Patent Grant
10626834
The present disclosure is related to fuel injectors for direct injection spark ignition engines. More particularly, the present disclosure relates to a coating on a valve member to reduce chemical and physical wear degradation of the sealing capability of the valve member.
This section provides background information related to the present disclosure which is not necessarily prior art.
Vehicles powered by internal combustion engines have a fuel delivery system that stores and delivers fuels to the internal combustion engines. In general, the fuel system includes units that include a fuel tank, a fuel pump, a fuel filter, a sending unit, a fuel rail, fuel injectors, and a series of conduits that transports fuel between the units. Because various units of the fuel system contact fuel, some at elevated temperatures, the units desirably withstand thermal-induced and/or fuel-induced corrosion.
Spark Ignited Direct Injection (SIDI) is a variant of fuel injection employed in some non-diesel two and four stroke internal combustion engines. The fuel is highly pressurized, and injected via a common rail fuel line directly into the combustion chamber of each cylinder. Some engines may have multi-point fuel injection that injects fuel into an intake tract, or cylinder port. Directly injecting fuel into a combustion chamber requires high pressure injection; low pressure can be used to inject fuel into an intake tract or cylinder port. Some advantages of SIDI engines are increased fuel efficiency and high power output. Some SIDI engines may have reduced emissions levels. Such advantages are achieved, in part, by precise control over the amount and timing of fuel injected into the combustion chamber.
Moreover, many vehicles have internal combustion engines that are powered at least partially, if not completely, by alternative fuels, which help reduce petroleum use and greenhouse gas emissions. Some vehicles, i.e., flexible-fuel vehicles or dual-fuel vehicles (also known as “flex-fuel vehicles”) have internal combustion engines that are designed to run on more than one fuel, such as a blend of gasoline and an alternative fuel.
One such alternative fuel is ethanol, which may be generated from corn, grain, or other biomass sources. Whereas some vehicles have internal combustion engines that run on pure 100% ethanol, i.e., E100 fuels, other vehicles have internal combustion engines that run on ethanol blended fuels, such as E5 (5% ethanol), E7 (7% ethanol), E10 (10% ethanol), E20 (20% ethanol), E22 (22% ethanol), E25 (25% ethanol), E70 (70% ethanol), E75 (75% ethanol), E85 (85% ethanol), or E95 (95% ethanol) fuels. Because ethanol causes corrosion on various materials, vehicle components, such as units of fuel delivery systems, that contact fuels containing ethanol benefit from coatings that resist corrosion. With the increasing use of fuels containing ethanol throughout the world, there is a need for new coatings that withstand corrosion caused by ethanol or a combination of ethanol and heat.
This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.
The current technology provides a vehicle component that includes a surface that is configured to contact a fuel containing ethanol and zinc ions, and a sacrificial carbon layer disposed on the surface. The sacrificial carbon layer has a thickness of greater than or equal to about 250 nm to less than or equal to about 5 μm. The sacrificial carbon layer includes carbon that is configured to complex with and solubilize ZnO deposited on the surface, wherein the ZnO forms from the zinc ions carried by the fuel.
In various embodiments, the surface includes a steel alloy or a ceramic.
In various embodiments, the sacrificial carbon layer includes a dopant selected from the group consisting of calcium (Ca), zinc (Zn), iron (Fe), boron (B), tungsten (W), platinum (Pt), gold (Au), silver (Ag), copper (Cu), chromium (Cr), aluminum (Al), titanium (Ti), nitrogen (N), phosphorous (P), silicon (Si), cobalt (Co), vanadium (V), zirconium (Zr), niobium (Nb), molybdenum (Mo), hafnium (Hf), tantalum (Ta), rhenium (Re), and combinations thereof.
