CN108284562A - Zirconium-based amorphous alloy part and plastic part composite and preparation method thereof - Google Patents
Zirconium-based amorphous alloy part and plastic part composite and preparation method thereof Download PDFInfo
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- CN108284562A CN108284562A CN201710017377.1A CN201710017377A CN108284562A CN 108284562 A CN108284562 A CN 108284562A CN 201710017377 A CN201710017377 A CN 201710017377A CN 108284562 A CN108284562 A CN 108284562A
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- Prior art keywords
- zirconium
- amorphous alloy
- base amorphous
- alloy part
- hole
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 96
- 239000004033 plastic Substances 0.000 title claims abstract description 78
- 229920003023 plastic Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title abstract 3
- 239000002253 acid Substances 0.000 claims abstract description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 25
- 238000001994 activation Methods 0.000 claims description 18
- 238000005238 degreasing Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000005300 metallic glass Substances 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- -1 salt compounds Chemical class 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical group C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000012815 thermoplastic material Substances 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000004913 activation Effects 0.000 abstract 1
- 150000003754 zirconium Chemical class 0.000 abstract 1
- 229960002050 hydrofluoric acid Drugs 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical group C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B29C45/14778—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
- 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
- B29C45/14811—Multilayered articles
-
- 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
- C23F1/26—Acidic compositions for etching refractory metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/08—Etching of refractory metals
-
- 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
- B29C2045/14803—Porous or permeable material, e.g. foam the injected material entering minute pores
-
- 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
- B29C2045/1486—Details, accessories and auxiliary operations
- B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- ing And Chemical Polishing (AREA)
Abstract
A preparation method of a composite body of a zirconium-based amorphous alloy part and a plastic part comprises the following steps: providing a zirconium-based amorphous alloy part; immersing the zirconium-based amorphous alloy piece in an acid solution for activation treatment; performing electrochemical corrosion on the surface of the activated zirconium-based amorphous alloy piece to enable the zirconium-based amorphous alloy piece to form a plurality of mutually communicated holes from the surface to the inside so as to form a porous layer, wherein the porous layer comprises a plurality of first holes and a plurality of second holes formed by inwards recessing the hole walls of the first holes; placing the electrochemically corroded zirconium-based amorphous alloy piece in a mixed acid solution consisting of hydrochloric acid and hydrofluoric acid for microetching; injecting molten plastic on the surface of the porous layer of the zirconium-based amorphous alloy part; solidifying the plastic to form a plastic part, thereby obtaining the composite of the zirconium-based amorphous alloy part and the plastic part.
Description
Technical field
The present invention relates to species complex and preparation method thereof, more particularly to a kind of zirconium-base amorphous alloy part and plastic part
The preparation method of complex and the complex.
Background technology
Nowadays, utilization of the nanometer injection molding technology in electronic product is more and more extensive, passes through metalwork and plastic part knot
Conjunction forms complex to meet the needs of various aspects such as appearance.And non-crystaline amorphous metal is a kind of novel metastable material, crystalline state knot
Structure is special, and non-crystaline amorphous metal is made to have excellent physics, chemical property, such as high-yield strength, high rigidity, super-elasticity, high abrasion
Damage property, highly corrosion resistant and excellent forging technology performance etc., can mold complicated part, such as use non-crystaline amorphous metal
Make electronic product casing or when framework, to solve common metal shell due to hardness and strength deficiency be susceptible to cut and
The problems such as being destroyed.However, the technology that existing non-crystaline amorphous metal is combined with plastics is often not suitable for mass production, and non-crystaline amorphous metal
Bond strength between plastics is insufficient.
Invention content
In view of this, it is necessary to provide a kind of preparation sides of the complex for the zirconium base peritectic alloy part and plastic part being firmly combined with
Method, to solve the above problems.
In addition, there is a need to the complex for providing a kind of zirconium base peritectic alloy part and plastic part prepared by above-mentioned preparation method.
