EP2752502B1 - Abriebfestes element aus einer aluminiumlegierung und herstellungsverfahren dafür - Google Patents

Abriebfestes element aus einer aluminiumlegierung und herstellungsverfahren dafür Download PDF

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Publication number
EP2752502B1
EP2752502B1 EP12828406.4A EP12828406A EP2752502B1 EP 2752502 B1 EP2752502 B1 EP 2752502B1 EP 12828406 A EP12828406 A EP 12828406A EP 2752502 B1 EP2752502 B1 EP 2752502B1
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Prior art keywords
aluminum alloy
substrate
layer
wear resistant
plating
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French (fr)
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EP2752502A1 (de
EP2752502A4 (de
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Yuka Yamada
Hideaki Matsuoka
Ken-Ichi Suzuki
Gaku Kitahara
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Toyota Central R&D Labs Inc
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Toyota Central R&D Labs Inc
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • C23C18/1696—Control of atmosphere
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
    • C25D5/40—Nickel; Chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment

Definitions

  • the present invention relates to a wear resistant aluminum alloy member and a method for producing the same.
  • JP 2-974836 B2 discloses a wear resistant aluminum alloy member, comprising a substrate comprising an aluminum alloy, wherein the aluminum alloy contains 4 % Fe, when a total mass of aluminum is taken as 100 %, and a coated layer coating at least a part of a surface of the substrate, wherein the aluminum alloy has a residual hardness of HRB95 when measured in a room temperature state after held in an atmospheric pressure environment at 400 °C for 60 minutes, and the coated layer comprises a crystalline Ni-P layer comprising Ni and Ni 3 P.
  • Processes for forming a hard layer or the like on an aluminum alloy are classified into dry processes and wet processes.
  • the dry processes are processes for forming a hard layer of TiN, CrN, DLC, Al 2 O 3 or the like on a surface of a substrate by PVD, CVD, ion nitriding, thermal spraying, etc.
  • the wet processes are processes for forming an anodic oxide layer or other various plated layers on a surface of an aluminum alloy by immersing the aluminum alloy in a certain solution.
  • Films formed by the dry processes have a Vickers Hardness of about 1000 to 3000 Hv and are harder than those formed by the wet processes.
  • the dry processes are low in mass productivity and high in equipment costs and processing costs.
  • the wet processes facilitate productivity improvement, cost reduction, and so on.
  • Cr plated layers which have good wear resistance, (800 to 1000 Hv) are not environmentally preferable because of use of hexavalent chromium.
  • plating solutions are difficult to be controlled because of their instability.
  • Ni-P plated layers are not as hard as films formed by dry processes or Cr plated layers, and generally lack wear resistance. Even a relatively hard low-P concentration Ni-P plated layer has a Vickers hardness of 500 to 700 Hv. It is known that upon heated to 300 deg. C or more, the Ni-P plated layers can attain a maximum hardness of 900 to 1000 Hv, which is comparable to Cr plated layers. Such heating, however, softens an aluminum alloy as a substrate (a base material) and prevents a resulting member from obtaining necessary strength.
  • the Ni-P plated layer sometimes cannot follow deformation of the substrate and may crack or peel off. As described heretofore, it is conventionally difficult for an aluminum alloy member to secure wear resistance by a Ni-P plated layer.
  • the present invention has been made in view of these circumstances. It is an object of the present invention to provide an aluminum alloy member having improved wear resistance by Ni-P plating, while taking mass productivity, production costs, and environmental friendliness into consideration. It is also an object of the present invention to provide a method for producing the same.
  • the present inventors have made earnest researches in order to solve these problems and succeeded in hardening a Ni-P plated layer formed on a surface of a substrate comprising an aluminum alloy without softening the aluminum alloy substrate.
  • the present inventors have made further researches on the basis of this fruit and completed the following present invention.
  • a wear resistant aluminum alloy member of the present invention comprises a substrate comprising an aluminum alloy as indicated in claim 1, and a coated layer coating at least part of a surface of the substrate, and is characterized in that the aluminum alloy has a residual hardness of 120 Hv or more when measured under a load dwell time of 20 seconds in a room temperature state after held in an atmospheric pressure environment at 400 deg. C for 10 hours, and the coated layer comprises a crystalline Ni-P layer comprising nickel (Ni) and phosphorus (P) and being crystalline.