In various embodiments, the sacrificial carbon layer includes a chelator selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA), diethylenetriaminepentaacetic acid (DTPA), N,N-bis(carboxymethyl)glycine (NTA) glutamic acid, N,N-diacetic acid (GLDA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethanoldiglycinic acid (EDG), 1,3-propylenediaminetetraacetic acid (PDTA), glucoheptonic acid, aspartic acid-N,N-diacetic acid (ASDA), 1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (CDTA), ethylenediamine-N,N′,diorthohydroxyphenylacetic acid (EDDHA), ethylenediamine-N,N′,diorthohydroxyparamethylphenylacetic acid (EDDHMA), ethlenediamine-N,N′-disuccinic acid (EDDS), N,N′-bis(2-hydroxybenzyl)-ethylenediamine-N,N′-diacetic acid (HBED), N-hydroxyethylethylenediamine, N,N′,N′-triacetic acid (HEDTA), imino-N,N-disuccinic acid (IDS), methylglycine-N,N-diacetic acid (MGDA), triethlenetetraamine-N,N,N′,N″,N′″,N′″-hexaacetic acid (TTHA), and combinations thereof.
In various embodiments, the sacrificial carbon layer is disposed directly on the surface of the vehicle component.
In various embodiments, the surface is a surface of a piston, an intake valve, a fuel injector, a spark plug, an exhaust valve, or a combination thereof.
In various embodiments, the vehicle component includes an adhesive layer disposed directly onto the surface of the vehicle component and a protective tungsten carbide carbon (WCC) layer disposed directly on the adhesive layer, wherein the protective WCC layer defines the surface and the sacrificial carbon layer is disposed directly the protective WCC layer.
In various embodiments, the vehicle component is a fuel injector, an intake valve, an exhaust valve, a cylinder, a piston, a spark plug, a fuel pump, a sending unit, a fuel tank, a ring, a gasket, or a combination thereof.
The current technology also provides a fuel injector for an internal combustion engine that includes an injector body having an inlet, an outlet, and a passageway for fuel to flow from the inlet to the outlet; a movable valve portion disposed in the passageway that translates between an open position and a closed position, wherein the movable valve portion defines a seat contacting element having an outermost exposed surface that has a sacrificial carbon layer; and a valve seat defined at the outlet, wherein in the closed position, the movable valve portion sealingly engages with the valve seat and in the open position, the movable valve portion is spaced from the valve seat to open the fuel injector permitting fuel to flow through the outlet.
In various embodiments, the sacrificial carbon layer further includes a chelating agent selected from the group consisting of ethylenediaminetetraacetic acid (EDTA), ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA), diethylenetriaminepentaacetic acid (DTPA), N,N-bis(carboxymethyl)glycine (NTA) glutamic acid, N,N-diacetic acid (GLDA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethanoldiglycinic acid (EDG), 1,3-propylenediaminetetraacetic acid (PDTA), glucoheptonic acid, aspartic acid-N,N-diacetic acid (ASDA), 1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (CDTA), ethylenediamine-N,N′,diorthohydroxyphenylacetic acid (EDDHA), ethylenediamine-N,N′,diorthohydroxyparamethylphenylacetic acid (EDDHMA), ethlenediamine-N,N′-disuccinic acid (EDDS), N,N′-bis(2-hydroxybenzyl)-ethylenediamine-N,N′-diacetic acid (HBED), N-hydroxyethylethylenediamine, N,N′,N′-triacetic acid (HEDTA), imino-N,N-disuccinic acid (IDS), methylglycine-N,N-diacetic acid (MGDA), triethlenetetraamine-N,N,N′,N″,N′″,N′″-hexaacetic acid (TTHA), and combinations thereof.
In various embodiments, the chelating agent is ethylenediaminetetraacetic acid (EDTA).
In various embodiments, the sacrificial carbon layer includes a dopant selected from the group consisting of calcium (Ca), zinc (Zn), iron (Fe), boron (B), tungsten (W), platinum (Pt), gold (Au), silver (Ag), copper (Cu), chromium (Cr), aluminum (Al), titanium (Ti), nitrogen (N), phosphorous (P), silicon (Si), cobalt (Co), vanadium (V), zirconium (Zr), niobium (Nb), molybdenum (Mo), hafnium (Hf), tantalum (Ta), rhenium (Re), and combinations thereof.
In various embodiments, the sacrificial carbon layer has a thickness from greater than or equal to about 0.250 μm to less than or equal to about 5 μm.
