US20190322020A1 - Composite article of aluminum alloy with resin and method for production thereof - Google Patents

Composite article of aluminum alloy with resin and method for production thereof Download PDF

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Publication number
US20190322020A1
US20190322020A1 US16/388,865 US201916388865A US2019322020A1 US 20190322020 A1 US20190322020 A1 US 20190322020A1 US 201916388865 A US201916388865 A US 201916388865A US 2019322020 A1 US2019322020 A1 US 2019322020A1
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Prior art keywords
aluminum alloy
resin
nmt
pieces
treatment
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US16/388,865
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English (en)
Inventor
Naoki Andoh
Yoshihiro Yamaguchi
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Taisei Purasu Co Ltd
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Taisei Purasu Co Ltd
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Assigned to TAISEI PLAS CO., LTD. reassignment TAISEI PLAS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ANDOH, NAOKI, YAMAGUCHI, YOSHIHIRO
Publication of US20190322020A1 publication Critical patent/US20190322020A1/en
Priority to US17/517,679 priority Critical patent/US11931988B2/en
Abandoned legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
    • B29C45/14795—Porous or permeable material, e.g. foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14008—Inserting articles into the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/72—Heating or cooling
    • B29C45/73—Heating or cooling of the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/78—Measuring, controlling or regulating of temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/0081—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for slabs; for billets
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/36—Alkaline compositions for etching aluminium or alloys thereof
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium
    • 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
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • 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
    • C25D11/16—Pretreatment, e.g. desmutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts
    • B29K2705/02—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars

Definitions

  • the present invention relates to a composite of a metal and polyphenylene sulfide (hereinafter referred to as “PPS”) resin composition joined by injection molding, and a method for manufacturing the same.
  • PPS polyphenylene sulfide
  • the present invention relates to a composite of a metal and PPS resin that has properties suitably used for moving machines such as automobiles, outdoor facilities, machines used outdoor, or the like.
  • NMT is a technology of joining an aluminum alloy with a resin composition providing a method, in which a molten engineering resin is injected onto a metal part preliminarily inserted into a metallic mold for injection molding thereby forming a resin portion and at the same time the molded article and the metal part are joined (hereinafter this will be referred to as “joining by injection molding”).
  • Patent Document 1 discloses a technology (NMT), in which a PPS resin composition is joined by injection molding onto an aluminum alloy that has been subjected to a specific surface treatment.
  • Patent Document 2 discloses a technology (“NMT 2” as named by the present inventors) in which joining strength by injection molding is raised, improving surface treatment method of aluminum alloy in NMT.
  • NMT 2 a technology in which amine molecules are chemically adsorbed onto surface of an aluminum alloy.
  • NMT, NMT 2 and new NMT as referred to in the present invention, will be explained in more details below.
  • NMT as a technology of joining by injection molding using an aluminum alloy, following four or five conditions are defined as required conditions for realizing it. For the first, following (1) and (2) are required conditions for the side of an aluminum alloy. It is called as “NMT treatment” to treat the surface of aluminum alloy chemically so as to satisfy the two conditions.
  • the entire surface should be covered with ultrafine concaves having diameter of 20 to 50 nm.
  • a resin composition should be used such that contains highly crystalline thermoplastic resin as a main component.
  • the highly crystalline resin composition should react chemically with amine molecules under high temperature.
  • the resin composition should contain a resin as an auxiliary component that is compatibly soluble into the main component resin or can be compatibly soluble by adding a third resin component, even if not compatibly soluble itself into the main component resin.
  • NMT and NMT 2 are such that the above (1) to (4) are satisfied and hydrazine hydrate is selected as the amine compounds in the above (2).
  • NMT was discovered initially with PBT (polybutylene terephthalate resin), after then it was confirmed that also PPS can be used (Patent Document 1), and in the next it was confirmed that also polyamide resin or the like can be used. After this, a method concerning surface treatment of aluminum alloy was discovered such that joining strength by injection molding is raised adjusting chemical adsorption rate of hydrazine hydrate (Patent Document 2) and this was named as “NMT 2” by the present inventors.
  • PBT polybutylene terephthalate resin
  • new NMT in which various metal materials and resin compositions can be joined by injection molding even without surface treatment with amine molecules. Following five conditions were defined as required conditions for realizing it. At first, following three conditions are required for the side of a metal material. It is referred to as “new NMT treatment” in the present invention to make chemical surface treatment of a metal material so as to satisfy the three conditions.
  • the entire surface should be covered with a surface having surface roughness of 0.8 to 10 ⁇ m period.
  • a resin composition containing highly crystalline thermoplastic resin as a main constituent should be used.
  • the resin composition should contain a resin as an auxiliary constituent that is compatibly soluble into the main constituent resin or can be compatibly soluble by adding a third resin constituent, even if not compatibly soluble itself into the main component resin.
  • a composite with a high joining strength by injection molding can be formed through penetration of injected resin that can easily be subjected to chemical reaction with the amine molecules under high temperature into the ultrafine concaves in a situation where the amine molecules are chemically adsorbed onto the ultrafine concaves on the surface of aluminum alloy.
  • the injected resin is a resin composition that satisfies the above condition (5), joining strength of the composite formed by injection molding is raised further, because crystallization rate at urgent cooling is restrained so that resin penetrates more easily into the ultrafine concaves on the surface of the aluminum alloy.
  • Patent Document 3 new NMT in which aluminum alloy is used (Patent Document 3), only surface configuration of dual irregularities according to the above conditions (1) and (2) are defined for surface configuration on the side of aluminum alloy and there is no condition for chemical adsorption of amine molecules. Due to this, decrease in joining strength of the composite formed by injection molding could not be avoided compared with NMT depending on the absence of chemical adsorption of amine molecules.
  • NMT and NMT 2 seemed to be superior to new NMT in respect of joining strength of composites formed by injection molding.
  • the present inventors thought it to be necessary to develop further the advantageous result of new NMT, because such a problem as follows is found in the field of actual manufacturing.
  • a time (day) lag occurs from completion of surface treatment step of aluminum alloy until beginning of the next step of joining by injection molding. For example, this may occur when there is a long distance from a factory for chemical conversion treatment, where surface treatment is performed, to a factory for joining by injection molding, where joining by injection molding is performed, so that a long time is required for transportation. Further, it may also be a cause for the time lag that a longer time is required for the step of joining by injection molding than the step of surface treatment, because of setup, etc. There may be a case where it takes a length of time (referred to “days of storage” below) of several days to one or two weeks to transport the aluminum alloy having the step of surface treatment completed and begin the next step of joining by injection molding.
