as Ni—Nickel, Fe—Iron, Cu—Copper, Co—Cobalt, Ir—Iridium, Au—Gold, C—Carbon, gallium, indium, mercury, bismuth, tin, and Pd—Palladium. The metal alloy can be constructed in a solid solution process where the elements are combined with molten metal or metal alloy. Alternatively, the metal alloy could be constructed with a powder metallurgy process. The expandable metal can be cast, forged, extruded, a combination thereof, or may be a slurry of expandable metal particles.
Optionally, non-expanding components may be added to the starting expandable metal. For example, ceramic, elastomer, glass, or non-reacting metal components can be embedded in the expandable metal or coated on the surface of the metal. Alternatively, the starting expandable metal may be the metal oxide. For example, calcium oxide (CaO) with water will produce calcium hydroxide in an energetic reaction. Due to the higher density of calcium oxide, this can have a 260% volumetric expansion where converting 1 mole of CaO goes from 9.5 cc to 34.4 cc of volume. In one variation, the expandable metal is formed in a serpentinite reaction, a hydration and metamorphic reaction. In one variation, the resultant material resembles a mafic material. Additional ions can be added to the reaction, including silicate, sulfate, aluminate, and phosphate. The expandable metal can be alloyed to increase the reactivity or to control the formation of oxides.
The expandable metal can be configured in many different fashions, as long as an adequate volume of material is available for fully expanding. For example, the expandable metal may be formed into a single long tube, multiple short tubes, rings, alternating steel and swellable rubber and expandable metal rings, among others. Additionally, a coating may be applied to one or more portions of the expandable metal to delay the expanding reactions.
In application, the downhole tool assembly 180 can be moved down the wellbore 120 via the downhole conveyance 170 to a desired location. Once the downhole tool assembly 180, including the downhole tool 185 and/or the wellbore anchor 190 reaches the desired location, one or both of the downhole tool 185 and/or the wellbore anchor 190 may be set in place according to the disclosure. In one embodiment, one or both of the downhole tool 185 and/or the wellbore anchor 190 include the expandable metal, and thus are subjected to a wellbore fluid sufficient to expand the one or more expandable metal members into contact with a nearby surface, and thus in certain embodiments seal or anchor the one or more downhole tools within the wellbore.
In the embodiment of 
In certain embodiments, it is desirable or necessary to accelerate and/or decelerate the expansion of the expandable metal. The present disclosure has recognized that a voltage (e.g., provided via a power source, whether uphole or downhole) may be used to accelerate and/or decelerate the expansion process. Accordingly, the applied voltage may be used to accelerate and/or decelerate the setting of any downhole tool that includes the expandable metal. In accordance with one embodiment, a first electrode is located between a first connection of a power source and the expandable metal, and a second electrode is located between a second connection of the power source and a downhole conductive feature. In accordance with this embodiment, the expandable metal is a first side of the electrical circuit, wherein the downhole conductive feature is the second side of the electrical circuit. In at least one embodiment, the electrodes are configured so that at least part of the electrical current passes through fluid surrounding the expandable metal. For example, at least a portion of one or both of the first electrode or the second electrode could be exposed to the wellbore fluid surrounding the expandable metal.
A positive voltage may be applied so that the expandable metal spends at least part of its time as an anode of the circuit. In one embodiment, the positive voltage accelerates the expansion process by up to at least 2×. In another embodiment, the positive voltage accelerates the expansion process by up to at least 5×. In yet another embodiment, the positive voltage accelerates the expansion process by up to at least 10×, and in yet another embodiment of 20× or 100×, or more.
In another embodiment, a negative voltage may be applied so that the expandable metal spends at least part of its time as a cathode of the circuit. In one embodiment, the negative voltage decelerates the expansion process by up to at least 2×. In another embodiment, the negative voltage protects the expanded metal from acid corrosion. For example, a voltage of −2.8 volts may be used to protect a magnesium containing expandable metal from corrosion, a voltage of −1.8 volts may be used to protect an aluminum containing expandable metal from corrosion, and a voltage of −1 volts may be used to protect a zinc containing expandable metal from corrosion, among others.
The electrical power can be applied from a battery, an electrical cable, or from a downhole power generator. In at least one embodiment, the downhole power generator is fluid flow turbine. The voltage, in at least one embodiment, is between 0.01 volts and 200 volts. In yet another embodiment, the voltage is between 0.5 volts and 10 volts. In at least one embodiment, the electrical current is between 0.5 milliamps and 100 amps, and in yet another embodiment is between 0.05 amps and 5 amps.
