Patent Publication Number: US-9840887-B2

Title: Wear-resistant and self-lubricant bore receptacle packoff tool

Description:
BACKGROUND 
     There are many different downhole tools in the oil and gas industry which require that a seal be established in the annulus between a fluid transmission conduit or tubing string disposed in a well bore and the outer well casing. These tools may relate to the drilling and completion of the well, the production of the well, the servicing of the well, or the abandonment of the well. In addition to conventional packers, polished bore receptacle (PBR) packoffs have also been used to isolate the production-tubing conduit or setting tools from the annulus. Current PBR packoffs typically include a seal member formed from plastics and rubbers. However, plastics and rubbers are prone to wear caused by high temperature, high pressure, and corrosive environments such as found in the oil and gas industry. Accordingly, seals formed from plastics and rubbers may experience a limited service life or are restricted from certain service environments. Furthermore, the large friction between plastic or rubber seals and PBR bore requires large setting force, which can increase the operating costs as well as roll-over failures. Thus the industry would be receptive to new packoffs having improved wear-resistant and lubrication properties. 
     BRIEF DESCRIPTION 
     The above and other deficiencies in the prior art are overcome by, in an embodiment, a packoff element comprising a carbon composite; a wear-resistant member at least partially encapsulating the seal; and a guide member disposed on an end of the packoff element. 
     In another embodiment, a packoff assembly comprises: a tubing connectable mandrel; and at least one packoff element disposed on the mandrel; the packoff element comprising: an annular seal comprising a carbon composite and having an inner surface and an opposing outer surface; the inner surface being in contact with a surface of the mandrel; a wear-resistant member at least partially encapsulating the seal; an annular guide member disposed on the mandrel; and a retainer member disposed between the guide member and the mandrel for securing the guide member to a predetermined position on the mandrel. 
     A method of sealing comprises positioning at least one annular packoff element onto a mandrel; guiding the packoff element towards a wellbore casing; compressing the packoff element; and sealing an annular area between the mandrel and the wellbore casing. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike: 
         FIG. 1  illustrates the structure of a packoff assembly according to an embodiment of the disclosure; 
         FIG. 2  illustrates the structure of a packoff assembly according to another embodiment of the disclosure; 
         FIG. 3  illustrates the structure of a packoff assembly according to yet another embodiment of the disclosure; 
         FIG. 4  illustrates the run-in of a packoff assembly with a casing bore receptacle; 
         FIG. 5  is a cross-sectional view of an exemplary embodiment of a packoff element positioned on a mandrel; 
         FIG. 6  illustrates the wear-resistant layer of the packoff element; and 
         FIG. 7  shows the friction testing results of various materials. 
     
    
    
     DETAILED DESCRIPTION 
     The inventors hereof have found that carbon composites can be used to make polished bore receptacle packoffs. Compared with packoffs having a seal made from plastics or rubbers, packoffs containing carbon composites allow for reliable performance in much harsher high temperature high pressure and corrosive conditions. In addition, packoffs containing carbon composites dramatically reduce the setting force and minimize roll-over failures due to the self-lubrication properties of the carbon composites. A packoff element, for example, a polished bore receptacle packoff element of the disclosure comprises a carbon composite seal; a wear-resistant member at least partially encapsulating the seal; and a guide member disposed on an end of the packoff element. The utilization of wear-resistant member addresses the galling problem of conventional graphite materials, which further enables reliable performance of the packoffs. 
     The carbon composites in the seal comprise carbon and a binder. The carbon can be graphite. As used herein, graphite includes one or more of natural graphite; synthetic graphite; expandable graphite; or expanded graphite. Advantageously, the carbon composites comprise expanded graphite. Compared with other forms of the graphite, expanded graphite has high flexibility, high compression recovery, and larger anisotropy. The composites formed from expanded graphite and the binder can thus have excellent elasticity in addition to desirable mechanical strength. 
     In an embodiment, the carbon composites in the seal comprise carbon microstructures having interstitial spaces among the carbon microstructures; wherein the binder is disposed in at least some of the interstitial spaces. The interstitial spaces among the carbon microstructures have a size of about 0.1 to about 100 microns, specifically about 1 to about 20 microns. A binder can occupy about 10% to about 90% of the interstitial spaces among the carbon microstructures. 