A kind of preparation method of the complex of zirconium-base amorphous alloy part and plastic part comprising following steps：
One zirconium-base amorphous alloy part is provided；
The zirconium-base amorphous alloy part is immersed in acid solution and carries out activation process；
The surface of zirconium-base amorphous alloy part after above-mentioned activation process is subjected to electrochemical corrosion, so that described zirconium-base amorphous
Alloy components form multiple interconnected holes to form a porous layer inwardly by the surface, and the porous layer includes several
One hole and several hole walls by first hole are recessed the second hole of formation inwardly；
Zirconium-base amorphous alloy part after above-mentioned electrochemical corrosion is placed in the mixed acid solution being made of hydrochloric acid and hydrofluoric acid
Middle progress microetch processing, to remove the oxide particle formed in electrochemical corrosion course in the porous layer surface；
There is provided an injection forming mold, and treated that zirconium-base amorphous alloy part is placed in the injection molding by above-mentioned microetch
In mold, the plastics of melting are molded in the surface of the porous layer of the zirconium-base amorphous alloy part；
Cure the plastics and form plastic part, to which the complex of the zirconium-base amorphous alloy part and plastic part be made.
Further, the aperture of first hole is 200 μm~500 μm, and hole depth is 1 μm~200 μm；Second hole
The aperture in hole is 100nm~1000nm, and hole depth is 100nm~1000nm.
Further, step " surface of the zirconium-base amorphous alloy part after above-mentioned activation process is subjected to electrochemical corrosion, with
The zirconium-base amorphous alloy part is set to form multiple interconnected holes inwardly by the surface to form a porous layer, it is described more
Aperture layer includes that multiple first holes and multiple hole walls by first hole are recessed the second hole of formation inwardly " specific packet
It includes：
Using the zirconium-base amorphous alloy part after the activation process as anode, stainless steel substrates or graphite flake are placed in electricity as cathode
It is powered in solution liquid, the current density that control passes through the zirconium-base amorphous alloy part is 10mA/cm2-400mA/cm2, the electrolyte
Temperature be 10 degrees Celsius~60 degrees Celsius, time of electrochemical corrosion is 1min~20min, the electrolysis of the electrochemical corrosion
Liquid includes the salt compounds and 1g/L~30g/L of sour, a concentration of 10g/L~200g/L of a concentration of 1mL/L~200mL/L
Additive.
Further, the acid in the electrolyte of the electrochemical corrosion is selected from nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid
At least one of, the salt compounds are selected from copper chloride, frerrous chloride, ferrous sulfate, iron chloride, ammonium chloride, hydrogen fluoride
At least one of ammonium and aluminum sulfate, the additive are selected from potassium chromate, glycerine, thiocarbamide, citric acid, sodium citrate, Wu Tuo
At least one of Lip river product, sodium potassium tartrate tetrahydrate and sodium molybdate.
Further, the temperature of the microetch processing is 20 degrees Celsius~100 degrees Celsius, and the time of microetch processing is 3min
~20min, sour mass concentration is 5%~20% in the mixed acid solution, and hydrochloric acid and states hydrogen in the mixed acid solution
The ratio of the mass concentration of fluoric acid is 2：1~9：1.
Further, mass concentration sour in the acid solution when activation process is 1%~10%, the acidity
Acid in solution includes at least one of nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, the activation process time be 1min~
5min。
Further, further include surfactant in the acid solution.
Further, before the activation process, the preparation side of the complex of the zirconium-base amorphous alloy part and plastic part
Method further includes：
Degreasing degreasing processing is carried out to the zirconium-base amorphous alloy part.
Further, the material of the plastic part is crystalline thermoplastic material.A kind of zirconium-base amorphous conjunction as described above
The complex of zirconium-base amorphous alloy part and plastic part prepared by the preparation method of the complex of golden part and plastic part, including zirconium base are non-
Peritectic alloy part and injection molding are incorporated into the plastic part on zirconium-base amorphous alloy part surface, the zirconium-base amorphous alloy part and the modeling
Materials and parts junction forms a porous layer, and the porous layer includes several interconnected the first hole and the second hole, and described the
Two holes are recessed by the hole wall of first hole and are formed inwardly, and the plastic part is incorporated into the zirconium-base amorphous alloy part and institute
State porous layer combination.
