Abstract:
Graphene has been used in nanocomposites as constituents/doping in plastics or epoxy providing dramatic enhancement of the mechanical properties but have not progressed past the laboratory level novelty. This invention can provide a graphene based composite structure with a density less that 1.9 g/cm 3  for a fiber, yarn, rope or cable and a density less that 1.5 g/cm 3  for a sheet both structure have tensile and shear strength greater than either Aluminum or Steel; thus providing a graphene material that is both much lighter and stronger.

Description:
FIELD OF INVENTION 
       [0001]    The present invention relates in general to the field of nanocomposites, and more particularly, to a graphene based composite structure. 
       BACKGROUND ART 
       [0002]    Without limiting the scope of the invention, its background is described in connection with composite materials. 
         [0003]    Graphene is one of the strongest materials ever tested. Measurements have shown that graphene has a breaking strength 200 times greater than steel, with a tensile modulus (stiffness) of 1 TPa (150,000,000 psi). An atomic Force Microscope (AFM) has been used to measure the mechanical properties of a suspended graphene sheet. Graphene sheets, held together by van der Waals forces, were suspended over SiO 2  cavities where an AFM tip was probed to test its mechanical properties. Its spring constant was in the range 1-5 N/m and the Young&#39;s modulus was 0.5 TPa (500 GPa) thereby demonstrating that graphene can be mechanically very strong and rigid. Despite these nanoscale mechanical properties, Graphene has not been able to transition to a macro-scale mechanical structure. Various research institutes have loaded plastic/polymer/epoxy with carbon nanotubes (CNT), graphene flakes (GF), and graphene oxide (GO) and seen up a 200% increase in tensile strength in the loaded plastic/polymer/epoxy. The process of producing a loaded plastic/polymer/epoxy does not translate to a viable composite structure. The inability to translate the technology to a viable composite structure is combination of technical issues and cost factors. The technical limitation includes stochastic process in the curing of the plastic/polymer/epoxy that results in random shrinkage phenomena that is exacerbated in larger composite structures/devices. The distribution of the laded mechanical structural materials (CNT, GF, and GO) is non-uniform creating weak regions and failure points in the loaded plastic/polymer/epoxy material. The superior properties of graphene compared to polymers are also reflected in polymer/graphene nanocomposites. Polymer/graphene nanocomposites show superior mechanical, thermal, gas barrier, electrical and flame retardant properties compared to the neat polymer. Improvement in the physicochemical properties of the nanocomposites depends on the distribution of graphene layers in the polymer matrix as well as interfacial bonding between the graphene layers and polymer matrix. The combination low yield and high cost of the CNT, GF, and GO materials makes the approach not viable. Interfacial bonding between graphene and the host polymer dictates the final properties of the graphene reinforced polymer nanocomposite. 
         [0004]    Graphene is an allotrope of carbon. Graphene&#39;s structure is a one-atom-thick planar sheet of sp2-bonded carbon atoms that are densely packed in a honeycomb or hexagonal crystal lattice. The carbon-carbon bond length in graphene is about 1.42 Å. Graphene sheets stack to form graphite with an inter-planar spacing of 3.35 Å. Multiple graphene sheets/flakes are bonded together by van der Waals forces. 
         [0005]    Graphene can be oxidized by a number of processes including thermal, chemical or chemical-mechanical. Reduction of graphite oxide monolayer films e.g. by hydrazine, annealing in argon/hydrogen was reported to yield graphene films of low quality. 
         [0006]    Graphene can be produced in significant quantities from microcrystalline graphite that is treated with a mixture of acids such as sulfuric, nitric, and other oxidizing chemical in combination mechanical and/or thermal energy elements. This processing will produce graphene flakes ranging from a few nanometers to tens of microns depending and the specific processing environment. If one uses a shaker mill in conjunction with an oxidizing agent the time duration in the mill will determine the size of the flake of graphene. In general, the longer the processing time in the mill the smaller the graphene flake. The oxidizing process produces a carboxyl group on the perimeter of the graphene flake. The resulting graphene flakes can be on the order of 5 Å in thick and can be suspended in a number of solutions including but not limited to: tetrahydrofuran, tetrachloromethane, water, and/or dichloroethane. 
