EP1831408A2 - Composition and process for enhanced properties of ferrous components - Google Patents
Composition and process for enhanced properties of ferrous componentsInfo
- Publication number
- EP1831408A2 EP1831408A2 EP05853711A EP05853711A EP1831408A2 EP 1831408 A2 EP1831408 A2 EP 1831408A2 EP 05853711 A EP05853711 A EP 05853711A EP 05853711 A EP05853711 A EP 05853711A EP 1831408 A2 EP1831408 A2 EP 1831408A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- coating
- metal alloy
- surface region
- chemo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/32—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for gear wheels, worm wheels, or the like
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/185—Hardening; Quenching with or without subsequent tempering from an intercritical temperature
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/78—Combined heat-treatments not provided for above
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/007—Heat treatment of ferrous alloys containing Co
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/02—Hardening by precipitation
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/04—Hardening by cooling below 0 degrees Celsius
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D7/00—Modifying the physical properties of iron or steel by deformation
- C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
- C22C38/105—Ferrous alloys, e.g. steel alloys containing cobalt containing Co and Ni
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
- C23C8/22—Carburising of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/80—After-treatment
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H55/00—Elements with teeth or friction surfaces for conveying motion; Worms, pulleys or sheaves for gearing mechanisms
- F16H55/02—Toothed members; Worms
- F16H55/06—Use of materials; Use of treatments of toothed members or worms to affect their intrinsic material properties
Definitions
- the present invention relates generally to the combination of near- net-shape (NNS) forging, a class of high-strength, high-toughness (HSHT) ferrous alloys, and the application of thermo-chemical processing to enhance the surface properties of the alloy class forgings. More particularly, the invention relates to applying the NNS forging, alloy i o selection, and thermo-chemical processing to gears and other components within power transmission systems.
- NNS near- net-shape
- HSHT high-toughness
- Alloys used for gear applications need, for example, the ability to withstand shear strain, bending fatigue loads, and surface degradation via pitting and contact wear.
- Conventional gear alloys are still limited in the strength and toughness required for very high performance applications.
- thermo-chemical treatments are typically required to improve the performance of conventional alloys.
- iron-based metal alloy components such as power-transmission components
- the hardened or chemically altered surface case provides wear and corrosion resistance, while the core provides toughness, impact resistance, and bending-fatigue strength.
- Conventional methods used to achieve the properties include carburizing and nitriding; alternatively, novel, unconventional thermo-chemical processes, such as high current density ion implantation, may be applied to achieve or retain desired case and core properties.
- the methods for forming a hardened surface case on gears also involve many sequential processing steps that increase manufacturing time and cost.
- the near-net-shape forging process producing a gear, for example, eliminates the need for hobbing the gear and augments the mechanical properties, which are further improved by the use of a class of HSHT ferrous alloys possessing improved high-strength and high-toughness.
- the alloy class has surface properties that may be enhanced through thermo-chemical surface processing via methods that also reduce manufacturing time and costs, and the surface roughness of as- processed articles may be isotropically superfinished via chemo- mechanica! means to further enhance the surface properties, including pitting fatigue and wear resistance.
- An embodiment of the invention is a method whereby a billet of alloy is near-net-shaped forged to the finished gear shape, but with a small stock allowance for any subsequent heat treatment and thermo- chemical surface processing prior to finish machining and superfinishing.
- Another embodiment of the invention is a method wherein the gear alloy is a selected from a class of high-strength, high-toughness alloys.
- Another embodiment of the invention is a method wherein the near-net-shape forged high-strength, high-toughness alloys are heat treated and thermo-chemically processed, such as to synergistically combine selected surface engineering and bulk alloy heat treatment steps, thereby effecting significant savings in processing times, cost, and delivery, while retaining the desired increase in performance capability.
- Another embodiment of the invention is a method wherein the near-net-shape forging comprising the high-strength, high- toughness alloys that are heat treated and thermo-chemically processed to synergistically combine selected surface engineering and bulk alloy heat treatment steps, are further afforded a subsequent chemo- mechanical processing step to reduce the surface roughness and further enhance the resulting surface properties, while retaining the desired increase in bulk and surface performance capabilities.
