WO2016043876A1

WO2016043876A1 - Carbon composites

Info

Publication number: WO2016043876A1
Application number: PCT/US2015/044950
Authority: WO
Inventors: Zhiyue Xu; Lei Zhao
Original assignee: Baker Hughes Incorporated
Priority date: 2014-09-17
Filing date: 2015-08-13
Publication date: 2016-03-24
Also published as: EP3194335A1; EP3194335A4; US10202310B2; EP3194335B1; JP6699049B2; JP2017535499A; CA2961167C; CN106660887B; CN106660887A; US20160176764A1; CA2961167A1; US9325012B1

Abstract

A carbon composite comprises carbon microstructures having interstitial spaces among the carbon microstructures; and a binder disposed in at least some of the interstitial spaces; wherein the carbon microstructures comprise unfilled voids within the carbon microstructures.

Description

CARBON COMPOSITES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Application No. 14/488851, filed on September 17, 2014, which is incorporated herein by reference in its entirety.

BACKGROUND

[0002] Graphite is an allotrope of carbon and has a layered, planar structure. In each layer, the carbon atoms are arranged in hexagonal arrays or networks through covalent bonds. Different carbon layers however are held together only by weak van der Waals forces.

[0003] Graphite has been used in a variety of applications including electronics, atomic energy, hot metal processing, coatings, aerospace and the like due to its excellent thermal and electrical conductivities, lightness, low friction, and high heat and corrosion resistances. However, graphite is not elastic and has low strength, which may limit its further applications. Thus, the industry is always receptive to new graphite materials having improved elasticity and mechanical strength. It would be a further advantage if such materials also have improved high temperature corrosion resistance.

BRIEF DESCRIPTION

[0004] The above and other deficiencies in the prior art are be overcome by, in an embodiment, a carbon composite comprising carbon micro structures having interstitial spaces among the carbon microstructures; and a binder disposed in at least some of the interstitial spaces; wherein the carbon microstructures comprises unfilled voids within the carbon microstructures.

[0005] In another embodiment, a carbon composite comprises: at least two carbon microstructures; and a binding phase disposed between the at least two carbon

microstructures; wherein the binding phase includes a binder comprising Si0₂, Si, B, B₂0₃, a metal, an alloy of the metal, or a combination comprising at least one of the foregoing;

wherein the metal is at least one of aluminum, copper, titanium, nickel, tungsten, chromium, iron, manganese, zirconium, hafnium, vanadium, niobium, molybdenum, tin, bismuth, antimony, lead, cadmium, and selenium.

[0006] The composites can be in the form of a bar, block, sheet, tubular, cylindrical billet, toroid, powder, or pellets. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:

[0008] FIG. 1 is a scanning electron microscopic ("SEM") image of a

composition containing expanded graphite and a micro- or nano-sized binder blended at room temperature and atmospheric pressure;

[0009] FIG. 2 is a SEM image of a carbon composite formed from expanded graphite and a micro- or nano-sized binder under high pressure and high temperature conditions according to one embodiment of the disclosure;

[0010] FIG. 3 is a SEM image of carbon microstructures according to another embodiment of the disclosure;

[0011] FIG. 4 is a schematic illustration of a carbon composite according to an embodiment of the disclosure;

[0012] FIG. 5 shows stress-strain curves of (A) natural graphite; (B) expanded graphite; (C) a mixture of expanded graphite and a micro- or nano-sized binder, where the sample is compacted at room temperature and high pressure; (D) a carbon composite according to one embodiment of the disclosure compacted from a mixture of expanded graphite and a micro- or nano-sized binder at a high temperature and a low pressure (also referred to as "soft composite"); and (E) a carbon composite according to another embodiment of the disclosure formed from expanded graphite and a micro- and nano-sized binder under high pressure and high temperature conditions (also referred to as "hard composite");

[0013] FIG. 6 shows loop test results of a carbon composite at different loadings;

[0014] FIG. 7 shows hysteresis results of a carbon composite tested at room temperature and 500°F respectively;

[0015] FIG. 8 compares a carbon composite before and after exposing to air at 500°C for 25 hours;

[0016] FIG. 9 (A) is a photo of a carbon composite after a thermal shock; FIG. 9 (B) illustrates the condition for the thermal shock;

[0017] FIG. 10 compares a carbon composite sample (A) before and (B) after exposing to tap water for 20 hours at 200°F, or (C) after exposing to tap water for 3 days at 200°F; [0018] FIG. 11 compares a carbon composite sample (A) before and (B) after exposing to 15% HC1 solution with inhibitor at 200°F for 20 hours, or (C) after exposing to 15% HC1 solution at 200°F for 3 days; and

[0019] FIG. 12 shows the sealing force relaxation test results of a carbon composite at 600°F.