       SUMMARY OF INVENTION 
       [0007]    The present invention includes graphene in the form of flat graphene flakes that have oxidized edges. Suspended oxidized-edge graphene can be electroplated on a metalized substrate substrates or foils. A wide number or metals, semiconducting, or metalized substrates can be used effectively as long as they do not form an insulating layer that limits the electric field from penetration into the solution. The materials that can work in this process include ITO (Indium Tin Oxide) a full conductive oxide, Tin Oxide a semiconducting oxide, Indium Oxide a semiconducting oxide, RuO 2  a conductive oxide steel, stainless steel, Copper, and Nickel. Copper and Nickel have also been show to be excellent seed layers in efforts to grow epitaxial films of graphene by metal organic chemical vapor deposition (MOCVD) and other thin film deposition/growth processes that range from nickel, stainless steel and/or copper as either bulk or foils. 
         [0008]    One embodiment of the present invention includes a method of making a high-strength composite, comprising: plating a nickel surface on a substrate; electroplating flat graphene flakes onto the conducting surface from a water suspension of graphene flakes in a vessel to give a plated layer, wherein the flakes 1 to 20 micron across, whereby electroplated graphene flakes are covalently bonded together; removing the plated substrate from the vessel; drying to remove carrier fluid from the plated graphene; applying a layer of polymer containing a solvent to infiltrate between the graphene flakes, wherein the polymer is chemically bondable to the graphene, and the solvent-containing polymer has a viscosity between 1 and 30,000 centipoises, whereby polymer is chemically bondable to two adjacent graphene flakes to provide chemical bonds between flakes; and removing solvent from the polymer and air from between the graphene flakes infiltrated by said bondable polymer layer. In one aspect, the step of removing solvent from the polymer and air from between the graphene flakes from said bondable polymer layer is vacuum facilitated. 
         [0009]    Another embodiment of the present invention includes a method of making a high-strength composite, comprising: plating conducting surface on a substrate; electroplating flat graphene flakes onto the conducting surface from a carrier fluid suspension of graphene flakes in a vessel to give a plated layer, wherein the flakes 0.5 to 100 micron across; removing the plated substrate from the vessel; drying to remove carrier fluid from the plated graphene; applying a layer of polymer containing a solvent to infiltrate between the graphene flakes, wherein the polymer is chemically bondable to the graphene, and the solvent containing polymer has a viscosity between 1 and 30,000 centipoises; and removing air from between the graphene flakes infiltrated by said bondable polymer layer. 
         [0010]    Yet another embodiment of the invention includes a method of making a high-strength composite, can comprise: Plating conducting surface on a substrate; Electroplating flat graphene flakes onto the conducting surface from a water suspension of graphene flakes in a vessel to give a plated layer, wherein the flakes 1 to 100 micron across; Removing the plated substrate from the vessel; Drying to remove water from the plated graphene; Applying a layer of polymer containing a solvent to the dried graphene, wherein the polymer is chemically bondable to the graphene, and the solvent containing polymer has a viscosity between 1 and 30,000 centipoises; and Vacuum drying said bondable polymer. 
         [0011]    Electroplating flat graphene flakes out of pure water creates an unusually strong bond between the graphene and the nickel and on initial layers of graphene to graphene. On further layers of graphene, capillary action of the drying (e.g.) water, by adhesion and surface tension exerts forces pulling which are not covalently bounded surfaces of graphene together. A polymer which is chemically bondable to two adjacent graphene flakes can provide chemical bonds between flakes. Vacuum drying of the bondable polymer can generally avoid bubbles and may be assisted by capillary action. Because of the extraordinary strength of graphene, a relatively thin layer of graphene can be flexible and quite strong. Chemical modifications may be made; e.g., silver nitrate, electroless nickel plating or other metallization process and electric field, of the surface to increase graphene-fiber interaction strengths. Graphene can be dispersed as a suspension in water, e.g. using paper making techniques; the monolayer flakes can bond very powerfully when electroplated. 
         [0012]    The surface can be on at least one of fiber, flat surface, shaped surface, or formed surface. The substrate can also be at least one of plastic, wood, metal, grass cellulose, or rayon, etc. The substrate can be shaped before the plating of the conducting surface. The substrate can also be shaped after electroplating, but before applying a layer of polymer. The drying to remove carrier fluid can be done in a vacuum-furnace chamber. The drying of bondable polymer can be done in a vacuum-furnace chamber. 
