WO2001049904A1 - Pieces en aluminium et leur procede de production - Google Patents

Pieces en aluminium et leur procede de production Download PDF

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Publication number
WO2001049904A1
WO2001049904A1 PCT/JP2000/000051 JP0000051W WO0149904A1 WO 2001049904 A1 WO2001049904 A1 WO 2001049904A1 JP 0000051 W JP0000051 W JP 0000051W WO 0149904 A1 WO0149904 A1 WO 0149904A1
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WIPO (PCT)
Prior art keywords
alumite
aluminum
treatment
film
piston
Prior art date
Application number
PCT/JP2000/000051
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English (en)
Japanese (ja)
Inventor
Hirotaka Kurita
Original Assignee
Yamaha Hatsudoki Kabushiki Kaisha
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Filing date
Publication date
Application filed by Yamaha Hatsudoki Kabushiki Kaisha filed Critical Yamaha Hatsudoki Kabushiki Kaisha
Priority to PCT/JP2000/000051 priority Critical patent/WO2001049904A1/fr
Publication of WO2001049904A1 publication Critical patent/WO2001049904A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/02—Light metals
    • F05C2201/021—Aluminium

Definitions

  • the present invention relates to an aluminum component having an alumite layer formed thereon and a method of manufacturing the same, and more specifically to, for example, a piston, a cylinder block, and the like of an internal combustion engine and a surface treatment method thereof. Improvement of abrasion resistance and lubricity of holes and inner surfaces of cylinder bores. Background art
  • Aluminum alloys for bistons manufactured through material forming by forging and forging are used in which an aluminum base material contains 10 to 20% by weight of i. Particularly in such pistons. Biton pin holes are under severe sliding conditions, and higher wear resistance is required. If this type of aluminum alloy biston is not subjected to surface hardening, for example, on the inner surface of the biston pin hole, the base material will wear first and the Si particles will be in a floating state, and the concentrated load on the Si particles This causes a problem that the particles are broken and function as abrasive powder, resulting in significant wear of the piston pin holes.
  • the conventional process of alumite treatment for the surface of the biston hole Dissolves the Si particles exposed on the surface by the mixed acid treatment before the alumite treatment, thereby increasing the surface area of the electric passage and lowering the current density. Preventing.
  • the mixed acid treatment reduces the surface roughness before the alumite treatment, and this also reduces the surface roughness of the alumite film after the alumite treatment. For this reason, in the conventional method, in order to improve the surface roughness, roller-panishing is performed in the final step.
  • the conventional alumite treatment consists of the following four steps.
  • Biston pin hole machining Adjust pin hole diameter and surface roughness.
  • Alumite treatment An alumite film (anodized film) is formed on the pin hole surface. In the case of lubricating alumite treatment, a secondary electrolysis step in a solution of ammonium molybdate is added.
  • This alumite treatment is performed by immersing the aluminum component in the electrolytic solution, connecting the component to the anode side, and performing an electrolytic operation.
  • an alumite film many pinholes are formed from the surface toward the inner surface. These pinholes are formed in accordance with the temperature of the electrolytic solution. When the temperature is high, many pinholes are formed and the alumite film becomes porous.
  • the piston sliding surface (the inner surface of the cylinder pore) of the cylinder block of the internal combustion engine is required to have heat resistance and wear resistance, and must have sufficiently high strength and lubricity at high temperatures. Is necessary.
  • This cylinder block is usually a gravity or high-pressure product made of aluminum alloy or a die-cast product, and the piston block is formed along the inner surface of a cylindrical die or a sleeve that is press-fitted or inserted into a cylinder bore.
  • the sliding surface is anodized and its pinhole is impregnated with solid lubricant. It has been proposed.
  • the pinholes of the alumite film are fine (pore diameter of about 0.01 m or less), and cannot be sufficiently impregnated with lubricating oil or solid lubricant to maintain lubrication for a long period of time. As a result, wear resistance cannot be maintained. In addition, the lubricating properties of the entire sliding surface cannot be sufficiently improved with the scattered pinholes.
  • the anodizing treatment for forming the alumite film is performed by immersing the aluminum component in an electrolytic solution tank and connecting the component to the anode side by an electrolytic action.
  • an electrolytic solution sulfuric acid is conventionally used.
  • this sulfuric acid has a strong dissolving power for the alumite film, and is dissolved by the sulfuric acid even if an anodized film that is an anodized film is formed by the electrolytic action. For this reason, the pinhole of the film formed during the anodizing treatment is enlarged by dissolution, and the surface hardness is reduced.
  • the alumite film is formed on the sliding surface of the internal combustion engine, there is a problem that sufficient abrasion resistance cannot be obtained.
  • the present invention has been made in view of the above-mentioned conventional problems, and by controlling the alumite processing conditions while simplifying the processing steps, it is possible to improve the surface roughness at a low cost and thereby effectively reduce the pin hole wear. It is an object of the present invention to provide an aluminum part having a wear-resistant hard anodized film and capable of sufficiently enhancing the wear resistance and lubricity of the entire sliding surface, and a method of manufacturing the same. Disclosure of the invention
  • the Si particles or the SiC particles having a film thickness of 30 ⁇ 10 m are exposed on the surface portion of the biston pin hole of the aluminum alloy-made internal combustion engine. It is an aluminum part characterized by having an alumite film.
  • the invention of claim 2 is characterized in that, in claim 1, an alumite film is formed on the inner end face of the pin boss portion having the piston pin hole, which face the small end of the condole.
  • the invention according to claim 3 is characterized in that a piston hole of a piston for an internal combustion engine made of an aluminum alloy is machined to adjust a pin hole diameter and a surface roughness, and that an electrolysis time and a current density are measured on the surface of the piston pin hole. An alumite treatment is performed while cooling the surface of the piston pin hole to form an alumite film with a film thickness of 30 ⁇ 1 O wm. is there.
  • the invention according to claim 4 is an aluminum component, wherein an alumite film is formed on a surface of a component made of an aluminum alloy, and a network-like crack is formed in the alumite film.
  • the invention according to claim 5 includes an alumite forming step of forming an alumite film on the surface of a component made of an aluminum alloy, and a crack forming step of forming a network-like crack in the alumite film after the alumite film forming step.