     The carbon microstructures can also comprise voids within the carbon microstructures. The voids within the carbon microstructures are generally between about 20 nanometers to about 1 micron, specifically about 200 nanometers to about 1 micron. As used herein, the size of the voids or interstitial spaces refers to the largest dimension of the voids or interstitial spaces and can be determined by high resolution electron or atomic force microscope technology. In an embodiment, to achieve high elasticity for the seal, the voids within the carbon microstructures are not filled with the binder or a derivative thereof. 
     The carbon microstructures are microscopic structures of graphite formed after compressing graphite into highly condensed state. They comprise graphite basal planes stacked together along the compression direction. As used herein, carbon basal planes refer to substantially flat, parallel sheets or layers of carbon atoms, where each sheet or layer has a single atom thickness. The graphite basal planes are also referred to as carbon layers. The carbon microstructures are generally flat and thin. They can have different shapes and can also be referred to as micro-flakes, micro-discs and the like. In an embodiment, the carbon microstructures are substantially parallel to each other. 
     The carbon microstructures have a thickness of about 1 to about 200 microns, about 1 to about 150 microns, about 1 to about 100 microns, about 1 to about 50 microns, or about 10 to about 20 microns. The diameter or largest dimension of the carbon microstructures is about 5 to about 500 microns or about 10 to about 500 microns. The aspect ratio of the carbon microstructures can be about 10 to about 500, about 20 to about 400, or about 25 to about 350. In an embodiment, the distance between the carbon layers in the carbon microstructures is about 0.3 nanometers to about 1 micron. The carbon microstructures can have a density of about 0.5 to about 3 g/cm 3 , or about 0.1 to about 2 g/cm 3 . 
     In the carbon composites, the carbon microstructures are held together by a binding phase. The binding phase comprises a binder which binds carbon microstructures by mechanical interlocking. Optionally, an interface layer is formed between the binder and the carbon microstructures. The interface layer can comprise chemical bonds, solid solutions, or a combination thereof. When present, the chemical bonds, solid solutions, or a combination thereof may strengthen the interlocking of the carbon microstructures. It is appreciated that the carbon microstructures may be held together by both mechanical interlocking and chemical bonding. For example the chemical bonding, solid solution, or a combination thereof may be formed between some carbon microstructures and the binder or for a particular carbon microstructure only between a portion of the carbon on the surface of the carbon microstructure and the binder. For the carbon microstructures or portions of the carbon microstructures that do not form a chemical bond, solid solution, or a combination thereof, the carbon microstructures can be bound by mechanical interlocking. The thickness of the binding phase is about 0.1 to about 100 microns or about 1 to about 20 microns. The binding phase can form a continuous or discontinuous network that binds carbon microstructures together. 
     Exemplary binders include a nonmetal, a metal, an alloy, or a combination comprising at least one of the foregoing. The nonmetal is one or more of the following: SiO 2 ; Si; B; or B 2 O 3 . The metal can be at least one of aluminum; copper; titanium; nickel; tungsten; chromium; iron; manganese; zirconium; hafnium; vanadium; niobium; molybdenum; tin; bismuth; antimony; lead; cadmium; or selenium. The alloy includes one or more of the following: aluminum alloys; copper alloys; titanium alloys; nickel alloys; tungsten alloys; chromium alloys; iron alloys; manganese alloys; zirconium alloys; hafnium alloys; vanadium alloys; niobium alloys; molybdenum alloys; tin alloys; bismuth alloys; antimony alloys; lead alloys; cadmium alloys; or selenium alloys. In an embodiment, the binder comprises one or more of the following: copper; nickel; chromium; iron; titanium; an alloy of copper; an alloy of nickel; an alloy of chromium; an alloy of iron; or an alloy of titanium. Exemplary alloys include steel, nickel-chromium based alloys such as Inconel*, and nickel-copper based alloys such as Monel alloys. Nickel-chromium based alloys can contain about 40-75% of Ni and about 10-35% of Cr. The nickel-chromium based alloys can also contain about 1 to about 15% of iron. Small amounts of Mo, Nb, Co, Mn, Cu, Al, Ti, Si, C, S, P, B, or a combination comprising at least one of the foregoing can also be included in the nickel-chromium based alloys. Nickel-copper based alloys are primarily composed of nickel (up to about 67%) and copper. The nickel-copper based alloys can also contain small amounts of iron, manganese, carbon, and silicon. These materials can be in different shapes, such as particles, fibers, and wires. Combinations of the materials can be used. 