  • the wear resistant aluminum alloy member of the present invention (hereinafter referred to as the "wear resistant member” when appropriate) exhibits good wear resistance because a surface of its substrate is coated with a coated layer comprising a crystalline Ni-P layer. Moreover, the wear resistant member of the present invention can also exhibit good heat resistance, corrosion resistance, fatigue resistance and durability. However, reason why the wear resistant member of the present invention exhibits good characteristics is not all clear. The reason is assumed as follows under the present circumstances.
  • the crystalline Ni-P layer is very hard, unlike an amorphous Ni-P plated layer formed by electroless Ni-P plating or the like (hereinafter referred to as the "amorphous Ni-P layer" when appropriate).
  • This crystalline Ni-P layer not only when having a low P concentration but also when having a high P concentration, exhibits a sufficient hardness in accordance with degree of crystallinity. This is supposed to be because the crystalline Ni-P layer has a composite structure in which a precipitate phase such as Ni 3 P is dispersed in a crystallized Ni parent phase.
  • a high compressive residual stress may occur in the crystalline Ni-P layer.
  • This compressive residual stress is assumed to be caused by a difference in thermal expansion volume between the coated layer and the substrate, and precipitation of crystalline Ni and Ni-P upon heating of the amorphous Ni-P layer.
  • the coated layer thermally expands without peeled off from the thermally expanding substrate just like the substrate expands.
  • the crystalline Ni-P layer in which such compressive residual stress is present hardly cracks. This contributes not only to an improvement in wear resistance but also to an improvement in corrosion resistance and fatigue strength under repeated application of load (an improvement in fatigue resistance) or the like.
  • the wear resistant member of the present invention stably exhibits good wear resistance owing to a synergistic action of the substrate having good softening resistance and the crystalline Ni-P layer (the coated layer) having good wear resistance.
  • the wear resistant member of the present invention can exhibit sufficient wear resistance and strength and so on even in a high temperature environment.
  • a subject matter described herein can be applied not only to the wear resistant member of the present invention but also to the method for producing the same.
  • a constituent element of the production method can be a constituent element of the object when understood as a product by process. Any one or more constituent elements selected from the present description can be added to the aforementioned constituent elements of the present invention. Which embodiment is best or not differs depending on application targets, required performance and so on.
  • the coated layer of the present invention comprises a crystalline Ni-P layer, but the term "crystalline" does not mean that the entire coated layer needs to be a perfect crystal. It is sufficient that crystalline portions are present to a degree to be detected by X-rays.
  • element composition or metallic structure of the crystalline Ni-P layer is not limited in the present invention.
  • the metallic structure of the crystalline Ni-P layer is not specified in general, but is supposed to be constituted, for example, by a crystalline phase of Ni and a precipitate phase of Ni 3 P or the like. This metallic structure differs depending on element composition, degree of crystallization, heat history, etc. of the crystalline Ni-P layer.
  • a P content in the crystalline Ni-P layer is appropriately controlled with a use purpose, function, required specification and so on of the wear resistant member.
  • the crystalline Ni-P layer (especially when formed through electroless Ni-P plating) contains 1 to 13 % by mass of P when a total mass of the layer is taken as 100 % by mass (hereinafter simply referred to as "%"), a uniform plated layer is stably formed. That is to say, if the P content is excessively small, a content of sodium hypophosphite or the like as a reducing agent is small, so reducing power decreases and plating is hard to precipitate. If the P content is excessively large, a plating solution is unstable and realistically it is difficult to plate a substrate.
  • the crystalline Ni-P layer of the present invention can exhibit a sufficient hardness even when containing a large amount of P.
  • the crystalline Ni-P layer of the present invention is obtained, for example, by heating a Ni-P plated layer, which has been formed on a surface of a substrate by electroless Ni-P plating, at 300 to 500 deg. C, more preferably, 350 to 450 deg. C.
  • the Ni-P plated layer as formed by electroless Ni-P plating is amorphous and may keep the amorphous phase until about 200 deg. C. However, if the amorphous Ni-P plated layer is heated to 200 deg. C or more, crystallization gradually proceeds. In accordance with degree of crystallization, hardness of the crystalline Ni-P layer and compressive residual stress present in the crystalline Ni-P layer can also increase.