  • a method for manufacturing an aluminum component characterized by having:
  • a sixth aspect of the present invention is characterized in that, in the fifth aspect, the crack forming step comprises a heat treatment.
  • the invention according to claim 7 is characterized in that, in claim 5, the crack forming step comprises a burnishing process.
  • the invention of claim 8 is characterized in that, in any one of claims 5 to 7, the aluminum alloy contains copper.
  • the invention of claim 9 is directed to an aluminum component in which an alumite film is formed on the treated surface of the aluminum alloy component by anodizing treatment through an electrolytic solution.
  • the electrolytic solution contains sulfuric acid, and further contains one or both of oxalic acid and citric acid.
  • a tenth aspect of the present invention is characterized in that, in the ninth aspect, the electrolytic solution is stored in a stationary bath, and the aluminum component is immersed in the electrolytic solution to perform anodizing treatment.
  • the invention of claim 11 is characterized in that, in claim 9, the electrolytic solution circulates and flows on the processing surface of the aluminum component.
  • the invention according to claim 12 is an aluminum part characterized in that 0.5% or more of copper is contained in an alumite film formed on the surface of a part made of an aluminum alloy.
  • a thirteenth aspect of the present invention is characterized in that, in the thirteenth aspect, the aluminum component contains 0.8 to 5% of copper.
  • FIG. 1 is a front sectional view showing a state in which a piston according to a first embodiment of the present invention is connected to a crankshaft.
  • FIG. 2 is an enlarged sectional side view of the biston according to the first embodiment.
  • FIG. 3 is an enlarged schematic sectional view of the alumite film of the biston of the first embodiment.
  • FIG. 4 is a schematic view showing the anodizing apparatus for biston of the first embodiment.
  • FIG. 5 is a characteristic diagram showing the biston electrolysis conditions for the alumite treatment of the biston according to the first embodiment.
  • FIG. 6 is a graph showing the relationship between the electric quantity and the film thickness of the 4TT biston almaite film of the first embodiment.
  • FIG. 7 is a graph showing the relationship between the quantity of electricity and the hardness of the coating according to the first embodiment.
  • FIG. 8 is a graph showing the relationship between the quantity of electricity and the roughness of the coating showing the effect of the quantity of electricity on the roughness of the coating in the first embodiment.
  • FIG. 9 is an electrolysis time-electrolysis voltage characteristic diagram showing a change in electrolysis voltage according to the electrolysis time in the i-th embodiment.
  • FIG. 10 is a time-wear amount characteristic diagram for explaining an effect showing a comparison of wear resistance with the conventional treatment of the first embodiment.
  • FIG. 11 is a schematic view showing a general form of wear of a biston pin hole.
  • FIG. I2 is a configuration diagram of an internal combustion engine according to the second embodiment of the present invention.
  • FIG. 13 is a configuration diagram of the alumite processing apparatus according to the second embodiment.
  • FIG. 14 is a flowchart of the sleeveless cylinder block manufacturing process of the second embodiment.
  • FIG. 15 is an explanatory diagram of cracks in the alumite film of the second embodiment.
  • FIG. 16 is a front view of the sleeve-embedded cylinder block manufacturing process of the second embodiment.
  • FIG. 17 is a flowchart of the sleeve press-fitting cylinder block manufacturing process of the second embodiment.
  • FIG. 18 is a flowchart of the biston manufacturing process of the second embodiment.
  • FIG. 19 is a configuration diagram of a stationary bath for alumite-treating the piston according to the second embodiment.
  • FIG. 20 is an enlarged cross-sectional view of the biston ring of the second embodiment.
  • FIG. 21 is a flowchart of the alumite treatment process of the second embodiment.
  • FIG. 12 is a sectional view sequentially showing the aluminum component manufacturing process of the second embodiment.
  • FIG. 23 is a cross-sectional view sequentially showing another manufacturing process of the aluminum component of the second embodiment. —
  • FIG. 24 is a graph showing the effect of bath temperature on the hardness of the alumite of the second embodiment.
  • -FIG. 25 is a graph showing the effect of oxalic acid and citric acid concentrations on the film thickness and hardness in the above-described second embodiment with the sulfuric acid concentration kept constant (20 g / 1).
  • FIG. 26 is a graph showing the effect on the film thickness and hardness when the sulfuric acid concentration of the second embodiment is changed, using oxalic acid and citric acid concentrations as parameters.
  • FIG. 27 is a graph showing the effect of the copper content in the alumite film of the second embodiment on the hardness.
  • FIGS. 1 to 11 are views for explaining a piston of an internal combustion engine and a method of manufacturing the same (particularly, a surface treatment method) according to the first embodiment of the present invention.
  • reference numeral 1 denotes a piston
  • the piston 1 is slidably inserted into a cylinder pore 2 a of a cylinder block 2.
  • a small end 3a of a condole 3 is connected to the piston 1 via a bearing 4.
  • a piston pin 5 is connected to a crank pin 6a of a crankshaft 6. Connected.
  • the above-mentioned biston 1 is made of an aluminum alloy (AC 8 A to AC 8 C, AC 9 A, AC 9 B, etc. shown in Table 1).
  • top surface 1a and the inner surface 1b are not machined to the mirror surface, and the outer peripheral surface (cylinder sliding surface) is machined to a predetermined shape.
  • First and second ring grooves 7a and 7b are formed in the upper part of the outer peripheral surface by machining, and top ring 1 la and second ring are formed in the second ring grooves 7a and 7b. 1 lb is installed.
  • a pair of pin bosses 1c, 1c are formed to protrude inward, and a piston pin hole 7c is formed in the pin bosses lc, 1c so as to penetrate in the radial direction.
  • the piston pin 5 is rotatably inserted into the piston pin hole 7c.
  • a locking groove 7d is formed at both outer ends of the pin hole 7c, and a snap ring 8.8 is mounted in the locking groove 7d.
  • the snap ring 8 is for preventing the biston pin 5 from moving in the axial direction.
  • An alumite-treated film 10 is formed on the surface by anodizing (anodizing) treatment.
  • the alumite film 10 has a film thickness (however, since the film thickness cannot be completely uniform over the entire film, the thickness of the film varies within a certain width in the spread of the film. It is set within the range of 30 ⁇ 10 / m, and as a result, the surface roughness of the film is controlled to Ra 1.5 to 3.0 as described below. Become .