The power supply can be started from a timer, a transmitted signal through a wire, a transmitted signal sent wirelessly, or from a sensing of the operation of the wellbore, among other mechanisms. In at least one other embodiment, temperature change through fluid swapping could be used as the signal to start the power supply.
Referring to 
In one embodiment, the power (e.g., voltage) is delivered from an electric line 230, such as a TEC (tubing encapsulated conductor), coupled to an uphole power source. The electric line 230 may be connected to sensors and actuators downhole. The electric line 230 may also deliver power (e.g., voltage) to accelerate the chemical reaction of the one or more downhole packers 220. The power (e.g., voltage) can be through a direct connection to the wire or through an inductive coupling or a capacitive coupling. In another embodiment, the power (e.g., voltage) is delivered from a chemical battery, such as a lithium battery or an alkaline battery. In another embodiment, the power (e.g., voltage) is delivered from a fluid-flow driven power generator, such as a turbine power generator.
An experiment was conducted, wherein the reaction time of the expandable metal was compared between an applied voltage and no voltage. The mass of the unreacted metal is shown in 
In an alternative embodiment, the opposite voltage is used to delay the initiation of the chemical reaction. Thus, while applying a positive voltage accelerates the chemical reaction, applying a negative voltage to the expandable metal will inhibit the reaction. This can ensure that the expandable metal does not react (e.g., expand) until the desired time. Additionally, the negative voltage can protect the metal from acid based corrosion.
A Pourbaix diagram for Mg, Al, and Zn are shown in 
Turning to 
In the illustrated embodiment of 
Further to this embodiment, an electrical insulator 550 physically separates the expandable metal 520 and the downhole tubular 510 from one another. This electrical insulator 550 helps to ensure that the electrical current passes through the fluid rather than through direct electrical contact (e.g., by way of a physical connection between the expandable metal 520 and the downhole tubular 510). The electrical insulator 550, thus, reduces the power requirements. As illustrated in 
Turning to 
In one embodiment, the power is created from a DC voltage. As shown in 
Turning to 
In the illustrated embodiment of 
Turning to 
The one or more expandable metal members 820, in accordance with the disclosure, comprise a metal configured to expand in response to hydrolysis, as discussed in detail above. Furthermore, a combined volume of the one or more expandable metal members should be sufficient to expand to anchor one or more downhole tools within the wellbore in response to the hydrolysis. In one embodiment, the combined volume of the one or more expandable metal members 820 is sufficient to expand to anchor at least about 100,000 Newtons (e.g., about 25,000 lbs.) of weight within the wellbore. In yet another embodiment, the combined volume of the one or more expandable metal members 820 is sufficient to expand to anchor at least about 200,000 Newtons (e.g., about 50,000 lbs.) of weight within the wellbore, and in yet another embodiment sufficient to expand to anchor at least about 300,000 Newtons (e.g., about 70,000 lbs.) of weight within the wellbore. In one embodiment, for example where the one or more expandable metal members 820 are seals, they may be capable of holding pressures up to about 1000 psi. In another embodiment, the one or more expandable metal members are capable of holding pressures up to about 10,000 psi, and in even yet another embodiment up to about 20,000 psi, or more.
In the illustrated embodiment of 
In the illustrated embodiment of 
Turning to 
Turning to 
In the particular embodiment of 
Turning to 
Turning to 
The downhole tool 1200 illustrated in 
Turning to 
In the illustrated embodiment of 
Turning to 
Turning to 
Aspects disclosed herein include:
A. A method for setting a downhole tool, the method including: 1) positioning a downhole tool within a wellbore, the downhole tool including expandable metal configured to expand in response to hydrolysis; 2) subjecting the expandable metal to a wellbore fluid to expand the expandable metal into contact with one or more surfaces; and 3) applying a voltage to the expandable metal while the expandable metal is being subjected to the wellbore fluid.
B. A downhole tool, the downhole tool including: 1) a downhole conductive feature; expandable metal positioned proximate the downhole conductive feature, the expandable metal configured to expand in response to hydrolysis; 2) a first electrode coupled to the expandable metal and operable to couple to a first connection of a power source, and thereby provide a voltage to the expandable metal; and 3) a second electrode coupled to the downhole conductive feature and operable to couple to a second connection of the power source.