In various embodiments, the seat contacting element further includes a substrate with an adhesive interlayer disposed directly on the substrate, a tungsten carbide carbon (WCC) layer disposed directly on the adhesive interlayer, and the sacrificial carbon layer disposed directly on the WCC layer.
In various embodiments, the seat contacting element is a spherical cap.
In various embodiments, the valve seat has a seat surface complementary to the seat contacting element, wherein the seat surface also includes a sacrificial carbon layer.
In various embodiments, the seat contacting element further includes a substrate having a hardness from about HRC 58 to about HRC 60.
In various embodiments, the sacrificial carbon layer is a silicon-doped carbon layer.
In various embodiments, the silicon-doped carbon layer has a thickness of greater than or equal to about 0.5 μm to less than or equal to about 2 μm, and wherein an amount of silicon ranges from about 1 wt. % to about 15 wt. % of the silicon-doped carbon layer.
In various embodiments, the seat contacting element includes a substrate with chromium interlayer disposed directly on the substrate, a tungsten carbide carbon (WCC) layer disposed directly on the chromium interlayer, and the sacrificial carbon layer disposed directly on the WCC layer.
In various embodiments, the sacrificial carbon layer is to compensate for carbon chemical loss from the seat contacting element due to a reaction with zinc oxide in the fuel.
In various embodiments, the seat contacting element is a spherical cap.
In various embodiments, the valve seat has a seat surface complementary to the seat contacting element.
In various embodiments, the substrate has a hardness from about HRC 58 to about HRC 60.
In various embodiments, the sacrificial carbon layer increases WCC thermal stability by about 100 degrees C., shields heat from a sealing band to the WCC layer due to a lower thermal conductivity of graphitic carbon in the sacrificial carbon layer than that of diamond-like carbon, and reduces physical wear loss due to SiO2 acting as a lubricant.
The current technology also provides a vehicle that includes an internal combustion engine including at least one fuel injector for injecting fuel directly into a combustion chamber. The at least one fuel injector includes an injector body having an inlet, an outlet, and a passageway for fuel to flow from the inlet to the outlet; a movable valve portion movable in the passageway between an open and a closed position; a valve seat defined at the outlet, wherein the movable valve portion is to sealingly engage the valve seat in the closed position and wherein the movable valve portion is to be spaced from the valve seat in the open position to open the fuel injector for the fuel to flow through the outlet; and a seat contacting element defined on the movable valve portion, wherein the seat contacting element includes a sacrificial carbon layer at an outermost surface of the seat contacting element.
In various embodiments, the sacrificial carbon layer further includes a chelating agent.
In various embodiments, the chelating agent is ethylenediaminetetraacetic acid (EDTA).
In various embodiments, the sacrificial carbon layer is a silicon-doped carbon layer.
The current technology also provides a method of protecting a vehicle component from corrosion resulting from contact with fuel containing ethanol. The method includes disposing a sacrificial carbon layer on a surface of a vehicle component that is configured to contact fuel containing ethanol and zinc ions; and contacting the surface of the vehicle part having the sacrificial carbon layer to fuel containing ethanol. The sacrificial carbon layer includes carbon that complexes and solubilizes ZnO deposited on the surface, wherein the ZnO forms from the zinc ions carried by the fuel.
In various embodiments, the vehicle component is a fuel injector, an intake valve, an exhaust valve, a cylinder, a piston, a spark plug, a fuel pump, a sending unit, a fuel tank, a ring, a gasket, or a combination thereof.
In various embodiments, the disposing is performed by a process selected from the group consisting of filtered cathodic vacuum arc, ion beam deposition, plasma enhanced chemical vapor deposition, pulsed laser deposition, plasma immersion ion implantation, and combinations thereof.
In various embodiments, the disposing a sacrificial carbon layer comprises disposing a sacrificial carbon layer having a thickness of greater than or equal to about 250 nm to less than or equal to about 5 μm to a surface of a vehicle component.
Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.
The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.
Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.
Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific compositions, components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well-known technologies are not described in detail.