  • the alumite film 10 is formed such that the surface a of the film body 10a is located outside the exposed surface b of Si 10b, in other words, Si 1 O b is moved from the film body 1 O a.
  • a piston material is prepared by structure using an aluminum alloy containing Si (AC8A, AC8B, AC8C, AC9A, AC9B) shown in Table 1.
  • an aluminum alloy containing Si AC8A, AC8B, AC8C, AC9A, AC9B
  • a burette in which alloys 1 to 3 in Table 1 are continuously drawn out of the melting furnace into a rod shape and cooled and cut, or the powders of alloys 4 to 6 are extruded from the heating furnace to join the powders together.
  • a piston material manufactured by using a burette obtained by cutting a bar material in a state of being used is used.
  • the piston material is subjected to a heat treatment (T6 or T7 treatment).
  • the T6 and T7 treatments are a solution treatment of rapidly cooling after heating at a high temperature, and a treatment of applying an artificial aging treatment or a stabilizing heat treatment of gradually cooling after heating and holding under the treatment conditions shown in Tables 2 and 3.
  • the heat-treated biston material is subjected to primary mechanical processing such as piston pin hole processing, piston ring groove processing, and jig insertion section processing, followed by alumite processing (described later). Further, secondary machining including outer surface machining and finishing is performed, and the piston 1 is manufactured.
  • the alumite treatment of the present embodiment is performed in the following procedure without performing the conventional mixed acid treatment after machining the piston hole. That is, the first machined piston material is received, jigs are attached, degreasing, water washing, anodizing, water washing, jig removal, and hot water washing are sequentially performed.
  • the oil components and the like on the surface of the component are removed by immersing the component in a degreasing bath having the composition shown in Table 4 for a predetermined time.
  • alumite treatment as shown in FIG. 4, the piston material 1 ′ attached to the jig 12 is immersed in an alumite bath (electrolyte bath) 13 having the composition shown in Table 5, and Connect the anode of the constant current DC power supply 14 to 12 and the cathode of the power supply 14 to the cathode plate 15 in the alumite bath 13 and allow the cooled electrolyte to flow through the piston material 1 '.
  • the slope of the figure is adjusted so that the amount of electricity becomes 3 000 to 6000 (C / dm 2 ).
  • the alumite treatment is performed while controlling the current density and the electrolysis time within the range of the line.
  • 20 is a radiator for cooling the electrolyte
  • 21 is the radiator for cooling the electrolyte.
  • 22 is a circulation path for cooling the electrolyte
  • 23 is a circulation pump.
  • the low-temperature and low-pressure liquid-phase refrigerant that has passed through an expansion valve (not shown) is guided to the evaporation coil 24 a in the radiator 20 by the low-pressure pipe 24.
  • Alumite treatment Since the temperature of the anodized layer of Biston 1 'is prevented from increasing, the hardness of the alumite layer can be prevented from decreasing.
  • the temperature is detected by a temperature sensor 26 provided in the lower part of the bathtub 13 or on the piston material 1 ', and based on this temperature, the controller 27 detects the higher the temperature detected, the higher the temperature in the circulation path.
  • the liquid flow rate may be increased or the capacity of the refrigerant circulation pump 25 or a compressor (not shown) may be increased to prevent a rise in the temperature of the alumite treatment layer of the biston 1.
  • the temperature of the downstream portion of the cooler 20 may be detected by the temperature sensor 26 ′, and this temperature may be controlled to 30 ° C. or less.
  • cooling with the cooling liquid of the discharge nozzle 21 or air cooling may be used.
  • FIG. 9 is a characteristic diagram showing the relationship between the electrolysis time and the electrolysis voltage when the current density is 6.3 A / dm 2 , and the electrolysis voltage increases as the electrolysis time elapses.
  • the current density decreases as the electrolysis time elapses and the thickness of the alumite layer increases, and the rate of increase in the alumite layer thickness per hour decreases.
  • the current density increases and the film surface temperature rises due to the heat generated by anodic oxidation, and the alumite layer is formed by sulfuric acid in the electrolyte. Dissolves and the surface becomes rough. Therefore, it is preferable to cool the electrolytic solution at the beginning of the alumite treatment. Alternatively, the current value may be detected, and the electrolytic solution may be cooled as the current value increases.
  • FIG. 10 shows the results of an experiment performed to confirm the effects of the present embodiment.
  • the electrolytic bath temperature 0 ° C.
  • Current density 6. and 3 A / dm z performs anodized while cooling by applying the electrolyte solution to be processed material in a jet state
  • FIG 6-8 An alumite-treated film with the film thickness, hardness and surface roughness shown in Fig. 4 was formed. Then, the relationship between the operating time of the engine using the piston and the wear amount of the piston hole was determined.
  • A is a Arumai Bok processing wear amount of processing time has been subjected piston pin hole, such as the quantity of electricity per unit area is 6 0 0 0 C / dm z of this embodiment
  • a ' is present type condition piston pin Arumai preparative process the wear amount of the amount of electricity 3 0 0 0 C / dm 2 to become such processing time decorated with piston bore per unit area
  • B is that Arumai preparative process according to the conventional method is applied for The abrasion loss of the hole
  • C shows the abrasion loss of the biston pin hole when the alumite treatment is not performed.
  • the operation time was 20 hours and the amount of wear reached 20 juni, whereas in the case of the present embodiment method, A and A ′ were used.
  • the amount of wear is about 1 O jum, which indicates that there is no practical problem.
  • the wear amount reached 20 immediately after the operation in an extremely short time, indicating that it cannot be put to practical use.
  • the alumite treatment was immediately performed without performing the mixed acid treatment, and the electrolysis conditions in that case were controlled to the shaded region shown in FIG. It is possible to obtain low cost bistons for automobile engines with excellent performance.
  • the small end 3a of the connector 3 comes into contact with the inner end surface 1b 'of the pin post, and the portion is worn, and the abrasion powder enters the piston pin hole. This wears the piston pin hole 7c.
  • the thickness of the hard anodized film 10 is 3 Om.