C. A well system, the well system including: 1) a wellbore extending through one or more subterranean formations; 2) a power source, the power source including a first connection and a second connection; and 3) a downhole tool located within the wellbore, the downhole tool including; a) a downhole conductive feature; b) expandable metal positioned proximate the downhole conductive feature, the expandable metal configured to expand in response to hydrolysis; c) a first electrode coupled between the expandable metal and the first connection of the power source, the first electrode operable to provide a voltage to the expandable metal; and d) a second electrode coupled between the downhole conductive feature and the second connection of the power source.
Aspects A, B, and C may have one or more of the following additional elements in combination: Element 1: further including coupling a first electrode between a first connection of a power source and the expandable metal, and coupling a second electrode between a second connection of the power source and a downhole conductive feature. Element 2: wherein at least a portion of the first electrode is electrically exposed to the wellbore fluid. Element 3: wherein at least a portion of the second electrode is electrically exposed to the wellbore fluid. Element 4: wherein an electrical insulator physically separates the expandable metal and the downhole conductive feature. Element 5: wherein the first connection is a positive terminal of the power source, thereby causing the expandable metal to function as an anode, and the second connection is a negative terminal of the power source, thereby causing the downhole conductive feature to function as a cathode. Element 6: wherein the downhole conductive feature is conductive tubing located within the wellbore. Element 7: wherein the power source is a direct current (DC) power source. Element 8: wherein the expandable metal is a first expandable metal feature and the downhole conductive feature is a second expandable metal feature. Element 9: wherein the first expandable metal feature and the second expandable metal feature are positioned radially about a conductive tubular. Element 10: further including one or more electrical insulators physically separating at least one of the first expandable metal feature and the second expandable from the conductive tubular. Element 11: wherein the power source is an alternating current (AC) power source, the alternating current (AC) power source causing the first expandable metal to alternate between functioning as an anode and a cathode and causing the second expandable metal feature to oppositely alternative between functioning as the cathode and the anode. Element 12: wherein the expandable metal is a slurry of expandable metal particles, and further including a conductive plate coupled to the first electrode for applying the voltage to the slurry of expandable metal particles. Element 13: wherein the voltage is a positive voltage operable to accelerate the expansion of the expandable metal. Element 14: wherein the voltage is a negative voltage operable to decelerate the expansion of the expandable metal. Element 15: wherein the voltage is a negative voltage operable to protect the expandable metal from acid corrosion. Element 16: wherein the voltage ranges from 0.01 volts to 200 volts. Element 17: wherein the voltage ranges from 0.5 volts to 10 volts. Element 18: wherein a current associated with the voltage ranges from 0.05 amps to 5 amps. Element 19: wherein the downhole conductive feature is conductive tubing positionable within a wellbore. Element 20: wherein the expandable metal is a first expandable metal feature and the downhole conductive feature is a second expandable metal feature. Element 21: wherein the first expandable metal feature and the second expandable metal feature are positioned radially about a conductive tubular. Element 22: further including one or more electrical insulators physically separating at least one of the first expandable metal feature and the second expandable from the conductive tubular. Element 23: wherein the downhole conductive feature is conductive tubing positioned within the wellbore. Element 24: wherein the expandable metal is a first expandable metal feature and the downhole conductive feature is a second expandable metal feature. Element 25: wherein the first expandable metal feature and the second expandable metal feature are positioned radially about a conductive tubular. Element 26: further including one or more electrical insulators physically separating at least one of the first expandable metal feature and the second expandable from the conductive tubular. Element 27: wherein the power source is a downhole battery power supply. Element 28: wherein the power source is a downhole power generator. Element 29: wherein the power source is an uphole power source, and further including an electric line extending from the uphole power source to the downhole tool. Element 30: wherein the electric line is a tubing encapsulate conductor (TEC). Element 31: wherein the downhole tool is a downhole tool is a packer. Element 32: wherein the downhole tool is a downhole anchor.
Those skilled in the art to which this application relates will appreciate that other and further additions, deletions, substitutions and modifications may be made to the described embodiments.
This application claims the benefit of U.S. Provisional Application Ser. No. 62/962,901, filed on Jan. 17, 2020, entitled “VOLTAGE TO ACCELERATE EXPANDABLE METAL,” commonly assigned with this application and incorporated herein by reference in its entirety.