- NMS near-net-shape
- HSHT high-toughness
- the combination comprises a novel approach to the improvement of component or system properties, for example, to enhance the bending- and surface-fatigue design allowables for gears and other components within power-transmission systems.
- Figure 1 shows a schematic view of a metal alloy.
- Figure 2 shows a schematic view of a crystal structure.
- Figure 3 shows a schematic view of a metal alloy during surface processing.
- Figure 4 shows a schematic view of a metal alloy and hardened surface region.
- Figure 5 shows a schematic view of a plasma (ion) nitriding chamber.
- Figure 6 shows a nitrogen concentration profile over a depth of a hardened surface region.
- Figure 7 shows a schematic view of a nitride compound on a surface region of a metal alloy.
- Figure 8 shows a schematic view of a coating on a hardened surface region of a metal alloy.
- Figure 9 shows a schematic view of a coating on an intermediate coating on a surface region of a metal alloy.
- Figure 1 shows a schematic view of a metal alloy 10, including a core 12 and a surface region 14 on the core 12.
- the metal alloy 10 is an iron-based alloy that is generally nitrogen-free and has an associated composition and hardening heat treatment, including a tempering or aging temperature.
- the tempering or aging temperature is dependent on the metal alloy 10 composition and is the temperature at which the metal alloy is heat processed to alter characteristics of the metal alloy 10, such as hardness, strength, and toughness.
- the composition of the metal alloy 10 is essentially a Ni-Co secondary hardening martensitic steel, which provides high strength and high toughness.
- the ultimate tensile strength of the metal alloy 10 is greater than about 170 ksi and the yield stress is greater than about 140 ksi and in some examples the ultimate tensile strength is approximately 285 ksi and the yield stress is about 250 ksi.
- High strength and high toughness provide desirable performance in such applications as power transmission components.
- Conventional vacuum melting and remelting practices are used and may include the use of gettering elements including, for example, rare earth metals, Mg, Ca, Si, Mn and combinations thereof, to remove impurity elements from the metal alloy 10 and achieve high strength and high toughness.
- Impurity elements such as S, P, O, and N present in trace amounts may detract from the strength and toughness.
- the alloy content of the metal alloy 10 and the tempering (aging) temperature satisfy the thermodynamic condition that the alloy carbide, M 2 C where M is a metallic carbide-forming element, is more stable than F ⁇ 3C (a relatively coarse precursor carbide), such that Fe 3 C will dissolve and M 2 C alloy carbides precipitate.
- the M 2 C alloy carbide-forming elements contribute to the high strength and high toughness of the metal alloy 10 by forming a fine dispersion of M 2 C precipitates that produce secondary hardening during a conventional precipitation-heat process prior to any surface processing.
- the preferred alloy carbide-forming elements include Mo and Cr, which combine with carbon in the metal alloy 10 to form M 2 C.
- the metal alloy 10 includes between 1.5wt% and 15wt% Ni, between 5wt% and 30wt% Co, and up to 5wt% of a carbide-forming element, such as Mo, Cr, W, V or combinations thereof, which can react with up to approximately 0.5wt% C to form metal carbide precipitates of the form M 2 C. It is to be understood that the metal alloy 10 may include any one or more of the preferred alloy carbide-forming elements.
- the carbide-forming elements provide strength and toughness advantages because they form a fine dispersion of M 2 C.
- Certain other possible alloying elements such as Al, V, W, Si, Cr, may also form other compounds such as nitride compounds. These alloying elements and the carbide-forming elements influence the strength, toughness, and surface hardenability of the metal alloy 10.
- metal alloy 10 is hardened by heat treating above ⁇ 15OO°F in the austenite phase region (austenitizing) to re-solution carbides, etc. It is then quenched and refrigerated at approximately - (minus) 100 0 F to transform the austenite structure to martensite.
- the latter is a very hard, brittle, metastable phase having a body-centered tetragonal (BCT) crystal structure because of the entrapped carbon atoms.
- BCT body-centered tetragonal
- the tetragonal crystal structure 16 includes atomic lattice sites 17 forming sides having length 18 which are essentially perpendicular to sides having length 20.