         [0013]    The bondable polymer can be an epoxy. The bondable polymer can be thermoplastic. The bondable polymer can be thermosetting. The bondable polymer can be a mixture of thermoplastic and thermosetting plastics. The bondable polymer can be hydrophilic solvent. 
         [0014]    The flakes can be 5 to 50 micron across, or 1 to 20 micron across, or 5 to 14 micron across. The degree of oxidation of the flakes should cover the edges, but any oxidation of the flakes&#39; flat surfaces should be limited. Some limited stacking of flakes bonded by van der Waals, but bonded by polymer, is acceptable. Our experiments showed the electroplating deposition of a ˜1 μm thick layer of graphene flakes were covalently bonded to each other and chemically bonded to the nickel foil. 
         [0015]    The removing air from between the graphene flakes from said bondable polymer layer can be vacuum facilitated. The surface of the bondable polymer layer can be metalized and another electroplating deposition of a ˜1 μm thick layer of graphene flakes covalently bonded to each other and chemically bonded to the nickel foil can be added (then be covered by another bondable polymer layer), and these steps can be repeated as needed for additional strength. 
         [0016]    In one embodiment, the conducting surface is composed of nickel or copper. The grass can be bamboo or other similar plant derivatives. The carrier fluid can be water. Covalent and/or chemical bonding graphene can be done on rayon fiber as substrate. Exposing the fiber to vacuum to induce bonding/adhesion (e.g. by cold—welding, epoxy chemical bonding or other bonding may be used) of the deposited graphene on fiber. 
         [0017]    Heat, vacuum and forming gas, hydrogen gas or hydrogen plasma or remote plasma may be used to enhance bonding. Hydrogen and Nitrogen are non-toxic and are mixed by a laboratory in the following ratio: 95% Nitrogen and 5% hydrogen. In this concentration the hydrogen is inert (that means it is impossible to ignite). Exposing a coated fiber or surface to heat, can speed up the drying process and may improve bonding/adhesion. 
         [0018]    Yet another embodiment of the present invention includes a high-strength composite made by the method of: plating a conducting surface on a substrate; electroplating flat graphene flakes onto the conducting surface from a carrier fluid suspension of graphene flakes in a vessel to give a plated layer, wherein the flakes 0.5 to 100 micron across; removing the plated substrate from the vessel; drying to remove carrier fluid from the plated graphene; applying a layer of polymer containing a solvent to infiltrate between the graphene flakes, wherein the polymer is chemically bondable to the graphene, and the solvent containing polymer has a viscosity between 1 and 30,000 centipoises; and removing air from between the graphene flakes infiltrated by said bondable polymer layer. 
     
    
     DESCRIPTION OF THE INVENTION 
       [0019]    While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention. 
         [0020]    To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims. 
         [0021]    As used herein, the term “graphene” refers to a polycyclic aromatic molecule with carbon atoms covalently bonded to each other. The covalently bonded carbon atoms can form a six-member ring as a repeating unit, and may also include at least one of a five-member ring and a seven-member ring. Multiple graphene layers are referred to in the art as graphite. Thus, graphene may be a single layer, or also may comprise a multiple layers of graphene that are stacked on other layers of graphene. Generally, graphene will have a maximum thickness of about 100 nanometers (nm), specifically about 10 nm to about 90 nm, more specifically about 20 nm to about 80 nm. 
         [0022]    As used herein, the term “graphene flake” refers to a crystalline or “flake” form of graphene that includes many graphene sheets stacked together. 
         [0023]    Theoretical calculations predict with sufficient electric potential one can achieve chemical bonding between the graphene flakes and between the graphene flakes to the metalized substrate. This has been shown experimentally by electroplating graphene oxide on a nickel foil where the deposited graphene flakes survive a scotch tape adhesion test without the loss of any material. The scotch tape test is an accurate standard test to determine if the bonds exceed of the material exceed van der Waals forces. If no material is removed after pressing the scotch tape on the surface of the deposited graphene, then the bonds exceed van der Waals forces and are chemical bonds. Additional theoretical calculations predict that if the spacing between flakes can be reduced to less than 3 Å the graphene flakes could form covalent bonds between the layers. Researchers have speculated that applying a vacuum and drawing the flakes close enough together might achieve this reaction. To date no one has demonstrated the ability to draw a vacuum hard enough to allow adjacent graphene flakes to become covalently bonded. As a consequence, achieving a graphene material that has a chemical bond instead of the weak van der Waals forces is critical for the development of a macro-scale high strength structural composite. 