     The binder used to make the carbon composite is micro- or nano-sized. In an embodiment, the binder has an average particle size of about 0.05 to about 250 microns, about 0.05 to about 100 microns, about 0.05 to about 50 microns, or about 0.05 to about 10 microns. Without wishing to be bound by theory, it is believed that when the binder has a size within these ranges, it disperses uniformly among the carbon microstructures. 
     When an interface layer is present, the binding phase comprises a binder layer comprising a binder and an interface layer bonding one of the at least two carbon microstructures to the binder layer. In an embodiment, the binding phase comprises a binder layer, a first interface layer bonding one of the carbon microstructures to the binder layer, and a second interface layer bonding the other of the at least two microstructures to the binder layer. The first interface layer and the second interface layer can have the same or different compositions. 
     The interface layer comprises one or more of the following: a C-metal bond; a C—B bond; a C—Si bond; a C—O—Si bond; a C—O-metal bond; or a metal carbon solution. The bonds are formed from the carbon on the surface of the carbon microstructures and the binder. 
     In an embodiment, the interface layer comprises carbides of the binder. The carbides include one or more of the following: carbides of aluminum; carbides of titanium; carbides of nickel; carbides of tungsten; carbides of chromium; carbides of iron; carbides of manganese; carbides of zirconium; carbides of hafnium; carbides of vanadium; carbides of niobium; or carbides of molybdenum. These carbides are formed by reacting the corresponding metal or metal alloy binder with the carbon atoms of the carbon microstructures. The binding phase can also comprise SiC formed by reacting SiO 2  or Si with the carbon of carbon microstructures, or B 4 C formed by reacting B or B 2 O 3  with the carbon of the carbon microstructures. When a combination of binder materials is used, the interface layer can comprise a combination of these carbides. The carbides can be salt-like carbides such as aluminum carbide, covalent carbides such as SiC and B 4 C, interstitial carbides such as carbides of the group 4, 5, and 6 transition metals, or intermediate transition metal carbides, for example the carbides of Cr, Mn, Fe, Co, and Ni. 
     In another embodiment, the interface layer comprises a solid solution of carbon such as graphite and a binder. Carbon has solubility in certain metal matrices or at certain temperature ranges, which can facilitate both wetting and binding of a metal phase onto the carbon microstructures. Through heat-treatment, high solubility of carbon in metal can be maintained at low temperatures. These metals include one or more of Co; Fe; La; Mn; Ni; or Cu. The binder layer can also comprise a combination of solid solutions and carbides. 
     The carbon composites comprise about 20 to about 95 wt. %, about 20 to about 80 wt. %, or about 50 to about 80 wt. % of carbon, based on the total weight of the composites. The binder is present in an amount of about 5 wt. % to about 75 wt. % or about 20 wt. % to about 50 wt. %, based on the total weight of the composites. In the carbon composites, the weight ratio of carbon relative to the binder is about 1:4 to about 20:1, or about 1:4 to about 4:1, or about 1:1 to about 4:1. The weight ratio of the carbon to the binder can be varied to obtain carbon composites having desired properties. To achieve large elasticity and to provide energized force for high sealing rate, less binder is used. 