  • days of storage referred to “days of storage” below
  • joining by injection molding was performed using Sastille (registered trade mark) “SGX120” (produced by Tosoh Corporation: main company in Tokyo, Japan) of a PPS resin as a resin to be injected.
  • Sastille registered trade mark
  • SGX120 produced by Tosoh Corporation: main company in Tokyo, Japan
  • a joined composite joined by injection molding of the aluminum alloy with this resin was brought into an ion exchange water set to be in a temperature of 98° C.
  • a commercially available electric pot as a heating-heat retention device for boiling water was used for setting the temperature of 98° C. of the ion exchange water.
  • the present invention employs following means in order to solve the above described problems.
  • a composite of aluminum alloy and resin according to the present invention 1 including:
  • a resin composition consisting of a total resin part and a filler part, the total resin part containing a polyphenylene sulfide resin as a main component by 70 mass % or more of a resin part, and a modified polyolefin resin as an auxiliary component by 30 mass % or less of the resin part, and further containing a resin of third component having ability for promoting compatibility of the polyphenylene sulfide resin and the modified polyolefin resin, and the filler part of reinforcing fiber being 15 to 30 mass % of an entire resin composition;
  • a joining strength between two parts of an integrated entity of the aluminum alloy and the resin composition as a molded entity is a high joining strength equal to or greater than 30 MPa for both of shear joining strength and tensile joining strength.
  • the composite according to the present invention 2 is such that, in the composite of aluminum alloy and resin according to the present invention 1, the surface having ultrafine irregularities is one having porous structure formed by an anodization method.
  • the composite according to the present invention 3 is such that, in the composite of aluminum alloy and resin according to the present invention 1 or 2, amine molecules are chemically adsorbed onto the surface having ultrafine irregularities.
  • a method according to the present invention 4 is a method for manufacturing the composite of aluminum alloy and resin according to the present invention 1 or 2, in which the aluminum alloy and resin composition that are integrally joined is performed in a manner such that:
  • amine molecules are chemically adsorbed onto the surface having ultrafine irregularities formed by chemical treatment, and
  • the aluminum alloy is inserted into a metallic mold for injection molding, after which the resin composition is injected into the metallic mold.
  • the metal used in the composite of the present invention is a pure aluminum or an aluminum alloy.
  • Aluminum alloy in the present invention will be referred to as such in a concept including a pure aluminum below.
  • the surface of the aluminum alloy according to the present invention realizes a higher joining strength between this aluminum alloy and resin than with the above NMT treatment, etc. Examples of electronic microscope photographs will be shown specifically concerning Experimental Examples explained later. That is, aluminum alloy articles having been subjected to treatment of NMT, NMT 2, etc., are shown through observation with an electronic microscope. As seen in an electronic microscope photograph in magnification of 1000 times, the surface seems plate-like with little variance. The same surface reveals, in an electronic microscope photograph in a magnification of 10000 times, crystal grain boundary lines depressed like grooves.
  • grooves are formed by chemical etching for removing dirt attached by acid or basic aqueous solution and it seems that the etching has exhibited stronger action near the crystal grain boundary lines. It is observed with an electronic microscope that the diameter of most of the metal crystals of aluminum alloy is within a range of 1 to 5 ⁇ m, the period of irregularities is 1 to 5 ⁇ m and surface of smooth roughness with shallow (low) depth (height) can be seen. On the other hand, concaves with 20 to 50 nm diameter seems to cover the entire surface in an electronic microscope photograph in a magnification of 100000 times.
  • the present inventors continued inferring based on a principle that configuration giving a minimum basic unit for creating joining strength consists in a surface having ultrafine irregularities of 20 to 50 nm period, and came to think of enlarging the area of the surface having ultrafine irregularities as the basic unit by more than several times. That is, it was thought to establish a shaped article that has clearly rough surface having several decades to a hundred ⁇ m period in a photograph in a magnification of 1000 times and additionally has surface configuration having irregularities of several ⁇ m period in strict clearness in a photograph in a magnification of 10000 times by etching in the part of crystal grain boundary line more deeply.
  • the inventors came to think of preparing several kinds of chemical etching liquid set to have a little thicker acid or basic concentration, forming a rough surface having roughness of several decades to a hundred ⁇ m period and along with this clearly forming a rough surface having fine roughness of 1 to 5 ⁇ m period utilizing crystal grain boundary for each aluminum alloy by use of combination of the above kinds of chemical etching liquid.
  • Forming a surface having ultrafine irregularities of several decades nm period after this was set to be performed in a conventional manner. It was inferred that, if this is possible, the summed area (the entire area) of the surface having ultrafine irregularities in the area for attachment as the surface area of the metal part increases at least by 10 times.
  • NMT 7 An article treated with hydrazine hydrate adsorbed by a suitable amount similarly as NMT 2 (referred to as “NMT 7” in the present invention and specific matter will be explained later).
  • NMT 7-Oxy An article treated so as to have a similar surface configuration as described above but have no amine molecules adsorbed thereon (referred to as “NMT 7-Oxy” in the present invention and specific matter will be explained later).
  • An article treated in a manner in which ultrafine irregularities on the metal surface are formed not by immersing in an aqueous solution of hydrazine hydrate but by anodic oxidation referred to as “Ano-7” in the present invention and specific matter will be explained later.
  • a target regarding aluminum alloy having been subjected to surface treatment according to the present invention was set based on a wish such that composites joined by injection molding that have a high joining strength obtained by NMT 2 and have ability of preserving the strength under heat and moisture over a long time can be obtained even if days of storage are extended to two weeks.
  • the measure 1 is to increase surface area of the aluminum alloy. It was thought that, if surface area for joining can be increased by an amount of, e.g. 10 times of articles subjected to NMT 2 treatment even on the quite same principle of joining by injection molding as in NMT 2, increase of area for joining would give much disadvantageous effect on joining strength even if detachment phenomena of adsorbed amine occurs over time.
  • This joining face is a portion where a metal part and a resin part confront each other and it is supposed that, regarding distance between the metal part and resin part, sites with various distance are arranged in a not periodic manner from zero distance (called for a narrow tiny gap where even water molecules, oxygen molecules or nitrogen molecules cannot pass through) to several nm distance.
  • Al atoms, becoming ions, are dissolved into water aggregated in such a manner and further are changed to be aluminum hydroxide (rust), thus being precipitated on the side of aluminum alloy to be attached there.
  • rust aluminum hydroxide
  • Water molecules or oxygen molecules penetrating into the central portion of the joining face after this are restricted to those having been diffused through a thick resin layer, and penetration speed is rather low. Therefore, while the gaps (spaces) in the central portion of the joining face are filled up gradually with rust, water molecules are not supplied in such an amount as to have a power of pushing up the resin part so that no new internal stress is generated.