  • the crystalline Ni-P layer can be obtained not only by electroless Ni-P plating but also by electrolytic Ni-P plating. While electroless Ni-P plating causes P to be co-deposited using sodium hypophosphite as a reducing agent, electrolytic Ni-P plating causes P to be co-deposited by using sodium phosphite. In electrolytic Ni-P plating, electric current density easily changes with shape of a substrate, and the amount of P to be co-deposited and plated layer thickness are not easy to be controlled. Therefore, it is preferred that the crystalline Ni-P layer of the present invention is formed via electroless Ni-P plating.
  • the coated layer of the present invention is not limited in its forming method, and is formed, for example, by the following electroless Ni-P plating method.
  • a cleaning step removes an oxide layer formed on a surface of a substrate, oil stains attached on the surface of the substrate by machine processing, and so on. Owing to this cleaning step, a next pretreatment step can be efficiently performed and adhesion of a Ni-P plated layer, etc. can be improved.
  • the cleaning step comprises an etching step of removing an oxide layer by bringing the substrate in contact with an alkaline solution, and a desmutting step of removing smut formed after the etching step with an acid solution.
  • a desmutting step of removing smut formed after the etching step with an acid solution.
  • kind and concentration of the alkaline solution and the acid solution can be suitably controlled. If the cleaning step is performed by chemical polishing or electrolytic polishing instead of these steps, smoothing of the substrate surface can also be achieved.
  • An aluminum alloy is a difficult material to be plated. Even if a cleaning step is performed, as soon as contacting the air, an aluminum alloy is covered with a dense strong oxide layer and becomes inactive and formation of a Ni-P plated layer is liable to be blocked.
  • the zincate treatment is a treatment to bring a substrate in contact with a zincate solution (for example, an aqueous sodium hydroxide solution in which zinc oxide is dissolved), thereby forming zinc substitution plating to serve as an intermediate coated layer on a surface of the substrate.
  • a zincate solution for example, an aqueous sodium hydroxide solution in which zinc oxide is dissolved
  • This zincate treatment facilitates formation of a Ni-P plated layer having high adhesion on the substrate surface.
  • zincate treatment is performed twice or more, a Ni-P plated layer having high adhesion can be easily obtained. Therefore, zincate treatment is also effective in the present invention as one pretreatment of plating.
  • This activating step is a step of activating the substrate surface by bringing the substrate surface in contact with a treatment solution of pH 3 to 12.
  • This treatment solution (the activating treatment solution) is classified into an acid activating treatment solution and an alkaline activating treatment solution.
  • the acid activating treatment solution include hydrochloric acid, hydrofluoric acid, and an aqueous solution of ammonium hydrogen fluoride.
  • the alkaline treatment solution include aqueous solutions of sodium hydroxide, sodium carbonate, ammonium hydroxide, or various amines.
  • the activating step is performed after the cleaning step.
  • the activating step can also serve as the aforementioned cleaning step.
  • the activating step has the following meaning.
  • electroless plating is performed on an aluminum-based substrate, since aluminum as an element does not have catalytic activity for starting a reaction of a reducing agent, electroless plating reaction does not automatically start.
  • practical aluminum-based substrates contain more than a subtle amount of elements having catalytic activity such as iron and nickel as impurities or adding elements. If these elements can be exposed to a surface of an aluminum-based substrate, the electroless plating reaction can automatically start.
  • a surface of the aluminum-based substrate which has been through a cleaning step such as degreasing, etching, and immersion in acid is covered with a passive layer (aluminum oxide) and the aforementioned active sites comprising precipitates of iron, nickel, etc.
  • the activating step for about several minutes is sufficient but can be applied twice or more, if necessary. In any case, it is important that the substrate surface is sufficiently activated by this activating step. This judgment can be done by whether natural (standard) electrode potential of the substrate subjected to activating treatment is high or low.
  • the natural electrode potential can be measured, for example, by immersing the substrate after the activating treatment and an Ag/AgCl electrode in an alkaline aqueous solution controlled to pH 11.5 (a measurement solution) and immediately measuring natural electrode potential of the substrate by a potentiometer. When this natural electrode potential shifts to -1.4 to -1.35 V, it is determined that the substrate surface is suitably activated for plating. That is to say, the activating step of bringing the substrate surface in contact with the activating treatment solution should be made until natural electrode potential of the substrate reaches a desired value.