The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprises,” “comprising,” “including,” and “having,” are inclusive and therefore specify the presence of stated features, elements, compositions, steps, integers, operations, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Although the open-ended term “comprising,” is to be understood as a non-restrictive term used to describe and claim various embodiments set forth herein, in certain aspects, the term may alternatively be understood to instead be a more limiting and restrictive term, such as “consisting of” or “consisting essentially of.” Thus, for any given embodiment reciting compositions, materials, components, elements, features, integers, operations, and/or process steps, the present disclosure also specifically includes embodiments consisting of, or consisting essentially of, such recited compositions, materials, components, elements, features, integers, operations, and/or process steps. In the case of “consisting of,” the alternative embodiment excludes any additional compositions, materials, components, elements, features, integers, operations, and/or process steps, while in the case of “consisting essentially of,” any additional compositions, materials, components, elements, features, integers, operations, and/or process steps that materially affect the basic and novel characteristics are excluded from such an embodiment, but any compositions, materials, components, elements, features, integers, operations, and/or process steps that do not materially affect the basic and novel characteristics can be included in the embodiment.
Any method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed, unless otherwise indicated.
When a component, element, or layer is referred to as being “on,” “engaged to,” “connected to,” or “coupled to” another element or layer, it may be directly on, engaged, connected or coupled to the other component, element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being “directly on,” “directly engaged to,” “directly connected to,” or “directly coupled to” another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion (e.g., “between” versus “directly between,” “adjacent” versus “directly adjacent,” etc.). As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items.
Although the terms first, second, third, etc. may be used herein to describe various steps, elements, components, regions, layers and/or sections, these steps, elements, components, regions, layers and/or sections should not be limited by these terms, unless otherwise indicated. These terms may be only used to distinguish one step, element, component, region, layer or section from another step, element, component, region, layer or section. Terms such as “first,” “second,” and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first step, element, component, region, layer or section discussed below could be termed a second step, element, component, region, layer or section without departing from the teachings of the example embodiments.
Throughout this disclosure, the numerical values represent approximate measures or limits to ranges to encompass minor deviations from the given values and embodiments having about the value mentioned as well as those having exactly the value mentioned. Other than in the working examples provided at the end of the detailed description, all numerical values of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all instances by the term “about” whether or not “about” actually appears before the numerical value. “About” indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by “about” is not otherwise understood in the art with this ordinary meaning, then “about” as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters. For example, “about” may comprise a variation of less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and in certain aspects, optionally less than or equal to 0.1%.
As used herein, the terms “composition” and “material” are used interchangeably to refer broadly to a substance containing at least the preferred chemical constituents, elements, or compounds, but which may also comprise additional elements, compounds, or substances, including trace amounts of impurities, unless otherwise indicated. In addition, disclosure of ranges includes disclosure of all values and further divided ranges within the entire range, including endpoints and sub-ranges given for the ranges.
Example embodiments will now be described more fully with reference to the accompanying drawings.
Ethanol-blended fuels and various fuel additives have corrosive properties and potentially can damage vehicle components that they contact, especially in combination with thermal stress. In particular, ion contamination has a deleterious effect on vehicle components that contact ethanol-blended fuels. Ion contamination includes the presence of zinc, iron, chromium, copper, and nickel ions, as non-limiting examples, in ethanol-blended fuels and fuel delivery systems that precipitate and deposit on surfaces of fuel delivery system components that directly contact ethanol-blended fuel. For example, zinc (Zn) ions contribute to corrosion and delamination of tungsten carbide carbon (WCC) layers that are disposed on surfaces of various vehicle components that contact ethanol-blended fuels. Zinc ions may come from ethanol-blended fuel, from fuel delivery pathways (e.g., filters in injector passageways), from zinc-based coatings on surfaces of vehicle components that contact ethanol-blended fuel, or combinations thereof. Therefore, the ethanol-blended fuel may include small amounts of zinc, which may originate from zinc coatings or the ethanol-containing fuel may itself contain zinc (e.g., from zinc ions that get deposited as zinc oxide (ZnO)). The zinc from the ethanol-containing fuel may be deposited on vehicle components, which potentially results in corrosion and delamination.