  • the hardness is HmV405, and the surface roughness is Ra1.9. Since the control of 6 to 2.60 uu is performed, it is possible to prevent the outer portion 7c 'and the central portion 7c' 'of the piston pin hole 7c shown in FIGS.
  • An alumite coating was formed on the inner surface 1 b ′ of the piston inner surface 1 b, especially on the inner end surface 1 b ′ facing the small end 3 a of the connector 3.
  • the inner end surface 1 b ′ can be prevented from being worn by the contact, and the abrasion of the biston pin hole 7 c due to the Si powder generated by the abrasion can be prevented.
  • the alumite film is also formed on the ring groove, it is possible to prevent the ring groove from being worn.
  • the alumite treatment described above may be performed not before the second machining but after. In this case, the wear durability of the outer periphery of the piston 1 can be improved. However, it is necessary to cut off extra by the first machining process due to the expansion due to the application of the alumite film. Further, when the thickness distribution of the alumite film is not uniform and undulating irregularities are formed on the outer surface, it is preferable to perform finish polishing.
  • Alumite bath composition (unit: g / l)
  • FIGS. 12 to 27 are views for explaining a cylinder block, a piston (aluminum port) and a method of manufacturing the same according to a second embodiment of the present invention.
  • a four-stroke internal combustion engine 101 is composed of a cylinder head 102, a cylinder block 103, and a crank case 104, which are formed by a low-pressure aluminum alloy cast. It is composed.
  • An intake pipe # 05 is connected to one side of the cylinder head 102, and an intake valve 106 is attached to an intake opening 105a at a downstream end thereof.
  • An exhaust pipe 7 is connected to the other side of the cylinder 102, and an exhaust valve 108 is attached to an exhaust opening 107a at an upstream end thereof.
  • Biston 109 slides along the inner surface of the cylinder bore of the cylindrical cylinder holder 103.
  • a piston ring 110 is mounted on the peripheral surface of the piston 109.
  • the piston 110 is connected to a crankshaft 114 via a piston pin 111, a connector 111 and a crank arm 113.
  • the inner surface of the cylinder bore of the cylinder block 103 serving as the sliding surface of the piston 109 that is, the inner surface of the cylinder, has a sleeve in which an aluminum alloy sleeve (not shown) is mounted by press-fitting or embedding.
  • an aluminum alloy sleeve (not shown) is mounted by press-fitting or embedding.
  • the piston 109 directly contacts the cylindrical inner surface of the cylinder block 103 without mounting.
  • the alumite treatment is applied to the inner cylindrical surface to reinforce the sliding surface of the biston 109 in all types.
  • FIG. 13 is a configuration diagram of the alumite processing apparatus according to the embodiment of the present invention.
  • an alumite treatment is performed on the inner surface of the sleep 1 17 which is the sliding surface of the piston mounted on the cylinder block 103.
  • the cylinder block 103 is mounted on the support base 116 via the gasket 115.
  • the gasket 115 is a sealing material for preventing leakage of the electrolytic solution, and also functions as an insulating material for allowing more electrolytic current to flow from the cylinder bore surface.
  • An electrode rod 1 29 is inserted into the sleeve 1 17 in the axial direction.
  • the electrode rod 19 is connected to the negative electrode side of the DC power supply 131, which is converted from the AC power supply 130 to DC through the rectifier 124 and the control circuit 125.
  • the positive side of DC power supply 13 1 is connected to cylinder block 103 on which sleeve 1 17 is mounted.
  • the electrolyte is interposed between the electrode rod 1 29 on the negative electrode side and the inner surface of the sleep 1 117 on the positive electrode side opposed to the electrode rod 1 9 at an interval.
  • an anodizing layer is formed on the inner surface of the sleeve 117 as described later.
  • An electrolyte circulation channel 120 is connected to the cover 119 and communicates therewith.
  • the lower end (not shown) of the support base 116 is also sealed, and the electrolyte 127 in the electrolyte bath 126 is fed into the support base 116 by the circulation pump 128.
  • the electrolyte flows between the sleeve 1 17 and the electrode rod 1 29 and circulates in the circulation channel 120.
  • the electrolytic solution layer 126 is arranged in the middle of the circulation channel 120, and a circulation pump 128 is provided.
  • a cooling device 13 2 is further provided on the circulation channel 10. That is, the electrolyte tank 1 26 constituting the circulation flow path 10, the circulation pump 1 28, the pipeline between the electrolyte tank 1 26 and the circulation pump 1 28, the sleeve 1 17 and the electrode rod 1
  • the current passage for alumite treatment between 2 and 9 the pipe between the circulation pump 1 28 and the current passage for alumite treatment, and the passage between the current passage for alumite treatment and the electrolyte tank 1 26
  • the cooling devices 132 are arranged in series or in parallel in the flow direction of the processing liquid.
  • the cooling device 132 may be, for example, a heat exchanger provided with a cooling coil 123 constituting an evaporator of a refrigerator to which a refrigerant pipe 122 is connected.
  • cooling water may be circulated through the cooling coils 123.
  • cooling fins are provided on the pipeline in the middle of the circulation channel 120, and an air-cooled cooling device that cools with a fan is provided. After passing through a cooling device arranged in parallel with the cooling water, it may join the circulation channel 120.
  • a cooling coil through which cooling water passes is immersed in the electrolytic solution tank 126, a water jacket for circulating cooling water is provided in the circulation pump ⁇ 28 itself, or an electrode rod 129 is provided.
  • the cooling device 132 may be configured such that a water jacket for cooling water circulation is provided inside the cooling device.
  • cooling water may be circulated to a water jacket 103A around the cylinder bore of the cylinder block 103.
  • a temperature sensor 121 is mounted near the outlet of the sleeve 1 17 of the circulation channel 120 to detect the temperature of the electrolyte.
  • the temperature sensor 12 1 is connected to, for example, a control device (not shown), and drives the cooling device 13 2 when the detected temperature rises above a set temperature.
  • the drive of the circulation pump 128 is controlled to increase the circulation flow rate of the electrolyte when the temperature rises, and to reduce the reaction rate accompanying the temperature rise due to heat generation in the anodization reaction. The decrease may be prevented. Further, the DC power supply 13 1 may be controlled to increase the voltage when the temperature rises, thereby increasing the reaction speed.