  • the plating step forms a Ni-P plated layer on the pretreated substrate surface.
  • This Ni-P plated layer is efficiently formed by using an electroless Ni-P plating solution. Composition and temperature of the electroless plating solution, and plating time can be suitably controlled.
  • the Ni-P plated layer immediately after plating is amorphous and does not always have high adhesion.
  • the substrate after the plating step can be heated at about 200 deg. C for about one hour independently of a next crystallizing step.
  • the crystallizing step changes the amorphous Ni-P plated layer formed on the substrate surface into a hard crystalline Ni-P plated layer.
  • it is basically suitable to heat the Ni-P plated layer at 300 to 500 deg. C or preferably 350 to 450 deg. C. Heating time of this heating can be about 0.5 to 10 hours.
  • the substrate comprises an aluminum alloy which does not soften even if heated in the crystallization step.
  • the aluminum alloy only needs to have such a softening resistance to have a residual hardness of 120 Hv or more when measured in a room temperature state after held at 400 deg. C for 10 hours, and its composition or producing method is not limited.
  • the following aluminum alloy is suitably employed.
  • Fe is an element which enhances strength, hardness and the like of an aluminum alloy. Specifically, a proper amount of Fe forms an intermetallic compound with Al (an Al-Fe based intermetallic compound: a first compound phase) in a parent phase ( ⁇ -Al phase) . This first compound phase enhances strength and hardness of the aluminum alloy.
  • the aluminum alloy consists of 1 to 7 % of Fe, 0.5 to 3 % of zirconium (Zr), and 0.5 to 3 % of titanium (Ti), and optionally 0.5 to 5 % of magnesium (Mg), when a total mass of the aluminum alloy is taken as 100 % by mass (hereinafter this phrase is omitted), the remainder being Al and inevitable impurities. It is preferred that the aluminum alloy contains 3 to 6 %, 4 to 6 %, or 4.5 to 5.5 % of Fe. If the Fe content is excessively small, the aluminum alloy cannot obtain a sufficient strength or hardness. If the Fe content is excessively large, ductility decreases and strength is too high, so the aluminum alloy is difficult to be shaped or processed.
  • Fe is not only effective in increasing strength of the aluminum alloy but also capable to serve as a catalytic element (an activating element) in the aforementioned electroless Ni-P plating. That is to say, if Fe is partially exposed to the substrate surface after the aforementioned activating treatment step, exposed points act as starting points of formation of a Ni-P plated layer. Therefore, a Ni-P plated layer having high adhesion and uniformity is formed by using a Fe-containing aluminum alloy as a substrate. This tendency is greater as the Fe content of the aluminum alloy increases in a range of 1 % or more.
  • Zr and Ti are important elements in forming a second compound phase, which improves heat resistance of the aluminum alloy, in cooperation with Al.
  • the aforementioned first compound phase is not always thermally stable and may undergo phase transformation or shape change (coarsening) when exposed to a high temperature atmosphere for a long time.
  • Proper amounts of Zr and Ti form an Al- (Zr, Ti) based intermetallic compound having L1 2 structure (a second compound phase or a precipitate phase) together with Al.
  • This second compound phase is coherent with the parent phase, and appears in neighborhood of a boundary (an interface) between the Al-Fe based intermetallic compound and the parent phase and is stable up to a high temperature range.
  • the second compound phase hardly undergoes phase transformation or coarsening at least at or below a temperature at which the phase starts precipitating.
  • the second compound phase which has precipitated in the neighborhood of a boundary between the first compound phase and the parent phase stably suppresses (what is called, pins) the first compound phase, which contributes to strength and hardness of the aluminum alloy, from undergoing phase transformation, shape change or the like at elevated temperatures. It is supposed that an aluminum alloy exhibiting good softening resistance and heat resistance can be obtained owing to a synergistic action of the first compound phase and the second compound phase.
  • the term "coherent” herein means that the second compound phase has the same basic crystal structure as the parent phase and atomic planes or atomic rows are continuous without excess or shortage at a boundary (an interface) between the second compound phase and the parent phase. Although dislocation induced by processing may cause irregularities of atomic rows or point defects, these are not taken into consideration.
