CN114750475A - Amorphous alloy and plastic composite and preparation method thereof - Google Patents
Amorphous alloy and plastic composite and preparation method thereof Download PDFInfo
- Publication number
- CN114750475A CN114750475A CN202210343687.3A CN202210343687A CN114750475A CN 114750475 A CN114750475 A CN 114750475A CN 202210343687 A CN202210343687 A CN 202210343687A CN 114750475 A CN114750475 A CN 114750475A
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- Prior art keywords
- amorphous alloy
- alloy substrate
- acid
- plastic
- composite
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- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 301
- 239000004033 plastic Substances 0.000 title claims abstract description 128
- 229920003023 plastic Polymers 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 159
- 239000000463 material Substances 0.000 claims abstract description 139
- 238000002347 injection Methods 0.000 claims abstract description 47
- 239000007924 injection Substances 0.000 claims abstract description 47
- 238000004381 surface treatment Methods 0.000 claims description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 238000005488 sandblasting Methods 0.000 claims description 31
- 238000005238 degreasing Methods 0.000 claims description 29
- 238000000137 annealing Methods 0.000 claims description 28
- 239000000654 additive Substances 0.000 claims description 23
- 238000001746 injection moulding Methods 0.000 claims description 23
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000005530 etching Methods 0.000 claims description 20
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 14
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- -1 polybutylene terephthalate Polymers 0.000 claims description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 7
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 7
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 7
- 150000002193 fatty amides Chemical class 0.000 claims description 7
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 7
- 239000000174 gluconic acid Substances 0.000 claims description 7
- 235000012208 gluconic acid Nutrition 0.000 claims description 7
- 229950006191 gluconic acid Drugs 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229940116315 oxalic acid Drugs 0.000 claims description 7
- 239000011698 potassium fluoride Substances 0.000 claims description 7
- 235000003270 potassium fluoride Nutrition 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000002639 sodium chloride Nutrition 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- 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 7
- 229960001790 sodium citrate Drugs 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 239000011775 sodium fluoride Substances 0.000 claims description 7
- 235000013024 sodium fluoride Nutrition 0.000 claims description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 7
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 7
- 229940039790 sodium oxalate Drugs 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920002530 polyetherether ketone Polymers 0.000 claims description 6
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- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
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- 238000005422 blasting Methods 0.000 claims description 5
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011148 porous material Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 20
- 239000002585 base Substances 0.000 description 32
- 238000005507 spraying Methods 0.000 description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- 230000001154 acute effect Effects 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
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- B32B38/00—Ancillary operations in connection with laminating processes
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- B32B38/162—Cleaning
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
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- 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
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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
- B29C2045/1486—Details, accessories and auxiliary operations
- B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
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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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
- B29L2009/003—Layered products comprising a metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
- B32B2038/002—Sandblasting
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B32B2307/00—Properties of the layers or laminate
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Abstract
The embodiment of the disclosure discloses a composite of amorphous alloy and plastic and a preparation method thereof; the composite comprises an amorphous alloy substrate, wherein micron-sized holes are formed in the surface of the amorphous alloy substrate; and a plastic material is injection molded on the surface of the amorphous alloy substrate and is embedded into the micron-sized holes. The embodiment of the disclosure provides a composite of amorphous alloy and plastic, which not only improves the strength of an amorphous alloy material and the waterproof performance, but also can meet the lightweight design requirement of the amorphous alloy material.
Description
Technical Field
The invention relates to the field of metal materials and high polymer materials, in particular to a composite of amorphous alloy and plastic and a preparation method thereof.
Background
Amorphous alloy (also called liquid metal), which is a new metastable material. The amorphous alloy has a special crystalline structure, so that the amorphous alloy has high strength, high hardness, extremely strong wear resistance, corrosion resistance and scratch resistance, and good resilience. The strength of the amorphous alloy is 10 times of that of magnesium-aluminum alloy and 2 times of that of stainless steel and titanium alloy; the hardness is more than 10 times of that of magnesium-aluminum alloy and more than 1.5 times of that of stainless steel and titanium alloy; the elastic deformability is 10 times greater than that of stainless steel. Compared with the traditional stainless steel and aluminum alloy materials, the amorphous alloy has small interference on antenna signals, and is very suitable for being applied to shells and structural parts of electronic products, such as middle frames or shells of the electronic products, rotating shafts of folding screen electronic products, rotating shafts of TWS earphone charging boxes and the like.
Although the amorphous alloy has the characteristics of large elastic deformation degree, high strength and good resilience, the amorphous alloy is relatively brittle, particularly when a notch, an acute angle, a defect and the like exist on the amorphous alloy material, the overall strength of the amorphous alloy is greatly reduced, and the amorphous alloy has the risk of being cracked once falling or being impacted.
Disclosure of Invention
The invention aims to provide a composite of amorphous alloy and plastic and a new technical scheme of a preparation method.