Accordingly, the present technology provides vehicle components that are protected from thermal damage and corrosive damage resulting from contact with fuels comprising ethanol and/or fuels comprising corrosive additives. In particular, a sacrificial carbon layer is disposed on at least a portion of surfaces of vehicle components that contact ethanol-blended fuels. The surfaces can be surfaces of the components or surfaces of protective layers (e.g., WCC layers) disposed on the components. As discussed in more detail below, the sacrificial carbon layer reacts with and eliminates contaminants that can damage vehicle components that contact ethanol-blended fuel. The sacrificial carbon layer is thermally stable at temperatures emitted from running engines and minimizes corrosion and delamination to help protect vehicle components from ethanol-blended fuel-induced corrosion and delamination. For instance, the sacrificial carbon layer withstands temperatures of less than or equal to about 450° C., of less than or equal to about 400° C., of less than or equal to about 350° C., or of less than or equal to about 300° C. The sacrificial carbon layer provides excellent thermal and chemical inertness to corrosive fluids and reduces friction and wear to vehicle components that are subjected to thermal stress and/or contact with corrosive fluids, such as ethanol-blended fuels and corrosive additives. Because the sacrificial carbon layer minimizes or protects against corrosion, which inhibits fuel leaks, emissions may also be improved.
As used herein, “ethanol-blended fuels” are fuels that comprise ethanol. Therefore, ethanol-blended fuels include greater than or equal to about 0.5% ethanol by volume to less than or equal to 100% ethanol by volume. Some ethanol-blended fuels comprise less than 100% ethanol and also comprise gasoline. Non-limiting examples of ethanol-blended fuels include E5 (5% ethanol), E7 (7% ethanol), E10 (10% ethanol), E20 (20% ethanol), E22 (22% ethanol), E25 (25% ethanol), E70 (70% ethanol), E75 (75% ethanol), E85 (85% ethanol), E95 (95% ethanol), and E100 (100% ethanol) fuels.
Vehicles that have components that come in contact with ethanol-blended fuel are not limited. Nonetheless, exemplary vehicles include cars, trucks, recreational vehicles, motorcycles, scooters, boats, personal watercraft, tanks, and airplanes.
Ethanol-blended fuels are introduced to internal combustion engines by fuel delivery systems.
Fuel injectors are particularly susceptible to corrosion and delamination resulting from ion contamination and thermal stress. Therefore, components of fuel injectors that have surfaces that contact ethanol-blended fuels may benefit from having a sacrificial carbon layer disposed thereon.
A valve seat 76 is defined at the outlet 66. The movable valve portion 70 is to sealingly engage the valve seat 76 in the closed position. As used herein, the term “sealingly engage” means that the movable valve portion 70 contacts the valve seat 76 to prevent leakage when the movable valve portion 70 is in the closed position. Leakage is defined as flowing more than 2.5 mm3/minute of N-heptane at a pressure of 5 MPa in an operating temperature range of greater than or equal to about −40° C. to less than or equal to about 150° C.
In an open position (not shown), the movable valve portion 70 is spaced from the valve seat 76 to open the fuel injector 60 enabling the fuel to flow through the outlet 66. A seat contacting element 78 is defined on the movable valve portion 70. An outermost surface 80 of the seat contacting element 78 is subject to corrosion and delamination as it comes in contact with the ethanol-containing fuel that passes by it.
As depicted in
Further, the movable valve portion 70 may include a needle 86 as depicted in
The valve seat 76 has a seat surface 94 complementary to the seat contacting element 78. As depicted in
Therefore, the present disclosure contemplates disposing a sacrificial carbon layer on a surface of a component of the fuel injector 60 that contacts ethanol-blended fuel protects the component from corrosion. In various aspects of the current technology, a sacrificial carbon layer is disposed on at least the outermost surface 80 of the seat contacting element 42, on the seat surface 94 of the valve seat 76, on the outer tip surface 90 of the outlet 66, on a surface of the needle 86, on a surface of the passageway 68, or a combination thereof.