  • the second compound phase has a nanoparticle shape and has a high Zr concentration at its center and a high Ti concentration at its outer periphery. That is to say, it is known that Zr and Ti concentrations in Al 3 (Zr, Ti) are inclined from the center to the outer periphery.
  • Zr is present in a larger amount than Ti and that a ratio by mass of Zr to Ti (Zr/Ti) falls in a predetermined range.
  • Zr is contained in a range of 0.66 to 1.5%, 0.7 to 1.3%, or 0. 8 to 1.2%.
  • Ti is contained in a range of 0.6 to 1 %, or 0.7 to 0.9 %. If the Zr content or the Ti content is excessively small, the effect decreases. If the Zr content or the Ti content is excessively large, melting temperature is extremely high, so production costs are high and Zr and Ti tend to form coarse crystalized or precipitated products together with Al, and workability and formability of the aluminum alloy tend to be low.
  • heat energy can be applied after strain energy is applied, for example, by applying heat treatment after cold working or hot working. If both heat energy and strain energy are applied, precipitation of the second compound phase is accelerated, so a heat-resistant high-strength aluminum alloy can be efficiently obtained in a short time.
  • Mg is an effective element in improving strength (especially strength at room temperature) of an aluminum alloy. It is preferred that a Mg content is in a range of 0.5 to 5 %, 0.6 to 2.2 %, 1 to 2 %, or 1.2 to 1.8 %. An excessively small Mg content exhibits no effect, while an excessively large content causes a decrease in workability and formability of the aluminum alloy.
  • the aluminum alloy of the present invention has an alloy composition comprising: 3 to 6 % of Fe, 0.66 to 1.5 % of Zr, 0.6 to 1 % of Ti, a ratio by mass of Zr to Ti (Zr/Ti) : 1.1 to 1.5, and a remainder being Al and inevitable impurities with/without (a) reforming element(s).
  • the "reforming element” mentioned herein is an element which is other than Al, Fe, Zr, Ti and Mg and is effective in improving a characteristic of the aluminum alloy.
  • the characteristic to be improved is not limited in kind and is exemplified by strength, hardness, toughness, ductility, and dimensional stability in a high temperature range or a room temperature range.
  • Specific examples of such a reforming element includes Cr, Co, manganese (Mn), nickel (Ni), scandium (Sc), yttrium (Y), lanthanum (La), vanadium (V), hafnium (Hf), and niobium (Nb). Mixing ratio of respective elements is arbitrarily chosen but in general their contents are extremely small.
  • the "inevitable impurities” are impurities contained in raw materials to be melted or impurities mixed during the respective steps, and are elements which are difficult to be removed for cost or technical reasons.
  • An example of inevitable impurities in the aluminum alloy of the present invention is silicon (Si).
  • the aforementioned aluminum alloy has a composite structure having at least the Al parent phase ( ⁇ phase), the Al-Fe based intermetallic compound phase (the first compound phase) , and the Al- (Zr, Ti) based intermetallic compound (the second compound phase).
  • the second intermetallic compound phase has an average size in a range of 1 to 30 nm, 2 to 20 nm, or 3 to 15 nm.
  • the average size is a value obtained by observing a sample selected at random from the aluminum alloy through a transmission electron microscope (TEM) and analyzing an average diameter of more than 30 dispersed nanoparticles of the second compound phase by image processing technique.
  • TEM transmission electron microscope
  • a billet extrusion ratio is preferably in a range of 5 to 30 or 10 to 20. If the extrusion ratio is excessively small, powder particles or pulverized flakes are insufficiently welded to each other under pressure, so desired strength or ductility cannot be obtained. If the extrusion ratio is excessively large, processing force increases so that shape forming is difficult.
  • relative density volume density/real density of a billet to be used for extruding or the like is not limited, but it is preferred that the relative density is not less than 60 %, not less than 70 %, not less than 80 %, not less than 85 %, or not less than 90 %. If the relative density is excessively small, shape retention ability and handling ability of the billet decreases. An upper limit of the relative density is not limited, but 95 % or less is preferred in view of productivity.