According to one aspect of the invention, a composite body of amorphous alloy and plastic is provided, the composite body comprises an amorphous alloy substrate, and micron-sized holes are formed on the surface of the amorphous alloy substrate;
and a plastic material is injection molded on the surface of the amorphous alloy substrate and is embedded into the micron-sized holes.
Optionally, the diameter of the micron-sized hole is 1 μm to 4 μm.
Optionally, the amorphous alloy substrate comprises at least one of a cobalt-based amorphous alloy, a zirconium-based amorphous alloy, an iron-based amorphous alloy, a magnesium-based amorphous alloy, a copper-based amorphous alloy and a titanium-based amorphous alloy.
Optionally, the plastic material comprises at least one of polybutylene terephthalate resin PBT, polyphenylene sulfide resin PPS, polyamide resin PA, polyetheretherketone resin PEEK, polycarbonate PC, polyethylene terephthalate PET and polyetherimide PEI.
Optionally, the plastic material is glass fiber reinforced resin or carbon fiber reinforced resin, wherein the content of the glass fiber or the carbon fiber is 10% to 50%.
According to an aspect of the present invention, there is provided a method for preparing a composite of an amorphous alloy and a plastic, the method comprising:
providing an amorphous alloy substrate;
carrying out surface treatment on the amorphous alloy substrate to form micron-sized holes on the surface of the amorphous alloy substrate;
and (3) injecting a plastic material on the surface of the amorphous alloy substrate, and embedding the plastic material into the micron-sized holes to obtain a composite of the amorphous alloy and the plastic.
Optionally, before the step of performing surface treatment on the amorphous alloy substrate, the method further includes:
carrying out sand blasting treatment on the amorphous alloy base material;
carrying out degreasing treatment on the amorphous alloy base material obtained after sand blasting treatment; and
and cleaning the amorphous alloy substrate obtained after the degreasing treatment.
Optionally, the grain size range of the spraying material subjected to sand blasting is 100-800 meshes, the spraying material is zirconia sand grains, and the sand blasting pressure is 2-8 bar;
the degreasing treatment adopts thermal degreasing.
Optionally, the surface treatment of the amorphous alloy substrate by electrochemical etching includes:
placing the amorphous alloy substrate in a surface treatment solution at 5-60 ℃, and taking the amorphous alloy substrate as an anode to perform electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 0.5-100V, and the treatment time is 2-60 min.
Optionally, the surface treatment fluid comprises an acid, an additive and a surfactant;
the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 5 g/L-300 g/L;
the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 0.5 g/L-50 g/L;
the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 0.5 g/L-5 g/L.
Optionally, after the step of performing surface treatment on the amorphous alloy substrate, the method further includes:
carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after surface treatment; and
and drying the amorphous alloy base material obtained after ultrasonic cleaning.
Optionally, before the step of injection molding the plastic material on the surface of the amorphous alloy substrate, the method further comprises: preheating the amorphous alloy substrate at 100-250 ℃.
Optionally, in the process of injection molding a plastic material on the surface of the amorphous alloy substrate, the injection parameters include a holding pressure and a holding time, wherein the holding pressure includes an injection first-stage holding pressure and an injection second-stage holding pressure;
the first-stage pressure maintaining pressure of the injection is 600 bar-2000 bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 200 bar-1200 bar, and the pressure maintaining time of the injection second section is 0-5S.
Optionally, after the step of injection molding the plastic material on the surface of the amorphous alloy substrate, the method further includes:
and annealing the injection-molded amorphous alloy and plastic composite, wherein in the annealing process, the annealing temperature is 100-200 ℃, and the annealing time is 60-300 min.
The embodiment of the disclosure provides a scheme of a composite body of amorphous alloy and plastic, wherein a plastic material is injected on the surface of an amorphous alloy substrate, so that the amorphous alloy substrate and the plastic material are tightly combined together, and the formed composite body can improve the brittleness of the amorphous alloy material, improve the drop resistance and impact resistance of the amorphous alloy material, and provide excellent waterproof performance for an amorphous alloy product; because the plastic material is used for replacing part of the amorphous alloy structure, the design requirement of light weight of the amorphous alloy product can be met.
Other features of the present invention and advantages thereof will become apparent from the following detailed description of exemplary embodiments of the invention, which proceeds with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is a schematic structural diagram of a composite of an amorphous alloy and a plastic provided by an embodiment of the disclosure;
FIG. 2 is a flowchart of a method for manufacturing a composite of amorphous alloy and plastic according to an embodiment of the disclosure;
fig. 3 is a second flowchart of a method for manufacturing a composite of amorphous alloy and plastic according to an embodiment of the disclosure.
Reference numerals:
1. an amorphous alloy substrate; 2. a plastic material; 3. micron-sized holes.
Detailed Description
Various exemplary embodiments of the present invention will now be described in detail with reference to the accompanying drawings. It should be noted that: the relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the present invention unless specifically stated otherwise.
