Patent Publication Number: US-11661812-B2

Title: Fluid barriers for dissolvable plugs

Description:
BACKGROUND 
     In horizontal or deviated wells, drag forces may hinder casing from reaching total depth (TD) by exceeding a hook load or a casing buckling capacity. In order to reduce the drag forces, the casing in a horizontal or deviated section may be filled with air or a lightweight fluid for buoyancy. After the casing reaches TD, a rupture disc is burst, and the air or lightweight fluid chamber is filled with fluid. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       These drawings illustrate certain aspects of some of the embodiments of the present disclosure and should not be used to limit or define the disclosure. 
         FIGS.  1 A and  1 B  illustrate an exemplary process that procures a fluid barrier on opposing ends of a dissolvable salt plug, in accordance with examples of the present disclosure; 
         FIG.  2    illustrates additional fluid barriers placed on opposing ends of the dissolvable salt plug, in accordance with examples of the present disclosure; 
         FIG.  3    illustrates a system implementing the dissolvable salt plug, in accordance with examples of the present disclosure; 
         FIG.  4    illustrates a flow chart for forming fluid barriers on opposing ends of the dissolvable salt plug, in accordance with examples of the present disclosure; and 
         FIG.  5    illustrates a flow chart for separating fluids in a subterranean formation with a dissolvable salt plug, in accordance with examples of the present disclosure. 
     
    
    
     DETAILED DESCRIPTION 
     The present disclosure relates to dissolvable salt plugs that may be utilized to separate fluids within a wellbore. Specifically, systems, methods, and apparatuses of the present disclosure may utilize dissolvable salt plugs that include a film deposited from an emulsion of rubber in water. The film may provide a layer that provides a fluid barrier that is impenetrable by downhole fluids. The film may prevent dissolution of the dissolvable salt plug, as the dissolvable salt plug is run in hole (“RIH”) or disposed in the wellbore. 
     In certain examples, the dissolvable salt plugs may be utilized with a buoyancy assisted casing tool. The dissolvable salt plug may provide a barrier between a fluid disposed up-hole to the dissolvable salt plug and a lightweight fluid contained in a buoyancy chamber, of the buoyancy assisted casing tool, that is disposed downhole from the dissolvable salt plug. The buoyancy assisted casing tool may be attached to the casing string at a surface of a wellbore before the buoyancy assisted casing tool is moved downhole within a subterranean formation. The fluid disposed up-hole to the dissolvable salt plug may include various fluids utilized for downhole operations in the oilfield. Non-limiting examples of the various fluids include drilling fluids, cement compositions, fresh water, brine, chemical additives, or combinations thereof. The drilling fluids may include oil-based muds or water-based muds, for example. 
     The lightweight fluid contained within the buoyancy chamber downhole to or below the dissolvable salt plug may have a density that is less than the fluid disposed up-hole to the dissolvable salt plug. Non-limiting examples of the lightweight fluid may include nitrogen, carbon dioxide, air, or combinations thereof. 
     The dissolvable salt plug contains or seals the lightweight fluid within the buoyancy chamber created by the buoyancy assisted casing tool until TD or a desired depth. At TD, a rupture disc of the buoyancy assisted casing tool may be burst, thereby allowing the dissolvable salt plug to dissolve. Removal of the salt plug releases the lightweight fluid from the buoyancy chamber and allows the buoyancy chamber to fill with the fluid that is disposed up-hole to the dissolvable salt plug. Filling of the buoyancy chamber enables the casing to be prepared for cementing operations. 
     The films of the present disclosure may replace polyisoprene elastomer diaphragms that may protect (e.g., encompass) a downhole plug as the downhole plug is moved into a wellbore. The polyisoprene elastomer diaphragms may prevent premature dissolution of the dissolvable salt plug. However, the polyisoprene elastomer diaphragms may travel to a float collar or float shoe during RIH and may become trapped in a poppet valve thereof which may hinder fluid flow through the poppet valve (e.g., prevents closure of the valve). 
     By replacing the polyisoprene elastomer diaphragms with films deposited from an emulsion of rubber in water, the amount of elastomer in the buoyancy assisted casing tool is substantially reduced, as well as risk to the float equipment. Upon contact of the emulsion with the salt surface of the dissolvable salt plug, the rubber instantaneously precipitates on the salt surface. As a solvent of the emulsion evaporates, a film is formed or produced on the contacted salt surface. 