  • the upper side of the sleeve 117 is completely sealed with the cover 119 on the outlet side of the sleeve 117, and a circulation passage is formed in the center of the electrode rod 127.
  • the liquid may be returned to the electrolytic solution tank 1 26.
  • the cooling device 13 2 can be provided on the pipe on the suction side or the discharge side of the circulation pump 128 to cool the electrolyte.
  • FIG. 14 is a flowchart showing a manufacturing process of the sleeveless cylinder block.
  • a cylinder block is formed by die casting of an aluminum alloy (step S1).
  • As the material of the cylinder block any one of ADC1 to ADC14 of the materials shown in Table 6 is used.
  • 'it may be mixed S i C like metal carbide or other intermetallic compound 9
  • step S 2 After die casting, annealing is performed to remove residual stress (step S 2).
  • a condition in which a die cast product is held at about 250 for 4 hours is employed.
  • machining is performed on each part of the cylinder block to adjust its shape (step S3).
  • burnishing is performed on the cylinder bore (step S4), and poling is further performed (step S5), and the inner surface of the cylinder bore, which is the piston sliding surface, is finished by a compression pressing action.
  • step S4 the finishing by burnishing may be omitted.
  • step S6 alumite treatment is performed on the inner surface of the cylinder bore that has been subjected to the finishing process, so that the inner surface of the cylinder bore is strengthened.
  • the details of the alumite processing conditions will be described later.
  • the alumite film is subjected to a heat treatment for crack formation (step S7).
  • the heat treatment is performed, for example, by heating the entire cylinder block at 250 ° C for 30 minutes.
  • the alumite film on the inner surface of the cylinder bore is subjected to a bathing process to further form a crack (step S8).
  • the cracks formed by this burnishing process have a higher hardness and a lower ductility than the aluminum alloy of the base metal, so that even if the base material is stretched when pressure is applied to the alumite coating by nicking, the coating follows this. It cannot be extended and cracks occur.
  • the strength of the base material can be increased by performing a heat treatment such as T6 treatment or T7 treatment. This will be described in detail later.
  • FIG. 15 shows the shape of the crack described above.
  • a network-like crack having a size of about 0.1 to about 5 is formed on the surface of the alumite film.
  • This crack has a width of about 0.1 to 10 zm and a depth of about 30 to 50 Aim, as shown in a sectional view in FIG.
  • the lubricating action is enhanced as compared to the case of pinholes scattered in a dotted pattern or cracks formed in one direction.
  • the frictional resistance of the alumite film surface during biston sliding is greatly reduced, and the wear resistance of the sliding surface is greatly improved.
  • the solid lubricant for example, amorphous fluororesin, molybdenum disulfide, tungsten disulfide, graphite, carbon fluoride, boron nitride and the like can be used.
  • Example The range of ⁇ is set to 0.001 to 0.005, and the amount of burnishing and sosh applied to the inner surface of the cylinder having the dimension 070 before processing is set to 0.01 to 0.3I5 mm.
  • step S7 Cracks are formed in the alumite film by the above heat treatment (step S7) and burnishing (step S8).
  • the heat treatment (step S7) and the burnishing (step S8) may be performed only on one of them, and the other may be omitted.
  • step S9 the manufacturing process of the sleeveless cylinder block including the alumite treatment on the inner surface of the cylinder bore is completed.
  • Figure 16 is a flowchart showing the process of manufacturing a cylinder block with a sleeve.
  • an aluminum alloy pipe material serving as a sleeve material is prepared (step S10).
  • the sleep material any of the materials shown in Table 7 can be used.
  • metal carbides such as SiC having high hardness and other intermetallic compounds may be mixed.
  • step S11 a predetermined solution treatment and age hardening treatment are performed on the pipe material by T6 treatment to increase the strength.
  • step S12 the pipe material is machined into a sleeve shape.
  • step S13 the sleeve is subjected to T6 treatment to increase the strength. Table 8 shows the T6 treatment conditions for this sleeve material.
  • the sleeve thus formed is rusted into a cylinder block and die-molded with a die cast (step S14).
  • the cylinder block is made of the same material as the sleeveless case described above.
  • Step S2 After manufacturing the cylinder block with the mirrored sleeve, the cylinder block is subjected to steps S2 to S9 in the same manner as the sleeveless flow of Fig. 14 described above. That is, annealing for removing residual stress (Step S
  • the cylinder block is formed by die casting (step S1), the residual stress is removed (step S2), and each part is mechanically worked to form a cylinder block (step S1). S 3).
  • the aluminum alloy pipe material (step S10) is subjected to T6 treatment (step S11), machined (step S12), and further T 6 Process is performed (Step S13) to produce a sleeve.
  • Step S15 the cylinder block into which the sleep is press-fitted is subjected to the processes in steps S3 to S9, that is, the cylinder, in the same manner as the above-described flow of the leave and the flow of the write in FIG. Machine processing of each part of the block (Step S3).
  • the cylinder block 103 is formed by a high-pressure cylindrical die cast. It may be made by low pressure molding. In that case, the material of cylinder block 103
  • FIG. 18 is a flowchart of a piston manufacturing process of the internal combustion engine according to the embodiment of the present invention.
  • a piston material having a rough piston shape is formed by rusting or forging an aluminum alloy (step S30). Any of the alloys shown in Table 9 can be used as the aluminum alloy for this piston.
  • high hardness metal carbides such as SiC and other intermetallic compounds may be mixed.
  • the T7 treatment is a heat treatment in which the aging treatment after the solution treatment is lengthened and the stabilization is enhanced compared to the T6 treatment described above.
  • each part of the biston is machined (step S32).
  • step S33 an alumite treatment described later is performed on the outer surface of the piston including the pin hole and the ring groove of the piston (step S33).
  • step S34 the outer surface of the piston is machined.
  • step S35 finishing is performed in accordance with the accurate camshaft of the shaped piston.
  • FIG. 19 is a configuration diagram of a stationary bath for performing alumite treatment of a piston.
  • a cylindrical electrode tube is arranged in place of the cylinder block 103 in the alumite treatment device shown in FIG. 13 described above, and the electrode rod 12 is provided inside the support base 116.
  • a piston support rod was placed in place of 9 and the piston rod was placed inside the electrode tube.