  • joining strength is once lowered in lapse of a day, when they are subjected to pot wet-heat test, then joining strength, e.g., shear joining strength, begins to be raised for the initial one of 36 to 40 MPa in lapse of two days, and little change can be seen after lapse of three days. Further, in a case where composites are subjected to high temperature-high humidity test, joining strength is once lowered to a minimum value during lapse of 200 to 1000 hours and then turns to a recovering state towards the initial joining strength, and no change can be seen after lapse of 2000 hours. It is thought that the above inference by the present inventors is correct, for explaining this creature-like change of joining strength.
  • width of gaps in the peripheral wall may be small, ratio of a portion of high joining strength remaining in the central portion of the joining face is high and the joining strength returns to the initial state after once lowered, in a case where maximum width of gaps in portions opened beforehand is extremely narrow as of several nm level.
  • width of gaps in the peripheral wall becomes large and area of a portion high joining strength becomes small relatively, in a case where maximum width of gaps in the opened portions is near to 10 nm. In such a case, although joining strength is inclined to be recovered after once having been lowered over time, it is not recovered to a state of the initial joining strength.
  • the measure 2 is a method of changing kinds of adsorbed amine compounds in NMT 2.
  • Hydrazine hydrate has been conventionally used as the amine compounds. This is based on a consideration such that, if elongation of days of storage causes physical property of a composite joined by injection molding to be degraded, hydrazine hydrate should be replaced by amine molecules, as material to be adsorbed, having a larger weight and a higher boiling point than the former.
  • this is a method of surface treatment based on a presumption such that the problem will be solved by making detachment speed of amine molecules slower. Specifically used was triethanolamine.
  • NMT 8 treatment method by “NMT 8”, as referred to in the present invention, was developed.
  • a composite joined by injection molding with sufficient joining strength can be obtained.
  • SGX120 as PPS resin
  • a composite can be obtained in which not only joining strength is high but also the joining strength maintains moisture resistance and heat resistance for long time.
  • a joined composite of an aluminum alloy and molded thermoplastic resin is of light weight compared with a worked article of steel material.
  • joining strength of this joined composite has high grade of moisture resistance and heat resistance, it will be very useful as a material of parts for moving machines such as automobiles, aircrafts, moving robots, etc.
  • NMT 2 allows it to be possible, it has problems yet. That is, a most serious problem is that the step of joining by injection molding must be finished before several days lapses after NMT 2 treatment has been performed, in order to completely secure physical property of a joined composite in a highest level such that joining strength has moisture resistance and heat resistance.
  • joining strength of the composite joined by injection molding is not lowered irrespective of days of storage from a step of surface treating to a step of joining by injection molding, joining strength is not apt to be lowered over time, and also its moisture resistance and heat resistance are in a high level to cause its joining strength not to be easily lowered.
  • FIG. 1 is a view showing a composite of a metal and resin joined by injection molding as a shaped article (composite) for measuring shear joining strength between the metal part and the molded resin.
  • FIG. 2 is a view showing a composite of a metal and resin joined by injection molding as a shaped article (composite) for measuring tensile joining strength between the metal part and the molded resin.
  • FIG. 3 is a view showing an assistant jig for containing the shaped article shown in FIG. 1 for measuring shear joining strength by placing the article shown in FIG. 1 with the assistant jig in a tensile test machine to create tensile breaking.
  • FIG. 4 is an electron microscope photograph of an aluminum alloy A5052 having been subjected to “NMT treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 1).
  • FIG. 5 is an electron microscope photograph of an aluminum alloy A5052 having been subjected to “NMT 2 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 2).
  • FIG. 6 is an electron microscope photograph of an aluminum alloy A5052 having been subjected to “NMT 7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 3).
  • FIG. 7 is an electron microscope photograph of an aluminum alloy A5052 having been subjected to “NMT 7-Oxy treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 10).
  • FIG. 8 is an electron microscope photograph of an aluminum alloy A5052 having been subjected to “Ano-7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 11).
  • FIG. 9 is an electron microscope photograph of an aluminum alloy A5052 having been subjected to “NMT 8 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 12).
  • FIG. 10 is an electron microscope photograph of an aluminum alloy A7075 having been subjected to “NMT 7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 4).
  • FIG. 11 is an electron microscope photograph of an aluminum alloy A6063 having been subjected to “NMT 7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 5).
  • FIG. 12 is an electron microscope photograph of an aluminum alloy A2017 having been subjected to “NMT 7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 8).
  • FIG. 13 is an electron microscope photograph of an aluminum alloy A6061 having been subjected to “NMT 7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 7).
  • FIG. 14 is an electron microscope photograph of an aluminum alloy A1100 having been subjected to “NMT 7 treatment” in a magnification of 1000 times, 10000 times and 100000 times (Examination Example 6).
  • Aluminum alloy composing a composite of the present invention is thought to be pure aluminum, various aluminum alloys including those as malleable ones or for casting, aluminum plated steel plates, aluminum clad materials or the like.
  • Surface configuration required for pure aluminum or aluminum alloys according to the present invention is not limited to that obtained by specific surface treatment methods, but that of aluminum alloy obtained as a result by various surface treatment methods. Further, also aluminum alloys can be used in a case where amine molecules are adsorbed onto their surface. Specifically, the surface provides following (1) or (2).
  • the surface of an aluminum alloy for composing a composite according to the present invention is (1) one having threefold irregularities such that rough surface having surface roughness of 10 to 100 ⁇ m period is observed with an electron microscope in a magnification of 1000 times, surface having fine irregularities of 1 to 5 ⁇ m period based on crystal grain boundary is observed with an electron microscope in a magnification of 10000 times and surface having ultrafine irregularities covered with concaves or holes of 30 to 100 nm diameter thereon is confirmed with an electron microscope in a magnification of 100000 times, or (2) one in which either the surface having ultrafine irregularities of the above (1) has no attached amine compounds or molecules thereon, or water soluble amine compounds or molecules such as hydrazine (including hydrazine hydrate), triethanolamine, etc. are adsorbed thereon.
  • the preliminary treatment is a step of forming clearly surface configuration with dual irregularities of rough surface having surface roughness of 10 to 100 ⁇ m period and surface having fine irregularities of 1 to 5 ⁇ m period based on crystal grain boundary folded thereon. While specific preliminary treatment methods are various for the species of aluminum alloys, a same preliminary treatment method is implemented in a case where the above four kinds of treatment methods are implemented for a species of aluminum alloy. Further, main treatment methods following the preliminary treatment methods are as follows.