DETAILED DESCRIPTION

[0020] The inventors hereof have found that carbon composites formed from graphite and micro- or nano-sized binders at high temperatures have improved balanced properties as compared to graphite alone, a composition formed from the same graphite but different binders, or a mixture of the same graphite and the same binder blended at room temperature under atmospheric pressure or high pressures. The new carbon composites have excellent elasticity. In addition, the carbon composites have excellent mechanical strength, heat resistance, and chemical resistance at high temperatures. In a further advantageous feature, the composites keep various superior properties of the graphite such as heat conductivity, electrical conductivity, lubricity, and the alike.

[0021 ] Without wishing to be bound by theory, it is believed that the

improvement in mechanical strength is provided by a binding phase disposed between carbon microstructures. There are either no forces or only weak Van der Waals forces exist between the carbon microstructures, thus the graphite bulk materials have weak mechanical strength. At high temperatures, the micro- and nano-sized binder liquefies and is dispersed evenly among carbon microstructures. Upon cooling, the binder solidifies and forms a binding phase binding the carbon nano structures together through mechanical interlocking.

[0022] Further without wishing to be bound by theory, for the composites having both improved mechanical strength and improved elasticity, it is believed that the carbon microstructures themselves are laminar structures having spaces between the stacked layers. The binder only selectively locks the microstructures at their boundaries without penetrating the microstructures. Thus the unbounded layers within the microstructures provide elasticity and the binding phase disposed between the carbon microstructures provides mechanical strength.

[0023] 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.

[0024] There are two types of voids in the carbon composites - voids or interstitial spaces between carbon microstructures and voids within each individual carbon

microstructures. The interstitial spaces between the carbon microstructures have a size of about 0.1 to about 100 microns, specifically about 1 to about 20 microns whereas the voids within the carbon microstructures are much smaller and are generally between about 20 nanometers to about 1 micron, specifically about 200 nanometers to about 1 micron. The shape of the voids or interstitial spaces is not particularly limited. 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.

[0025] The interstitial spaces between the carbon microstructures are filled with a micro- or nano-sized binder. For example, a binder can occupy about 10 % to about 90 % of the interstitial spaces between the carbon microstructures. However, the binder does not penetrate the individual carbon microstructures and the voids within carbon microstructures are unfilled, i.e., not filled with any binder. Thus the carbon layers within the carbon microstructures are not locked together by a binder. Through this mechanism, the flexibility of the carbon composite, particularly, expanded carbon composite can be preserved.

[0026] 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/cm³, or about 0.1 to about 2 g/cm³.

[0027] As used herein, graphite includes natural graphite, synthetic graphite, expandable graphite, expanded graphite, or a combination comprising at least one of the foregoing. Natural graphite is graphite formed by Nature. It can be classified as "flake" graphite, "vein" graphite, and "amorphous" graphite. Synthetic graphite is a manufactured product made from carbon materials. Pyro lytic graphite is one form of the synthetic graphite. Expandable graphite refers to graphite having intercallant materials inserted between layers of natural graphite or synthetic graphite. A wide variety of chemicals have been used to intercalate graphite materials. These include acids, oxidants, halides, or the like. Exemplary intercallant materials include sulfuric acid, nitric acid, chromic acid, boric acid, SO₃, or halides such as FeCl₃, ZnCl₂, and SbCl₅. Upon heating, the intercallant is converted from a liquid or solid state to a gas phase. Gas formation generates pressure which pushes adjacent carbon layers apart resulting in expanded graphite. The expanded graphite particles are vermiform in appearance, and are therefore commonly referred to as worms.