  • the piston is connected to the negative electrode side of the 30 and the positive electrode side of the DC power supply 130, respectively, and the electrolyte is circulated between the skirt of the outer periphery of the piston and the electrode tube.
  • the alumite treatment may be performed using a static bath in which a piston is immersed in an electrolyte bath as shown in FIG.
  • an electrolytic solution I 51 is accommodated in an electrolytic solution bath 150, and a biston 153 held by a holder 152 is immersed in the electrolytic solution.
  • This holder 15 2 holds two pistons 15 3 in upper and lower two-stage holding frames 15 2 a, respectively, and the figure shows a state in which a total of four pistons 15 3 are held.
  • a plurality of such holders 152 may be further immersed in the electrolyte bath 150 in a direction perpendicular to the drawing.
  • Cathode plates 154 are arranged on both sides of piston 153.
  • the holder for holding the biston 15 2 is connected to the anode of the DC power supply 15 5, and the cathode plate 15 4 is connected to the cathode of the DC power supply 15 5.
  • the stationary bath electroplating bath 150
  • an alumite film is formed on the surface of the piston 153 by anodic oxidation.
  • reference numeral 200 denotes a radiator for cooling the electrolyte
  • reference numeral 201 denotes a discharge nozzle for discharging the cooling liquid for the electrolyte
  • reference numeral 202 denotes a circulation path for cooling the electrolyte
  • 0 3 is a circulation pump.
  • the low-temperature and low-pressure liquid-phase refrigerant that has passed through an expansion valve (not shown) is led to the evaporator coil 204 a in the radiator 200 by the low-pressure line 204.
  • the temperature of the alumite treatment layer of the piston 153 is prevented from rising, so that the hardness of the alumite layer can be prevented from decreasing.
  • the temperature is detected by a temperature sensor 205 provided in the lower part of the bathtub 150 or in the biston 1503, and the controller 206 increases the flow rate of the electrolyte flowing through the circulation path as the temperature increases.
  • the refrigerant discharge pressure of a compressor (not shown) may be increased to prevent a rise in the temperature of the alumite treatment layer of Biston 153.
  • the temperature may be detected by a temperature sensor 205 ′ downstream of the radiator 200, and this temperature may be controlled to 30 ° C. or less. With these, the temperature rise of the alumite-treated layer during the alumite treatment can be more reliably prevented, and the hardness of the alumite layer can be more reliably prevented from lowering.
  • the piston pin holes should be arranged in the direction of discharge of the coolant from the discharge nozzle 201.
  • the radiator 200 may be cooled with groundwater or may be air-cooled.
  • FIG. 20 is a sectional view of a piston ring mounted on the piston.
  • This piston ring is composed of a ring body 156 and a coating portion 157 formed by surface-treating the outer peripheral surface that is a sliding surface thereof.
  • Table 10 shows an example of the ring material of the ring body 156
  • Table 11 shows an example of the treatment of the coating portion 157 which has been surface-treated.
  • the coating portion 157 is compatible with the inner peripheral surface of the cylinder bore when sliding on the inner peripheral surface of the anodized cylinder bore in the above embodiment.
  • the wear of the alumite treatment layer on the inner peripheral surface of the cylinder pore can be reduced.
  • cracks are formed as described above, and the cracks are impregnated with lubricating oil or solid lubricant, or as described below, intermetallic compounds such as Si particles exposed on the inner peripheral surface of the cylinder bore are removed.
  • the effect is remarkable in the case where the one removed by the mixed acid etching treatment is subjected to alumite treatment and the recesses are formed more actively in addition to the cracks so that the lubricant and the solid lubricant are more impregnated.
  • the alumite film is a state where metal carbides such as Si particles and high hardness S i C and other intermetallic compounds are exposed on the surface.
  • the ring body 156 constantly collides with the ring groove surface in the state of being housed in the ring groove. Since the recesses formed on the surface of the alumite treatment layer can be impregnated with lubricating oil or solid lubricant based on the removal of cracks and Si particles, the ring groove surface. Wear can be prevented. In addition, the ring body 156 prevents wear of the ring groove surface even when intermetallic compounds such as Si particles and high hardness SiC are contained in the ring groove exposed on the surface. Can be.
  • the adaptability between the ring groove surface and the ring body 156 can be improved by adopting the ring material of the ring body I56 shown in Table 10 and the back surface of the ring is made of oil. And the passage of combustion gas can be prevented.
  • Fig. 21 shows the alumite treatment process (step S6) in each of the cylinder block manufacturing flow (Fig. 14, Fig. 16, and Fig. 17) and the alumite treatment in the piston manufacturing flow (Fig. 18). This is a detailed flowchart of the process (Step S33).
  • a degreasing treatment is performed to remove oil on the surface of the base material of the aluminum alloy (step S16).
  • This degreasing treatment includes (1) an acid degreasing method and (2) an alkali degreasing method. Either method is used.
  • Table 12 shows the degreasing conditions for each degreasing method.
  • a water washing treatment is performed to remove the degreasing agent (Step S17).
  • a water washing treatment is performed to remove the degreasing agent (Step S17).
  • an alkali etching process step S18
  • a mixed acid etching process step S20
  • a water washing process for removing the etching solution is performed (Step S19, Step S21).
  • Table 13 shows the etching conditions for alkali etching
  • Table 14 shows the etching conditions for mixed acid etching.
  • the surface of the base material is etched away leaving silicon (S i) particles and intermetallic compound particles scattered in the base material of the aluminum alloy, and silicon / intermetallic compound particles project on the surface. Then, the base material surface is removed.
  • silicon particles and intermetallic compound particles are etched, and concavities are formed on the surface of the base material, where silicon particles and intermetallic compounds are removed. If there is a possibility that the surface dirt may not be sufficiently removed in the previous degreasing process, such an etching process performs both the re-etching and the mixed acid etching to completely complete the surface layer. Removal is desirable to increase the reliability of the subsequent anodizing process.
  • the depression in the trace from which the silicon particles and intermetallic compounds have been removed by the mixed acid etching can be used as a depression for impregnating oil or a solid lubricant.
  • Step S22 anodizing is performed on the base material surface thus etched to form an alumite film. This anodization is performed, for example, as shown in FIG.