| Number | Name | Date | Kind | 
|---|---|---|---|
| 1525740 | Howard | Feb 1925 | A | 
| 2075912 | Roye | Apr 1937 | A | 
| 2590931 | Cabaniss | Apr 1952 | A | 
| 2743781 | Lane | May 1956 | A | 
| 2865454 | Richards | Dec 1958 | A | 
| 3206536 | Goodloe | Sep 1965 | A | 
| 3371716 | Current | Mar 1968 | A | 
| 3616354 | Russell | Oct 1971 | A | 
| 3706125 | Hopkins | Dec 1972 | A | 
| 4270608 | Hendrickson | Jun 1981 | A | 
| 4424859 | Sims | Jan 1984 | A | 
| 4424861 | Carter | Jan 1984 | A | 
| 4442908 | Steenbock | Apr 1984 | A | 
| 4446932 | Hipp | May 1984 | A | 
| 4457379 | McStravick | Jul 1984 | A | 
| 4527815 | Frick | Jul 1985 | A | 
| 4977636 | King | Dec 1990 | A | 
| 4979585 | Chesnutt | Dec 1990 | A | 
| 5139274 | Oseman | Aug 1992 | A | 
| 5220959 | Vance | Jun 1993 | A | 
| 5424139 | Shuler | Jun 1995 | A | 
| 5492173 | Kilgore | Feb 1996 | A | 
| 5517981 | Taub et al. | May 1996 | A | 
| 5662341 | Ezell et al. | Sep 1997 | A | 
| 5667015 | Harestad | Sep 1997 | A | 
| 5803173 | Fraser et al. | Sep 1998 | A | 
| 6089320 | LaGrange | Jul 2000 | A | 
| 6106024 | Herman et al. | Aug 2000 | A | 
| 6840325 | Stephenson | Jan 2005 | B2 | 
| 6907930 | Cavender | Jun 2005 | B2 | 
| 6942039 | Tinker | Sep 2005 | B2 | 
| 7104322 | Whanger et al. | Sep 2006 | B2 | 
| 7152687 | Gano | Dec 2006 | B2 | 
| 7322408 | Howlett | Jan 2008 | B2 | 
| 7347274 | Patel | Mar 2008 | B2 | 
| 7350590 | Hosie et al. | Apr 2008 | B2 | 
| 7402277 | Ayer | Jul 2008 | B2 | 
| 7578043 | Simpson et al. | Aug 2009 | B2 | 
| 7673688 | Jones | Mar 2010 | B1 | 
| 7677303 | Coronado | Mar 2010 | B2 | 
| 7696275 | Slay et al. | Apr 2010 | B2 | 
| 7963321 | Kutac | Jun 2011 | B2 | 
| 7996945 | Nosker | Aug 2011 | B2 | 
| 8042841 | Viegener | Oct 2011 | B2 | 
| 8109339 | Xu | Feb 2012 | B2 | 
| 8225861 | Foster et al. | Jul 2012 | B2 | 
| 8266751 | He | Sep 2012 | B2 | 
| 8430176 | Xu | Apr 2013 | B2 | 
| 8453736 | Constantine | Jun 2013 | B2 | 
| 8459367 | Nutley et al. | Jun 2013 | B2 | 
| 8469084 | Clark et al. | Jun 2013 | B2 | 
| 8490707 | Robisson | Jul 2013 | B2 | 
| 8579024 | Mailand et al. | Nov 2013 | B2 | 
| 8684096 | Harris | Apr 2014 | B2 | 
| 8794330 | Stout | Aug 2014 | B2 | 
| 8807209 | King | Aug 2014 | B2 | 
| 8875800 | Wood et al. | Nov 2014 | B2 | 
| 8894070 | Bhat et al. | Nov 2014 | B2 | 
| 8993491 | James | Mar 2015 | B2 | 
| 9004173 | Richard | Apr 2015 | B2 | 
| 9217311 | Slup | Dec 2015 | B2 | 
| 9249904 | Duquette | Feb 2016 | B2 | 
| 9279295 | Williamson et al. | Mar 2016 | B2 | 
| 9347272 | Hewson et al. | May 2016 | B2 | 
| 9353606 | Bruce et al. | May 2016 | B2 | 
| 9393601 | Ranck | Jul 2016 | B2 | 
| 9404030 | Mazyar | Aug 2016 | B2 | 
| 9534460 | Watson et al. | Jan 2017 | B2 | 
| 9611715 | Smith | Apr 2017 | B1 | 
| 9644459 | Themig | May 2017 | B2 | 
| 9708880 | Solhaug | Jul 2017 | B2 | 
| 9725979 | Mazyar et al. | Aug 2017 | B2 | 