[0028] Advantageously, the carbon composites comprise expanded graphite microstructures. Compared with other forms of the graphite, expanded graphite has high flexibility and compression recovery, and larger anisotropy. The composites formed from expanded graphite and micro- or nano-sized binder under high pressure and high temperature conditions can thus have excellent elasticity in addition to desirable mechanical strength.

[0029] 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 micro structure only between a portion of the carbon on the surface of the carbon micro structure 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 bounded 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.

[0030] Exemplary binders include Si0₂, Si, B, B₂0₃, a metal, an alloy, or a combination comprising at least one of the foregoing. The metal can be aluminum, copper, titanium, nickel, tungsten, chromium, iron, manganese, zirconium, hafnium, vanadium, niobium, molybdenum, tin, bismuth, antimony, lead, cadmium, and selenium. The alloy includes the alloys of aluminum, copper, titanium, nickel, tungsten, chromium, iron, manganese, zirconium, hafnium, vanadium, niobium, molybdenum, tin, bismuth, antimony, lead, cadmium, and selenium. In an embodiment, the binder comprises copper, nickel, chromium, iron, titanium, an alloy of copper, an alloy of nickel, an alloy of chromium, an alloy of iron, an alloy of titanium, or a combination comprising at least one of the foregoing metal or metal alloy. 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, 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.

[0031] 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 10 microns, specifically, about 0.5 to about 5 microns, more specifically about 0.1 to about 3 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 micro structures.

[0032] 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 micro structures to the binder layer. In an embodiment, the binding phase comprises a binder layer, a first interface layer bonding one of the carbon micro structures to the binder layer, and a second interface layer bonding the other of the microstructures to the binder layer. The first interface layer and the second interface layer can have the same or different compositions.

[0033] The interface layer comprises a C-metal bond, a C-B bond, a C-Si bond, a C-O-Si bond, a C-O-metal bond, a metal carbon solution, or a combination comprising at least one of the foregoing. The bonds are formed from the carbon on the surface of the carbon microstructures and the binder.

[0034] In an embodiment, the interface layer comprises carbides of the binder. The carbides include carbides of aluminum, titanium, nickel, tungsten, chromium, iron, manganese, zirconium, hafnium, vanadium, niobium, molybdenum, or a combination comprising at least one of the foregoing. 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 Si0₂ or Si with the carbon of carbon microstructures, or B₄C formed by reacting B or B₂0₃ 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, B₄C, interstitial carbides such as carbides of the group 4, 5, and 5 transition metals, or intermediate transition metal carbides, for example the carbides of Cr, Mn, Fe, Co, and Ni.

[0035] In another embodiment, the interface layer comprises a solid solution of carbon and the binder. Carbon have solubility in certain metal matrix or at certain temperature range, which helps both wetting and binding of metal phase onto carbon microstructures. Through heat-treatment, high solubility of carbon in metal can be maintained at low temperature. These metals include Co, Fe, La, Mn, Ni, or Cu. The binder layer can also comprises a combination of solid solutions and carbides.

[0036] 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 binding is about 1 :4 to about 20: 1, or about 1 :4 to about 4:1, or about 1 : 1 to about 4: 1.

[0037] FIG. 1 is a SEM image of a composition containing expanded graphite and a micro- or nano-sized binder blended at room temperature and atmospheric pressure. As shown in FIG. 1, the binder (white area) is only deposited on the surface of some of the expanded graphite worms.

[0038] FIG. 2 is a SEM image of a carbon composite formed from expanded graphite and a micro- or nano-sized binder under high pressure and high temperature conditions. As shown in FIG. 2, a binding phase (light area) is evenly distributed between the expanded graphite microstructures (dark area).

[0039] A SEM image of carbon graphite microstructures are shown in FIG. 3. An embodiment of a carbon composite is illustrated in Fig 4. As shown in FIG. 4, the composite comprises carbon microstructures 1 and binding phase 2 locking the carbon microstructures. The binding phase 2 comprises binder layer 3 and an optional interface layer 4 disposed between the binder layer and the carbon microstructures. The carbon composite contains interstitial space 5 among carbon microstructures 1. Within carbon microstructures, there are unfilled voids 6. [0040] The carbon composites can optionally comprise a filler. Exemplary filler includes carbon fibers, carbon black, mica, clay, glass fiber, ceramic fibers, and ceramic hollow structures. Ceramic materials include SiC, S1₃N₄, Si0₂, BN, and the like. The filler can be present in an amount of about 0.5 to about 10 wt. % or about 1 to about 8%.