  • the aluminum alloy pieces having been subjected to preliminary treatment are immersed in an aqueous solution of hydrazine hydrate with a concentration of several % for about a minute to form surface having ultrafine irregularities, and then they are immersed in an aqueous solution of hydrazine hydrate with a low concentration less than 1% for several minutes to adsorb hydrazine hydrate (hydrazine) onto the surface of the aluminum alloy pieces.
  • This treatment step is same as in a case of “NMT 2”.
  • NMT-7 Oxy treatment is a treatment in which the aluminum alloy pieces are immersed in a thin aqueous solution of hydrogen peroxide after having “NMT 7 treatment” finished to break down adsorbed hydrazine, thus resulting in a treatment method causing aluminum alloy pieces to have no adsorbed amine compounds or molecules thereon.
  • “Ano-7 treatment” is a surface treatment method in which a bath for anodization with an aqueous solution of phosphoric acid in concentration of 5 to 10% filled therein is prepared and anodization is performed with an aluminum alloy piece having been subjected to preliminary treatment in the anodic side for about 15 minutes under a voltage of 20 to 25 V.
  • NMT 8 treatment is a surface treatment method in which aluminum alloy pieces having been subjected to “Ano-7 treatment” are immersed in a thin aqueous solution of triethanolamine, thus adsorbing trimethanolamine.
  • Specific treatment method in these four kinds of preliminary treatment steps is as follows. At first, aluminum alloys with oil content attached thereon are degreased in a degreasing bath and rinsed with water. This treatment is performed for removing machine oil or oil content attached onto the aluminum alloys during steps of mechanical working, etc., for shaping to have specific forms. In the next, the degreased aluminum alloys are immersed in an aqueous solution of caustic soda having a somewhat thick concentration for a short time to forcibly dissolve natural oxide film or rust, thus making the surface of aluminum alloys clean and activated. In the next, crystal grain boundary is dissolved sufficiently with an aqueous solution of chloric acid and then an aqueous solution of sulfuric acid further digs in deeply there.
  • the aluminum alloys are immersed in a thin aqueous solution of caustic soda to dissolve aluminum alloy alone in the alloys in a high speed and enlarge height (depth) of rough surface, though restricted to those containing abundant alloy constituency.
  • pickling of the aluminum alloys is performed in an aqueous solution of nitric acid having a concentration of several % to dissolve and remove smut (insoluble matter) generated in the previous steps, after which the aluminum alloys are rinsed with water.
  • a standard treatment method is as such.
  • Resin composition for joining by injection molding is same as in NMT 2 or NMT 2.
  • Condition of preparation of resin composition is described in the above explained NMT theory or new NMT theory. That is, a resin composition that can be used both in NMT and new NMT is one containing a highly crystalline thermoplastic resin (other than polyolefin resin) as a main component and a resin compatibly soluble with the main component resin as an auxiliary component, or one containing a resin as a third component resin that, even if the auxiliary component resin is not compatibly soluble with the main component resin, promotes compatibility with the main component resin even in part.
  • “SGX120” as a PPS resin for joining by injection molding is a mixed composition of the latter type.
  • a main component in the resin part is PPS
  • an auxiliary component is a modified polyolefin resin
  • a third component resin is added for making the former two kinds of resin compatibly soluble with each other even in part as it is difficult for the two kinds of resins to be compatibly soluble with each other.
  • This third component resin is a composition selected by resin manufacturers and is not an inevitable component for constituting the present invention, but is of a trade secret. So, it is not disclosed in detail here.
  • reinforcing fiber such as glass fiber (GF), carbon fiber (CF), etc.
  • inorganic powder such as calcium carbide, talc, etc.
  • GF glass fiber
  • CF carbon fiber
  • inorganic powder such as calcium carbide, talc, etc.
  • commercially available “SGX120” used frequently as a PPS resin for joining by injection molding contains GF by 20% added to resin part of 80%.
  • crystalline thermoplastic resin has a linear expansion coefficient higher than that of amorphous thermoplastic resin, both of these linear expansion coefficients of the resins are far higher than that of metal materials.
  • “SGX115” contains resin portion more than “SGX120”, and hence modified polyolefin resin is contained more, so that the resin not only has a high restraining ability of crystallization at urgent cooling, but also has a low water absorption rate.
  • the low water absorption rate lowers diffusion rate of water molecules in the resin, resulting in improvement of moisture resistance and heat resistance of joining strength.
  • tensile strength of the resin itself is lower than that of “SGX120” by 15% due to decrease of contained GF, so that shear joining strength of a composite with an aluminum alloy having been subjected to NMT treatment joined by injection molding is 34 MPa.
  • a blended resin containing GF by 20% is of a supreme composition, because rather having a high joining strength provides actually most effective arms for preventing an accident. Therefore, a direction for further improvement in manufacturing composites for use in moving machines will be in raising performance of “SGX120” further, that is, in what a mixed ratio for a mixture of GF and CF (carbon fiber) to employ. This will be variable depending on what a position the used composite is disposed at for use in the moving machine, and is of a study to be made after the present invention is practically realized. So, the present inventors remain to say as follows.
  • the method for manufacturing a composite according to the present invention is a general purpose method for joining by injection molding.
  • a most suitable condition can be actually obtained by try and error and minor adjustment of conditions of joining by injection molding for obtaining composites joined by injection molding having various shapes.
  • temperature at injection and speed of injection are substantially same as in a case of usual injection molding of PPS, it is preferable to set temperature at injection and temperature of a metallic mold to be a little higher. That is, it is preferable that temperature at injection is 300 to 310° C. and temperature of a metallic mold is near to 140° C.
  • injection is performed after waiting at least about one minute from the time when the metallic mold has been closed with the aluminum alloy inserted there. Further, it is preferable to perform injection molding as in said process after preheating in a temperature of 60 to 80° C. before inserting the aluminum alloy into the metallic mold. With these operation, temperature of surface of aluminum alloy becomes near to the temperature of the metallic mold at the time when resin is injected, which, even in a case of a large type of aluminum alloy, provides at once setting of condition near to one in a case where a small type of aluminum alloy is inserted into the metallic mold to form a small type of composite joined by injection molding as shown in FIG. 1 or FIG. 2 .
  • the formed composite according to the present invention is preferably subjected to “annealing” treatment by placing it in a hot air drier adjusted to a temperature of about 170° C. to be heated there for about one hour in the same day.
  • the essence of performing annealing treatment consists in that, although the formed composite joined by injection molding is one integrated with a high joining strength, resin part shrinks by some extent in mold shrinkage during a course of cooling to a room temperature after demolding. Shrinkage rate by mold shrinkage is taken to be about 1% for crystalline resin such as PPS resin or the like and about 0.5% for amorphous resin such as ABS resin, and these are most important values for designing a metallic mold.