  • Table 15 shows examples of this alumite treatment.
  • Table (A) shows an example in which the alumite treatment was applied to the inner surface of the cylinder bore of the sleeveless cylinder block composed of ACD12 in Table 6 above, and Table (B) shows the example in Table 7 above. This is an example in which an alumite treatment is applied to the inner surface of the sleeve of a cylinder block into which a sleeve made of A6601 is inserted.
  • Table (C) shows an example in which the alumite treatment was applied to the piston made of alloy 105 in Table 9 described above.
  • oxalic acid and citric acid were added in addition to sulfuric acid as an electrolyte.
  • Sulfuric acid has a strong film dissolving power and dissolves this anodic oxide film after the anodic oxide film is formed by electrolysis. For this reason, the pinholes formed on the oxide film surface during the anodic oxidation treatment dissolve and enlarge, and as a result, the surface hardness decreases.
  • the film dissolving power of sulfuric acid is reduced, and the film hardness can be increased.
  • the entire electrolytic solution is oxalic acid or citric acid
  • the electric conductivity of the electrolytic solution that is, the charge transport function decreases, and the reaction rate decreases.
  • the electric conductivity was increased, the processing time required to obtain an alumite film of a predetermined thickness was shortened, and the ratio of sulfuric acid was small, so that the electrolyte was formed.
  • the hardness of the film can be prevented from decreasing due to the dissolving action of the alumite film.
  • FIG. 24 is a diagram showing the effect of bath temperature on hardness with constant electrolysis conditions.
  • A shows the current density of 3 A / dm 2 (Amps / 100 ci) on an aluminum alloy of A0.61.
  • Current waveform DC
  • electrolysis time 20 minutes
  • electrolyte solution sulfuric acid concentration: 2 0 g / oxalic acid + citric acid concentration: Data when alumite treatment was performed under the condition of 40 g / 1, Hv 380 or more can be obtained at a bath temperature of 30 ° C or less .
  • the alumite film is practically used as the inner peripheral surface of the cylinder on which the piston slides by controlling the bath temperature to about 30 ° C or less and performing alumite treatment. Hardness Hv380 or higher to obtain sufficient wear resistance.
  • Fig. 2B shows the data when the concentration of the sulfuric acid in the electrolyte was 2 Og / l, the concentration of oxalic acid and citric acid was 0 g Zl, and the other conditions were the same as those in (a). It shows that Hv380 or more can be obtained at 20 ° C or less.
  • Figure 25 shows the relationship between the film thickness and hardness when the sulfuric acid concentration was maintained at a constant 20 g / 1.
  • FIG. 26 is a graph showing the effect of electrolyte composition on film thickness and hardness over a range of oxalic acid and citric acid concentrations when the sulfuric acid concentration was varied.
  • Other electrolysis conditions were as follows: the aluminum alloy to be treated was A6 61, current density 3 A / dm 2 , current waveform: DC. Electrolysis time: 20 minutes, Rakuon 13 "C.
  • A 0
  • the film hardness is approximately Hv300, and cannot be ⁇ ⁇ 380 or more necessary for abrasion resistance.
  • a water washing treatment is performed to remove the electrolytic solution (step S23), and a secondary electrolytic treatment is performed (step S24).
  • solid lubricant is deposited by electrolytic action on the bottom of pinholes formed innumerably on the surface of the alumite film and deposited, and the interior of the pinhole is filled with solid lubricant from the bottom. I do. This further enhances the lubricity of the film surface and further improves the wear resistance.
  • step S25 the solid lubricant electrolyte is removed by washing with water (step S25), this water is removed by air blow, and the cylinder block is dried to complete the alumite treatment (step S26).
  • FIG. 22 and FIG. 23 are cross-sectional views of the base material surface portion in each step of the above-described cylinder block and piston manufacturing process.
  • Figure 22 shows the etch after degreasing
  • FIG. 23 shows, in order, a flow in which alumite treatment is performed after mixed acid etching is performed.
  • FIG. 22 (A) shows the state after the degreasing treatment. Silicon particles, metal carbides such as SiC, and other intermetallic compound particles 141 are scattered in the base material 140 made of an aluminum alloy. Dirt such as oil on the surface 140a of the base material 140 is removed by degreasing.
  • an alumite treatment is performed to form an alumite film i 42 on the base material 140 as shown in FIG. Silicon particles 144 are also scattered in the alumite film 144. Bubbles 144 are generated in the alumite film 144. As described above, many of the bubbles 144 are generated when the base metal 140 contains a copper component.
  • FIG. 23 (A) shows the state after the mixed acid etching treatment.
  • the silicon particles 14 1 on the surface of the base material 140 are removed by etching to form a depression 1 45.
  • An alumite treatment is performed in this state, and an alumite film 142 is formed on the surface of the base material 140 as shown in FIG.
  • the surface of the alumite film 142 has a dent 145 left thereon.
  • heat treatment or burnishing is performed, and cracks 144 are formed in the alumite film 144, as shown in FIG.
  • the surface of the base material 140 is removed while leaving silicon particles 141 by alkali etching.
  • the silicon particles protrude from the surface of the alumite film 144 even after the honing in the final step.
  • silicon particles hidden under the surface of the alumite film I 42 are also exposed by the HOUNG, so that the average hardness of the surface of the alumite film 142 is increased, and the wear resistance is improved.
  • Table 16 shows the chemical composition of the alumite film when the A1-110Si-4Cu alloy contained in Alloy 5 shown in Table 9 was anodized.
  • the alumite film made of sulfuric acid means that sulfuric acid (concentration: 200/1) is used as the electrolyte and the current density is 3 AZ dm 2 (ampano 100 cm 2 ).
  • the inventor of the present application has found that the use of a oxalic acid mixed solution as an electrolytic solution can reduce the elution of copper from the alumite film, the hardness of the alumite film and the content of copper in the alumite film. I found the relationship.
  • Figure 27 shows the results obtained by using an A1-10Si-4C ⁇ ⁇ aluminum alloy as the base material, a oxalic acid mixture as the electrolyte, and changing the electrolysis conditions (sulfuric acid concentration and processing time).
  • the results of an experiment in which the surface hardness (Hv) of the alumite film when the copper content% in the alumite film was changed are shown.