  • the wear resistant member of the present invention is suitable as a sliding member which contacts another member or fluid (liquid or gas).
  • specific examples include pistons, impellers, air intake valves, connecting rods, and rotors.
  • the wear resistant member of the present invention is especially suitable as a member to be used in a high temperature environment.
  • the wear resistant member of the present invention is suitable for pistons of internal combustion engines, impellers of superchargers and the like.
  • the wear resistant member of the present invention is suitable to be used in compressors, shafts, rollers, pipes, brake cylinders, automatic transmission components, dies and molds, screws, etc.
  • An aluminum alloy of Base Material No. 11 (Al-5%Fe-1%Zr-0.85%Ti-1.5%Mg) was selected as an example from a number of aluminum alloys having good softening resistance shown in Table 1 and substrates (specimens) comprising the aluminum alloy were prepared. It should be noted that these substrates were produced by processing a raw material extruded at 430 deg. C to have a diameter of 50 mm into disks of 30 mm in diameter and 3 mm in thickness. It should be also noted that "%" means % by mass, unless otherwise specified.
  • These substrates were etched by an alkaline solution comprising an aqueous solution of sodium hydroxide (concentration: 50 g/L), thereby removing oxide layers formed on surfaces of the substrates (an etching step).
  • an etching step After the etched substrates were washed with water, smut formed on the surfaces of the substrates were removed by an aqueous solution of nitric acid (concentration: 30 %) and then the treated substrates were washed again with water (a desmutting step). Thus the surfaces of the substrates were cleaned (a cleaning step).
  • the cleaned substrates were further subjected to activating treatment by being immersed in a pH 11.5 aqueous sodium carbonate solution.
  • the activating treatment was continued until standard (natural) electrode potential of the substrates shifted to -1.4 to -1.35 V (vs Ag/AgCl) .
  • the standard electrode potential was measured by a potentiometer by immersing the substrates after the activating treatment and an Ag/AgCl electrode in the aforementioned measurement solution.
  • pretreatment for direct plating was performed without applying zincate treatment.
  • the pretreated substrates were immersed in a plating solution at 90 deg. C for 60 minutes.
  • the plating solution used was a commercially available electroless nickel phosphorus plating solution (Top Nicoron BL produced by Okuno Chemical Industries. Ltd.)
  • a Ni-P plated layer was formed on a surface of each of the substrates.
  • the plated substrates were placed in a heating furnace and heated in an atmospheric pressure environment for one hour. Heating temperature was 200 deg. C, 300 deg. C, 350 deg. C, 400 deg. C, and 450 deg. C. Thus, a plurality of specimens heated at the different heating temperatures were obtained.
  • Figs. 1 and 2 show hardness of the coated layers measured only about the specimens comprising Base Material No. 11, but the specimens comprising the other base materials showed similar results.
  • hardness of the substrates comprising Base Material No. 11 hardly changed even though heated to 450 deg. C. More specifically, hardness of the substrates was stable in a range of 160 to 170 Hv throughout the heating step, and the change was about 10 to 15 Hv at most. Additionally speaking, the substrates comprising Base Material No. 11 showed a tendency to have a higher hardness as heated at a higher temperature.
  • the substrate after subjected to the plating step and then heated at 400 deg. C had a hardness (a residual hardness) of 165 Hv, which is almost the same as residual hardness of the aluminum alloy as a single substance of Base Material No. 11 shown in Table 1.
  • hardness of the substrates comprising Base Material Nos. C1 and C2 rapidly decreased after heated to 200 deg. C or more. Hardness (residual hardness) of the substrates after heated at 400 deg. C was smaller than 80 Hv. In any case, the substrates comprising Base Material Nos. C1 or C2 after heated at 400 deg. C had residual hardness of less than 120 Hv or less than 100 Hv.
  • hardness of the Ni-P plated layers rapidly increased.
  • Hardness after heated at 300 deg. C was as high as 1000 Hv
  • hardness after heated at 350 deg. C was as high as 1180 Hv
  • hardness after heated at 400 deg. C was as high as 1300 Hv.
  • high compressive residual stress of 900 to 1200 MPa occurred on the surfaces of these Ni-P plated layers, and compressive residual stress increased in proportion to heating temperature.