| 9732578 | McRobb | Aug 2017 | B2 | 
| 9745451 | Zhao et al. | Aug 2017 | B2 | 
| 9765595 | Themig et al. | Sep 2017 | B2 | 
| 9771510 | James et al. | Sep 2017 | B2 | 
| 9945190 | Crowley | Apr 2018 | B2 | 
| 9976380 | Davis et al. | May 2018 | B2 | 
| 9976381 | Martin et al. | May 2018 | B2 | 
| 10030467 | Al-Gouhi | Jul 2018 | B2 | 
| 10060225 | Wolf | Aug 2018 | B2 | 
| 10119011 | Zhao et al. | Nov 2018 | B2 | 
| 10179873 | Meng | Jan 2019 | B1 | 
| 10316601 | Walton et al. | Jun 2019 | B2 | 
| 10337298 | Braddick | Jul 2019 | B2 | 
| 10344570 | Steele | Jul 2019 | B2 | 
| 10352109 | Sanchez | Jul 2019 | B2 | 
| 10364636 | Davis | Jul 2019 | B2 | 
| 10472933 | Steele | Nov 2019 | B2 | 
| 10533392 | Walton et al. | Jan 2020 | B2 | 
| 10718183 | Bruce et al. | Jul 2020 | B2 | 
| 10758974 | Sherman | Sep 2020 | B2 | 
| 10794152 | Lang et al. | Oct 2020 | B2 | 
| 10961804 | Fripp | Mar 2021 | B1 | 
| 11359448 | Fripp | Jun 2022 | B2 | 
| 11365611 | Gibb | Jun 2022 | B2 | 
| 11428066 | Andersen | Aug 2022 | B2 | 
| 11512552 | Fripp | Nov 2022 | B2 | 
| 20020088616 | Swor et al. | Jul 2002 | A1 | 
| 20030132001 | Wilson | Jul 2003 | A1 | 
| 20030164236 | Thornton | Sep 2003 | A1 | 
| 20030164237 | Butterfield, Jr. | Sep 2003 | A1 | 
| 20030205377 | Streater | Nov 2003 | A1 | 
| 20040194970 | Eatwell | Oct 2004 | A1 | 
| 20050051333 | Weber | Mar 2005 | A1 | 
| 20050061369 | De Almeida | Mar 2005 | A1 | 
| 20050072576 | Henriksen | Apr 2005 | A1 | 
| 20050093250 | Santi et al. | May 2005 | A1 | 
| 20050199401 | Patel et al. | Sep 2005 | A1 | 
| 20060144591 | Gonzalez | Jul 2006 | A1 | 
| 20060272806 | Wilkie et al. | Dec 2006 | A1 | 
| 20070089875 | Steele et al. | Apr 2007 | A1 | 
| 20070089910 | Hewson et al. | Apr 2007 | A1 | 
| 20070095532 | Head | May 2007 | A1 | 
| 20070137826 | Bosma et al. | Jun 2007 | A1 | 
| 20070144734 | Xu et al. | Jun 2007 | A1 | 
| 20070151724 | Ohmer et al. | Jul 2007 | A1 | 
| 20070163781 | Walker | Jul 2007 | A1 | 
| 20070221387 | Levy | Sep 2007 | A1 | 
| 20070246213 | Hailey | Oct 2007 | A1 | 
| 20070267824 | Baugh et al. | Nov 2007 | A1 | 
| 20070277979 | Todd et al. | Dec 2007 | A1 | 
| 20080047708 | Spencer | Feb 2008 | A1 | 
| 20080135249 | Fripp | Jun 2008 | A1 | 
| 20080149351 | Marya | Jun 2008 | A1 | 
| 20080290603 | Laflin | Nov 2008 | A1 | 
| 20090014173 | Macleod | Jan 2009 | A1 | 
| 20090084555 | Lee | Apr 2009 | A1 | 
| 20090102133 | Ruddock | Apr 2009 | A1 | 
| 20090159278 | Corre | Jun 2009 | A1 | 
| 20090200028 | Dewar | Aug 2009 | A1 | 
| 20090250227 | Brown et al. | Oct 2009 | A1 | 
| 20090250228 | Loretz | Oct 2009 | A1 | 
| 20090272546 | Nutley et al. | Nov 2009 | A1 | 
| 20090321087 | Victorov | Dec 2009 | A1 | 
| 20100072711 | Doane | Mar 2010 | A1 | 
| 20100078173 | Buytaert et al. | Apr 2010 | A1 | 
| 20100096143 | Angman | Apr 2010 | A1 | 
| 20100108148 | Chen | May 2010 | A1 | 
| 20100122819 | Wildman | May 2010 | A1 | 