     In addition to carbon composites, the seal can optionally contain at least one elastic metallic structure. The at least one elastic metallic structure comprise metals having porous structures and can be in the form of a V ring; an O ring; a C ring; or an E ring. Exemplary materials for the elastic metallic structures include one or more of the following: an iron alloy, a nickel-chromium based alloy, a nickel alloy, copper, or a shape memory alloy. An iron alloy includes steel such as stainless steel. Nickel-chromium based alloys include Inconel™. Nickel-chromium based alloys can contain about 40-75% of Ni and about 10-35% of Cr. The nickel-chromium based alloys can also contain about 1 to about 15% of iron. Small amounts of Mo, Nb, Co, Mn, Cu, Al, Ti, Si, C, S, P, B, or a combination comprising at least one of the foregoing can also be included in the nickel-chromium based alloys. Nickel alloy includes Hastelloy™. Hastelloy is a trademarked name of Haynes International, Inc. As used herein, Hastelloy can be any of the highly corrosion-resistant superalloys having the “Hastelloy” trademark as a prefix. The primary element of the Hastelloy™ group of alloys referred to in the disclosure is nickel; however, other alloying ingredients are added to nickel in each of the subcategories of this trademark designation and include varying percentages of the elements molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon, and tungsten. Shape memory alloy is an alloy that “remembers” its original shape and that when deformed returns to its pre-deformed shape when heated. Exemplary shape memory alloys include Cu—Al—Ni based alloys, Ni—Ti based alloys, Zn—Cu—Au—Fe based alloys, and iron-based and copper-based shape memory alloys, such as Fe—Mn—Si, Cu—Zn—Al and Cu—Al—Ni. 
     The packoff element includes a wear-resistant member at least partially encapsulating the seal. In an embodiment, the wear-resistant member comprises a wear-resistant coating disposed on a surface of the seal. The wear-resistant coating can comprise a carbon composite and a reinforcing agent. 
     The carbon composites in the wear-resistant coating and the seal can be the same or different. In an embodiment, the carbon composite in the wear-resistant coating is the same as the carbon composite in the seal. In another embodiment, the binder in the wear-resistant coating has a higher corrosion/abrasion resistance as compared to the binder in the seal. 
     Erosion/abrasion resistant binders include one or more of the following: Ni; Ta; Co, Cr, Ti, Mo; Zr, Fe, W; and their alloys. It is appreciated that the erosion/abrasion resistant binders should be relatively ductile as well so that the seal can conform sufficiently to seal rough surfaces. Given their high toughness, the erosion resistant binders, if used, can be limited to wear-resistant coating. More ductile binders can be used in the seal. In this manner, the packoff can be erosion/abrasion resistant and at the same time deform sufficiently under limited setting force. In an embodiment, the binder in the carbon composite of the wear-resistant coating comprises an erosion/abrasion resistant binder. 
     The reinforcing agent in the wear-resistant coating comprises one or more of the following: an oxide, a nitride, a carbide, an intermetallic compound, a metal, a metal alloy, a carbon fiber; carbon black; mica; clay; a glass fiber; or a ceramic material. The metals include Ni; Ta; Co; Cr; Ti; Mo; Zr; Fe; or W. Alloys, oxides, nitrides, carbides, or intermetallic compounds of these metals can be also used. Ceramic materials include SiC, Si 3 N 4 , SiO 2 , BN, and the like. Combinations of the reinforcing agent may be used. In an embodiment the reinforcing agent is not the same as the binder in the carbon composition of the first member or the carbon composite in the second member. 
     The weight ratio of the carbon composite to the reinforcing agent in the wear-resistant coating can be about 1:100 to about 100:1, about 1:50 to about 50:1, or about 1:20 to about 20:1. Advantageously, the wear-resistant coating has a gradient in the weight ratio of the carbon composite to the reinforcing agent. The gradient extends from an inner portion proximate the seal toward an outer portion away from the seal. The gradient can comprise a decreasing weight ratio of the carbon composite to the reinforcing agent from the inner portion of the wear-resistant coating to the outer portion of the wear-resistant coating. For example, the weight ratio of the carbon composite to the reinforcing agent may vary from about 50:1, about 20:1, or about 10:1 from the inner portion of the wear-resistant coating to about 1:50, about 1:20, or about 1:10 at the outer portion of the wear-resistant coating. In an embodiment, the gradient varies continuously from the inner portion of wear-resistant coating to the outer portion of the wear-resistant coating. In another embodiment, the gradient varies in discrete steps from the inner portion of the wear-resistant coating to the outer portion of the wear-resistant coating. 
     The wear-resistant coating may have any suitable thickness necessary to prevent the galling of the seal. In an exemplary embodiment, the wear-resistant coating has a thickness of about 50 microns to about 10 mm or about 500 microns to about 5 mm. 
     Alternatively, the wear-resistant member comprises a mesh encapsulating the seal, the mesh comprising one or more of a metal mesh; a glass mesh; a carbon mesh; or an asbestos mesh. The mesh pore size can be determined based on the specific application. In an embodiment, the mesh completely encapsulates the seal. 