  • the mold shrinkage rate of the resin is about 0.5%, because this resin contains GF by 20%.
  • shrinkage rate of a metal piece is 0.28% as a product of linear expansion coefficient (2.3 ⁇ 10 ⁇ 5 ° C. ⁇ 1 ) with temperature difference, provided that temperature of the metal piece is lowered from the temperature of the metallic mold to a room temperature and this lowered temperature is taken to be 120° C. in a case of the temperature of the metallic mold of 140° C.
  • resin part shrinks clearly in a larger extent, thus generating a high inner stress in the joining face of the formed composite joined by injection molding.
  • shear joining strength of a composite formed to have a shape as shown in FIG. 1 is measured in a case of a composite joined by injection molding of “SGX120” with aluminum alloy having been subjected to NMT 2 treatment, shear joining strength is no more than about 30 MPa for a composite before annealing and about 40 MPa for a composite having been subjected to annealing by cooling. This results in that, for a shaped article shown in FIG. 1 , the difference between joining strength and remaining stress in an adverse direction corresponds substantially to 10 MPa.
  • Annealing treatment of a composite according to the present invention is performed in order to this remaining stress once to be removed.
  • crystallization in resin part has been sufficiently proceeding (molding shrinkage in resin part has ended) and after this both of the aluminum alloy material and resin material shrink only corresponding to their linear expansion coefficients, even under cooling. Due to this, stress remaining in the joining face after cooling is far lower than before cooling.
  • shear joining strength and tensile joining strength are sufficiently high as of 40 MPa or more in the present invention.
  • Embodiments of the present invention will be explained in detail and methods for evaluating and measuring composite obtained through the embodiments will be exemplified below.
  • SEM Scanning electron microscopes
  • breaking force of a composite (shown in FIG. 1 ) joined by injection molding at tensile breaking on a tensile test machine is called as shear joining strength.
  • an assistant jig shown in FIG. 3 was used.
  • breaking force of a composite (shown in FIG. 2 ) joined by injection molding at tensile breaking on a tensile test machine is called as tensile joining strength.
  • “AG-500N/1 kN” manufactured by Shimadzu-seisakusho Co. Ltd.: main company in Kyoto, Japan
  • Joining strength was measured according to ISO19095 in any time.
  • Multitude of composites (shown in FIG. 1 ) were placed side by side on cardboard in a high temperature and high humidity test machine “IH400” (manufactured by Yamato Scientific Co. Ltd.: main company in Tokyo, Japan) set to be in a circumstance of a temperature of 85° C. and a humidity of 85% and maintained for up to 8000 hours.
  • Composites taken out of the test machine were dried in a hot air drier at 80° C. for 10 hours and further in an ordinary temperature drier for 10 hours, after which shear joining strength of the composites when broken in a tensile test machine was measured.
  • Experiment example 1 is “NMT treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm and ones with a size of 50 mm ⁇ 10 mm ⁇ 2 mm were manufactured from commercially available plates of aluminum alloy A5052 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” (made by Meltex Co. Ltd.: main company in Tokyo, Japan) by 10% was filled to be at 60° C. in a tank for immersion, in which the above aluminum alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • an aqueous solution of hydrochloric acid having a concentration of 1% was made ready to be at 40° C. in another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 3 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C. in still another tank, in which the pieces were immersed for 1 minute, and then the pieces were immersed in an aqueous solution of hydrazine hydrate having a concentration of 0.5% at 40° C. made ready in still another tank for 0.5 minute, and after then the pieces were rinsed with water. Then, the aluminum alloy pieces having been subjected to the above treatment were placed in a warm air drier set to be at a temperature of 67° C. for 15 minutes and dried there.
  • FIG. 4 shows electron microscope photographs of aluminum alloy A5052 having been subjected to the above treatment in magnifications of 1000 times, 10000 times and 100000 times respectively. Only a substantially flat surface is observed in a photograph of 1000 times. It is observed in a photograph of 10000 times that there is nearly flat surface configuration where low islands of about 1 ⁇ m diameter seem to float in crystal grain boundary as a boundary of metal crystal grain, that is, there is a surface having shallow irregularities of 1 ⁇ m period. In a photograph of 100000 times, existence of specific configuration is observed in which ultrafine concaves of 20 nm diameter covers entirely the above surface configuration.
  • Al atoms in the surface layer up to a depth of 1 to 3 nm that can be analyzed are composed of about 70% of Al+ 3 and about 30% of Al 0 and the metal aluminum phase is covered with a thin layer of aluminum oxide with a thickness of about 2 nm (extremely thin natural oxide layer).
  • Nitrogen atoms can be recognized in this natural oxide layer with accumulation analysis in about ten times and recognized that amine molecules (hydrazine hydrate) having been used in ultrafine etching treatment are chemically adsorbed thereto.
  • Experiment example 2 is “NMT 2 treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm and ones with a size of 50 mm ⁇ 10 mm ⁇ 2 mm were manufactured from commercially available plates of aluminum alloy A5052 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • an aqueous solution of hydrochloric acid having a concentration of 1% was made ready to be at 40° C.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 4 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 3 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C.
  • FIG. 5 shows electron microscope photographs of aluminum alloy A5052 having been subjected to similar treatment in magnifications of 1000 times, 10000 times and 100000 times respectively. It can be seen that there are nearly flat surface configurations similar to FIG. 4 in the photographs of 1000 times and 10000 times of FIG. 5 , and that somewhat more vivid ultrafine concaves of 20 nm diameter covers entire surface in 100000 times of FIG. 5 than in 100000 times of FIG. 4 .
  • surface configuration of the aluminum alloy A5052 piece having been subjected to this treatment is not substantially different from that of Experiment example 1, this is because Experiment example 2 is such that merely chemical adsorption promoting step is added to Experiment example 1.
  • Experiment example 3 is “NMT 7 treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm and ones with a size of 50 mm ⁇ 10 mm ⁇ 2 mm were manufactured from commercially available plates of aluminum alloy A5052 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C.
  • FIG. 6 which shows photographs in magnifications of 1000 times, 10000 times and 100000 times respectively.
  • such a surface configuration is clear in the electron microscope photograph of 100000 times in which ultrafine concaves of 20 to 40 nm diameter covers the entire surface.
  • Experiment example 4 is “NMT 7 treatment” referred to in the present invention with a base metal material different from that of Experiment Example 3.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A7075 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution containing ammonium-hydrogendifluoride in a concentration of 2% and sulfuric acid in a concentration of 10% set to be at 40° C. was made ready still in another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C.