The preparation method of the above-mentioned zirconium-base amorphous alloy part of the present invention and the complex of plastic part, preparation system is simple,
Operability is strong, is convenient for mass production, to improve production efficiency, and non-crystaline amorphous metal prepared by above-mentioned preparation method
The complex of part and plastic part, by being formd on zirconium-base amorphous alloy part with several the first interconnected holes and by institute
State the first hole hole wall be recessed inwardly formation the second hole porous layer so that the plastic part of various materials can with it is described
Zirconium-base amorphous alloy part is securely joined with.
Description of the drawings
Fig. 1 is the schematic cross-sectional view of the zirconium-base amorphous alloy part of better embodiment of the present invention.
Fig. 2 is the schematic cross-sectional view that porous layer is formed on zirconium-base amorphous alloy part shown in Fig. 1.
Fig. 3 is 200 times of 3D microscope figures of the first hole of porous layer shown in Fig. 2.
Fig. 4 is 5000 times of scanning electron microscope (SEM) photographs of the second hole of porous layer shown in Fig. 2.
Fig. 5 is 20000 times of scanning electron microscope (SEM) photographs of the second hole of porous layer shown in Fig. 2.
Fig. 6 is that the zirconium-base amorphous conjunction obtained after plastic part is formed on the porous layer of zirconium-base amorphous alloy part shown in Fig. 2
The diagrammatic cross-section of the complex of golden part and plastic part.
Fig. 7 is the scanning electron microscope (SEM) photograph in the section of the complex of zirconium-base amorphous alloy part and plastic part shown in fig. 6.
Main element symbol description
Compound the 100 of zirconium-base amorphous alloy part and plastic part
Body
Zirconium-base amorphous alloy part 10
Porous layer 13
Plastic part 20
Following specific implementation mode will be further illustrated the present invention in conjunction with above-mentioned attached drawing.
Specific implementation mode
For can the present invention is further explained reaches the technological means and effect that predetermined goal of the invention is taken, below in conjunction with figure
1- Fig. 7 and better embodiment, the specific implementation to the complex of non-crystaline amorphous metal part of the present invention and plastic part and preparation method thereof
Mode, structure, feature and its effect, detailed description are as follows.
Please refer to Fig.1-Fig. 7, the system of the non-crystaline amorphous metal part of a better embodiment of the invention and the complex 100 of plastic part
Preparation Method includes the following steps：
Step S1, referring to Fig. 1, providing a zirconium-base amorphous alloy part 10.
In present embodiment, the zirconium-base amorphous alloy part 10 is the zirconium-base amorphous alloy part of Cu-Ni-Al-Zr systems.
In other embodiment, the zirconium-base amorphous alloy part 10 can be the zirconium-base amorphous alloy part of other systems.
Step S2 carries out degreasing degreasing processing, so that the zirconium-base amorphous alloy part to the zirconium-base amorphous alloy part 10
10 surface cleaning.
In present embodiment, the technique of degreasing degreasing processing is：Using cleaning agent to the zirconium-base amorphous alloy part 10
Carry out ultrasonic cleaning.The cleaning agent is the cleaning agent conventionally used for removing grease such as alcohol, acetone.The ultrasonic cleaning when
Between preferably 2min~10min.It in other embodiments, can also be by other conventional degreasing degreasing treatment process to institute
Zirconium-base amorphous alloy part 10 is stated to be handled.
Step S3, by above-mentioned degreasing degreasing, treated that zirconium-base amorphous alloy part 10 is soaked in acid solution activates
Processing is then taken out and is washed.The activation process time is 1min~5min.