  • the copper content in the alumite film should be at least 0.5% in order to obtain sufficient hardness.
  • the Arumai DOO coating is sufficient by copper coating in addition to the hardness of A l 2 0 3 itself is distributed between the A 1 2 0 3 Hardness
  • Copper-containing% in the alumite film is required to be 0.5% or more, more preferably to copper in the coating so as to disperse between A 1 2 0 3, as a base material of the aluminum alloy part the copper-containing 0/0 using those from 0.8 to 5%, it is necessary to alumite treatment using oxalic acid mixture is the electrolytic solution thereon, thereby easily aforementioned improvement in hardness The effect is obtained.
  • the base material of the aluminum alloy component having a copper content of 0.8 to 5% has sufficient strength, and the strength can be further increased by performing a solution treatment or an aging treatment.
  • ADC3 0.6 or less 3-. Up to 10.0 0.4-0.6 0.S or less 1.3JUT 0.3WT 0.S or less 0.1 or less «Section
  • ADC10 2.0 ⁇ 0 7.5-9.5 below 0.3tt below 1.0 below 1.3 below 0.5 below 0.5tt 0.3 «below
  • ADC14 4.0-5.0 16.0-1 8.0 0.45 ⁇ 0.60 1.5 or less. Under 1.3JU 0.5 or less 0.5CI 0.3 or less »section
  • Electrolyte composition (g / l) Degree of ioL Flow waveform Current density Solution time Film hardness
  • composition (g / l) Degree Electric form density Electrolysis time Film hardness Film thickness Oxalic acid Sulfuric acid Sulfuric acid Dissolved AI C) (A dm2) (min) (HV) ( ⁇ m)
  • the anodizing is performed without cooling the surface of the piston pin hole without controlling the electrolysis time and current density without performing the conventional mixed acid treatment.
  • the alumite-treated film with a film thickness of 30 ⁇ 10 / m was formed by applying the treatment, so that even if the current density was high, the alumite heat treatment was possible in a short time without generating heat on the alumite surface. Since the surface hardness of the alumite layer does not decrease while the processing is simplified, and the surface roughness of the film is approximately Ra (center line average roughness defined in JISBO601), it can be controlled to 5 to 3.0 m.
  • a piston for an internal combustion engine having excellent wear resistance of the piston pin hole can be provided at low cost.
  • the inner end surface is prevented from being worn due to contact with the small end of the conrod. It is possible to prevent abrasion of the biston pin holes caused by the abrasion powder penetrating into the biston pin holes.
  • the crack forming step is performed by heat treatment.
  • the crack forming step is burnished.
  • the cracks are formed in the alumite film by a simple process because it is performed by the treatment, and the lubricity and wear resistance described above are achieved. It is possible to obtain the above effect.
  • an anodic oxide film (alumite film) is formed.
  • the electrolyte solution contains sulfuric acid and further contains oxalic acid or citric acid
  • the film dissolving power due to sulfuric acid is reduced, and a decrease in surface hardness can be prevented.
  • the elution of the copper component in the aluminum alloy can be suppressed. In this way, the wear resistance of the sliding surface can be further enhanced, particularly when the aluminum component is a piston-cylinder of an internal combustion engine.
  • the electrolytic solution is stored in a stationary bath, and the aluminum article is immersed in the electrolytic solution to perform anodizing. Since the electrolytic solution is circulated and flows on the treated surface of the aluminum article, an alumite film can be reliably formed on the surface of the aluminum component. Furthermore, in the invention of claim 12, since 0.5% or more of copper is contained in the alumite film, the hardness of the alumite film can be increased, and in the invention of claim 13, Since the base material (aluminum component) is formed from an aluminum alloy containing 0.8 to 5% of copper, 0.5% or more of copper can be easily and reliably contained in the alumite film.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)

Abstract

L'invention porte sur un enrobage (10) en alunite dont l'épaisseur est de 30?10 νm et comportant des particules de Si exposées et des particules de SiC, cet enrobage étant formé sur la partie superficielle avant d'un orifice (7c) d'un piston (1) en alliage d'aluminium d'un moteur à combustion interne.
PCT/JP2000/000051 2000-01-07 2000-01-07 Pieces en aluminium et leur procede de production WO2001049904A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138813A (ja) * 2005-11-17 2007-06-07 Hitachi Ltd 往復動圧縮機
JP2007260624A (ja) * 2006-03-29 2007-10-11 Tokyo Electron Ltd 真空装置に用いる真空容器及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5423042A (en) * 1977-07-21 1979-02-21 Seiko Instr & Electronics Ltd Formation of anodic oxide film on aluminum or its alloy
EP0324325A1 (fr) * 1988-01-15 1989-07-19 International Business Machines Corporation Revêtement anodique sur aluminium pour empaquetage d'un circuit
JPH01190951A (ja) * 1988-01-26 1989-08-01 Toyota Motor Corp 内燃機関用ピストン
JPH03113175A (ja) * 1989-09-25 1991-05-14 Yamaha Motor Co Ltd 摺動部材の表面構造
JPH09316693A (ja) * 1996-05-29 1997-12-09 Sky Alum Co Ltd フッ素樹脂塗装アルミニウム合金部材およびその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5423042A (en) * 1977-07-21 1979-02-21 Seiko Instr & Electronics Ltd Formation of anodic oxide film on aluminum or its alloy
EP0324325A1 (fr) * 1988-01-15 1989-07-19 International Business Machines Corporation Revêtement anodique sur aluminium pour empaquetage d'un circuit
JPH01190951A (ja) * 1988-01-26 1989-08-01 Toyota Motor Corp 内燃機関用ピストン
JPH03113175A (ja) * 1989-09-25 1991-05-14 Yamaha Motor Co Ltd 摺動部材の表面構造
JPH09316693A (ja) * 1996-05-29 1997-12-09 Sky Alum Co Ltd フッ素樹脂塗装アルミニウム合金部材およびその製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007138813A (ja) * 2005-11-17 2007-06-07 Hitachi Ltd 往復動圧縮機
JP2007260624A (ja) * 2006-03-29 2007-10-11 Tokyo Electron Ltd 真空装置に用いる真空容器及びその製造方法

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