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses.
Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate.
In all examples shown and discussed herein, any particular value should be construed as merely illustrative, and not limiting. Thus, other examples of the exemplary embodiments may have different values.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, further discussion thereof is not required in subsequent figures.
The embodiment of the present disclosure provides a composite of amorphous alloy and plastic, as shown in fig. 1, the composite includes an amorphous alloy substrate 1, and a micron-sized hole 3 is formed on a surface of the amorphous alloy substrate 1; the surface of the amorphous alloy substrate 1 is injection molded with a plastic material 2, and the plastic material 2 is embedded into the micron-sized hole 3.
The complex body of amorphous alloy and plastics that this application embodiment provided is through moulding plastics plastic material 2 on the surface at amorphous alloy substrate 1 for amorphous alloy substrate 1 and plastic material 2 can be closely combined together, and the complex body that forms like this not only can improve the brittleness of amorphous alloy material, thereby has improved the resistant falling of amorphous alloy material, shock resistance, can also provide good waterproof performance for the amorphous alloy product. Meanwhile, the plastic material is used for replacing part of the amorphous alloy structure, so that the light design requirement of the amorphous alloy product can be met.
It can be understood that the amorphous alloy material has the characteristics of large elastic deformation degree, high strength and good resilience, but is relatively brittle. Particularly, when the amorphous alloy material has defects such as a notch and an acute angle, the overall strength of the amorphous alloy material is greatly reduced, and the amorphous alloy material is likely to be broken after falling or being impacted.
Aiming at the shortages in the brittleness aspect of the amorphous alloy material, the nano injection molding technology is adopted in the embodiment of the application, so that the amorphous alloy substrate 1 and the plastic material 2 are compounded, and the formed compound body can well solve the brittleness problem of the amorphous alloy.
The amorphous alloy forming process generally uses semi-solid die-casting forming.
In the embodiment of the application, the nano injection molding technology is adopted, so that the amorphous alloy material and the plastic material are compounded together, the plastic material can replace a part of semi-solid die-casting structure which cannot be formed and needs numerical control machining, and the processing cost can be further reduced.
That is, in the embodiment of the present application, dense and uniform micron-sized holes 3 are formed on the surface of the amorphous alloy substrate 1 through a surface treatment process, and then the plastic material 2 is injected onto the surface of the amorphous alloy substrate 1 through a combined injection molding process and firmly anchored into the micron-sized holes 3 on the surface of the amorphous alloy substrate 1. Thus, the amorphous alloy substrate 1 and the plastic material 2 are firmly bonded to form an integrated structure.
However, it should be noted that in the embodiments of the present application, the bonding between the amorphous alloy substrate 1 and the plastic material 2 is not dependent on forming a chemical bond, and the amorphous alloy substrate 1 and the plastic material 2 are physically bonded, and the bonding force therebetween is relatively large.
The complex body of amorphous alloy and plastics that this application embodiment provided, it has solved that amorphous alloy is breakable, resistant falls and the poor problem of shock resistance, can provide very good waterproof performance for the product simultaneously, has satisfied the lightweight design demand of product. The composite provided by the embodiment of the application is very suitable for being applied to the field of electronic products, such as high-end 3C electronic product shells, structural parts and the like.
In some examples of the present application, the micro-scale holes 3 have a diameter of 1 μm to 4 μm.
That is, the micron-sized holes 3 are formed on the surface of the amorphous alloy substrate 1, and the diameter size range of the micron-sized holes 3 can be controlled to be 1 μm to 4 μm, within the range, the surface of the amorphous alloy substrate 1 is not excessively damaged, and meanwhile, a large amount of plastic material 2 can be accommodated, so that the plastic material 2 and the amorphous alloy substrate 1 can be firmly combined together.
For example, the size of the micro-scale pores 3 may be 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, or the like, or may be any value within a range of 1 μm to 4 μm.
Of course, the size of the micron-scale holes 3 formed on the surface of the amorphous alloy substrate 1 can be adjusted as appropriate according to specific situations, and is not limited in this embodiment.
In addition, the micron-sized holes 3 also extend from the surface of the amorphous alloy substrate 1 to the inside thereof, and the depth thereof can be controlled to be 1-6 μm. The diameter of the micro-scale holes 3 is 1-4 microns, so that more plastic materials can be contained in the formed micro-scale holes, and the bonding force between the amorphous alloy base material and the plastic materials is increased.
In some examples of the present application, the amorphous alloy substrate 1 includes at least one of a cobalt-based amorphous alloy, a zirconium-based amorphous alloy, an iron-based amorphous alloy, a magnesium-based amorphous alloy, a copper-based amorphous alloy, and a titanium-based amorphous alloy.
The current amorphous alloy materials are mainly of the above-mentioned kind.