[0041] The composites can have any desired shape including a bar, block, sheet, tubular, cylindrical billet, toroid, powder, pellets, or other form that may be machined, formed or otherwise used to form useful articles of manufacture. The sizes or the dimension of these forms are not particularly limited. Illustratively, the sheet has a thickness of about 10 μιη to about 10 cm and a width of about 10 mm to about 2 m. The powder comprises particles having an average size of about 10 μιη to about 1 cm. The pellets comprise particles having an average size of about 1 cm to about 5 cm.

[0042] One way to form the carbon composites is to compress a combination comprising carbon and a micro- or nano-sized binder to provide a green compact by cold pressing; and to compressing and heating the green compact thereby forming the carbon composites. In another embodiment, the combination can be pressed at room temperature to form a compact, and then the compact is heated at atmospheric pressure to form the carbon composite. These processes can be referred to as two-step processes. Alternatively, a combination comprising carbon and a micro- or nano-sized binder can be compressed and heated directly to form the carbon composites. The process can be referred to as a one-step process.

[0043] In the combination, the carbon such as graphite is present in an amount of about 20 wt.% to about 95 wt.%, about 20 wt.% to about 80 wt.%, or about 50 wt.% to about 80 wt.%, based on the total weight of the combination. 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 combination. The graphite in the combination can be in the form of chip, powder, platelet, flake, or the like. In an embodiment, the graphite is in the form of flakes having a diameter of about 50 microns to about 5,000 microns, preferably about 100 to about 300 microns. The graphite flakes can have a thickness of about 1 to about 5 microns. The density of the combination is about 0.01 to about 0.05 g/cm³, about 0.01 to about 0.04 g/cm³, about 0.01 to about 0.03 g/cm³ or about 0.026 g/cm³. The combination can be formed by blending the graphite and the micro- or nano-sized binder via any suitable methods known in the art. Examples of suitable methods include ball mixing, acoustic mixing, ribbon blending, vertical screw mixing, and V-blending. [0044] Referring to the two-step process, cold pressing means that the

combination comprising the graphite and the micro-sized or nano-sized binder is compressed at room temperature or at an elevated temperature as long as the binder does not significantly bond with the graphite microstructures. In an embodiment, greater than about 80 wt.%, greater than about 85 wt.%, greater than about 90 wt.%, greater than about 95 wt.%, or greater than about 99 wt.% of the microstructures are not bonded in the green compact. The pressure to form the green compact can be about 500 psi to about 10 ksi and the temperature can be about 20°C to about 200°C. The reduction ratio at this stage, i.e., the volume of the green compact relative to the volume of the combination, is about 40% to about 80%. The density of the green compact is about 0.1 to about 5 g/cm³, about 0.5 to about 3 g/cm³, or about 0.5 to about 2 g/cm³.

[0045] The green compact can be heated at a temperature of about 350°C to about 1200°C, specifically about 800°C to about 1200°C to form the carbon composites. In an embodiment, the temperature is above the melting point of the binder, for example, about 20°C to about 100°C higher or about 20°C to about 50°C higher than the melting point of the binder. When the temperature is higher, the binder becomes less viscose and flows better, and less pressure may be required in order for the binder to be evenly distributed in the voids between the carbon microstructures. However, if the temperature is too high, it may have detrimental effects to the instrument.

[0046] The temperature can be applied according to a predetermined temperature schedule or ramp rate. The means of heating is not particularly limited. Exemplary heating methods include direct current (DC) heating, induction heating, microwave heating, and spark plasma sintering (SPS). In an embodiment, the heating is conducted via DC heating. For example, the combination comprising the graphite and the micro- or nano-sized binder can be charged with a current, which flows through the combination generating heat very quickly. Optionally, the heating can also be conducted under an inert atmosphere, for example, under argon or nitrogen. In an embodiment, the green compact is heated in the presence of air.