     The film provides a fluid barrier that is impenetrable by downhole fluids. A thickness of the film may be substantially thinner than the elastomeric diaphragms resulting in less residual polymer debris downhole. A thinner coating of the film produces less debris and reduces the risk of interference with the float equipment operation. Upon dissolution of the salt of the dissolvable salt plug, the film disintegrates. In certain examples, the film be applied by brushing, pouring, or spraying the emulsion onto opposing ends of the dissolvable salt plug. Film thickness may be controlled by applying subsequent layers. The film may be applied to one, both or multiple surfaces that may contact fluids. In some examples, an additional fluid barrier may be fastened to the film by a press-fit, for example. 
       FIGS.  1 A and  1 B  illustrate an exemplary process that procures a film on opposing ends of a dissolvable salt plug  100  in accordance with examples of the present disclosure. Lateral cross-sectional views of the dissolvable salt plug  100  are illustrated in  FIGS.  1 A and  1 B , for example. 
     The dissolvable salt plug  100  may be a solid structure or matrix that may include sand and salt, for example. Types of salt included in the dissolvable salt plug  100  may include alkali metal halides and/or alkaline earth metal halides. Specific examples may include, but are not limited to, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, or combinations thereof. The dissolvable salt plug  100  may be made from the salt, water, and sand that are mixed and cured at high temperatures and pressures to form a solid unitary and rigid structure or matrix that may withstand pressures ranging from 9,000 pounds per square inch (“psi”) (62,053 kilopascals (“kPa”) to 10,000 psi (68,948 kPa). 
     As shown on  FIG.  1 A , the diameter of the dissolvable salt plug  100  may vary along a length, L, of the dissolvable salt plug  100 . In certain examples, the dissolvable salt plug  100  may include a circumferential tapered section  101  including sections S 1  and S 2 , each of which extends around or about a circumference and along a length, L, of the dissolvable salt plug  100 . The dissolvable salt plug  100  may include a first circumference or diameter, D 1 , at a first end or up-hole portion  102  (oriented in an up-hole direction), and a second circumference or diameter, D 2 , at a second opposing end or downhole portion  104  (oriented in a downhole direction). D 1  may be equal to D 2 . The diameter of the dissolvable salt plug  100  may decrease from D 1  to the smallest diameter, D s , and increase from D s  to D 2 , along L of the dissolvable salt plug  100 , as shown. S 1  may extend from D 1  to D s . S 2  may extend from D s  to D 2 . 
     The diameters of the dissolvable salt plug  100  may correspond with various casing diameters. The diameters may range from about 3 inches (8 cm) to about 9 inches (23 centimeters (cm). For example, the diameters may include 3.5 inches (9 cm), 4.5 inches (11 cm), 5.5 inches (14 cm), or 7 inches (18 cm). Lengths for the dissolvable salt plug  100  may range from about 4 inches (10 cm) to about 8 inches (20 cm), for example. 
     At least a portion of the dissolvable salt plug  100  may contact an emulsion  106 . For example, the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100  may be treated with the emulsion  106 . The up-hole portion  102  may be positioned opposite to the downhole portion  104 . The up-hole portion  102  may be similar to the downhole portion  104 . As shown on a close-up view  108  of a portion  109  of the emulsion  106 , the emulsion  106  may be an emulsion of rubber in water. For example, the emulsion  106  may include polymer particles  110  which may be present in a latex solution  112 . Upon contact of the emulsion  106  with the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100 , the rubber (e.g., the polymer particles  110 ) instantaneously precipitates on and adheres to the up-hole portion  102  and the downhole portion  104 . 
     As shown on  FIG.  1 B , the latex solution  112  (e.g., a solvent) may evaporate thereby leaving films  114   a  and  114   b  on the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100 . The films  114   a  and  114   b  may be polymer films made of the polymer particles  110 . The film  114   a  may be similar to the film  114   b . Specific examples of suitable polymer films may include, but are not limited to, styrene-butadiene copolymer, acrylonitrile-butadiene styrene copolymer, isobutylene, polyisoprene, polyvinyl alcohol, polyacrylate, or combinations thereof. The polymers by be crosslinked or not crosslinked. 