That is, in the composite provided in the embodiments of the present application, the material of the amorphous alloy substrate 1 covers almost all amorphous alloy materials that can be produced currently, which also diversifies the types of the composite formed by the amorphous alloy and the plastic, and has a wider application range.
Among the above amorphous alloy materials, the zirconium-based amorphous alloy has the most mature forming process and is most widely used. Therefore, it is preferable to use a zirconium-based amorphous alloy for the amorphous alloy substrate 1.
For example, the composite according to the embodiment of the present application includes a zirconium-based amorphous alloy substrate, and micron-scale holes 3 are formed in a surface of the zirconium-based amorphous alloy substrate, a plastic material 2 is injection molded on the surface of the zirconium-based amorphous alloy substrate, and the plastic material 2 is embedded in the micron-scale holes 3, so that the amorphous alloy substrate and the plastic material can be bonded together.
Of course, in other embodiments, the amorphous alloy substrate 1 may also be other amorphous alloy materials as described above, and those skilled in the art may flexibly adjust the materials according to needs, which is not specifically limited in the examples of the present application.
In some examples of the present application, the plastic material 2 comprises at least one of polybutylene terephthalate resin PBT, polyphenylene sulfide resin PPS, polyamide resin PA, polyetheretherketone resin PEEK, polycarbonate PC, polyethylene terephthalate PET and polyetherimide PEI.
In the embodiment of the present application, the plastic material 2 is, for example, a thermoplastic resin material. These materials have better fluidity during injection molding, which is beneficial for filling each micron-sized hole 3 on the surface of the amorphous alloy substrate 1.
In some examples of the present application, the plastic material 2 may also be a glass fiber reinforced resin or a carbon fiber reinforced resin, wherein the content of the glass fiber or the carbon fiber is 10% to 50%.
When the plastic material 2 is made of glass fiber reinforced resin or carbon fiber reinforced resin, compared with the thermoplastic resin material, the strength of the composite material is higher, and the expansion coefficient can be reduced, so that the performance of the finally formed amorphous alloy and plastic composite is better.
The content of the glass fiber or the carbon fiber is 10% to 50%.
When the addition amount of the glass fiber or the carbon fiber is within this range, the formed resin material has good fluidity and good filling capability during injection molding. However, when the content of the glass fiber or the carbon fiber is too large or too small, the fluidity of the resin material is affected and the filling ability is deteriorated.
According to another embodiment of the present application, there is provided a method for preparing a composite of an amorphous alloy and a plastic, as shown in fig. 2, the method comprising:
providing an amorphous alloy substrate;
carrying out surface treatment on the amorphous alloy substrate to form micron-sized holes on the surface of the amorphous alloy substrate;
and (3) injecting a plastic material on the surface of the amorphous alloy substrate, and embedding the plastic material into the micron-sized holes to obtain a composite of the amorphous alloy and the plastic.
The preparation process of the composite provided by the embodiment of the application is simple, the amorphous alloy substrate 1 and the plastic material 2 are not combined through chemical bonds, but are combined only in a physical mode, and thus, a chemical reaction cannot occur at the contact position of the amorphous alloy substrate and the plastic material.
According to the preparation method provided by the embodiment of the application, the plastic material 2 can be embedded into the micron-sized hole 3, so that the plastic material 2 can form deeper embedding on the amorphous alloy substrate 1, the bonding firmness between the amorphous alloy substrate 1 and the plastic material 2 is improved, and the amorphous alloy substrate 1 and the plastic material 2 are connected into an integrated structure more tightly and stably.
Optionally, before the step of performing the surface treatment on the amorphous alloy substrate 1, the method further includes the following steps:
carrying out sand blasting treatment on the amorphous alloy base material;
carrying out degreasing treatment on the amorphous alloy base material obtained after sand blasting treatment; and
and cleaning the amorphous alloy substrate obtained after the degreasing treatment.
The surface quality of the amorphous alloy material formed by semi-solid die-casting, i.e. the amorphous alloy substrate 1, is relatively poor, such as the existence of defects of left marks, abnormal colors, and the like. By carrying out sand blasting on the amorphous alloy substrate, the surface quality of the amorphous alloy substrate can be effectively improved, and the defects such as residual marks, color difference and the like can be removed, so that the surface quality of the amorphous alloy substrate 1 is better improved.
Among them, the purpose of the degreasing treatment is to remove oil stains on the surface of the amorphous alloy base material after the sandblasting treatment. In one example of the present application, the degreasing treatment may be thermal degreasing.
The degreasing agent is generally alkaline and mainly comprises alkali, additives and surfactants. The degreasing agent can be subjected to saponification reaction with grease in oil stains, so that the grease and the oil stains on the surface are removed.
Preferably, the degreasing is performed by ultrasonic heat degreasing.
The degreasing agent is alkaline and can be subjected to saponification reaction with esters in the grease so as to remove the grease, and the degreasing effect is better by adding ultrasonic vibration. In addition, the ultrasonic wave has a cleaning function, and the degreasing effect is better.