  • high compressive residual stress of 1017 (MPa) occurred when one of the Ni-P plated layers was heated at 400 deg. C. It should be noted that residual stress on the surfaces of the Ni-P plated layers having broad X-ray diffraction peaks could not be precisely evaluated by the aforementioned method.
  • Base Material No. 11 contains about 5 % of Fe, but Base Material No. C3 is pure aluminum for industrial use and is substantially free of Fe as impurities (Fe: 0.40 % or less/JIS).
  • Wear track depth obtained by measuring a surface of each of the specimens after the test by a surface roughness meter is also shown in Table 2.
  • cross-sectional shapes of wear tracks of the respective specimens after the test are shown in Figs. 6A to 6C . It should be noted that the Ni-P plated layers before the ball-on-disk test had a thickness of 10 ⁇ m.
  • Specimen No. 1 which comprised a substrate having a sufficient residual hardness and a coated layer formed on the substrate and comprising a Ni-P plated layer subjected to high temperature treatment, was hardly worn away and exhibited high wear resistance.
  • the specimens except Specimen No. 1 were deeply worn away even on a substrate side. It is apparent from these results that the wear resistant member of the present invention comprising the substrate and the coated layer exhibited good wear resistance owing to a synergistic action of good residual hardness of the substrate comprising the aluminum alloy and thermal hardening characteristics of the Ni-P plated layer.
  • Aluminum alloys (base materials) suitable for the aforementioned substrate can be obtained, for example, as follows. Molten aluminum alloys having composition shown in Table 1 were prepared (a molten metal preparing step). These molten alloys were sprayed in a vacuum atmosphere, thereby obtaining air atomized powders (solid bodies) (a solidifying step). Particles of the obtained air atomized powders (atomized particles) were sieved, thereby preparing atomized powders having a particle size of 150 ⁇ m or less. Note that a relation between size of powder particles obtained by air atomizing and cooling rate is known. Therefore, it can be said that the aforementioned atomized powders comprised particles rapidly solidified at a cooling rate of 10 4 deg. C/sec. or more.
  • the atomized powders were compacted by cold isostatic pressing (CIP), thereby obtaining extrusion billets (raw materials) having a size of 40 mm in diameter and 40 mm in length and a relative density of 85 %.
  • CIP cold isostatic pressing
  • the extrusion billets were charged in a container of an extruder (not shown) . Then the extrusion billets were heated to 430 deg. C by a heater attached to the container and then extruded, thereby obtaining (solid-core) rods (processing materials) of 12 mm in diameter and 400 mm in length (a hot plastic processing/processing step).
  • An extrusion ratio (a ratio of a cross sectional area of each raw material to a cross sectional area of each processing material) was 11.1. Samples were taken out of the thus obtained aluminum alloy rods and subjected to the following measurements.
  • a tensile test was performed by using specimens cut out from the respective samples in order to measure strength and ductility at room temperature and strength at 300 deg. C (without preheating) . Results are also shown in Table 1. It should be noted that the tensile test was performed according to JIS Z 2241. Strength shown in Table 1 is breaking strength, and ductility is an elongation rate of a distance between two reference points in a period from a start of the test to fracture.
  • Residual hardness of the respective specimens was also measured. Specifically, the specimens were held in an atmospheric environment at 400 deg. C for 10 hours, cooled to room temperature, and then measured for Vickers hardness. The Vickers hardness measurement was carried out in a room temperature environment by a Vickers hardness tester under a load of 0.98N and a load dwell time of 20 seconds.

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Claims (10)

  1. Verschleißbeständiges Aluminiumlegierungselement, umfassend:
    ein Substrat, das eine Aluminiumlegierung umfasst, wobei die Aluminiumlegierung aus 1 bis 7 % Eisen (Fe), 0,5 bis 3 % Zirkonium (Zr) und 0,5 bis 3 % Titan (Ti) sowie gegebenenfalls 0,5 bis 5 % Magnesium (Mg) besteht, wenn die Gesamtmasse der Aluminiumlegierung als 100 % angesetzt wird, wobei es sich bei dem Rest um Al und unvermeidbare Verunreinigungen handelt, und
    eine aufgebrachte Schicht, die mindestens einen Teil einer Oberfläche des Substrats bedeckt, wobei:
    die Aluminiumlegierung eine Resthärte von 120 Hv oder mehr aufweist, wenn diese bei einer Belastungshaltezeit von 20 Sekunden in einem Raumtemperaturzustand nach dem Halten in einer Atmosphärendruckumgebung bei 400 °C für 10 Stunden gemessen worden ist, und
    die aufgebrachte Schicht eine kristalline Ni-P-Schicht umfasst, die Nickel (Ni) und Nickelphosphid (Ni3P) umfasst.