[0047] The heating can be conducted at a pressure of about 500 psi to about 30,000 psi or about 1000 psi to about 5000 psi. The pressure can be a superatmospheric pressure or a subatmospheric pressure. Without wishing to be bound by theory, it is believed that when a superatmospheric pressure is applied to the combination, the micro- or nano- sized binder is forced into the voids between carbon microstructures through infiltration. When a subatmospheric pressure is applied to the combination, the micro- or nano-sized binder can also be forced into the voids between the carbon micro structures by capillary forces.

[0048] In an embodiment, the desirable pressure to form the carbon composites is not applied all at once. After the green compact is loaded, a low pressure is initially applied to the composition at room temperature or at a low temperature to close the large pores in the composition. Otherwise, the melted binder may flow to the surface of the die. Once the temperature reaches the predetermined maximum temperature, the desirable pressure required to make the carbon composites can be applied. The temperature and the pressure can be held at the predetermined maximum temperature and the predetermined maximum temperature for 5 minutes to 120 minutes.

[0049] The reduction ratio at this stage, i.e. the volume of the carbon composite relative to the volume of the green compact, is about 10% to about 70% or about 20 to about 40%. The density of the carbon composite can be varied by controlling the degree of compression. The carbon composites have a density of about 0.5 to about 10 g/cm³, about 1 to about 8 g/cm³, about 1 to about 6 g/cm³, about 2 to about 5 g/cm³, about 3 to about 5 g/cm³, or about 2 to about 4 g/cm³.

[0050] Alternatively, also referring to a two-step process, the combination can be first pressed at room temperature and a pressure of about 500 psi to 30,000 psi to form a compact; the compact can be further heated at a temperature higher than the melting point of the binder to make the carbon composite. In an embodiment, the temperature can be about 20°C to about 100°C higher or about 20°C to about 50°C higher than the melting point of the binder. The heating can be conducted at atmospheric pressure.

[0051] In another embodiment, the carbon composite can be made from the combination of the graphite and the binder directly without making the green compact. The pressing and the heating can be carried out simultaneously. Suitable pressures and temperatures can be the same as discussed herein for the second step of the two-step process.

[0052] Hot pressing is a process that applies temperature and pressure

simultaneously. It can be used in both the one-step and the two-step processes to make carbon composites.

[0053] The carbon composites can be made in a mold through a one-step or a two- step process. The obtained carbon composites can be further machined or shaped to form a bar, block, tubular, cylindrical billet, or toroid. Machining includes cutting, sawing, ablating, milling, facing, lathing, boring, and the like using, for example, a miller, saw, lathe, router, electric discharge machine, and the like. Alternatively, the carbon composite can be directly molded to the useful shape by choosing the molds having the desired shape.

[0054] Sheet materials such as web, paper, strip, tape, foil, mat or the like can also be made via hot rolling. In an embodiment, the carbon composite sheets made by hot rolling can be further heated to allow the binder to effectively bond the carbon microstructures together.

[0055] Carbon composite pellets can be made by extrusion. For example, a combination of the graphite and the micro- or nano-sized binder can be first loaded in a container. Then combination is pushed into an extruder through a piston. The extrusion temperature can be about 350°C to about 1200°C or about 800°C to about 1200°C. In an embodiment, the extrusion temperature is higher than the melting point of the binder, for example, about 20 to about 50°C higher than the melting point of the binder. In an embodiment, wires are obtained from the extrusion, which can be cut to form pellets. In another embodiment, pellets are directly obtained from the extruder. Optionally, a post treatment process can be applied to the pellets. For example, the pellets can be heated in a furnace above the melting temperature of the binder so that the binder can bond the carbon microstructures together if the carbon microstructures have not been bonded or not adequately bonded during the extrusion.

[0056] Carbon composite powder can be made by milling carbon composites, for example a solid piece, through shearing forces (cutting forces). It is noted that the carbon composites should not be smashed. Otherwise, the voids within the carbon microstructures may be destroyed thus the carbon composites lose elasticity.

[0057] The carbon composites have a number of advantageous properties for use in a wide variety of applications. In an especially advantageous feature, by forming carbon composites, both the mechanical strength and the elastomeric properties are improved.