- the length 18 does not equal the length 20.
- Subsequent aging heat treatments are used to both soften the martensite structure and also transform the F ⁇ 3 C phase to M 2 C which strengthens the structure. The latter reaction tends to dominate, leading to secondary hardening. These reactions can lead to concomitant changes in crystal structure as the metastable martensitic BCT structure transitions to other phases, such as austenite and/or ferrite depending on the exposure temperature and time.
- the iron-based alloy may be formed instead with other crystal structures such as, but not limited to, face-centered cubic (e.g. austenite) and body-centered cubic (e.g. ferrite). These phase transitions may lead to dimensional changes.
- face-centered cubic e.g. austenite
- body-centered cubic e.g. ferrite
- Figure 3 shows a schematic cross-sectional view of the metal alloy 10 during transformation of the surface region 14 into a hardened surface region 28 as illustrated in Figure 4.
- a high current density ion implantation (high intensity plasma ion processing) nitriding process is used to form the hardened surface region, although other surface hardening processes may be utilized such as, but not limited to, nitrocarburizing, carburizing, boronizing, and chromizing.
- the high current density ion implantation (high intensity plasma ion processing) nitriding process is conducted in an appropriate reactor, an example of which is illustrated schematically in Figure 5.
- the metal alloy 10 is placed in the reactor 34.
- the metal alloy 10 is placed in the high current density ion implantation (high intensity plasma ion processing) chamber 36 on a cathode 38.
- the cathode 38 provides a voltage bias to the metal alloy 10, thereby heating the metal alloy 10 to a desired temperature that is below the heat treating temperature, such as an aging or tempering temperature, of the metal alloy 10.
- Heating the metal alloy 10 to a temperature above the heat treating temperature may alter the incumbent crystal structure 16, relieve residual stresses in the metal alloy 10, otherwise undesirably alter the microstructure and properties of the core, and undesirably alter the dimensions of the metal alloy 10.
- the strength, toughness, incumbent crystal structure 16, and dimensions of the metal alloy 10 are maintained through the high current density ion implantation (high intensity plasma ion processing) nitriding process. Subsequent processes to dimensionalize the metal alloy 10 or a power transmission component formed from the metal alloy 10 are eliminated.
- the heat treating temperature is between 700 0 F and about 1000 0 F.
- the heat treating temperature may be different.
- the chamber 36 includes a vacuum pump 40 which maintains a vacuum in the chamber 36 of the reactor 34.
- a sample bias device 42 provides a bias voltage of between 100V and 1500V to the cathode 38. Preferably, the bias voltage is between 150V and 700V.
- a thermocouple 44 attached to the cathode 38 detects the cathode 38 temperature and a cooling system 46 provides cooling capability to control the chamber 36 temperature.
- the chamber 36 is in fluid communication with precursor gases in storage tanks 48.
- the precursor gas storage tanks 48 may include gases such as nitrogen, hydrogen, and methane, although it should be noted that these gases are not all necessarily utilized during the high current density ion implantation (high intensity plasma ion processing) nitriding process.
- the conduit 50 connects the precursor gas storage tanks 48 to the inner chamber 40 and includes a gas metering device 52 to control the gas flow from the gas storage tanks 48.
- a plasma discharge voltage device at the filament 54 provides an ionizing voltage to a filament 56, which ionizes incoming gas from the conduit 50.
- the plasma discharge voltage at the filament is preferably between 30V and 150V and even more preferably is about 100V. It is to be understood that the configuration of the reactor 34 is not meant to be limiting and that alternative configurations of high current density ion implantation (high intensity plasma ion processing) reactors as well as reactors utilizing alternative surface processing processes may be used.
- the temperature, vacuum pressure in the chamber 36, precursor gas flow and ratio, time of processing, filament bias voltage, and sample bias voltage are controlled during the high current density ion implantation (high intensity plasma ion processing) nitriding process to provide a hardened surface region 28 ( Figure 4) on the metal alloy 10.