  2. Verschleißbeständiges Aluminiumlegierungselement nach Anspruch 1, bei dem die kristalline Ni-P-Schicht 1 bis 13 Massen-% (nachstehend einfach als "%" bezeichnet) P enthält, wenn die Gesamtmasse der kristallinen Ni-P-Schicht als 100 % angesetzt wird.
  3. Verschleißbeständiges Aluminiumlegierungselement nach Anspruch 1 oder 2, bei dem eine Restdruckspannung in der kristallinen Ni-P-Schicht vorliegt.
  4. Verschleißbeständiges Aluminiumlegierungselement nach Anspruch 1 oder 3, bei dem die Aluminiumlegierung 3 bis 6 % Eisen (Fe) enthält, wenn die Gesamtmasse der Aluminiumlegierung als 100 % angesetzt wird.
  5. Verfahren zur Herstellung des verschleißbeständigen Aluminiumlegierungselements nach einem der Ansprüche 1 bis 4, mit
    einem Plattierungsschritt des Bildens einer Ni-P-plattierten Schicht auf der Oberfläche des Substrats durch Inkontaktbringen der Oberfläche des Substrats mit einer Ni-P-Lösung zum stromlosen Plattieren, und
    einem Kristallisationsschritt des Kristallisierens der Ni-P-plattierten Schicht durch Erwärmen der Ni-P-plattierten Schicht.
  6. Verfahren zur Herstellung des verschleißbeständigen Aluminiumlegierungselements nach Anspruch 5, das vor dem Plattierungsschritt einen Vorbehandlungsschritt aufweist, der einen Aktivierungsschritt des Aktivierens der Oberfläche des Substrats durch Inkontaktbringen der Oberfläche des Substrats mit einer Behandlungslösung oder einen Zinkatschritt des Anwendens einer Zinkatbehandlung auf die Oberfläche des Substrats umfasst.
  7. Verfahren zur Herstellung des verschleißbeständigen Aluminiumlegierungselements nach Anspruch 6, das vor dem Vorbehandlungsschritt einen Reinigungsschritt des Reinigens der Oberfläche des Substrats umfasst.
  8. Verfahren zur Herstellung des verschleißbeständigen Aluminiumlegierungselements nach Anspruch 7, bei dem der Reinigungsschritt umfasst:
    einen Ätzschritt des Entfernens einer Oxidschicht durch Inkontaktbringen des Substrats mit einer alkalischen Lösung und
    einen Verunreinigungsentfernungsschritt des Entfernens von Verunreinigungen, die nach dem Ätzschritt gebildet worden sind, mit einer Säurelösung.
  9. Verfahren zur Herstellung des verschleißbeständigen Aluminiumlegierungselements nach einem der Ansprüche 5 bis 8, bei dem das Substrat eine Aluminiumlegierung umfasst, die durch
    einen Erstarrungsschritt des Erhaltens eines Festkörpers durch schnelles Erstarrenlassen einer geschmolzenen Legierung und
    einen Wärmebehandlungsschritt des Erwärmens des Festkörpers erhalten worden ist.
  10. Verfahren zur Herstellung des verschleißbeständigen Aluminiumlegierungselements nach Anspruch 9, bei dem der Wärmebehandlungsschritt ein Warmbearbeitungsschritt des Durchführens einer plastischen Warmbearbeitung mit dem Festkörper ist.
EP12828406.4A 2011-08-31 2012-08-03 Abriebfestes element aus einer aluminiumlegierung und herstellungsverfahren dafür Not-in-force EP2752502B1 (de)

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US10781701B2 (en) 2016-06-01 2020-09-22 Mitsubishi Heavy Industries Engine & Turbocharger, Ltd. Impeller for rotary machine, compressor, forced induction device, and method for manufacturing impeller for rotary machine
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