Sour mass concentration is 1%~10% in the acid solution.Acid in the acid solution includes nitric acid, sulphur
At least one of acid, hydrochloric acid and hydrofluoric acid.It may also include surfactant in the acid solution.It, will in present embodiment
1min then takes in the sulfuric acid solution that above-mentioned degreasing degreasing treated zirconium-base amorphous alloy part 10 is soaked in mass concentration is 6%
Go out and washes.
In general, zirconium-base amorphous alloy part surface can be formed with oxidation film layer through air oxidation.The activation process is used
To remove the oxidation film layer that zirconium-base amorphous alloy part surface is formed through air oxidation, to expose the zirconium with reactivity
Base noncrystal alloy surface.
Step S4 please refers to Fig. 2-Fig. 5, and it is rotten to carry out electrochemistry to the surface of the zirconium-base amorphous alloy part 10 after activation process
Erosion so that the zirconium-base amorphous alloy part 10 forms several interconnected holes to be formed more than one by the surface towards internal
Aperture layer 13.The porous layer 13 includes that several first holes and several hole walls by first hole are recessed the second of formation inwardly
The aperture of hole, first hole is 200 μm~500 μm, and hole depth is 1 μm~200 μm；The aperture of second hole is
100nm~1000nm, hole depth are 100nm~1000nm.
Specifically, being anode, stainless steel substrates or graphite flake conduct with the zirconium-base amorphous alloy part 10 after the activation process
Cathode is placed in electrolyte and is powered, and the current density that control passes through the zirconium-base amorphous alloy part 10 is 10mA/cm2-400mA/
cm2, the temperature of the electrolyte is 10 degrees Celsius~60 degrees Celsius, and the time of electrochemical corrosion is 1min~20min.
The electrolyte of the electrochemical corrosion includes sour, a concentration of 10g/L~200g/ of a concentration of 1mL/L~200mL/L
The salt compounds of L and the additive of 1g/L~30g/L.Acid in the electrolyte of the electrochemical corrosion be selected from nitric acid, phosphoric acid,
At least one of sulfuric acid, hydrochloric acid and hydrofluoric acid etc..The salt compounds are selected from copper chloride, frerrous chloride, ferrous sulfate, chlorine
Change at least one of iron, ammonium chloride, ammonium acid fluoride and aluminum sulfate etc..The additive be selected from potassium chromate, glycerine, thiocarbamide,
At least one of citric acid, sodium citrate, Adauto Luo product, sodium potassium tartrate tetrahydrate and sodium molybdate etc..
Zirconium-base amorphous alloy part 10 after electrochemical corrosion is placed in progress microetch processing in mixed acid solution by step S5,
And the mixed acid solution is stirred continuously in microetch processing procedure, it then takes out and washes and dry.Due to described zirconium-base amorphous
The porous layer 13 of alloy components 10 surface in electrochemical corrosion course can form oxide particle, which handles to remove electricity
The oxide particle being formed in chemical corrosion process on the porous layer 13 of the zirconium-base amorphous alloy part 10.
The temperature of the microetch processing is 20 degrees Celsius~100 degrees Celsius, and the time of microetch processing is 3min~20min.
Sour mass concentration is 5%~20% in the mixed acid solution.
The mixed acid solution is made of hydrochloric acid and hydrofluoric acid, the ratio of the hydrochloric acid and the mass concentration of the hydrofluoric acid
It is 2：1~9：1.
In present embodiment, by the zirconium-base amorphous alloy part 10 with deionized water ultrasound after being taken out in mixed acid solution
Clean 3~5min.In other embodiments, the water-washing process can also be other modes.
Step S6 please refers to Fig. 6-7, it is above-mentioned after microetch is handled and the zirconium-base amorphous alloy part 10 of washing drying it is more
The surface of aperture layer 13 carries out injection molding, is closed with forming plastic part 20 on the surface of the porous layer 13 to which amorphous be prepared
The complex 100 of golden part and plastic part.