- the preferred conditions include a temperature between 700 0 F and about 1000 0 F, a pressure between about 0.5 mtorr and 5.0 mtorr in the chamber 36, a precursor gases mixture of nitrogen and hydrogen in the range 10 to 100% nitrogen and a preferred range of 80 to 100% nitrogen, and a time in the range of about 5 to 200 hours and a preferred range of 10 to 100 hours. Even more preferably, the conditions are controlled to a temperature of about 800 0 F to about 875 0 F, a pressure of 0.75 mtorr in the chamber 36 ( Figure 5) and for a time of about twelve hours depending on the case depth required.
- nitrogen from the nitrogen atmosphere 26 ( Figure 3) in the chamber 36 diffuses into the surface region 14 of the metal alloy 10.
- the nitrogen interstitially diffuses into the surface region 14, thereby hardening the surface region 14 and transforming the surface region 14 into the hardened surface region 28.
- ions from the chamber 36 also bombard the surface region 14 without diffusing into the surface region 14. That is, the ions sputter the surface region 14 and thereby remove oxides and other impurities that may be present on the surface region 14.
- the bias voltages utilized for the sample bias and filament voltage may provide the benefit of more favorable processing kinetics compared to other nitriding processes that utilize lower operating voltages, such as plasma (ion) nitriding.
- the hardened surface region 28 has a gradual transition in nitrogen concentration over a depth D between an outer surface 30 of the hardened surface region 28 and an inner portion 32 of the hardened surface region 28.
- the line 62 in Figure 6 illustrates a gradual nitrogen concentration profile over the depth D.
- the line 64 represents the nitrogen concentration profile of a generally abrupt nitrogen concentration.
- the nitrogen concentration is relatively high compared to the nitrogen concentration in the core 12.
- the nitrogen concentration is relatively low and approaches the nitrogen concentration of the core 12. It is to be understood that a variety of nitrogen concentration profiles may result from varying the preferred conditions.
- Figure 7 shows a schematic view of a metal alloy 10 after another high current density ion implantation (high intensity plasma ion processing) nitriding process.
- Utilizing a temperature towards the ends of the preferred range of 700 0 F and about 1000 0 F or utilizing an additional gas such as methane may result in the formation of a compound 68 of iron and nitrogen, such as the ⁇ ' or ⁇ compounds, on the surface region 14.
- Formation of the compound 68 is generally not preferred if a coating will be subsequently deposited over the compound 68, however, the compound 68 may provide corrosion resistance for the metal alloy 10.
- alloying elements such as Al, V, W, Si, and Cr may be present in the metal alloy 10.
- Nitride compounds containing the alloying elements may form during the high current density ion implantation (high intensity plasma ion processing) nitriding process.
- the presence of the nitride compounds is generally detrimental to the mechanical properties of the metal alloy 10 and are particularly detrimental in a complex with iron nitride compounds that may be formed under certain nitriding processing conditions; however, the presence of these alloying elements may be required to acquire other characteristics in the metal alloy 10.
- Figure 9 shows a schematic view of a metal alloy 10 after a high current density ion implantation (high intensity plasma ion processing) nitriding process.
- the metal alloy 10 includes a coating 84 on the hardened surface region 28, which preferably has a gradual nitrogen concentration profile and essentially does not include an iron and nitrogen compound, such as the ⁇ ' or ⁇ compounds.
- the coating 84 is deposited on the hardened surface region 28 in a thickness between 0.5 micrometers and 10 micrometers by a vapor deposition or magnetron sputtering process, although other thicknesses may be desirable.
- the deposited coating 84 is a solid lubricious coating such as an amorphous hydrogenated carbon, although other coatings may be used.
- the amorphous hydrogenated carbon coating has a biaxial residual stress less than 800 MPa in compression at room temperature, is thermally stable at temperatures over 400 0 F, and has an abrasive wear rate less than 3x10 "15 m 3 m '1 N '1 in a slurry of AI 2 O 3 .
- the amorphous hydrogenated carbon coating may include a metal or transition metal such as titanium, chromium, tungsten or other transition metal to alter the lubricious characteristics of the coating 84. It should be noted that the above description represents a non-limiting example of the many types of a solid lubricious coating that may be applied to the surface of an alloy or component to improve certain performance characteristics.