         [0024]    Our results showed that electroplating deposition of a ˜1 μm thick layer of graphene flakes were covalently bonded to each other and chemically bonded to the nickel foil. A standard ASTM tensile strength test has shown an uncoated nickel foil had a tensile strength of 323 MPa and the graphene coated nickel foil had a tensile strength of 375 MPa. This result was repeated several times with a standard deviation of 2.0. This is a 15% increase in the tensile strength with a 0.5 μm coating on a 60 μm nickel foil. 
         [0025]    As additional layers of graphene oxide can be deposited, by the electroplating process, but the electric field is reduced as some of the applied voltage drops across the graphene that has been deposited. On thicker depositions of electroplated graphene some of the graphene flakes are held in place only by van der Waals forces. This was demonstrated by the removal of the ticker layers of graphene through a scotch tape test leaving the ˜0.5 μm layer that was chemically bonded to the metalized substrate. Thicker layers require an additional chemical bonding to form a mechanically sound structure/composite. This require the use of a polymer such as an epoxy that forms a chemical bond with graphene/graphene oxide and has viscosity between 1 and 30,000 centipoises enabling infiltration via capillary action/wicking forces. The capillary action/wicking forces can be augmented by applying a slight vacuum to accelerate the infiltration as the vacuum removes the air and solvent between the flakes driving the epoxy/polymer between the graphene flakes. EL-335 made by Adtech, Inc. is a high temperature, toughened, impact resistant laminating system for the fabrication of high-performance marine composites. The EL-335 epoxy is used with Graphite, S-Glass, E-Glass or Kevlar fabrics. The EL-335 epoxy has superior mechanical properties and a density of ˜1.5 g/cm 3 , performance at elevated temperatures and UV stability. The epoxy enables the use of graphene coatings much thicker than 0.5 to 1 μm that is chemically bonded to the metal. Using this approach to reinforce a metal can be used to make a thinner/lighter metal with &gt;7% enhanced strength. But to take advantage of the full potential of the technology one should use of a metalized sheet or fiber as the backbone for the composite. Steel has a density of 7.8 g/cm 3 , polystyrene has a density of 1.09 g/cm 3 , and graphene has a density ˜1.8 g/cm 3 . Using a 1 μm coating of nickel on plastic instead of a solid metal combined with a chemically bonded layer of graphene dramatically reduces the effective density of the composite. A viable composite can be created with graphene when it is formed into, e.g. either a fiber, a yarn, or a sheet design. 
         [0026]    Graphene can be deposited on to a metalized fiber, sheet, or other structure to form layers of a high strength composite, which often requires using a light weight media such as a plastic that is compatible with electroless plating. Electroless nickel plating (EN) is an auto-catalytic chemical technique used to deposit a layer of nickel-phosphorus or nickel-boron alloy on a solid workpiece, such as metal or plastic. The process relies on the presence of a reducing agent, for example hydrated sodium hypophosphite (NaPO 2 H 2 .H 2 O), which reacts with the metal ions to deposit metal. The alloys with different percentage of phosphorus, ranging from 2-5 (low phosphorus) to up to 11-14 (high phosphorus) are possible. The metallurgical properties of alloys depend on the percentage of phosphorus. Not all plastics can be plated with electroless plating methods. Plastics that are compatible with electroless plating include Polystryene, ABS, and other plastic media native or loaded with graphene. A thin layer (&lt;10 gm) of copper and then nickel are deposited sequentially on the plastic. The metalized plastic is then placed into an electroplating bath where graphene oxide is deposited. The graphene is deposited to a depth grater than ˜0.5 μm and less than 100 gm. The metalized plastic/graphene structure is then dried to remove any liquid from the previous deposition. The metalized plastic/graphene structure is sprayed or coated with an epoxy. The spacing between the flakes producing wicking forces and capillary action that draws the epoxy in between the graphene flakes. To accelerate wicking forces and capillary action drawing the epoxy between the graphene flakes the metalized plastic/graphene structure can be the placed into a large chamber where a vacuum is applied. The metalized plastic/graphene/epoxy structure is then placed into a press that can apply between 15 and 150 tons of pressure, where it is sprayed with an additional coat of epoxy and layered. Once the desired number of layers has been achieved the press is activated to apply substantial pressure and heat to form the composite. 