     The packoff element comprises at least one guide member disposed on an end of the packoff element. In an embodiment, the packoff element contains two guide members disposed on opposing ends of the packoff element. The guide member can prevent collision between the seal and the PBR bore inner surface. In addition, the guide member can work tougher with other components of the packoff element in order to secure the packoff element to a mandrel. 
     In an embodiment, the packoff element further comprises a retainer member operably disposed between the guide member and a mandrel. Exemplary retainer member includes a C ring or split ring. In use, the retainer member is disposed between a recess on the guide member and a cooperative recess on a mandrel thus securing the guide member to a predetermined position on a mandrel. 
     The guide member can comprise one or more of the following: a metal; a metal alloy; a carbonaceous material; or a reinforced carbon composite. In an embodiment, the guide member comprises a nickel alloy, steel, graphite, or a carbon composite. The carbon composite can be a reinforced carbon composite comprising a carbon composite and a reinforcing agent as disclosed herein. In an embodiment, the guide member is formed of the same material as the seal; and the seal and the guide member form a one-piece component. Optionally, the wear-resistant coating also covers the guide member. It is appreciated that the guide member is well machined to achieve smooth surface so as not to scratch honed inner surface of PBR. The guide member can be in the form of a guide ring, for example. 
     The packoff element can also include a spacing member disposed between the guide member and the seal. Preferably, the spacing member is mechanically locked with the guide member. For example, the spacing member is externally threaded and the guide member is internally threaded, which can engage the threads of the spacing member. Optionally, the packoff element has a backup member attached to the seal. The backup member can be a backup ring. 
     The packoff elements can be configured and disposed to inhibit the passage of fluid. A packoff assembly for a casing bore receptacle defining a polished bore surface comprises: a tubing connectable mandrel having a polished external cylindrical surface portion; and at least one packoff element disposed on the mandrel, the packoff element comprising: an annular seal comprising a carbon composite and having an inner surface and an opposing outer surface; the inner surface being in contact with the polished external cylindrical surface portion of the mandrel; a wear-resistant member at least partially encapsulating the seal; an annular guide member disposed on the polished external cylindrical surface portion of the mandrel; and a retainer member disposed between the guide member and the mandrel for securing the guide member to a predetermined position on the mandrel. Spacing members and backup members as disclosed herein can be optionally included. In a specific embodiment, the packoff element of the assembly has opposing first and second ends and includes an annular seal; a wear-resistant member at least partially encapsulating the seal; a first annular guide member disposed on the first end of the packoff element; a second guide member disposed on the second end of the packoff element; a first retainer member disposed between the first annular guide member and the mandrel for securing the first guide member to a first position on the mandrel and a second retainer member disposed between the second annular guide member and the mandrel for securing the second guide member to a second position on the mandrel. As both the first guide member and the second guide member are secured to the mandrel, the seal between the first and second guide members can be positioned at a desired location on mandrel. 
     Various embodiments of packoff assemblies are illustrated in  FIGS. 1-3 . As shown in  FIG. 1 , a packoff assembly comprises a mandrel  4 , an annular seal  2 , an annular guide member  1 , and a wear-resistant coating  3  disposed on a surface of seal  2 . 
     Referring to  FIG. 2 , in addition to carbon composites, seal  2  also contains elastic metallic structures  5 . The packoff assembly in  FIG. 2  contains a mandrel  4 , a seal  2 , a guide member  1 , and a wear-resistant coating  3 . 
     The structure of the wear-resistant coating  3  is illustrated in  FIG. 6 . As shown in  FIG. 6 , a wear-resistant coating can comprise carbon such as expanded graphite  8 , binder  10 , and reinforcing agent  9 . 
     Referring to  FIG. 3 , the wear-resistant member in the packoff assembly is mesh  7 , which completely encapsulates the seal  2 . The packoff assembly illustrated in  FIG. 3  contains mandrel  4 , seal  2  which includes a carbon composite and elastic metallic structures  5 , and a mesh  7 . 