  • Experiment example 5 is “NMT 7 treatment” referred to in the present invention with a base metal material different from that of Experiment Examples 3 and 4.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A6063 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the pieces were immersed for 8 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution containing ammonium-hydrogendifluoride in a concentration of 2% and sulfuric acid in a concentration of 10% set to be at 40° C. was made ready still in another tank, in which the pieces were immersed for 4 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C.
  • Experiment example 6 is “NMT 7 treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A1100 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C. in another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the pieces were immersed for 10 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C.
  • Experiment example 7 is “NMT 7 treatment” referred to in the present invention with a base metal material different from that of Experiment Example 6.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A6061 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the alloy pieces were immersed for 5 minutes, and after then the alloy pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the alloy pieces were immersed for 1 minutes, and after then the alloy pieces were rinsed with water.
  • an aqueous solution containing sulfuric acid in a concentration of 10% and ammonium-hydrogendifluoride in a concentration of 2% set to be at 40° C. was made ready still in another tank, in which the alloy pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the alloy pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the alloy pieces were immersed for 1.5 minutes, and after then the alloy pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C.
  • Experiment example 8 is “NMT 7 treatment” referred to in the present invention with a base metal material different from that of Experiment Examples 6 and 7.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A2017 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the aluminum alloy pieces were immersed for 5 minutes, and after then the alloy pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the aluminum alloy pieces were immersed for 1 minute, and after then the alloy pieces were rinsed with water.
  • an aqueous solution containing sulfuric acid in a concentration of 10% and ammonium-hydrogendifluoride in a concentration of 2% set to be at 40° C. was made ready still in another tank, in which the aluminum alloy pieces were immersed for 4 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the aluminum alloy pieces were immersed for 2 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the aluminum alloy pieces were immersed for 2.5 minutes, and after then the alloy pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C.
  • Experiment example 9 is “NMT 7 treatment” referred to in the present invention with a base metal material different from that of Experiment Examples 6, 7 and 8.
  • Multitude of rectangular pieces made of aluminum alloy ADC12 with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured through casting and mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the aluminum alloy pieces were immersed for 5 minutes, and after then the pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution of caustic soda having a concentration of 10% was made ready to be at 40° C.
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the alloy pieces were immersed for 4 minutes, and after then the alloy pieces were rinsed with water.
  • an aqueous solution containing ammonium-hydrogendifluoride in a concentration of 2% and sulfuric acid in a concentration of 10% set to be at 40° C. was made ready still in another tank, in which the aluminum alloy pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the aluminum alloy pieces were immersed for 4 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the aluminum alloy pieces were immersed for 2 minutes, and after then the pieces were placed in a tank with an ultrasonic transmitter provided for 5 minutes to remove attached smut and then immersed in the tank with the aqueous solution of nitric acid in a concentration of 3.5% at 40° C. contained there for 0.5 minute again, after which the pieces were rinsed with water.
  • an aqueous solution of hydrazine hydrate having a concentration of 3.5% was made ready to be at 60° C. in still another tank, in which the aluminum alloy pieces were immersed for 1 minute, after then the aluminum alloy pieces were immersed in an aqueous solution of hydrazine hydrate having a concentration of 0.5% at 33° C. in still another tank for 1 minute. After then the aluminum alloy pieces were rinsed with water. Then, the pieces were dried at a temperature of 67° C. and for 15 minutes.
  • Experiment Example 10 is “NMT 7-Oxy treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm and ones with a size of 50 mm ⁇ 10 mm ⁇ 2 mm were manufactured from commercially available plates of aluminum alloy A5052 through mechanical working.
  • NMT 7 treatment quite same operation as Experiment Example 3 (NMT 7 treatment) was performed.
  • the last immersion in a tank with agent was performed by immersing the alloy pieces in an aqueous solution of hydrazine hydrate having a concentration of 0.5% at 33° C. for 6 minutes and after then rinsing the pieces with water to finish treatment by liquid in NMT 7 treatment.
  • a tank for oxidation was prepared in which an aqueous solution containing hydrogen peroxide in a concentration of 1.5% was made ready and the aluminum alloy pieces were immersed there for 1 minute and then rinsed with water. After then the aluminum alloy pieces were placed in a warm air drier set to be at a temperature of 67° C. for 15 minutes and dried. The aluminum alloy pieces A5052 having been subjected to the treatment were observed with an electron microscope. The photographs as a result of observation are shown in FIG. 7 , which show photographs in magnifications of 1000 times, 10000 times and 100000 times respectively. As observed in the photograph of 1000 times of FIG.
  • Experiment example 11 is “Ano-7 treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm and ones with a size of 50 mm ⁇ 10 mm ⁇ 2 mm were manufactured from commercially available plates of aluminum alloy A5052 through mechanical working.
  • An aqueous solution containing degreaser for aluminum “NA-6” by 10% was set to be at 60° C. in a tank for immersion, in which the aluminum alloy pieces were immersed for 5 minutes, and after then the alloy pieces were rinsed with tap water (Ota city, Gumma prefecture, Japan).
  • tap water Ota city, Gumma prefecture, Japan
  • an aqueous solution containing hydrochloric acid in a concentration of 5% and aluminum chloride hydrate in a concentration of 1% set to be at 40° C. was made ready still another tank, in which the aluminum alloy pieces were immersed for 6 minutes, and after then the alloy pieces were rinsed with water.
  • an aqueous solution containing ammonium-hydrogendifluoride in a concentration of 2% and sulfuric acid in a concentration of 10% set to be at 40° C. was made ready still in another tank, in which the aluminum alloy pieces were immersed for 4 minutes, and after then the pieces were rinsed with water.
  • an aqueous solution of caustic soda having a concentration of 1.5% was made ready to be at 40° C. in still another tank, in which the aluminum alloy pieces were immersed for 1 minute, and after then the pieces were rinsed with water.
  • an aqueous solution of nitric acid having a concentration of 3% was made ready to be at 40° C. in still another tank, in which the aluminum alloy pieces were immersed for 1.5 minutes, and after then the alloy pieces were rinsed with water.
  • an aqueous solution of orthophosphoric acid in a concentration of 8% was made ready to be at 25° C.
  • anodization bath having a copper rod as a cathode and a titanium plate as an anode, in which the titanium plate is pressed onto the aluminum alloy pieces, and anodized for 15 minutes with an DC power supply “ZX-1600LA” (manufactured by Takasago-seisakusho Co. Ltd.: main company in Kawasaki, Japan) controlled to be at a constant voltage of 25 V.
  • Obtained anodized pieces were rinsed with ion exchange water for about 30 minutes, after then were placed in a warm air drier set to be at 67° C. for 15 minutes and dried and further after then were dried for 15 minutes in a hot air drier set to be at 90° C. After then the pieces were wrapped together with clean aluminum foil, entered into a plastic bag to be sealed and stored.