As noted above, zinc (Zn) ion contamination may have deleterious effects on fuel injectors and other components of fuel delivery systems that contact ethanol-blended fuels. For example, zinc ions may contribute to delamination of a tungsten carbide carbon (WCC) layer on a seat contacting element of a fuel injector that does not have the sacrificial carbon layer of the present disclosure to protect the WCC layer. The zinc ions may come from fuel and/or from fuel delivery pathways (e.g., filters 67 in the injector passageway 68 as shown in
The sacrificial carbon layer of the current technology is disposed on and protects fuel delivery system components, such as fuel injector seat contacting elements from delamination by converting ZnO to ZnCO3 and hydrogen gas. The ZnO is believed to react with carbon through the following series of reactions (wet chemistry):
C+H2O=CO+H2; CO+H2O=CO2+H2 (Carbon oxidation);
ZnO+2OH—+H2O═Zn(OH)42−(Complexation);
CO2+Zn(OH)42−═ZnCO3+2OH—+H2O (Carbonation);
The overall reaction is thus: C+ZnO+2H2O═ZnCO3+2H2, where complexation is the conversion of insoluble ZnO to soluble Zn(OH)42− to increase surface available for reaction.
In various aspects of the current technology, a sacrificial carbon layer protects the carbon in WCC composite layers so that a prolonged life of injector tips is attainable. The sacrificial carbon layer may be made with varying graphitic character and diamond-like character by adjusting deposition parameters (without need for additional tooling) to allow for quick implementation. Accordingly, in various aspects of the current technology, the sacrificial carbon layer is diamond like carbon (DLC). Non-limiting examples of deposition parameters that may be adjusted are: precursors; deposition time and temperature; gas and flow rate; bias current, etc.
DLC is a carbon-based material comprising a network of carbon-carbon sp2 hybrid bonds, carbon-carbon sp3 hybrid bonds, or both carbon-carbon sp2 hybrid bonds and carbon-carbon sp3 hybrid bonds. When both sp2 and sp3 bonds are present, the lower a carbon-carbon sp3 hybrid bond:carbon-carbon sp2 hybrid bond ratio (or higher sp2%), the more graphite-like the DLC material becomes. Conversely, the higher the carbon-carbon sp3 hybrid bond:carbon-carbon sp2 hybrid bond ratio (or higher sp3%), the more diamond-like the DLC material becomes.
A DLC material that contains a high hydrogen content, i.e., a hydrogen content of greater than about 40 atomic % (at. %) is referred to as hydrogenated DLC (H-DLC), wherein “at. %” refers to a percent of total atoms in the DLC material. Conversely, DLC material that contains a low hydrogen content, i.e., a hydrogen content of less than or equal to about 40 at. %, is referred to as non-hydrogenated-DLC (NH-DLC). The NH-DLC materials have a hydrogen content of greater than or equal to 0 at. % to less than or equal to about 40 at. %, less than or equal to about 30 at. %, less than or equal to about 20 at. %, less than or equal to about 10 at. %, less than or equal to about 5 at. %, or less than or equal to about 1 at. %. Therefore, NH-DLC materials have a hydrogen content of greater than or equal to about 0 at. % to less than or equal to about 40 at. %. In various aspects of the current technology, the NH-DLC material is substantially free of hydrogen, wherein “substantially free of hydrogen” means that hydrogen atoms are absent to the extent that undesirable and/or detrimental effects attendant with its presence are avoided. In certain embodiments, a NH-DLC material that is “substantially free” of hydrogen comprises less than about 1 at. % by weight of hydrogen in the material, optionally less than about 0.75 at. % by weight, optionally less than about 0.5 at. % by weight, optionally less than about 0.25 at. % by weight, optionally less than about 0.1 at. % by weight, optionally less than about 0.05 at. % and in certain embodiments, the material is free from any hydrogen and therefore comprises 0 at. % by weight hydrogen. Therefore, the sacrificial carbon layer of the current technology may include a H-DLC material or a NH-DLC material, which are generically referred to as “DLC materials.”
In various aspects of the current technology, the DLC material comprises a carbon content of from greater than or equal to about 70 at. % to less than or equal to about 100 at. %. For example, the DLC material can have a carbon content of greater than or equal to about 70 at. %, greater than or equal to about 75 at. %, greater than or equal to about 80 at. %, greater than or equal to about 85 at. %, greater than or equal to about 90 at. %, greater than or equal to about 95 at. %, or greater than or equal to about 99 at. %.