     A packoff assembly is illustrated in  FIG. 4 . As shown in  FIG. 4  a packoff assembly includes a mandrel  40  and a plurality of packoff elements  50  disposed on the mandrel. The packoff element seals an annular space between the mandrel  40  and polished bore receptacle  30 . The mechanism to engage the mandrel with the PBR is known in the art and is not particularly limited. Illustratively, the PBR  30  has an abutting means  20  which can engage a no-go should on mandrel  40 . 
       FIG. 5  is a cross-sectional view of a packoff element. The exemplary packoff element has a mandrel  400 , a seal  200  disposed on the mandrel, two guide members  100  located at opposing ends of the packoff element, two retainer rings  300  disposed between the guide member  100  and mandrel  400 , two spacing rings  500  mechanically locked with the guide member  100 , and back up rings  500  disposed between seal  200  and spacing rings  500 . Each of the retainer rings  300  is positioned between a recess on the mandrel and a corresponding recess on the guide member, thus securing the packoff element to a desired position on mandrel  400 . 
     A method of sealing comprises: positioning an annular packoff element onto a mandrel; guiding the packoff element towards a wellbore casing, for example, an inner surface of a casing bore receptacle; compressing the packoff element; and sealing an annular area between the mandrel and the wellbore casing such as the inner surface of the case bore receptacle. 
     Positioning the annular packoff element on a mandrel comprises disposing the retainer member on a cooperative recess on the mandrel. Guiding the packoff element towards a wellbore casing comprises sliding the guide member of the packoff element along a surface specifically a polished surface of a casing bore receptacle. In an embodiment, the packoff element is compressed when the packoff element is guided to a section of a casing bore receptacle having an inner bore diameter that is smaller than the outer diameter of the annular seal of the packoff element. 
     In an embodiment, when packoff assembly is lowered into a PBR bore, the guide member will slide along angled PBR inner surface to guide the seal smoothly into smaller ID region, where the seal is compressed or energized to provide reliable seal with honed PBR inner surface due to the excellent elasticity and conformability of the carbon composite material. 
     In addition to improved mechanical strength and high thermal conductivity, the carbon composites can also have excellent thermal stability at high temperatures. The carbon composites can have high thermal resistance with a range of operation temperatures from about −65° F. up to about 1200° F., specifically up to about 1100° F., and more specifically about 1000° F. 
     The carbon composites can also have excellent chemical resistance at elevated temperatures. In an embodiment, the carbon composites are chemically resistant to water, oil, brines, and acids with resistance rating from good to excellent. In an embodiment, the carbon composites can be used continuously at high temperatures and high pressures, for example, about 68° F. to about 1200° F., or about 68° F. to about 1000° F., or about 68° F. to about 750° F. under wet conditions, including basic and acidic conditions. Thus, the carbon composites resist swelling and degradation of properties when exposed to chemical agents (e.g., water, brine, hydrocarbons, acids such as HCl, solvents such as toluene, etc.), even at elevated temperatures of up to 200° F., and at elevated pressures (greater than atmospheric pressure) for prolonged periods. 
     The carbon composites can have excellent lubrication properties.  FIG. 7  shows the friction testing results of carbon composite, FFKM (perfluoroelastomer available under the trade name Kalrez* from DuPont), FEPM (tetrafluoroethylene/propylene dipolymers), NBR (acrylonitrile butadiene rubber), and PEEK (polyetheretherketones). As shown in  FIG. 7 , among the samples tested, carbon composite provides the lowest friction coefficient. 
     The packoff elements and the packoff assemblies thus have reliable sealing properties in much harsher high temperature high pressure and corrosive conditions. In addition, the packoff elements and packoff assemblies can be set with a low setting force. The setting failures can also be minimized. 
     All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including at least one of that term (e.g., the colorant(s) includes at least one colorants). “Or” means “and/or.” “Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event occurs and instances where it does not. As used herein, “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. “A combination thereof” means “a combination comprising one or more of the listed items and optionally a like item not listed.” All references are incorporated herein by reference. 
     The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Further, it should further be noted that the terms “first,” “second,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity). 
     While typical embodiments have been set forth for the purpose of illustration, the foregoing descriptions should not be deemed to be a limitation on the scope herein. Accordingly, various modifications, adaptations, and alternatives can occur to one skilled in the art without departing from the spirit and scope herein.