Specifically, by microetch, treated that the zirconium-base amorphous alloy part 10 with porous layer 13 is placed in and is molded by above-mentioned
In type equipment, the plastics of melting are injected in the surface of the porous layer 13, the plastics of high fluidity flow into the porous layer 13
To fill a hole and the second hole in first hole and the second hole so that the plastic part 20 formed after solidification with it is described
Porous layer 13 generates mechanical snap, to effectively raise the combination between plastic part 20 and the zirconium-base amorphous alloy part 10
Power so that have between the zirconium-base amorphous alloy part 10 and plastic part 20 in the complex 100 of the non-crystaline amorphous metal part and plastic part
There is higher bond strength.
The main material of the plastic part 20 can be but be not limited only to the crystalline thermoplastic material with high flowing, such as poly-
It is diphenyl sulfide (PPS) plastics, polyamide (PA) plastics, polybutylene terephthalate (PBT) (PBT) plastics, makrolon (PC), right
Ethylene terephthalate (PET) plastics etc..
Please refer to Fig. 6-7, the non-crystaline amorphous metal part of a better embodiment and the complex 100 of plastic part of the invention, packet
The plastic part 20 for including zirconium-base amorphous alloy part 10 and being combined with the zirconium-base amorphous alloy part 10.
The zirconium-base amorphous alloy part 10 forms a porous layer 13 with 20 junction of the plastic part.The porous layer 13 wraps
Include several interconnected the first holes and the second hole, second hole by first hole hole wall concave shape inwardly
At.The aperture of first hole is 200 μm~500 μm, and hole depth is 1 μm~200 μm；The aperture of second hole is
100nm~1000nm, hole depth are 100nm~1000nm.
The presence of the porous layer 13 makes the partly plastic of the plastic part 20 be embedded into described several interconnected
In one hole and the second hole, the effect of similar lock is generated, so that the plastic part 20 is securely joined in the zirconium
Base noncrystal alloy part 10.
The test of tensile strength, test are carried out to the complex 100 of the plastic part 20 obtained using different plastic materials
As a result it is recorded in table 1.
Table 1
The preparation method of the above-mentioned zirconium-base amorphous alloy part of the present invention and the complex 100 of plastic part, preparation system letter
Single, operability is strong, is convenient for mass production, to improve production efficiency, and amorphous prepared by above-mentioned preparation method
The complex 100 of alloy components and plastic part, due to being formd on zirconium-base amorphous alloy part 10 with several interconnected first
The porous layer 13 of hole and the second hole of formation that is recessed inwardly by the hole wall of first hole so that the plastics of various materials
Part 20 can be securely joined with the zirconium-base amorphous alloy part 10.
In addition, for those of ordinary skill in the art, can be made with technique according to the invention design other each
It is kind corresponding to change and deformation, and all these changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (10)
1. a kind of preparation method of the complex of zirconium-base amorphous alloy part and plastic part comprising following steps：
One zirconium-base amorphous alloy part is provided；
The zirconium-base amorphous alloy part is immersed in acid solution and carries out activation process；
The surface of zirconium-base amorphous alloy part after above-mentioned activation process is subjected to electrochemical corrosion, so that the zirconium-base amorphous alloy
Part forms multiple interconnected holes to form a porous layer inwardly by the surface, and the porous layer includes multiple first holes
Hole and multiple hole walls by first hole are recessed the second hole of formation inwardly；
By the zirconium-base amorphous alloy part after above-mentioned electrochemical corrosion be placed in the mixed acid solution being made of hydrochloric acid and hydrofluoric acid into
Row microetch processing, to remove the oxide particle formed in electrochemical corrosion course in the porous layer surface；
There is provided an injection forming mold, and treated that zirconium-base amorphous alloy part is placed in the injection forming mold by above-mentioned microetch
In, the plastics of melting are molded in the surface of the porous layer of the zirconium-base amorphous alloy part；And
Cure the plastics and form plastic part, to which the complex of the zirconium-base amorphous alloy part and plastic part be made.
2. the preparation method of the complex of zirconium-base amorphous alloy part as described in claim 1 and plastic part, it is characterised in that：Institute
The aperture for stating the first hole is 200 μm~500 μm, and hole depth is 1 μm~200 μm；The aperture of second hole be 100nm~
1000nm, hole depth are 100nm~1000nm.