         [0027]    An ABS plastic fiber with a diameter is less than 100 μm and the thickness of the sheet of plastic is less than 200 gm. ABS plastic has a density ˜1 g/cm 3 . The metal thin film is deposited by use of electroplating, electroless plating, sputtering, chemical vapor deposition (CVD) or other direct deposition technique. Graphene can be deposited by electroplating process. The epoxy can be deposited by use of emersion, dipping, spraying, spin coating or other coating technique. The surface tension of the epoxy forces the loosely bound graphene particles/flakes to become parallel to the surface of the fiber or sheet additionally the capillary forces the epoxy between the graphene flakes/particles. The infiltration of the epoxy can be facilitated and accelerated by applying a modest vacuum. The vacuum draws any remaining air and solvent from between the graphene flakes/particles replacing the air and solvent with the epoxy. The epoxy can be cured by time, temperature and/or vacuum. The fiber, sheet, or other structure can be placed into a chamber where it can be exposed to a vacuum and/or temperature. Once a sheet or fabric structure has been formed the structure may be shaped into the composite final form. The temperature cannot exceed the thermal limit of the plastic fiber, sheet, or other structure. The vacuum and/or heat the epoxy cures and chemically bonds the graphene flakes/particles together. The graphene coated fiber or sheet can then be combined into a yarn. The yarn can also be treated in a vacuum furnace performing chemical bonding between the threads of the yarn. The yarn can then be woven into a fabric, rope or cable. The rope or cable can be then be drawn through the epoxy bath to promote chemical bonding between the strands of the rope or cable. The rope or cable structure can be placed into a chamber where it can be exposed to a vacuum and/or temperature to facilitate curing. The fiber, rope or cable can also be cured/set at room temperature and pressure. The fiber, rope or cable can also be considered a final product. The fabric formed from the yarn can be shaped/cut at this point to take the final form of the composite. The shaped or unshaped fabric, created from the yarn can be treated with epoxy layered with other layer fabrics placed into a heated press to produce chemical bonding between the layers of the composite. Because the layer of nickel is a greater percentage of the fiber/rope/yarn/cable structure the density will be less than 1.9 g/cm 3  and have tensile and shear strength greater than either Aluminum or Steel. 
         [0028]    The sheet of ABS/Ni:Cu/Graphene/Epoxy can be treated with epoxy layered with other layer fabrics placed into a heated press to produce chemical bonding between to form a two dimensional or shaped composite structure. ABS plastic is a thermal plastic that can be placed into a heated press that takes the ABS plastic to its thermal set temperature, and cools it in that form producing the final shape. The nickel and graphene are a lower percentage of the final composite relative to the fiber structure and as such the density will be less than 1.5 g/cm 3  for a sheet structure have tensile and steer strength greater than either Aluminum or Steel. 
       Examples 
       [0029]    An ABS (Acrylonitrile butadiene styrene, (C 8 H 8 .C 4 H 6 .C 3 H 3 N) n  melting point of 105° C.) plastic fiber with a diameter a 10 μm can be metalized with a 1 μm thin film cooper/nickel by electroless plating. The graphene oxide can be then suspended in an aqueous solution and a 2-μm graphene layer can be deposited by electroplating process on the metalized ABS plastic fiber. The metalized graphene coated ABS fiber can be then dried in air. The dried metalized/graphene coated ABS fiber can be then drawn through a bath of EL-335 epoxy and then pulled into a vacuum chamber for curing. The cured fiber can be then used to form a yarn using standard textile manufacturing processes. The yarn created from the ABS/Ni:Cu/Graphene/Epoxy can be form into a rope or a fabric. The fiber, yarn, rope, or cables are composite structures. A fabric made from the yarn can be placed into a heated mechanical press that can apply between 15 and 150 tons of pressure where it can be layered with other fabrics with each layer coated with EL-335 epoxy. The layers of the material may be composed of the same fabric or of a different material. The press applies the pressure and heat to form a two dimensional composite structure. ABS plastic is a thermal plastic that can be trimmed to form the shape to the desired part/product, and then placed into heated press that takes the ABS plastic to its thermal set temperature, and cools it in that form producing the final shape. The nickel and graphene are a higher percentage of the final composite relative to the sheet structure and as such the density will be less than 1.9 g/cm 3  for a sheet structure and have tensile and shear strength greater than either Aluminum or Steel; thus providing a graphene material that is both much lighter and stronger. 