| 20100139930 | Patel | Jun 2010 | A1 | 
| 20100155083 | Lynde et al. | Jun 2010 | A1 | 
| 20100181080 | Levy | Jul 2010 | A1 | 
| 20100225107 | Tverlid | Sep 2010 | A1 | 
| 20100257913 | Storm, Jr. et al. | Oct 2010 | A1 | 
| 20100307737 | Mellemstrand | Dec 2010 | A1 | 
| 20110061876 | Johnson et al. | Mar 2011 | A1 | 
| 20110098202 | James | Apr 2011 | A1 | 
| 20110147014 | Chen et al. | Jun 2011 | A1 | 
| 20120018143 | Lembcke | Jan 2012 | A1 | 
| 20120048531 | Marzouk | Mar 2012 | A1 | 
| 20120048561 | Holderman | Mar 2012 | A1 | 
| 20120048623 | Lafuente et al. | Mar 2012 | A1 | 
| 20120049462 | Pitman | Mar 2012 | A1 | 
| 20120168147 | Bowersock | Jul 2012 | A1 | 
| 20120175134 | Robisson | Jul 2012 | A1 | 
| 20120273236 | Gandikota et al. | Nov 2012 | A1 | 
| 20130048289 | Mazyar et al. | Feb 2013 | A1 | 
| 20130056207 | Wood et al. | Mar 2013 | A1 | 
| 20130056209 | Mazyar et al. | Mar 2013 | A1 | 
| 20130081815 | Mazyar et al. | Apr 2013 | A1 | 
| 20130152824 | Crews | Jun 2013 | A1 | 
| 20130153236 | Bishop | Jun 2013 | A1 | 
| 20130161006 | Robisson et al. | Jun 2013 | A1 | 
| 20130186615 | Hallunbaek et al. | Jul 2013 | A1 | 
| 20130192853 | Themig | Aug 2013 | A1 | 
| 20130292117 | Robisson | Nov 2013 | A1 | 
| 20140026335 | Smith | Jan 2014 | A1 | 
| 20140034308 | Holderman | Feb 2014 | A1 | 
| 20140051612 | Mazyar | Feb 2014 | A1 | 
| 20140262352 | Lembcke | Sep 2014 | A1 | 
| 20150021049 | Davis et al. | Jan 2015 | A1 | 
| 20150075768 | Wright et al. | Mar 2015 | A1 | 
| 20150101813 | Zhao | Apr 2015 | A1 | 
| 20150113913 | Kim | Apr 2015 | A1 | 
| 20150184486 | Epstein | Jul 2015 | A1 | 
| 20150233190 | Wolf et al. | Aug 2015 | A1 | 
| 20150275587 | Wolf et al. | Oct 2015 | A1 | 
| 20150337615 | Epstein et al. | Nov 2015 | A1 | 
| 20150345248 | Carragher | Dec 2015 | A1 | 
| 20150368990 | Jewett | Dec 2015 | A1 | 
| 20150369003 | Hajjari et al. | Dec 2015 | A1 | 
| 20160024896 | Johnson et al. | Jan 2016 | A1 | 
| 20160024902 | Richter | Jan 2016 | A1 | 
| 20160137912 | Sherman et al. | May 2016 | A1 | 
| 20160138359 | Zhao | May 2016 | A1 | 
| 20160138559 | Bauer | May 2016 | A1 | 
| 20160145488 | Aines et al. | May 2016 | A1 | 
| 20160145968 | Marya | May 2016 | A1 | 
| 20160177668 | Watson et al. | Jun 2016 | A1 | 
| 20160194936 | Allen | Jul 2016 | A1 | 
| 20160208569 | Anderson et al. | Jul 2016 | A1 | 
| 20160230495 | Mazyar et al. | Aug 2016 | A1 | 
| 20160273312 | Steele et al. | Sep 2016 | A1 | 
| 20160319633 | Cooper et al. | Nov 2016 | A1 | 
| 20160326830 | Hallundbaek | Nov 2016 | A1 | 
| 20160326849 | Bruce | Nov 2016 | A1 | 
| 20160333187 | Bauer et al. | Nov 2016 | A1 | 
| 20170015824 | Gozalo | Jan 2017 | A1 | 
| 20170022778 | Fripp et al. | Jan 2017 | A1 | 
| 20170107419 | Roy et al. | Apr 2017 | A1 | 
| 20170107794 | Steele | Apr 2017 | A1 | 
| 20170113275 | Roy et al. | Apr 2017 | A1 | 
| 20170159401 | Saltel et al. | Jun 2017 | A1 | 