The degreased amorphous alloy substrate can be cleaned with purified water, so that the surface electrochemical etching treatment of the substrate is facilitated.
In the embodiment of the present application, optionally, the grain size of the blasting material of the sand blasting treatment ranges from 100 meshes to 800 meshes, the blasting material is zirconia sand grains, and the sand blasting pressure ranges from 2bar to 8 bar.
Under the condition of the sand blasting, the surface quality of the amorphous alloy base material 1 can be improved, and the performance of the amorphous alloy base material 1 cannot be damaged.
Optionally, the surface treatment of the amorphous alloy substrate may be performed by electrochemical etching, including:
and placing the amorphous alloy substrate in a surface treatment liquid at 5-60 ℃, and taking the amorphous alloy substrate as an anode to perform electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 0.5-100V, and the treatment time is 2-60 min.
The amorphous alloy substrate 1 placed in the surface treatment liquid may be subjected to the above-described sand blasting and degreasing treatment.
In the embodiment of the application, by performing electrochemical etching on the surface of the amorphous alloy substrate, micron-sized holes 3 can be formed in the surface of the amorphous alloy substrate 1, and then the plastic material 2 can be injected into the micron-sized holes 3 in the surface of the amorphous alloy substrate 1 through an injection molding process and anchored into the micron-sized holes 3 in the surface of the amorphous alloy substrate 1, so that the amorphous alloy substrate 1 and the plastic material 2 can be tightly and firmly combined together.
Optionally, the surface treatment liquid comprises an acid, an additive and a surfactant;
the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 5 g/L-300 g/L;
the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 0.5 g/L-50 g/L;
the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 0.5 g/L-5 g/L.
The surfactant can be used for reducing the surface tension of the surface treatment liquid and increasing the uniformity in chemical etching so as to etch a detailed structure. This facilitates the bonding of the amorphous alloy material with the plastic material. The acid and the additive are used for matching to carry out electrochemical etching on the surface of the amorphous alloy substrate.
Optionally, after the step of performing surface treatment on the amorphous alloy substrate, the method further includes:
carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after surface treatment; and
and drying the amorphous alloy base material obtained after ultrasonic cleaning.
That is, after the step of surface treatment of the amorphous alloy substrate is completed, the surface-treated amorphous alloy substrate is subjected to deep cleaning. In one embodiment of the present application, an ultrasonic deep cleaning method is adopted.
For example, the surface-treated amorphous alloy substrate is subjected to deep cleaning in an ultrasonic cleaning machine to remove the surface treatment liquid remaining on the surface thereof. The amorphous alloy substrate after being deeply cleaned by ultrasonic waves is placed into an oven to be dried so as to remove moisture on the surface of the amorphous alloy substrate, and thus, the subsequent step of injection molding of plastic materials on the surface of the amorphous alloy substrate can be smoothly carried out.
In addition, in order to deeply clean the amorphous alloy substrate after the surface treatment, a chemical immersion method or the like may be used. And drying the surface moisture after treatment.
Optionally, before the step of injection molding the plastic material on the surface of the amorphous alloy substrate, the method further comprises the following steps:
preheating the amorphous alloy substrate at 100-250 ℃.
That is, before the step of performing the plastic material injection molding, the amorphous alloy substrate after the surface treatment may be subjected to a preheating treatment, wherein the preheating temperature may be controlled between 100 ℃ and 250 ℃. Can prevent through preheating treatment that the temperature is lower because of the metallic glass substrate, it is too fast to cool off because of contacting behind the metallic glass substrate at injection plastics in-process plastic material, leads to the mobility to reduce, causes filling pressure too big, influences plastic material's filling effect.
And placing the amorphous alloy substrate subjected to preheating treatment in an injection mold, and combining the amorphous alloy substrate and the plastic material together through an injection molding process to form a composite of the amorphous alloy and the plastic material. The plastic material is partially injected into the micron-sized holes 3 on the surface of the amorphous alloy through an injection molding process, and is firmly anchored in the micron-sized holes 3, so that the amorphous alloy is firmly combined with the amorphous alloy base material.
Optionally, in the process of injection molding the plastic material on the surface of the amorphous alloy substrate, the injection parameters include a holding pressure and a holding time, wherein the holding pressure includes a first-stage holding pressure and a second-stage holding pressure;
the first-stage pressure maintaining pressure of the injection is 600 bar-2000 bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 200 bar-1200 bar, and the pressure maintaining time of the injection second section is 0-5S.
In the scheme provided by the embodiment of the application, in order to improve the bonding force between the amorphous alloy and the plastic material, higher pressure maintaining pressure is adopted.