- an intermediate coating 86 ⁇ may be deposited between the coating 84 and the hardened surface region 28 to strongly bond the coating 84 to the hardened surface region 28.
- the intermediate coating 86 bonds strongly to both the hardened surface region 28 and the coating 84.
- the intermediate coating 86 is a metal and even more preferably it is the same transition metal as is included in the amorphous hydrogenated carbon coating.
- like materials, such as two metals form stronger bonds than unlike materials, such as a metal and a non-metal. Therefore, the metal of the intermediate coating 86 strongly bonds to the metal hardened surface region 28 and to the transition metal in the amorphous hydrogenated carbon coating.
- Methods for producing gears involve many sequential processing steps. Typically, a forged billet stock is hobbed to a rough, oversized finish shape and thermo-chemically processed by carburization, for example, then slow cooled. This is followed by the mandatory or optional steps of re-austenitization, quenching, refrigerating by cryogenic treatment, tempering (aging), finish grinding, etch inspection, shot-peening, honing and final inspection.
- the methods lead to extended manufacturing process time and increased costs.
- the near-net-shape forging process producing a gear, for example, eliminates the need for hobbing the gear.
- the near-net-forging process benefits mechanical properties by promoting the material flow to follow the contours of the gears. This texturing also leads to microstructural alignment that promotes improvements in mechanical properties, including tooth bending fatigue.
- the gear material is selected from the the class of high- strength, high toughness ferrous alloys, the performance of the gear is further improved.
- the alloy class has surface properties that may be enhanced through thermo-chemical surface processing via methods that also reduce manufacturing time and costs.
- the performance characteristics of gears, bearings, and other components within a power-transmission system may be improved by the refinement in the roughness of the surfaces of such components through a process of superfinishing.
- One suitable superfinishing technique is described in U.S. Pat. No. 4,491 ,500, which discloses a process for refining metal surfaces in which a two-step process employing a liquid chemical is followed by a burnishing liquid. A relatively soft coating is formed, which is subsequently treated and physically removed.
- a mass of elements comprised of a quantity of objects with hard metal surfaces of arithmetic average roughness value in excess of about 15 microinches, is introduced into the container of mass finishing equipment.
- the mass of elements is wetted with a liquid substance capable of rapid reaction, under oxidizing conditions, to chemically convert the metal of the object surfaces to a stable film of substantially reduced hardness, and the mass is rapidly agitated, while maintaining the metal surfaces in a wetted condition with the liquid substance, to produce relative movement and abrasive contact among the elements thereof and to produce continuous oxygenation of the liquid substance.
- the reactivity of the liquid substance and the intensity of agitation of the mass are controlled to maintain the stable film on the metal surfaces at least at the level of visual perceptibility.
- the mass of elements introduced into the mass finishing equipment will include a quantity of abrasive finishing media, and the agitation step will be carried out for a period of less than six hours.
- the surfaces will be of a metal selected from the group consisting of iron, copper, zinc, aluminum, titanium, and the alloys thereof, and the stable film will comprise an oxide, phosphate, oxalate, sulfate, and/or chromate of the substrate metal.
- the liquid substance utilized to chemically convert the metal of the object surfaces will usually be a solution containing one or more of the radicals: phosphate, oxalate, sulfate, chromate, and mixtures thereof, and in certain instances it will be preferred for the substance to additionally include an oxidizing agent; generally, the liquid substance will have an acidic pH value. Solutions containing phosphate and oxalate radicals in combination with a peroxide compound are often found to be particularly effective for refining ferrous metal surfaces, and may be produced from a tripolyphosphate salt, oxalic acid, and hydrogen peroxide.
- the combination of selection of a member of the class of high-strength, high- toughness (HSHT) ferrous alloys and its processing to include near-net- shape (NNS) forging, thermo-chemical processing, a vibratory, chemo- mechanical process (chemically accelerated vibratory polishing), such as superfinishing, to enhance the surface properties of the alloy class forgings, and coating the surface; comprises a novel approach to the improvement of component or system properties.