| 20170175487 | Marcin et al. | Jun 2017 | A1 | 
| 20170175488 | Lisowski | Jun 2017 | A1 | 
| 20170191342 | Turley | Jul 2017 | A1 | 
| 20170198191 | Potapenko | Jul 2017 | A1 | 
| 20170234103 | Frazier | Aug 2017 | A1 | 
| 20170306714 | Haugland | Oct 2017 | A1 | 
| 20170314372 | Tolman | Nov 2017 | A1 | 
| 20170350237 | Giem et al. | Dec 2017 | A1 | 
| 20170356266 | Arackakudiyil | Dec 2017 | A1 | 
| 20180023362 | Makowiecki et al. | Jan 2018 | A1 | 
| 20180023366 | Deng et al. | Jan 2018 | A1 | 
| 20180038193 | Walton | Feb 2018 | A1 | 
| 20180078998 | Sherman | Mar 2018 | A1 | 
| 20180080304 | Cortez et al. | Mar 2018 | A1 | 
| 20180081468 | Bruce et al. | Mar 2018 | A1 | 
| 20180086894 | Roy | Mar 2018 | A1 | 
| 20180087350 | Sherman | Mar 2018 | A1 | 
| 20180094508 | Smith et al. | Apr 2018 | A1 | 
| 20180100367 | Perez | Apr 2018 | A1 | 
| 20180128072 | Larsen | May 2018 | A1 | 
| 20180128082 | Hollan et al. | May 2018 | A1 | 
| 20180209234 | Manera | Jul 2018 | A1 | 
| 20180223624 | Fripp | Aug 2018 | A1 | 
| 20180298708 | Schmidt et al. | Oct 2018 | A1 | 
| 20180334882 | Brandsdal | Nov 2018 | A1 | 
| 20180347288 | Fripp | Dec 2018 | A1 | 
| 20180363409 | Frazier | Dec 2018 | A1 | 
| 20190016951 | Sherman et al. | Jan 2019 | A1 | 
| 20190032435 | Kochanek et al. | Jan 2019 | A1 | 
| 20190039126 | Sherman | Feb 2019 | A1 | 
| 20190078414 | Frazier | Mar 2019 | A1 | 
| 20190128092 | Mueller et al. | May 2019 | A1 | 
| 20190136666 | Kent | May 2019 | A1 | 
| 20190178054 | Bruce | Jun 2019 | A1 | 
| 20190186228 | Beckett et al. | Jun 2019 | A1 | 
| 20190225861 | Reddy | Jul 2019 | A1 | 
| 20190249510 | Deng et al. | Aug 2019 | A1 | 
| 20190316025 | Sherman | Oct 2019 | A1 | 
| 20190383115 | Lees | Dec 2019 | A1 | 
| 20200032574 | Fripp et al. | Jan 2020 | A1 | 
| 20200056435 | Sherman | Feb 2020 | A1 | 
| 20200072019 | Onti et al. | Mar 2020 | A1 | 
| 20200080401 | Sherman | Mar 2020 | A1 | 
| 20200080402 | Lang et al. | Mar 2020 | A1 | 
| 20200240235 | Fripp et al. | Jul 2020 | A1 | 
| 20200308945 | Surjaatmadja et al. | Oct 2020 | A1 | 
| 20200325749 | Fripp et al. | Oct 2020 | A1 | 
| 20200362224 | Wellhoefer | Nov 2020 | A1 | 
| 20200370391 | Fripp et al. | Nov 2020 | A1 | 
| 20210017835 | Pelto et al. | Jan 2021 | A1 | 
| 20210040810 | Evers | Feb 2021 | A1 | 
| 20210123310 | Fripp et al. | Apr 2021 | A1 | 
| 20210123319 | Greci | Apr 2021 | A1 | 
| 20210172286 | Barlow | Jun 2021 | A1 | 
| 20210187604 | Sherman et al. | Jun 2021 | A1 | 
| 20210270093 | Fripp | Sep 2021 | A1 | 
| 20210270103 | Greci et al. | Sep 2021 | A1 | 
| 20210332673 | Fripp | Oct 2021 | A1 | 
| 20210363849 | Al Yahya | Nov 2021 | A1 | 
| 20220106847 | Dahl | Apr 2022 | A1 | 
| 20220186575 | Fripp | Jun 2022 | A1 | 
| 20220205336 | Asthana | Jun 2022 | A1 | 
| 20220372837 | Holderman et al. | Nov 2022 | A1 | 
| Number | Date | Country | 
|---|---|---|
| 2820742 | Sep 2013 | CA | 