     As illustrated in a close-up view  116  of a portion  111  of the film  114   a , the film  114   a  may include interconnected layers  113  of the polymer particles  110 , in some examples. That is, a layer  113  (e.g., 2-10 layers) may be added as needed. The films  114   a  and  114   b  may each have a thickness of 0.1 millimeter (“mm”) through 2 mm, in certain examples. In other examples, the films  114   a  and  114   b  may each have a thickness of 0.5 mm to 10 mm or 0.1 mm to 2 mm. The films  114   a  and  114   b  may attach or adhere to and completely cover the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100 , respectively. The films  114   a  and  114   b  may provide impenetrable seals (e.g., fluid barriers) that prevent fluid (e.g., a drilling fluid, water) from penetrating the dissolvable salt plug  100  from the up-hole portion  102  (e.g., fluid penetration from an up-hole direction) and the downhole portion  104  (e.g., fluid penetration from a downhole direction) of the salt plug  100 . In some examples, the dissolvable salt plug  100  may only be dissolvable upon contacting the circumferential tapered section  101  with fresh water (e.g., water with less than 500 parts per million (“ppm”) of dissolved salts). That is, the circumferential tapered section  101  may be a section of the salt plug  100  that receives the fresh water for dissolution of the dissolvable salt plug  100 . As the salt plug  100  is dissolved, the films  114   a  and  114   b  disintegrate. In certain examples, an additional fluid barrier may be placed over each of the films  114   a  and/or  114   b  to assist with sealing and to distribute any fluid pressure received over the films  114   a  and/or  114   b  to prevent any damage to the films  114   a  and/or  114   b.    
       FIG.  2    illustrates additional barriers  200   a  and  200   b  attached to the film  114   a  and the film  114   b  of the dissolvable salt plug  100 , in accordance with examples of the present disclosure. Each of the barriers  200   a  and  200   b  may include a rubber (e.g., a polymer) that is placed over and adjacent to the films  114   a  and  114   b  to assist with sealing the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100 . The barriers  200   a  and  200   b  may be fluid barriers with a thickness less than 1 mm, for example. The barriers  200   a  and  200   b  may be press-fitted onto the up-hole portion  102  and the downhole portion  104 . The barriers  200   a  and  200   b  may completely cover the films  114   a  and  114   b . As noted above, the barriers  200   a  and  200   b  may be placed over the films  114   a  and  114   b  to assist with sealing the dissolvable salt plug  100  from fluid present in the up-hole and downhole directions of a wellbore (e.g., the wellbore  302  shown on  FIG.  3   ). 
     The barriers  200   a  and  200   b  may also distribute any fluid pressure received or exerted over the films  114   a  and  114   b  to prevent any damage to the films  114   a  and  114   b . For example, the dissolvable salt plug  100  may be pressurized by a column of fluid within a wellbore during RIH. Further, the dissolvable salt plug  100  may be displacing a fluid (e.g., a drilling fluid) in the wellbore which may also exert fluid pressure against the film  114   b . After dissolution of the dissolvable salt plug  100 , the barriers  200   a  and  200   b  may collapse and be circulated out of the wellbore. 
     In some examples, the dissolvable salt plug  100  may be disposed within a seat  202  of a downhole tool. A shape or profile of the seat  202  may correspond to a shape or profile of the dissolvable salt plug  100  (including the circumferential tapered section  101 ) to ensure a snug fit between the seat  202  and the dissolvable salt plug  100 . 
       FIG.  3    illustrates a system  300  comprising the dissolvable salt plug  100  in accordance with examples of the present disclosure. In some examples, the system  300  may be located at a well site. A wellbore  302  (e.g., a wellbore drilled for hydrocarbon recovery) may extend from a surface  306  into a subterranean formation  308 . The wellbore  302  may include a horizontal or deviated section  304 . The section  304  may be angled or may deviate more than 10° from a vertical section  305  of the wellbore  302 . Although illustrated onshore, the wellbore  302  may be located offshore in certain examples. The wellbore  302  may be fluidly coupled to surface equipment such as a pump  310  and fluid storage  312  via conduits  314  and  316 , for example. The fluid storage  312  (e.g., a container or pit) may store various fluids such as fresh water, brine, cement compositions, drilling fluids, or chemical additives, that may be pumped downhole, for example. Although not illustrated, the system  300  may also include other equipment utilized at a well site to at least assemble, disassemble, or move various components and/or materials into and out of the wellbore  302 , as should be understood by one of skill in the art, with the benefit of this disclosure. 