  • FIG. 8 show photographs in magnifications of 1000 times, 10000 times and 100000 times respectively.
  • Surface configuration appearing in the photograph of 100000 times is different form one in the photograph of 100000 times shown in FIG. 6 by NMT 7.
  • ultrafine concaves are rather holes than concaves.
  • the surface is different from an article treated with an aqueous solution of hydrazine hydrate in that the area of holes including periphery thereof appears to be smooth.
  • Experiment Example 12 is “NMT 8 treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm and ones with a size of 50 mm ⁇ 10 mm ⁇ 2 mm were manufactured from commercially available plates of aluminum alloy A5052 through mechanical working.
  • NMT 7-Oxy treatment was performed.
  • the last immersion in a tank with agent was performed by immersing the alloy pieces in an aqueous solution containing hydrogen peroxide in a concentration of 1.5% in a tank and after then rinsing the pieces with water to finish treatment by liquid in NMT 7-Oxy treatment.
  • Experiment Example 13 is “NMT 8 treatment” referred to in the present invention.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A7075 through mechanical working. After then, same operation of surface treatment as Experiment Example 4 for NMT 7 treatment of aluminum alloy A7075 was performed.
  • NMT 8 treatment does not end with the last step in this NMT 7 treatment such that the pieces are immersed in a tank with an aqueous solution of hydrazine hydrate having a concentration of 0.5% at 33° C. therein for 2.5 minutes and after then rinsed with water.
  • a tank for oxidation with a hydrogen peroxide in a concentration of 1.5% contained therein was made ready, in which the aluminum alloy pieces were immersed for 1 minute and after then rinsed with water. Further, a tank for promoting adsorption with an aqueous solution containing triethanolamine in a concentration of 0.2% at 40° C. therein was made ready, in which the aluminum alloy pieces were immersed there for 10 minutes and after then rinsed with water. Then, the pieces were placed in a warm air drier set to be at 67° C. for 15 minutes and dried.
  • Experiment Example 14 is “NMT 8 treatment” referred to in the present invention with a base metal material different from that of Experiment Example 13.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A6063 through mechanical working. After then, operation of surface treatment by NMT 7 similar to Experiment Example 5 with a same base metal material was performed. Additionally after this, in this Experiment Example, a tank for oxidation with an aqueous solution containing hydrogen peroxide in a concentration of 1.5% therein was prepared, in which the alloy pieces were immersed for 1 minute and after then rinsed with water.
  • a tank for promoting adsorption with an aqueous solution containing triethanolamine in a concentration of 0.4% at 40° C. therein was prepared, in which the aluminum alloy pieces were immersed there for 8 minutes and after then rinsed with water. After this, the aluminum alloy pieces were placed in a warm air drier set to be at 67° C. for 15 minutes and dried.
  • Experiment Example 15 is “NMT 8 treatment” referred to in the present invention with a base metal material different from that of Experiment Examples 13 and 14.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A6061 through mechanical working. After then, operation of surface treatment by NMT 7 similar to Experiment Example 7 with a same base metal material was performed. Additionally after this, in this Experiment Example, a tank for oxidation with an aqueous solution containing hydrogen peroxide in a concentration of 1.5% therein was prepared, in which the alloy pieces were immersed for 1 minute and after then rinsed with water.
  • a tank for promoting adsorption with an aqueous solution containing triethanolamine in a concentration of 0.2% at 40° C. therein was prepared, in which the aluminum alloy pieces were immersed there for 5 minutes and after then rinsed with water. After this, the aluminum alloy pieces were placed in a warm air drier set to be at 67° C. for 15 minutes and dried.
  • Experiment Example 16 is “NMT 8 treatment” referred to in the present invention with a base metal material different from that of Experiment Examples 13, 14 and 15.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from commercially available plates of aluminum alloy A2017 through mechanical working.
  • operation of surface treatment by NMT 7 similar to Experiment Example 8 with a same base metal material was performed.
  • a tank for oxidation with an aqueous solution containing hydrogen peroxide in a concentration of 1.5% therein was prepared, in which the alloy pieces were immersed for 1 minute and after then rinsed with water.
  • a tank for promoting adsorption with an aqueous solution containing triethanolamine in a concentration of 0.2% at 40° C. therein was prepared, in which the aluminum alloy pieces were immersed there for 4 minutes and after then rinsed with water. After this, the aluminum alloy pieces were placed in a warm air drier set to be at 67° C. for 15 minutes and dried.
  • Experiment Example 17 is “NMT 8 treatment” referred to in the present invention with a base metal material different from that of Experiment Examples 13, 14, 15 and 16.
  • Multitude of rectangular pieces of aluminum alloy with a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm were manufactured from plates of aluminum alloy ADC12 through casting and mechanical working. After then, operation of surface treatment to Experiment Example 9 with a same base metal material was performed. Additionally after this, in this Experiment Example, a tank for oxidation with an aqueous solution containing hydrogen peroxide in a concentration of 1.5% therein was prepared, in which the alloy pieces were immersed for 1 minute and after then rinsed with water. Then the aluminum alloy pieces were placed in a hot air drier set to be at 80° C.
  • the pieces were placed in a hot air drier set to be at 100° C. for 15 minutes and subjected to heat processing.
  • the aluminum alloy pieces were immersed in a tank for rinsing with an ultrasonic transmitter provided for 7 minutes to remove attached smut.
  • a tank for promoting adsorption with an aqueous solution containing triethanolamine in a concentration of 0.1% at 40° C. therein was prepared, in which the aluminum alloy pieces were immersed there for 5 minutes and after then rinsed with water.
  • the aluminum alloy pieces were placed in a warm air drier set to be at 67° C. for 15 minutes and dried.
  • Experiment Example 18 is an experiment of change in joining strength of composites according to days of storage of base metal materials after their treatment as in Experiment Examples 1 to 17.
  • Each of one kind or two kinds of size of aluminum alloy pieces obtained in Experiment Examples were stored in a manner explained below and, experiment was performed, joining each of aluminum alloy pieces by injection molding for integrating it with resin on the day of treatment, one day later, seven days later, fourteen days later and twenty eight days later.
  • Storage of the aluminum alloy pieces was made in such a manner that each five aluminum alloy pieces was placed side by side on a sheet of OPP (oriented polypropylene) film and another sheet of OPP film was laid thereon to sandwich the aluminum alloy pieces, and then the pieces were stored for the above days.
  • OPP oriented polypropylene
  • the OPP bags with the aluminum alloy pieces therein were covered with cardboards and stacked on the table in a room of a factory. A large cardboard sheet is laid on the uppermost of the stacked so that sunlight entering through a window does not strike onto the alloy pieces through OPP film.