[0058] To illustrate the improvement of elastic energy achieved by the carbon composites, the stress-strain curves for the following samples are shown in FIG. 5 : (A) natural graphite, (B) expanded graphite, (C) a mixture of expanded graphite and a micro- or nano-sized binder formed at room temperature and atmospheric pressure, (D) a mixture of expanded graphite and a micro- or nano-sized binder formed by at a high temperature and atmospheric pressure; and (E) a carbon composite formed from expanded graphite and a micro- and nano-sized binder under high pressure and high temperature conditions. For the natural graphite, the sample was made by compressing natural graphite in a steel die at a high pressure. The expanded graphite sample was also made in a similar manner. [0059] As shown in Fig. 5, the natural graphite has a very low elastic energy (area under the stress-strain curve) and is very brittle. The elastic energy of expanded graphite and the elastic energy of the mixture of expanded graphite and a micro- or nano-sized binder compacted at room temperature and high pressure is higher than that of the natural graphite. Conversely, both the hard and soft carbon composites of the disclosure exhibit significantly improved elasticity shown by the notable increase of the elastic energy as compared to the natural graphite alone, the expanded graphite alone, and the mixture of expanded graphite and binder compacted at room temperature and high pressure. In an embodiment, the carbon composites have an elastic elongation of greater than about 4%, greater than about 6%, or between about 4% and about 40%.

[0060] The elasticity of the carbon composites is further illustrated in Figs 6 and 7. FIG. 6 shows loop test results of a carbon composite at different loadings. FIG. 7 shows hysteresis results of a carbon composite tested at room temperature and 500°F respectively. As shown in FIG. 7, the elasticity of the carbon composite is maintained at 500°F.

[0061] In addition to mechanical strength and elasticity, the carbon composites can also have excellent thermal stability at high temperatures. FIG. 8 compares a carbon composite before and after exposing to air at 500°C for 25 hours. FIG. 9 (A) is a photo of a carbon composite sample after a thermo shock for 8 hours. The condition for the thermal shock is shown in FIG. 9(B). As shown in Figs 8 and 9(A), there are no changes to the carbon composite sample after exposing to air at 500°C for 25 hours or after the thermal shock. 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.

[0062] The carbon composites can also have excellent chemical resistance at elevated temperatures. In an embodiment, the composite is 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 HC1, 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 chemical resistance of the carbon composite is illustrated in Figs 10 and 11. FIG. 10 compares a carbon composite sample before and after exposing to tap water for 20 hours at 200°F, or after exposing to tap water for 3 days at 200°F. As shown in FIG. 10, there are no changes to the sample. FIG. 11 compares a carbon composite sample before and after exposing to 15% HC1 solution with inhibitor at 200°F for 20 hours, or after exposing to 15% HC1 solution at 200°F for 3 days. Again, there are no changes to the carbon composite sample.

[0063] The carbon composites are medium hard to extra hard with harness from about 50 in SHORE A up to about 75 in SHORE D scale.

[0064] As a further advantageous feature, the carbon composites have stable sealing force at high temperatures. The stress decay of components under constant compressive strain is known as compression stress relaxation. A compression stress relaxation test also known as sealing force relaxation test measures the sealing force exerted by a seal or O-ring under compression between two plates. It provides definitive information for the prediction of the service life of materials by measuring the sealing force decay of a sample as a function of time, temperature and environment. FIG. 12 shows the sealing force relaxation test results of a carbon composite sample 600°F. As shown in FIG. 12, the sealing force of the carbon composite is stable at high temperatures. In an embodiment, the sealing force of a sample of the composite at 15% strain and 600°F is maintained at about 5800 psi without relaxation for at least 20 minutes.

[0065] The carbon composites are useful for preparing articles for a wide variety of applications including but are not limited to electronics, atomic energy, hot metal processing, coatings, aerospace, automotive, oil and gas, and marine applications. Exemplary articles include seals, bearings, bearing seats, packers, valves, engines, reactors, cooling systems, and heat sinks. Thus, in an embodiment, an article comprises the carbon composites. The carbon composites may be used to form all or a portion of an article.

[0066] The article can be a downhole element. Illustrative articles include seals, seal bore protector, swabbing element protector, components of frac plug, bridge plug, compression packing elements (premier seal), expanding packing elements (ARC seal), O- rings, bonded seals, bullet seals, subsurface safety valve (SSSV) dynamic seals, SSSV flapper seals, V rings, back up rings, drill bit seals, or ESP seals. In an embodiment, the article is a packer, a seal, or an O-ring.