     Casing string  318  may be disposed within the wellbore  302 . An annulus  319  may be defined between the casing string  318  and the wellbore  302 . A tool  320  (e.g., a downhole tubular connected via threads to the casing string  318 ) may be a section of the casing string  318 . The tool  320  may be a buoyancy assisted casing tool. At the surface  306 , the casing string may be made up with the tool  320  before the casing string  318  is moved into the wellbore  302 . The tool  320  may be exposed to the wellbore  302  (i.e., the casing  318  does not cover the tool  320 ). 
     The tool  320  may create a buoyancy chamber  322  which may be sealed between the dissolvable salt plug  100  and a float shoe or float collar  325 , for example. The dissolvable salt plug  100  may be positioned within the seat  202  of the tool  320 . The buoyancy chamber  322  may be filled with a fluid  323 . The fluid  323  may include a gas such as nitrogen, carbon dioxide, or air, for example. The buoyancy chamber  322  may be disposed down-hole from the salt plug  100  and may be filled with fluid that has a lower specific gravity than fluid in the wellbore  302  in which the tool  320  and the casing string  318  is run. Buoyancy of the buoyancy chamber  322  may be adjusted via selection of a specific fluid or an amount of that specific fluid contained within the buoyancy chamber  322 , for example. 
     The films  114   a  and  114   b  of the dissolvable salt plug  100  provide fluid barriers to separate the fluid  323  of the tool  320  from a fluid  326  disposed up-hole to the dissolvable salt plug  100 . The film  114   a  may contact the fluid  326  and the film  114   b  may contact the fluid  323 . The fluid  326  may have a density or specific gravity that is greater than a density or specific gravity of the fluid  323 . The fluid  326  may include various fluids, such as fresh water, brine, cement compositions, drilling fluids, or chemical additives, that may be pumped downhole, for example. 
     The tool  320  may also include a rupture disc  324  positioned adjacent or in close proximity to the dissolvable salt plug  100 . The rupture disc  324  may be made of metal and may be in fluid communication with the fluid  326 . The rupture disc  324  may have a rupture pressure greater than the hydraulic pressure encountered by the casing string  318  as the casing string  318  is RIH (e.g., run into the wellbore  302 ), in order to prevent premature bursting of the rupture disc  324 . The rupture disc  324  may withstand pressures ranging from 5,000 psi through 40,000 psi, for example. 
     As noted above, the casing string  318  may be made up at the surface  306  to include the tool  320 . That is, the tool  320  is in an interconnected (connecting end to end via threads) series of individual tubulars of the casing string  318 . After connecting the tool  320  to the casing string  318 , the casing string  318  and the tool  320  are run into the wellbore  302  until friction drag on the casing string  318  caused by a wellbore fluid  327  and/or walls of the wellbore  302 , prevents the casing string  318  from moving any further downhole within the wellbore  302  or until the desired depth for the casing has been achieved. The wellbore fluid  327  may include fluid similar to that of the fluid  326 . After progressive movement of the casing string ceases, circulating equipment at the surface  306  such as the pump  312  may circulate the fluid  326  through the casing string  318  such that the rupture disc  324  bursts. Bursting of the rupture disc  324  may allow fresh water to contact the circumferential tapered section  101  thereby releasing the dissolvable salt plug  100 . Once the dissolvable salt plug  100  is removed, the fluid above or up-hole to the dissolvable salt plug  100  is released to displace the lightweight fluid or gas from below or downhole to the dissolvable salt plug  100 . The lightweight material can either percolate within the casing string  318  to the surface  306  or be circulated outside the casing string  318  into the annulus  319  to be displaced to the surface  306 . 