  • the aluminum alloy pieces contained in several sets of the OPP bags are in a situation such that they are illuminated to some extent through gaps between the cardboards. It was taken care that the aluminum alloy pieces in storage are not illuminated directly by sunlight.
  • the place for storage was not a factory operated all day with air conditioner operated through all day but a common factory (in Ohta city, Gumma prefecture, Japan) with air conditioner in daytime alone.
  • the aluminum alloy pieces were divided according to days of storage to zero day (on the day of treatment), one day, a week, two weeks and four weeks, respectively. Then each of the aluminum alloy pieces was inserted into a metallic mold for injection molding and “SGX120” as a PPS resin for injection molding was injected, so that a composite joined by injection molding (test piece) as shown in FIG. 1 was obtained. Temperature of injection was set to be at 300° C. and temperature of the metallic mold was set to be at 140° C. The obtained composites joined by injection molding were placed in a hot air drier set to be at 170° C. for an hour to be subjected to annealing. In such a manner, more than ten pieces of composites (test pieces) in a shapes shown in FIG.
  • test pieces 1 or 2 for day (days) of storage were obtained.
  • shear joining strength and tensile joining strength were measured at a temperature of 23° C.
  • an average value of three pairs of test pieces in a same condition was taken as a result of test.
  • the result obtained for test pieces from ones having been joined by injection molding to ones with days of storage of two weeks and four weeks was shown in Table 1 respectively.
  • T 1 shows an example of A5052, where, for the articles having been subjected to NMT treatment, joining strength with two weeks of storage was somewhat lowered, though joining strength with days of storage up to a week is not changed.
  • NMT 2 treatment it was conventionally known that joining strength of all species of aluminum alloy with days of storage up to two weeks exhibits substantially same value of about 40 MPa, and the result in shown in Table 1 was similar too.
  • the values of tensile shear strength shown in Table 1 are average value of pairs of composites and the highest value of tensile joining strength was 48 MPa and the lowest value is 42 MPa for individual pairs of pieces by NMT 7 or NMT 8, which suggests that tensile joining strength will be raised further by adjusting surface treatment method. After all, it is not known yet in which level the value of the highest tensile joining strength by use of “SGX120” is. At least regarding days of storage, tensile joining strength of composites with two weeks of storage is in a similar level as those having been joined by injection molding on the instant day, if surface treatment for forming surface with fine irregularities is in a grade higher than NMT 2 by use of “SGX12000”, and joining strength reveals no change.
  • Experiment Example 19 two kinds of result of wet-heat test are shown. Using aluminum alloy pieces in a size of 18 mm ⁇ 45 mm ⁇ 1.5 mm dealt with in Experiment Examples 1 to 17, both of composites in a shape shown in FIG. 1 joined by injection molding, with PPS resin “SGX120” used, on the day of surface treatment and of composites in a shape shown in FIG. 1 joined by injection molding, with PPS resin “SGX120” used, on a day after days of storage lapse as shown in Experiment Example 18 were subjected to both of pot wet-heat test at a temperature of 98° C. and of high temperature-high humidity test at a temperature of 85° C. and humidity of 85% respectively.
  • aluminum alloy with which property of moisture resistance and heat resistance of composites joined by injection molding in a case of two weeks of storage is superior, appears to be limited to one other than articles by NMT treatment and NMT 2, that is, though similar in having surface with ultrafine irregularities of several decades to a hundred nm period, and yet to one that has rough surface of several decades of ⁇ m period (matted surface) and added existence of clear fine irregularities of several ⁇ m period. Main reason of it, without doubt, consists in that this change in configuration has created a dramatic increase of surface area.
  • Experiment Example 20 is “pot wet-heat test” referred to in the present invention. While this is test for measuring property of moisture resistance and heat resistance in various treatments of aluminum alloy similar to Experiment Example 19, pot wet-heat test of 5 days, with which not so many days are necessary for test, was performed regarding aluminum alloy A5052 and also alloys other than it here. The result is shown in Table 3.
  • Experiment Example 21 is test under wet-heat load by placing in a high temperature-high humidity test machine for a long time. While joining strength of composites after having been placed in a high temperature-high humidity test machine set to be at a temperature of 85° C. and a humidity of 85% for several thousand hours could be supposed with Experiment Example 19, this was certified here. As explained before, a composite of an article treated by NMT 2 joined by injection molding with “SGX120” on the instant day has an extraordinary high joining strength, rather merely high one, and has property of moisture resistance and heat resistance. Considering a reason for this, following situation can be understood clearly.
  • FIG. 4 Result of composites using aluminum alloy A5052 is shown in FIG. 4 and result of composites using other aluminum alloys is shown in FIG. 5 .
  • the values of joining strength, shown in FIGS. 4 and 5 after having been placed in a high temperature-high humidity test machine is ones, for which composites joined by injection molding taken out of the test machine is placed in a hot air drier set to be at 80° C. for 10 hours, further placed for 10 hours with the drier switched to blast drying at an ordinary temperature to be maintained in an equilibrium state with atmosphere below 23° C., after then joining strength is measured.
  • Experiment Example 22 is test under wet-heat load (referential example) in which composites are placed in a high temperature-high humidity test machine for a long time.
  • metal or metal alloy species that has, for the species themselves, precisely more durable to moisture (more difficult to rust) than aluminum alloy materials.
  • Ti alloy, stainless steel SUS304, stainless steel SUS430 are named as such.
  • the present inventors are developing innovated new NMT treatment method also for these various metal species, making best endeavor. This is implemented considering, as an object, that use of such materials are required as parts members for moving machines, machines or facilities used in outdoor circumstances.
  • Shear joining strength of various metal alloy/SGX120 composites joined by injection molding after high temperature-high hunidity test Shear joining strength after high temperature-high hunidity test (MPa) Species of Days of storage Initial after after after after metal alloy (days) value 250 h 500 h 1000 h 2000 h 4000 h 6000 h 64 Ti alloy Joining by 41.2 38.5 38.4 37.8 36.8 35.5 35.4 injection molding on the day next to instant day
  • Experiment Example 23 is test under wet-heat load by placing in high temperature-high humidity test machine set to be at 85° C. and humidity of 85% for a long time.
  • aluminum alloy A5052 was stored for two weeks and then joined by injection molding with “SGX120” as a PPS resin
  • property of moisture resistance and heat resistance of joining strength of the resulting composite was not in a highest level as shown in FIGS. 18 and 19 .
  • NMT 7 treatment, etc. Before methods by NMT 7 treatment, etc., have been developed, it was studied to overcome this result by using “SGX115” as a PPS resin having a low water absorbability.

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