- the combination enhances the bending- and surface-fatigue design allowables for gears and other components within power-transmission systems.
- the primary advantages of the present invention include: the identification of near-net-shape forging processes that eliminate hobbing while imparting enhanced strength, including axial- and bending-fatigue strength, the use of a new class of ferrous alloys possessing improved high-strength and high-toughness compared to conventional gear alloys, thermo-chemically processing them via conventional and/or novel means to enhance surface properties, reduction of the surface roughness of the as-thermo-chemically processed article, also to enhance surface properties and performance, and combining these elements in such a manner that the surface and bulk properties and performance are enhanced and manufacturing time and casts are reduced.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US63861204P | 2004-12-23 | 2004-12-23 | |
PCT/US2005/044862 WO2006071502A2 (en) | 2004-12-23 | 2005-12-13 | Composition and process for enhanced properties of ferrous components |
Publications (2)
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EP1831408A2 true EP1831408A2 (en) | 2007-09-12 |
EP1831408A4 EP1831408A4 (en) | 2010-07-21 |
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EP05853711A Withdrawn EP1831408A4 (en) | 2004-12-23 | 2005-12-13 | Composition and process for enhanced properties of ferrous components |
Country Status (6)
Country | Link |
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US (1) | US20080277030A1 (en) |
EP (1) | EP1831408A4 (en) |
JP (1) | JP4919968B2 (en) |
KR (1) | KR20070095935A (en) |
CA (1) | CA2592420A1 (en) |
WO (1) | WO2006071502A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110951962A (en) * | 2019-12-16 | 2020-04-03 | 武汉理工大学 | High-performance gear heat treatment method for realizing fine and homogenized structure |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2591093A1 (en) * | 2004-12-09 | 2006-06-15 | United Technologies Corporation | Method and process for thermochemical treatment of high-strength, high-toughness alloys |
EP2221389B1 (en) * | 2007-11-14 | 2018-01-03 | NTN Corporation | Method of heat-treating steel and process for producing a machine part. |
JP5397930B2 (en) * | 2008-03-18 | 2014-01-22 | Ntn株式会社 | Rolling bearing |
WO2009069547A1 (en) | 2007-11-27 | 2009-06-04 | Ntn Corporation | Machine component and rolling bearing |
JP5397927B2 (en) * | 2007-11-27 | 2014-01-22 | Ntn株式会社 | Machine parts |
WO2014169222A2 (en) * | 2013-04-12 | 2014-10-16 | University Of Virginia Patent Foundation | Corrosion resistant metal and metal alloy coatings containing supersaturated concentrations of corrosion inhibiting elements and methods and systems for making the same |
US20160251737A1 (en) * | 2015-02-26 | 2016-09-01 | General Electric Company | Corrosion pitting resistant martensitic stainless steel |
CN106756769A (en) * | 2016-12-09 | 2017-05-31 | 贵州群建精密机械有限公司 | A kind of antifatigue nitriding method of engine of heavy-duty car timing gears |
US11697857B2 (en) | 2021-03-09 | 2023-07-11 | General Electric Company | Corrosion pitting resistant martensitic stainless steel and method for making same |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4969378A (en) * | 1989-10-13 | 1990-11-13 | Reed Tool Company | Case hardened roller cutter for a rotary drill bit and method of making |
US5181375A (en) * | 1991-03-18 | 1993-01-26 | Caterpillar Inc. | Method for producing steel alloy gears |
US5240514A (en) * | 1990-09-28 | 1993-08-31 | Ndk, Incorporated | Method of ion nitriding steel workpieces |