       FIG.  4    illustrates a flow chart  400  for treating a salt plug with an emulsion to form an impenetrable film or fluid barrier on opposing ends of the salt plug in accordance with examples of the present disclosure. At step  402 , opposing ends of a salt plug (e.g., the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100  shown on  FIGS.  1 A,  1 B, and  2   ) may be treated with an emulsion of rubber in water (e.g., the emulsion  106 ). The emulsion  106  may be applied, as at least one layer, to the up-hole portion  102  and the downhole portion  104  by brushing, pouring, or spraying the emulsion  106  onto a surface of the up-hole portion  102  and the downhole portion  104 . 
     At step  404 , upon contacting the emulsion  106  with a salt surface of the up-hole portion  102  and/or the downhole portion  104  of the dissolvable salt plug  100 , polymer particles (e.g., the polymer particles  110  shown on  FIGS.  1 A and  1 B ) of the emulsion  106  may precipitate onto the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100  to completely cover each end of the dissolvable salt plug  100 . 
     At step  406 , after precipitation of the polymer particles  110 , a solvent of the emulsion  106  (e.g., the latex solution  112  shown on  FIG.  1 A ) may evaporate (e.g., due to ambient conditions or a dryer/heater), thereby producing impenetrable seals or fluid barriers comprising films (e.g., the films  114   a  and  114   b  shown on  FIGS.  1 B and  2   ) on the up-hole portion  102  and the downhole portion  104  of the dissolvable salt plug  100 . Multiple layers (e.g., 2-10 layers) of the emulsion  106  may be applied to the films  114   a  and  114   b , as desired, to provide increasing layers of sealing protection (e.g., the layers  113  shown on  FIG.  1 B ). 
     At step  408 , an additional rubber barrier (e.g., the barriers  200   a  and  200   b ) may be positioned (e.g., press fitted) over the films  114   a  and  114   b  to protect the films. 
       FIG.  5    illustrates a flow chart  500  for separating fluids in the subterranean formation  308  with the dissolvable salt plug  100 , in accordance with examples of the present disclosure. At step  502 , a casing string (e.g., the casing string  318  shown on  FIG.  3   ) is run into a wellbore (e.g., the wellbore  302  shown on  FIG.  3   ) until friction drag on the casing string  318  caused by fluid (e.g., drilling fluid) and/or walls of the wellbore  302  prevents the casing string  318  from moving any further downhole within the wellbore  302  (i.e., the casing string  318  has landed (e.g., TD has been reached) within the wellbore  302 ). The casing string  318  may include the tool  320  comprising the buoyancy chamber  322  sealed with the dissolvable salt plug  100  (e.g., shown on  FIG.  3   ). 
     At step  504 , the dissolvable salt plug  100  separates an up-hole fluid such as the fluid  326  shown on  FIG.  3    from a lightweight fluid contained in the tool  320  such as the fluid  323  also shown on  FIG.  3   . The dissolvable salt plug  100  may include fluid barriers or the films  114   a  and  114   b  disposed on opposing ends, and thus may only dissolve upon the circumferential tapered portion  101  contacting fresh water, as best shown on  FIG.  2   . 
     To facilitate understanding of various aspects of the present disclosure, the following example is provided. 
     Example 
     To evaluate the effectiveness of the latex coating, a core with a 1-inch (2.54 cm) diameter and a length of approximately 2 inches (5.08 cm), was taken from a sand/salt plug. The core was placed in a Hassler sleeve. A 1 mm to 2 mm latex coating was applied to a top surface of the core. After drying the film, 150 psi (1034 kPa) of pressure was applied to the film with water. No penetration was observed over a time period of 1 week. The temperature of the test assembly was increased to 150° F. (65.6° C.), and again no leakage was observed after 24 hours. 
     Accordingly, the present disclosure may provide systems, methods, and apparatuses that may utilize dissolvable salt plugs with a film deposited from an emulsion of rubber in water. The systems, methods, and apparatus may include any of the various features disclosed herein, including one or more of the following statements. 
     Statement 1. A dissolvable plug comprising: a first end comprising a first fluid barrier, the first fluid barrier comprising a polymer film; and a second end opposite to the first end, the second end comprising a second fluid barrier, the second fluid barrier comprising a polymer film; wherein the dissolvable plug comprises a solid structure made of a sand and salt mixture. 