Optionally, after the step of injection molding the plastic material on the surface of the amorphous alloy substrate, the method further includes: and annealing the injection-molded amorphous alloy and plastic composite, wherein in the annealing process, the annealing temperature is 100-200 ℃, and the annealing time is 60-300 min.
The injection molded composite of amorphous alloy and plastic material is placed in, for example, an oven, and the plastic material in the composite is annealed, so that the stress of the injection molded plastic can be relieved. The risk that the plastic is deformed and cracked or the amorphous alloy is separated from the plastic in the later use process is reduced.
In an embodiment of the present application, as shown in fig. 3, a method for preparing the composite of amorphous alloy and plastic includes:
step S1, providing an amorphous alloy substrate.
Step S2, performing sand blasting on the provided amorphous alloy substrate.
In the step of sand blasting, the grain size range of the spraying material subjected to the sand blasting is 100-800 meshes, the spraying material is zirconia sand grains, and the sand blasting pressure is 2-8 bar.
And step S3, degreasing the amorphous alloy base material after the sand blasting treatment.
Wherein the degreasing treatment adopts thermal degreasing.
For example, ultrasonic thermal degreasing;
and cleaning the amorphous alloy base material obtained after the degreasing treatment by adopting clear water so as to improve the cleanliness of the amorphous alloy base material.
Step S4, carrying out surface treatment on the degreased amorphous alloy base material to form micron-sized holes on the surface of the amorphous alloy base material.
Wherein, the size range of the micron-sized holes 3 is 1-4 μm.
Placing the amorphous alloy substrate in a surface treatment solution at 5-60 ℃, and taking the amorphous alloy substrate as an anode to perform electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 0.5-100V, and the treatment time is 2-60 min.
Wherein the surface treatment liquid comprises an acid, an additive and a surfactant;
the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 5 g/L-300 g/L;
the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 0.5 g/L-50 g/L;
the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 0.5-5 g/L.
And step S5, carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after the surface treatment, and drying the amorphous alloy substrate obtained after the ultrasonic cleaning.
For example, the surface-treated amorphous alloy substrate is subjected to deep cleaning in an ultrasonic cleaning machine to remove the surface treatment liquid remaining on the surface thereof. And (3) putting the amorphous alloy substrate subjected to ultrasonic deep cleaning into an oven for drying treatment to remove the moisture on the surface of the amorphous alloy substrate. Therefore, the subsequent step of injection molding the plastic material on the surface of the amorphous alloy substrate can be conveniently and smoothly carried out.
And step S6, carrying out preheating treatment on the amorphous alloy base material obtained after ultrasonic cleaning.
In step S6, the preheating temperature is controlled to 100 to 250 ℃.
Step S7, injecting a plastic material on the surface of the amorphous alloy substrate to enable the plastic material to be embedded into the micron-sized holes, so as to obtain a composite of the amorphous alloy and the plastic;
in step S7, in the process of injection molding the plastic material on the surface of the amorphous alloy substrate, the injection parameters include a dwell pressure and a dwell time.
Wherein the dwell pressure comprises a first-stage injection dwell pressure and a second-stage injection dwell pressure;
the first-stage pressure maintaining pressure of the injection is 600 bar-2000 bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 200 bar-1200 bar, and the pressure maintaining time of the injection second section is 0-5S.
And step S8, annealing the injection molded amorphous alloy and plastic composite.
In the annealing process, the annealing temperature is 100-200 ℃, and the annealing time is 60-300 min.
According to the preparation method of the amorphous alloy and plastic material composite body disclosed in the embodiment of the application, the surface of the amorphous alloy substrate 1 is firstly treated to prepare the dense and uniform micron-sized holes 3 on the surface, and then the plastic material 2 is injected to the surface of the amorphous alloy substrate 1 by combining with the injection molding process, so that part of the plastic material 2 is injected into the micron-sized holes 3 on the surface of the amorphous alloy substrate 1, and the amorphous alloy substrate 1 and the plastic material 2 can be tightly combined together. The processing cost of the amorphous alloy is reduced, the drop resistance and impact resistance of the amorphous alloy are greatly improved, and excellent waterproof performance is provided for the amorphous alloy product. Meanwhile, due to the use of the nanometer injection molding process, a wider space is provided for the design of an amorphous alloy product, the product design is thinner and lighter, and the requirement of light weight is met.