[0067] 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. All references are incorporated herein by reference.

[0068] 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).

[0069] 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.

Claims

CLAIMS What is claimed is:

1. A carbon composite comprising

carbon micro structures (1) having interstitial space (5) among the carbon

micro structures (1); and

a binder disposed in at least some of the interstitial space (5);

wherein the carbon micro structures (1) comprise unfilled voids (6) within the carbon microstructures (1).

2. The carbon composite of claim 1, wherein the interstitial space (5) have a size of about 0.1 micron to about 100 microns, and optionally the binder occupies about 10 % to about 90 % of the interstitial space (5) among the carbon microstructures (1).

3. The carbon composite of claim 1 or claim 2, wherein the binder comprises one or more of the following: Si0₂; Si; B; B₂0₃; a metal; or an alloy of the metal; wherein the metal is one or more of the following: aluminum; copper; titanium; nickel; tungsten;

chromium; iron; manganese; zirconium; hafnium; vanadium; niobium; molybdenum; tin; bismuth; antimony; lead; cadmium; or selenium.

4. A carbon composite comprising:

at least two carbon microstructures (1); and

a binding phase (2) disposed between the at least two carbon microstructures (1); wherein the binding phase (2) includes a binder comprising one or more of the following: Si0₂; Si; B; B₂0₃; a metal; or an alloy of the metal; wherein the metal is one or more of the following: aluminum; copper; titanium; nickel; tungsten; chromium; iron;

manganese; zirconium; hafnium; vanadium; niobium; molybdenum; tin; bismuth; antimony; lead; cadmium; or selenium.

5. The carbon composite of claim 4, wherein the binding phase (2) comprises a binder layer (3) and an interface layer (4) bonding one of the at least two carbon

microstructures (1) to the binder layer (3), optionally the interface layer (4) 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.

6. The carbon composite of any one of claims 1 to 5, wherein at least one of the following apply: the carbon microstructures (1) have a thickness of about 1 to about 200 microns; the carbon microstructures (1) have a diameter of about 10 to about 500 microns; or the unfilled voids (6) within the carbon microstructures (1) have a size of about 20 nm to about 1 micron.

7. The carbon composite of any one of claims 1 to 6, wherein the carbon micro structures (1) comprise micro structures of graphite.

8. The carbon composite of any one of claims 1 to 7, wherein the carbon micro structures (1) are bounded by mechanical interlocking, and optionally a chemical bond, a solid solution, or a combination thereof is formed at least between some carbon

micro structures (1) and the binder.

9. The carbon composite of any one of claims 1 to 8, wherein the binder comprises one or more of the following: steel; a nickel-chromium based alloy; or a nickel- copper based alloy.

10. The carbon composite of any one of claims 1 to 9, further comprising one or more of the following: carbon fiber; carbon black; mica; clay; glass fiber; ceramic fiber; or a ceramic hollow structure.

11. The carbon composite of any one of claims 1 to 10 comprising about 20 to about 80 wt. % of the carbon, based on the total weight of the carbon composite.

12. The carbon composite of any one of claims 1 to 11, wherein one or more of the following apply:

the carbon composite has an elastic elongation of greater than about 4%;

the carbon composite has a density of about 0.5 to about 10 g/cm³;

the carbon composite has thermal resistance with a range of operation temperatures from about -65°F up to about 1200°F;

the carbon composition is chemically resistant to water, oil, brines, and acids;

the carbon composite has a hardness from about 50 in SHORE A up to about 75 in SHORE D scale; or

a sample of the composite at 15% strain and 600°F is maintained at about 5800 psi without relaxation for at least 20 minutes.

13. The carbon composite of any one of claims 1 to 12, wherein the composite is in the form of a bar, block, sheet, tubular, cylindrical billet, toroid, powder, or pellets.

14. A sheet comprising the carbon composite of any one of claims 1 to 13, wherein the sheet has a thickness of about 10 μιη to about 10 cm.

15. A composition comprising the carbon composite of any one of claims 1 to 12, wherein the composition is a powder including particles having an average size of about 10 μιη to about 1 cm; or the composition comprises a plurality of pellets including particles having an average size of about 0.5 cm to about 5 cm.