3. the preparation method of the complex of zirconium-base amorphous alloy part as described in claim 1 and plastic part, it is characterised in that：Step
Suddenly " surface of the zirconium-base amorphous alloy part after above-mentioned activation process is subjected to electrochemical corrosion, so that the zirconium-base amorphous alloy
Part forms multiple interconnected holes to form a porous layer inwardly by the surface, and the porous layer includes multiple first holes
Hole and multiple hole walls by first hole are recessed the second hole of formation inwardly " it specifically includes：
Using the zirconium-base amorphous alloy part after the activation process as anode, stainless steel substrates or graphite flake are placed in electrolyte as cathode
Middle energization, the current density that control passes through the zirconium-base amorphous alloy part are 10mA/cm2-400mA/cm2, the temperature of the electrolyte
Degree is 10 degrees Celsius~60 degrees Celsius, and the time of electrochemical corrosion is 1min~20min, the electrolyte packet of the electrochemical corrosion
Include the addition of the salt compounds and 1g/L~30g/L of sour, a concentration of 10g/L~200g/L of a concentration of 1mL/L~200mL/L
Agent.
4. the preparation method of the complex of zirconium-base amorphous alloy part as claimed in claim 3 and plastic part, it is characterised in that：Institute
The acid stated in the electrolyte of electrochemical corrosion is selected from least one of nitric acid, phosphoric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, the salt
Class compound in copper chloride, frerrous chloride, ferrous sulfate, iron chloride, ammonium chloride, ammonium acid fluoride and aluminum sulfate at least one
Kind, the additive is selected from potassium chromate, glycerine, thiocarbamide, citric acid, sodium citrate, Adauto Luo product, sodium potassium tartrate tetrahydrate and molybdic acid
At least one of sodium.
5. the preparation method of the complex of zirconium-base amorphous alloy part as described in claim 1 and plastic part, it is characterised in that：Institute
The temperature for stating microetch processing is 20 degrees Celsius~100 degrees Celsius, and the time of microetch processing is 3min~20min, the mixed acid
In solution sour mass concentration be 5%~20%, and in the mixed acid solution hydrochloric acid and state hydrofluoric acid mass concentration ratio
Value is 2：1~9：1.
6. the preparation method of the complex of zirconium-base amorphous alloy part as described in claim 1 and plastic part, it is characterised in that：Institute
It is 1%~10% to state mass concentration sour in the acid solution when activation process, the acid in the acid solution include nitric acid,
At least one of sulfuric acid, hydrochloric acid and hydrofluoric acid, the activation process time are 1min~5min.
7. the preparation method of the complex of zirconium-base amorphous alloy part as claimed in claim 6 and plastic part, it is characterised in that：Institute
State in acid solution further includes surfactant.
8. the preparation method of the complex of zirconium-base amorphous alloy part as described in claim 1 and plastic part, it is characterised in that：
Before the activation process, the preparation method of the complex of the zirconium-base amorphous alloy part and plastic part further includes：
Degreasing degreasing processing is carried out to the zirconium-base amorphous alloy part.
9. the preparation method of the complex of zirconium-base amorphous alloy part as described in claim 1 and plastic part, it is characterised in that：Institute
The material for stating plastic part is crystalline thermoplastic material.
10. a kind of preparation side of such as complex of zirconium-base amorphous alloy part according to any one of claims 1 to 9 and plastic part
The complex of zirconium-base amorphous alloy part and plastic part prepared by method, including zirconium-base amorphous alloy part and injection molding are incorporated into the zirconium base
The plastic part on non-crystaline amorphous metal part surface, it is characterised in that：The zirconium-base amorphous alloy part forms one with the plastic part junction
Porous layer, the porous layer include multiple interconnected the first holes and the second hole, and second hole is by described first
The hole wall of hole is recessed to be formed inwardly, and the plastic part is combined with the porous layer.
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