Example 1
Providing an amorphous alloy substrate;
carrying out sand blasting treatment on the provided amorphous alloy base material, wherein the grain size range of a spraying material subjected to the sand blasting treatment is 100 meshes, the spraying material is zirconia sand grains, and the sand blasting pressure is 2 bar;
carrying out ultrasonic thermal degreasing on the amorphous alloy base material subjected to sand blasting treatment, and cleaning the amorphous alloy base material obtained after degreasing treatment by adopting clear water;
carrying out surface treatment on the degreased amorphous alloy base material to form micron-sized holes on the surface of the amorphous alloy base material: placing the amorphous alloy substrate in a surface treatment liquid at 5 ℃, taking the amorphous alloy substrate as an anode, and performing electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 0.5V, and the treatment time is 2 min;
wherein the surface treatment liquid comprises an acid, an additive and a surfactant; the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 5 g/L; the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 0.5 g/L; the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 0.5 g/L;
carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after the surface treatment, and drying the amorphous alloy substrate obtained after the ultrasonic cleaning;
preheating the amorphous alloy substrate subjected to ultrasonic cleaning, wherein the preheating temperature is 100 ℃;
injecting a plastic material on the surface of the amorphous alloy substrate, and embedding the plastic material into the micron-sized holes to obtain a composite of the amorphous alloy and the plastic; wherein, the pressurize pressure includes injection one section pressurize pressure and injection two sections pressurize pressure:
the first-stage pressure maintaining pressure of the injection is 600bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 200bar, and the pressure maintaining time of the injection second section is 0-5S.
And annealing the injection-molded amorphous alloy and plastic composite, wherein in the annealing process, the annealing temperature is 100 ℃, and the annealing time is 60 min.
Example 2
Providing an amorphous alloy substrate;
carrying out sand blasting treatment on the amorphous alloy base material, wherein the grain size range of a spraying material subjected to the sand blasting treatment is 500 meshes, the spraying material is zirconia sand grains, and the sand blasting pressure is 4 bar;
carrying out ultrasonic thermal degreasing on the amorphous alloy base material subjected to sand blasting, and cleaning the amorphous alloy base material obtained after degreasing by using clear water;
carrying out surface treatment on the degreased amorphous alloy base material to form micron-sized holes on the surface of the amorphous alloy base material: placing the amorphous alloy substrate in a surface treatment liquid at 35 ℃, taking the amorphous alloy substrate as an anode, and performing electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 55V, and the treatment time is 30 min;
wherein the surface treatment liquid comprises an acid, an additive and a surfactant; the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 180 g/L; the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 25 g/L; the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 2.5 g/L;
carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after the surface treatment, and drying the amorphous alloy substrate obtained after the ultrasonic cleaning;
preheating the amorphous alloy substrate subjected to ultrasonic cleaning, wherein the preheating temperature is 170 ℃;
injecting a plastic material on the surface of the amorphous alloy substrate, and embedding the plastic material into the micron-sized holes to obtain a composite of the amorphous alloy and the plastic; wherein, the dwell pressure includes one section of dwell pressure of injection and two sections of dwell pressure of injection:
the first-stage pressure maintaining pressure of the injection is 1600bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 700bar, and the pressure maintaining time of the injection second section is 0-5S.
And annealing the injection-molded amorphous alloy and plastic composite, wherein in the annealing process, the annealing temperature is 150 ℃ and the annealing time is 220 min.
Example 3
Providing an amorphous alloy substrate;
carrying out sand blasting treatment on the amorphous alloy base material, wherein the grain size range of a spraying material subjected to the sand blasting treatment is 800 meshes, the spraying material is zirconia sand grains, and the sand blasting pressure is 8 bar;
carrying out ultrasonic thermal degreasing on the amorphous alloy base material subjected to sand blasting, and cleaning the amorphous alloy base material obtained after degreasing by using clear water;
carrying out surface treatment on the degreased amorphous alloy base material to form micron-sized holes on the surface of the amorphous alloy base material: placing the amorphous alloy substrate in a surface treatment liquid at 60 ℃, taking the amorphous alloy substrate as an anode, and performing electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 100V, and the treatment time is 60 min;
wherein the surface treatment liquid comprises an acid, an additive and a surfactant; the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 300 g/L; the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 50 g/L; the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 5 g/L;
carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after the surface treatment, and drying the amorphous alloy substrate obtained after the ultrasonic cleaning;
preheating the amorphous alloy substrate subjected to ultrasonic cleaning, wherein the preheating temperature is 250 ℃;
injecting a plastic material on the surface of the amorphous alloy substrate, and embedding the plastic material into the micron-sized holes to obtain a composite of the amorphous alloy and the plastic; wherein, the dwell pressure includes one section of dwell pressure of injection and two sections of dwell pressure of injection:
the first-stage pressure maintaining pressure of the injection is 2000bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 1200bar, and the pressure maintaining time of the injection second section is 0-5S.
And annealing the injection-molded amorphous alloy and plastic composite, wherein in the annealing process, the annealing temperature is 100 ℃, and the annealing time is 60 min.
Although some specific embodiments of the present invention have been described in detail by way of examples, it should be understood by those skilled in the art that the above examples are for illustrative purposes only and are not intended to limit the scope of the present invention. It will be appreciated by those skilled in the art that modifications can be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (14)
1. The composite of the amorphous alloy and the plastic is characterized by comprising an amorphous alloy substrate, wherein micron-sized holes are formed on the surface of the amorphous alloy substrate;
and a plastic material is injection molded on the surface of the amorphous alloy substrate and is embedded into the micron-sized holes.