         [0030]    An ABS (Acrylonitrile butadiene styrene, (C 8 H 8 .C 4 H 6 .C 3 H 3 N) n  melting point of 105° C.) plastic sheet with a thickness a 50 μm can be trimmed, cut or stamped to form the shape of the final composite structure. The shaped ABS plastic sheet can be metalized with a 1 μm thin film cooper/nickel by electroless plating. Graphene oxide can be then suspended in an aqueous solution and a 10 μm graphene layers can be deposited by electroplating process on the metalized ABS plastic sheet. The metalized graphene coated ABS sheet can be then dried in air or in a slight vacuum. The dried metalized/graphene coated ABS sheet can be then coated with a thin layer of EL-335 epoxy by a spraying process akin to spray painting. The ABS/Ni:Cu/Graphene/Epoxy sheet can be placed into a vacuum chamber for curing. The sheets may also be cured at room temperature and pressure. The sheets can be placed into a heated mechanical press (reference) where it can be layered with other sheets with each sheet coated with EL-335 epoxy. The sheets of the material may be composed of the same fabric or of a different material. The press applies mechanical force and heat to form a two dimensional composite structure. ABS plastic in the ABS/Ni:Cu/Graphene/Epoxy structure is a thermal plastic that can be trimmed to form the shape to the desired part/product, and then placed into heated press that takes the ABS plastic to its thermal set temperature, and cools it in that form producing the final shape. The nickel and graphene are a lower percentage of the final composite relative to the fiber structure and as such the density will be less than 1.5 g/cm 3  and have tensile and shear strength greater than either Aluminum or Steel. 
         [0031]    Another approach of using graphene flake reinforcement is using a method of aligning graphene flakes in a structure comprising: suspending graphene flakes in a fluid; extruding the graphene flake-containing fluid in a direction, wherein the graphene flake-containing fluid is subjected to a magnetic field having lines of flux substantially parallel to the direction of extrusion; and solidifying the fluid. 
         [0032]    The graphene flake-containing fluid can be subjected to a magnetic field having lines of flux substantially parallel to the direction of extrusion prior to extrusion, during extrusion, after extrusion, or combinations thereof. Magnetic field can be created by electromagnetically, with one or more permanent magnets, or both. Diamagnetic material is preferably used to parallelize lines of flux. It can be used prior to extrusion, during extrusion, after extrusion, or combinations thereof. The extrusion tip can be boron carbide, and the extrusion tip can be elongated. The fluid can be plastic, glass, ceramic, or metal. The metal can be aluminum. 
         [0033]    It is contemplated that any embodiment discussed in this specification can be implemented with respect to any method, kit, reagent, or composition of the invention, and vice versa. Furthermore, compositions of the invention can be used to achieve methods of the invention. 
         [0034]    It will be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims. 
         [0035]    All publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. 
         [0036]    The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects. 
         [0037]    As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps. 
         [0038]    The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, MB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context. In certain embodiments, the present invention may also include methods and compositions in which the transition phrase “consisting essentially of” or “consisting of” may also be used. 
         [0039]    As used herein, words of approximation such as, without limitation, “about”, “substantial” or “substantially” refers to a condition that when so modified is understood to not necessarily be absolute or perfect but would be considered close enough to those of ordinary skill in the art to warrant designating the condition as being present. The extent to which the description may vary will depend on how great a change can be instituted and still have one of ordinary skilled in the art recognize the modified feature as still having the required characteristics and capabilities of the unmodified feature. In general, but subject to the preceding discussion, a numerical value herein that is modified by a word of approximation such as “about” may vary from the stated value by at least ±1, 2, 3, 4, 5, 6, 7, 10, 12 or 15%. 
         [0040]    All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.