| 203308412 | Nov 2013 | CN | 
| 205422632 | Aug 2016 | CN | 
| 107148444 | Sep 2017 | CN | 
| 108194756 | Jun 2018 | CN | 
| 107148444 | Jan 2019 | CN | 
| 108194756 | Aug 2020 | CN | 
| 15726 | Sep 1980 | EP | 
| 869257 | Oct 1998 | EP | 
| 940558 | Sep 1999 | EP | 
| 0940558 | Jan 2005 | EP | 
| 1757770 | Feb 2007 | EP | 
| 1910728 | Apr 2008 | EP | 
| 1910728 | Sep 2009 | EP | 
| 2447466 | May 2012 | EP | 
| 2501890 | Sep 2012 | EP | 
| 2501890 | Jul 2014 | EP | 
| 2447466 | Mar 2017 | EP | 
| 3144018 | Mar 2017 | EP | 
| 3144018 | May 2017 | EP | 
| 3196402 | Jul 2017 | EP | 
| 3144018 | Sep 2018 | EP | 
| 2447466 | Oct 2018 | EP | 
| 2444060 | May 2008 | GB | 
| 2444060 | Dec 2008 | GB | 
| 2003090037 | Mar 2003 | JP | 
| 2003293354 | Oct 2003 | JP | 
| 2004169303 | Jun 2004 | JP | 
| 2015175449 | Oct 2015 | JP | 
| 20020014619 | Feb 2002 | KR | 
| 20080096576 | Oct 2008 | KR | 
| 0202900 | Jan 2002 | WO | 
| 0202900 | May 2002 | WO | 
| 0202900 | Dec 2003 | WO | 
| 2005022012 | Mar 2005 | WO | 
| 2006045794 | May 2006 | WO | 
| 2007047089 | Apr 2007 | WO | 
| 2012094322 | Jul 2012 | WO | 
| 2012125660 | Sep 2012 | WO | 
| 2012094322 | Oct 2012 | WO | 
| 2012125660 | Feb 2013 | WO | 
| 2014028149 | Feb 2014 | WO | 
| 2014182301 | Nov 2014 | WO | 
| 2014193042 | Dec 2014 | WO | 
| 2015057338 | Apr 2015 | WO | 
| 2015069886 | May 2015 | WO | 
| 2015099909 | Jul 2015 | WO | 
| 2015069886 | Sep 2015 | WO | 
| 2015183277 | Dec 2015 | WO | 
| 2016000068 | Jan 2016 | WO | 
| 2016171666 | Oct 2016 | WO | 
| 2017100417 | Jun 2017 | WO | 
| 2018055382 | Mar 2018 | WO | 
| 2018085102 | May 2018 | WO | 
| 2019094044 | May 2019 | WO | 
| 2019122857 | Jun 2019 | WO | 
| 2019147285 | Aug 2019 | WO | 
| 2019151870 | Aug 2019 | WO | 
| 2019164499 | Aug 2019 | WO | 
| 2020005252 | Jan 2020 | WO | 
| 2020141203 | Jul 2020 | WO | 
| 2019164499 | Aug 2020 | WO | 
| 2020167288 | Aug 2020 | WO | 
| 2020204940 | Oct 2020 | WO | 
| 2021034325 | Feb 2021 | WO | 
| 2021086317 | May 2021 | WO | 
| 2021096519 | May 2021 | WO | 
| 2021126279 | Jun 2021 | WO | 
| Entry | 
|---|
| Fripp, Michael, and Zachary Walton. “Degradable Metal for Use in a Fully Dissolvable Frac Plug.” Paper presented at the Offshore Technology Conference, Houston, Texas, USA, May 2016. doi: https://doi.org/10.4043/27187-MS (Year: 2016). | 
| Merchant B. Gold, the noble metal and the paradoxes of its toxicology. Biologicals. Mar. 1998;26(1):49-59. doi: 10.1006/biol.1997.0123. PMID: 9637749. (Year: 1998). | 
| Fripp, et al. “Novel Expanding Metal Alloy for Non-Elastomeric Sealing and Anchoring.” Paper presented at the SPE Annual Technical Conference and Exhibition, Houston, Texas, USA, Oct. 2022. doi: https://doi.org/10.2118/210273-MS (Year: 2022). | 
| Number | Date | Country | |
|---|---|---|---|
| 20210222510 A1 | Jul 2021 | US | 
| Number | Date | Country | |
|---|---|---|---|
| 62962901 | Jan 2020 | US |