2. The composite of amorphous alloy and plastic as claimed in claim 1, wherein the micron-sized pores have a diameter of 1 μm to 4 μm.
3. The composite of amorphous alloy and plastic as claimed in claim 1, wherein the amorphous alloy substrate comprises at least one of cobalt-based amorphous alloy, zirconium-based amorphous alloy, iron-based amorphous alloy, magnesium-based amorphous alloy, copper-based amorphous alloy and titanium-based amorphous alloy.
4. The composite of amorphous alloy and plastic according to claim 1, wherein the plastic material comprises at least one of polybutylene terephthalate resin (PBT), polyphenylene sulfide resin (PPS), polyamide resin (PA), polyether ether ketone resin (PEEK), Polycarbonate (PC), polyethylene terephthalate (PET), and Polyetherimide (PEI).
5. The composite of amorphous alloy and plastic as claimed in claim 1, wherein the plastic material is glass fiber reinforced resin or carbon fiber reinforced resin, wherein the content of glass fiber or carbon fiber is 10-50%.
6. A preparation method of a composite of amorphous alloy and plastic is characterized by comprising the following steps:
providing an amorphous alloy substrate;
carrying out surface treatment on the amorphous alloy substrate to form micron-sized holes on the surface of the amorphous alloy substrate;
and (3) injecting a plastic material on the surface of the amorphous alloy substrate, and embedding the plastic material into the micron-sized holes to obtain a composite of the amorphous alloy and the plastic.
7. The method according to claim 6, further comprising, before the step of surface-treating the amorphous alloy substrate:
carrying out sand blasting treatment on the amorphous alloy base material;
carrying out degreasing treatment on the amorphous alloy base material obtained after sand blasting treatment; and
and cleaning the amorphous alloy substrate obtained after the degreasing treatment.
8. The method for preparing the amorphous alloy and plastic composite according to claim 7, wherein the grain size of the blasting material is in the range of 100-800 meshes, the blasting material is zirconia sand, and the blasting pressure is 2-8 bar;
the degreasing treatment adopts thermal degreasing.
9. The method for preparing the amorphous alloy and plastic composite according to claim 6, wherein the surface treatment of the amorphous alloy substrate by electrochemical etching comprises:
placing the amorphous alloy substrate in a surface treatment solution at 5-60 ℃, and taking the amorphous alloy substrate as an anode to perform electrochemical etching on at least part of the surface of the amorphous alloy substrate, wherein the voltage of the electrochemical etching is 0.5-100V, and the treatment time is 2-60 min.
10. The method of claim 9, wherein the surface treatment liquid comprises an acid, an additive and a surfactant;
the acid comprises at least one of phosphoric acid, tartaric acid, hydrofluoric acid, sulfuric acid, hydrochloric acid, perchloric acid, citric acid, nitric acid, boric acid, oxalic acid and chromic acid, and the concentration of the acid is 5 g/L-300 g/L;
the additive comprises at least one of sodium hexametaphosphate, gluconic acid, oxalic acid, sodium oxalate, sodium citrate, ammonium fluoride, sodium sulfate, sodium fluoride, potassium fluoride, sodium chloride and ammonium chloride, and the concentration of the additive is 0.5 g/L-50 g/L;
the surfactant comprises at least one of hexadecyl trimethyl ammonium chloride, sodium dodecyl benzene sulfonate, fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty amide, polyalcohol, fatty acid ester and sorbitol, and the concentration of the surfactant is 0.5 g/L-5 g/L.
11. The method according to claim 6, further comprising, after the step of surface-treating the amorphous alloy substrate:
carrying out ultrasonic cleaning on the amorphous alloy substrate obtained after surface treatment; and
and drying the amorphous alloy base material obtained after ultrasonic cleaning.
12. The method for preparing the amorphous alloy and plastic composite according to claim 6, further comprising, before the step of injection molding the plastic material on the surface of the amorphous alloy substrate:
preheating the amorphous alloy substrate at 100-250 ℃.
13. The method of claim 6, wherein the injection parameters include dwell pressure and dwell time during the injection molding of the plastic material on the surface of the amorphous alloy substrate, wherein the dwell pressure includes injection of a first dwell pressure and injection of a second dwell pressure;
the first-stage pressure maintaining pressure of the injection is 600 bar-2000 bar, and the first-stage pressure maintaining time is 0-5S;
the pressure maintaining pressure of the injection second section is 200 bar-1200 bar, and the pressure maintaining time of the injection second section is 0-5S.
14. The method as claimed in claim 6, further comprising, after the step of injection molding a plastic material on the surface of the amorphous alloy substrate:
and annealing the injection-molded amorphous alloy and plastic composite, wherein in the annealing process, the annealing temperature is 100-200 ℃, and the annealing time is 60-300 min.
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