US5482602A (en) * | 1993-11-04 | 1996-01-09 | United Technologies Corporation | Broad-beam ion deposition coating methods for depositing diamond-like-carbon coatings on dynamic surfaces |
JP2000257697A (en) * | 1999-03-11 | 2000-09-19 | Nissan Motor Co Ltd | High surface pressure resisting gear and manufacture therefor |
EP1111080A2 (en) * | 1999-12-24 | 2001-06-27 | Hitachi Metal, Ltd. | Maraging steel having high fatigue strength and maraging steel strip made of same |
JP2002081524A (en) * | 2000-09-06 | 2002-03-22 | Bosch Automotive Systems Corp | Differential gear mechanism |
US20030106617A1 (en) * | 2001-12-10 | 2003-06-12 | Caterpillar Inc. | Surface treatment for ferrous components |
WO2004108356A1 (en) * | 2003-05-30 | 2004-12-16 | Rem Technologies, Inc. | Superfinishing large planetary gear systems |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6043431B2 (en) * | 1976-04-06 | 1985-09-27 | 三菱製鋼株式会社 | Manufacturing method of nitrided machine parts for light loads |
US4491500A (en) * | 1984-02-17 | 1985-01-01 | Rem Chemicals, Inc. | Method for refinement of metal surfaces |
US4744836A (en) * | 1985-07-08 | 1988-05-17 | Tocco, Inc. | Method for selectively heating a workpiece subjected to low temperature thermomechanical processing |
JPH02163313A (en) * | 1988-12-16 | 1990-06-22 | Mazda Motor Corp | Manufacture of cast iron parts |
DE3933053C1 (en) * | 1989-10-04 | 1990-05-03 | Degussa Ag, 6000 Frankfurt, De | |
US5268044A (en) * | 1990-02-06 | 1993-12-07 | Carpenter Technology Corporation | High strength, high fracture toughness alloy |
JPH03267380A (en) * | 1990-03-16 | 1991-11-28 | Hitachi Metals Ltd | Combined surface treatment of cast iron material |
JPH0432548A (en) * | 1990-05-30 | 1992-02-04 | Daido Steel Co Ltd | Manufacture of power transmission parts |
US5244375A (en) * | 1991-12-19 | 1993-09-14 | Formica Technology, Inc. | Plasma ion nitrided stainless steel press plates and applications for same |
US7235212B2 (en) * | 2001-02-09 | 2007-06-26 | Ques Tek Innovations, Llc | Nanocarbide precipitation strengthened ultrahigh strength, corrosion resistant, structural steels and method of making said steels |
US5230234A (en) * | 1992-05-11 | 1993-07-27 | Ford Motor Company | Method of making roll-finished gears |
US5599404A (en) * | 1992-11-27 | 1997-02-04 | Alger; Donald L. | Process for forming nitride protective coatings |
JPH06336658A (en) * | 1993-05-31 | 1994-12-06 | Japan Steel Works Ltd:The | High strength and high toughness ni-co steel |
US5914494A (en) * | 1996-03-27 | 1999-06-22 | Thermoceramix, Llc | Arc chamber for an ion implantation system |
GB9614303D0 (en) * | 1996-07-08 | 1996-09-04 | Nsk Rhp Europe Technology Co Ltd | Surface treatment of bearing steels |
US5851313A (en) * | 1996-09-18 | 1998-12-22 | The Timken Company | Case-hardened stainless steel bearing component and process and manufacturing the same |
JP3098469B2 (en) * | 1997-08-29 | 2000-10-16 | 広島日本電気株式会社 | Ion implanter |
US6176946B1 (en) * | 1998-01-28 | 2001-01-23 | Northwestern University | Advanced case carburizing secondary hardening steels |
ATE292199T1 (en) * | 1999-12-07 | 2005-04-15 | Timken Co | CARBURIZING, LOW CARBON AND LOW CHROME FAST WORK STEELS |
US6660340B1 (en) * | 2000-02-08 | 2003-12-09 | Epion Corporation | Diamond-like carbon film with enhanced adhesion |
US6732606B1 (en) * | 2000-06-30 | 2004-05-11 | Eaton Corporation | Polished gear surfaces |
US6883235B2 (en) * | 2001-05-23 | 2005-04-26 | Meritor Heavy Vehicle Technology, Llc | Cast integral ring gear and differential case |