In various aspects of the current technology, the DLC material comprises a carbon-carbon sp3 hybrid bond content of greater than or equal to about 1%, greater than or equal to about 10%, greater than or equal to about 20%, greater than or equal to about 30%, greater than or equal to about 40%, greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 90%, or greater than or equal to about 95% of the total number to sp3 and sp2 hybrid bonds, such as a carbon-carbon sp3 hybrid bond content of from greater than or equal to about 1% to less than or equal to about 100%, greater than or equal to about 20% to less than or equal to about 100%, greater than or equal to about 30% to less than or equal to about 100%, greater than or equal to about 40% to less than or equal to about 100%, greater than or equal to about 50% to less than or equal to about 100%, greater than or equal to about 60% to less than or equal to about 100%, greater than or equal to about 70% to less than or equal to about 100%, greater than or equal to about 80% to less than or equal to about 100%, greater than or equal to about 90% to less than or equal to about 100%, or greater than or equal to about 95% to less than or equal to about 100%.
In various aspects of the current technology, the DLC material comprises a carbon-carbon sp2 hybrid bond content of greater than or equal to about 0%, greater than or equal to about 10%, greater than or equal to about 20%, greater than or equal to about 30%, greater than or equal to about 40%, greater than or equal to about 50%, greater than or equal to about 60%, greater than or equal to about 70%, greater than or equal to about 80%, greater than or equal to about 90%, or greater than or equal to about 95% of the total number to sp3 and sp2 hybrid bonds, such as a carbon-carbon sp2 hybrid bond content of from greater than or equal to about 0% to less than or equal to about 99%, greater than or equal to about 0% to less than or equal to about 95%, greater than or equal to about 0% to less than or equal to about 90%, greater than or equal to about 0% to less than or equal to about 80%, greater than or equal to about 0% to less than or equal to about 70%, greater than or equal to about 0% to less than or equal to about 60%, greater than or equal to about 0% to less than or equal to about 50%, greater than or equal to about 0% to less than or equal to about 40%, greater than or equal to about 0% to less than or equal to about 30%, greater than or equal to about 0% to less than or equal to about 20%, greater than or equal to about 0% to less than or equal to about 10%, greater than or equal to about 0% to less than or equal to about 5%, greater than or equal to about 0% to less than or equal to about 1%.
In various aspects of the current technology, the DLC material comprises a carbon-carbon sp3 hybrid bond:carbon-carbon sp2 hybrid bond ratio of from greater than or equal to about 1:1000 to less than or equal to about 1000:1, of from greater than or equal to about 1:750 to less than or equal to about 750:1, of from greater than or equal to about 1:500 to less than or equal to about 500:1, of from greater than or equal to about 1:250 to less than or equal to about 250:1, of from greater than or equal to about 1:100 to less than or equal to about 100:1, of from greater than or equal to about 1:50 to less than or equal to about 50:1.
In some aspects of the current technology, the sacrificial carbon layer further includes a chelating agent. It is to be understood that any suitable chelating agent may be used. Non-limiting examples of suitable chelating agents include ethylenediaminetetraacetic acid (EDTA), ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA), diethylenetriaminepentaacetic acid (DTPA), N,N-bis(carboxymethyl)glycine (NTA) glutamic acid, N,N-diacetic acid (GLDA), hydroxyethylethylenediaminetriacetic acid (HEDTA), ethanoldiglycinic acid (EDG), 1,3-propylenediaminetetraacetic acid (PDTA), glucoheptonic acid, aspartic acid-N,N-diacetic acid (ASDA), 1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (CDTA), ethylenediamine-N,N′,diorthohydroxyphenylacetic acid (EDDHA), ethylenediamine-N,N′,diorthohydroxyparamethylphenylacetic acid (EDDHMA), ethlenediamine-N,N′-disuccinic acid (EDDS), N,N′-bis(2-hydroxybenzyl)-ethylenediamine-N,N′-diacetic acid (HBED), N-hydroxyethylethylenediamine, N,N′,N′-triacetic acid (HEDTA), imino-N,N-disuccinic acid (IDS), methylglycine-N,N-diacetic acid (MGDA), triethlenetetraamine-N,N,N′,N″,N′″,N′″-hexaacetic acid (TTHA), and combinations thereof.