     Statement 2. The dissolvable plug of the statement 1, wherein a tapered section extends from the first end to the second end, wherein the tapered section does not comprise any fluid barrier. 
     Statement 3. The dissolvable plug of the statement 2, further comprising an additional fluid barrier disposed on each of the first and second fluid barrier. 
     Statement 4. The dissolvable plug of the statement 3, wherein the additional fluid barrier comprises a rubber. 
     Statement 5. The dissolvable plug of any of the preceding statements, wherein a sand of the sand and salt mixture comprises alkali metal halides or alkaline earth metal halides. 
     Statement 6. The dissolvable plug of any of the preceding statements, wherein the dissolvable plug comprises sodium chloride, potassium chloride, magnesium chloride, calcium chloride, or combinations thereof. 
     Statement 7. The dissolvable plug of any of the preceding statements, wherein a length of the dissolvable plug ranges from 4 inches to 8 inches. 
     Statement 8. A system for separating fluids in a wellbore, the system comprising: a dissolvable plug comprising: a first end comprising a first fluid barrier, the first fluid barrier comprising a polymer film; and a second end opposite to the first end, the second end comprising a second fluid barrier, the second fluid barrier comprising a polymer film; wherein the plug comprises a solid structure made of a sand and salt mixture; and casing extending in a direction that deviates at least 10° from a vertical direction, the dissolvable plug positioned in the casing. 
     Statement 9. The system of the statement 8, wherein a deviated section of the casing comprises a buoyancy assisted casing tool comprising a buoyancy chamber. 
     Statement 10. The system of the statement 9, wherein the dissolvable plug separates a first fluid from a second fluid, wherein the first fluid is up-hole from the dissolvable plug, wherein the second fluid is downhole from the dissolvable plug. 
     Statement 11. The system of the statement 10, wherein the first fluid is different from the second fluid. 
     Statement 12. The system of the statement 11, wherein the first fluid has a specific gravity that is greater than a specific gravity of the second fluid. 
     Statement 13. The system of the statement 12, wherein the second fluid is disposed in the buoyancy chamber. 
     Statement 14. The system of any of the statements 8-13, wherein the second fluid comprises nitrogen, carbon dioxide, or air. 
     Statement 15. A method for producing at least one fluid barrier on a salt plug, the method comprising: contacting a first end of the salt plug with an emulsion of rubber in water; evaporating a solvent of the emulsion; and forming at least one layer of polymer particles on the first end to protect the first end from fluid penetration. 
     Statement 16. The method of the statement 15, further comprising contacting a second end of the salt plug with the emulsion of rubber in water, the second end opposite from the first end; evaporating the solvent of the emulsion; and forming a second layer of polymer particles on the first end to protect the first end from fluid penetration. 
     Statement 17. The method of the statement 15 or the statement 16, wherein contacting the first and second ends of the salt plug comprises contacting the first and second ends of the salt plug with a latex solution comprising the polymer particles. 
     Statement 18. The method of any of the statements 15-17, wherein evaporating the solvent comprises evaporating a latex solution. 
     Statement 19. The method of any of the statements 15-18, further comprising disposing an additional fluid barrier on the at least one layer of polymer particles. 
     Statement 20. The method of any of the statements 15-19, further comprising disposing an additional fluid barrier on the second layer of polymer particles. 
     It should be understood that, although individual examples may be discussed herein, the present disclosure covers all combinations of the disclosed examples, including, without limitation, the different component combinations, method step combinations, and properties of the system. It should be understood that the compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods may also “consist essentially of” or “consist of” the various components and steps. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the elements that it introduces. The term “coupled” means directly or indirectly connected. 
     For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range are specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values even if not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited. 
     Therefore, the present examples are well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular examples disclosed above are illustrative only and may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Although individual examples are discussed, the disclosure covers all combinations of all of the examples. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. It is therefore evident that the particular illustrative examples disclosed above may be altered or modified and all such variations are considered within the scope and spirit of those examples. If there is any conflict in the usages of a word or term in this specification and one or more patent(s) or other documents that may be incorporated herein by reference, the definitions that are consistent with this specification should be adopted.