US20040164217A1 (en) * | 2002-11-12 | 2004-08-26 | H2Gen Innovations, Inc. | Unitary base and integral housing for chemical equipment |
JP2004307894A (en) * | 2003-04-03 | 2004-11-04 | Air Water Inc | Method for manufacturing corrosion resistant, abrasion resistant and non-magnetic metal product, and corrosion resistant, abrasion resistant non-magnetic metal product obtained thereby |
US7556699B2 (en) * | 2004-06-17 | 2009-07-07 | Cooper Clark Vantine | Method of plasma nitriding of metals via nitrogen charging |
US6881498B1 (en) * | 2004-06-24 | 2005-04-19 | Sikorsky Aircraft Corporation | Surface process involving isotropic superfinishing |
US7695573B2 (en) * | 2004-09-09 | 2010-04-13 | Sikorsky Aircraft Corporation | Method for processing alloys via plasma (ion) nitriding |
-
2005
- 2005-12-13 KR KR1020077015646A patent/KR20070095935A/en not_active Application Discontinuation
- 2005-12-13 CA CA002592420A patent/CA2592420A1/en not_active Abandoned
- 2005-12-13 WO PCT/US2005/044862 patent/WO2006071502A2/en active Application Filing
- 2005-12-13 JP JP2007548273A patent/JP4919968B2/en not_active Expired - Fee Related
- 2005-12-13 EP EP05853711A patent/EP1831408A4/en not_active Withdrawn
- 2005-12-13 US US11/793,847 patent/US20080277030A1/en not_active Abandoned
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4969378A (en) * | 1989-10-13 | 1990-11-13 | Reed Tool Company | Case hardened roller cutter for a rotary drill bit and method of making |
US5240514A (en) * | 1990-09-28 | 1993-08-31 | Ndk, Incorporated | Method of ion nitriding steel workpieces |
US5181375A (en) * | 1991-03-18 | 1993-01-26 | Caterpillar Inc. | Method for producing steel alloy gears |
US5482602A (en) * | 1993-11-04 | 1996-01-09 | United Technologies Corporation | Broad-beam ion deposition coating methods for depositing diamond-like-carbon coatings on dynamic surfaces |
JP2000257697A (en) * | 1999-03-11 | 2000-09-19 | Nissan Motor Co Ltd | High surface pressure resisting gear and manufacture therefor |
EP1111080A2 (en) * | 1999-12-24 | 2001-06-27 | Hitachi Metal, Ltd. | Maraging steel having high fatigue strength and maraging steel strip made of same |
JP2002081524A (en) * | 2000-09-06 | 2002-03-22 | Bosch Automotive Systems Corp | Differential gear mechanism |
US20030106617A1 (en) * | 2001-12-10 | 2003-06-12 | Caterpillar Inc. | Surface treatment for ferrous components |
WO2004108356A1 (en) * | 2003-05-30 | 2004-12-16 | Rem Technologies, Inc. | Superfinishing large planetary gear systems |
Non-Patent Citations (2)
Title |
---|
DATABASE COMPENDEX [Online] ENGINEERING INFORMATION, INC., NEW YORK, NY, US; 22 August 2003 (2003-08-22), MERCER C ET AL: "Material removal on lubricated steel gears with W-DLC-coated surfaces" XP002581360 Database accession no. E2003307554701 -& C. MERCER ET AL: "Material removal on lubricated steel gears with W-DLC-coated surfaces" SURFACE AND COATINGS TECHNOLOGY, vol. 173, no. 2-3, 22 August 2003 (2003-08-22), pages 122-129, XP002585035 * |
See also references of WO2006071502A2 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110951962A (en) * | 2019-12-16 | 2020-04-03 | 武汉理工大学 | High-performance gear heat treatment method for realizing fine and homogenized structure |
Also Published As
Publication number | Publication date |
---|---|
CA2592420A1 (en) | 2006-07-06 |
EP1831408A4 (en) | 2010-07-21 |
KR20070095935A (en) | 2007-10-01 |
JP4919968B2 (en) | 2012-04-18 |
JP2008525639A (en) | 2008-07-17 |
WO2006071502A3 (en) | 2006-12-07 |
WO2006071502A8 (en) | 2006-08-24 |
WO2006071502B1 (en) | 2007-01-18 |
US20080277030A1 (en) | 2008-11-13 |
WO2006071502A2 (en) | 2006-07-06 |
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