According to various aspects of the current technology, the sacrificial carbon layer is doped with a metal, metalloid, or nonmetal doping material to generate a doped sacrificial carbon layer. The doping material is, for example, calcium (Ca), zinc (Zn), iron (Fe), boron (B), tungsten (W), platinum (Pt), gold (Au), silver (Ag), copper (Cu), chromium (Cr), aluminum (Al), titanium (Ti), nitrogen (N), phosphorous (P), silicon (Si), cobalt (Co), vanadium (V), zirconium (Zr), niobium (Nb), molybdenum (Mo), hafnium (Hf), tantalum (Ta), rhenium (Re), or a combination thereof. When present, the sacrificial carbon layer has a doping material concentration of from greater than 0 wt. % to less than or equal to about 30 wt. %, to less than or equal to about 20 wt. %, to less than or equal to 10 wt. %, or to less than or equal to about 5 wt. %. In some embodiments, the sacrificial carbon layer is a silicon-doped carbon layer. It is to be understood that the silicon-doped carbon layer may have any thickness and silicon content as desired and/or suitable for a desired end use. In an example, the silicon-doped carbon layer has a thickness ranging from about 0.5 μm to about 2 μm, and an amount of silicon ranges from greater than or equal to about 1 wt. % to less than or equal to about 15 wt. % of the silicon-doped carbon layer.
The sacrificial carbon layer can be disposed directly on a surface of a vehicle component or directly on a surface of a protective layer disposed on a vehicle component, for example, by way of an adhesive layer.
In various embodiments, as depicted in
It is to be understood that the sacrificial carbon layer 108 of the present disclosure is multi-functional. Some of these functions include, but are not limited to the following. The sacrificial carbon layer 108 may compensate for carbon chemical loss from a seat contacting element due to carbon from the seat contacting element reacting with zinc oxide (ZnO) derived from zinc ions carried in the fuel. The sacrificial carbon layer may also: increase WCC thermal stability, e.g., by about 100° C.; shield heat from the sealing band to WCC due to a lower thermal conductivity of graphitic carbon than that of diamond-like carbon; and reduce physical wear loss due to SiO2 acting as a lubricant. The silica (SiO2) may be generated during operation of the engine through reacting with H2O which may be present in ethanol fuels.
Examples of the present disclosure provide a low-cost and implementable strategy (e.g., no additional tooling needed) for mitigating tip leakage. Further, examples of the present disclosure may extend the life of the WCC coating due to the sacrificial carbon layer which provides long-term tolerance for carbon loss. Examples of the present disclosure may be used with vehicles running on biofuels, e.g., E100.
The current technology also provides a method of protecting a vehicle part from thermal and corrosive damage resulting from contact with fuel comprising ethanol. The method comprises disposing a sacrificial carbon layer on at least a portion of a surface of a vehicle component that is configured to contact fuel comprising ethanol, and contacting the at least a portion of the surface of the vehicle component having the sacrificial carbon layer to fuel comprising ethanol. The sacrificial carbon layer comprises carbon that complexes and solubilizes ZnO carried deposited from the fuel comprising ethanol and zinc ions. The vehicle component is a fuel injector, an intake valve, an exhaust valve, a cylinder, a piston, a spark plug, a fuel pump, a sending unit, a fuel tank, a ring, a gasket, or a combination thereof. In various aspects of the current technology, the vehicle component is a component of a fuel injector described herein. The disposing is performed by filtered cathodic vacuum arc, ion beam deposition, plasma enhanced chemical vapor deposition, pulsed laser deposition, or plasma immersion ion implantation. In some embodiments, the disposing a layer comprises disposing a sacrificial carbon layer having a thickness of greater than or equal to about 250 nm to less than or equal to about 5 μm of a surface of a vehicle component.
The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.
This application claims the benefit of U.S. Provisional Application No. 62/331,403, filed on May 3, 2016. The entire disclosure of the above application is incorporated herein by reference.
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