CN117428995A - Metal plastic composite and preparation method thereof - Google Patents
Metal plastic composite and preparation method thereof Download PDFInfo
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- CN117428995A CN117428995A CN202210822677.8A CN202210822677A CN117428995A CN 117428995 A CN117428995 A CN 117428995A CN 202210822677 A CN202210822677 A CN 202210822677A CN 117428995 A CN117428995 A CN 117428995A
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- 239000002184 metal Substances 0.000 title claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 83
- 239000004033 plastic Substances 0.000 title claims abstract description 44
- 229920003023 plastic Polymers 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 19
- 238000001746 injection moulding Methods 0.000 claims abstract description 18
- 238000007788 roughening Methods 0.000 claims abstract description 16
- 238000003486 chemical etching Methods 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000002791 soaking Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 52
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- 229920001169 thermoplastic Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- 239000004416 thermosoftening plastic Substances 0.000 claims description 12
- -1 polybutylene terephthalate Polymers 0.000 claims description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 9
- 239000004952 Polyamide Substances 0.000 claims description 8
- 229920002647 polyamide Polymers 0.000 claims description 8
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 5
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims 1
- 238000004134 energy conservation Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 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 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005237 degreasing agent Methods 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010147 laser engraving Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 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
-
- 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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching 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
- 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)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- ing And Chemical Polishing (AREA)
Abstract
The preparation method of the metal plastic composite comprises the steps of laser roughening, acid etching by using an acid solution, chemical etching by using an etching solution, soaking by using a coating agent, injection molding and the like, so that the metal plastic composite with stronger binding force can be prepared, and the preparation method has higher yield, simple production process and energy conservation. The application also provides a metal plastic composite prepared by the preparation method.
Description
Technical Field
The application relates to the technical field of metal and plastic integration, in particular to a preparation method of a metal plastic composite and the metal plastic composite prepared by the method.
Background
At present, the metal and plastic nano forming process is more, such as: ECIM (electro chemistry insert molding), NMT (nano-processing technology), alplas, etc. The ECIM and the Alplas adopt electrochemical methods to form nanoscale holes on the metal surface, and the NMT adopts chemical etching methods to form nanoscale holes on the metal surface. However, the process has strong applicability to aluminum-plastic combination, and the titanium-plastic combination force of the titanium-plastic composite body obtained by adopting the process is far lower than that of the aluminum-plastic composite body. At present, the bonding force of titanium plastic in the industry is about 27MPa, and the further enhancement of the bonding force of titanium plastic is still a direction required by a person skilled in the art.
Disclosure of Invention
In view of this, the present application proposes a method for preparing a metal plastic composite with improved titanium plastic bonding force.
In addition, there is also a need to provide a metal plastic composite prepared by the preparation method.
An embodiment of the present application provides a method for preparing a metal plastic composite, which includes the following steps:
coarsening by laser: providing a metal matrix, and carrying out laser roughening on the metal matrix so as to form nanoscale holes on the surface of the metal matrix;
acid etching: carrying out acid etching on the metal matrix subjected to laser roughening by using an acid solution so as to form micron-sized holes on the surface of the metal matrix;
chemical etching: carrying out chemical etching on the metal matrix subjected to acid etching by using etching liquid so as to corrode the nano-scale holes and the micro-scale holes;
soaking: soaking the metal matrix subjected to chemical etching with a coating agent; and
injection molding: and placing the soaked metal matrix into a mould, and performing injection molding by using thermoplastic plastics to form the integrated metal-plastic composite.
In one embodiment, the nanoscale holes have a pore size of 70nm to 120nm, a depth of 40nm to 80nm, and a pitch of 0.02mm to 0.04mm.
In one embodiment, the nanoscale pores have a pore size of 100nm and a depth of 50nm.
In one embodiment, the micron-sized pores have a pore size of 10 μm to 100 μm and a depth of 20 μm to 150 μm.
In one embodiment, the processing parameters of the laser roughening are: the speed is 100 mm/s-500 mm/s, the frequency is 60 KHz-80 KHz, the spacing is 0.02 mm-0.04 mm, and the angle is 45 degrees or 135 degrees.
In one embodiment, the acidic solution comprises a 5% strength by mass hydrofluoric acid (HF) solution.
In one embodiment, the etching solution includes a compound containing ammonium ions, hydrogen peroxide, and an alkaline compound, and the etching solution has a pH of 9 to 12.
In one embodiment, the coating agent comprises vinyltrimethoxysilane.
In one embodiment, the metal matrix comprises titanium or a titanium alloy.
In one embodiment, the thermoplastic comprises at least one of polybutylene terephthalate (PBT), polyphenylene sulfide resin (PPS), polyamide resin (PA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), thermoplastic Polyimide (TPT), and polymethyl methacrylate (PMMA).
According to the preparation method of the metal plastic composite, the titanium plastic binding force of the prepared metal plastic composite is improved by about 20% by combining the processes of laser roughening, chemical etching, film soaking and the like, the yield of the preparation method is high, the production process is simple, and energy sources can be saved.
Drawings
Fig. 1 is a flowchart of a method for preparing a metal-plastic composite according to an embodiment of the present disclosure.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present application belong. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the examples of the application.
Referring to fig. 1, an embodiment of the present application provides a method for preparing a metal-plastic composite, which includes the following steps:
s1, laser coarsening: providing a metal matrix, and carrying out laser roughening on the metal matrix so as to form nanoscale holes on the surface of the metal matrix;
s2, acid etching: carrying out acid etching on the metal matrix subjected to laser roughening by using an acid solution so as to form micron-sized holes on the surface of the metal matrix;
s3, chemical etching: carrying out chemical etching on the metal matrix subjected to acid etching by using etching liquid so as to corrode the nano-scale holes and the micro-scale holes;
s4, soaking: soaking the metal matrix subjected to chemical etching with a coating agent; and
s5, injection molding: and placing the soaked metal matrix into a mould, and performing injection molding by using thermoplastic plastics to form the integrated metal-plastic composite.
It will be appreciated that the reference to steps is intended to clearly describe a particular method of preparation and is not intended to limit the order of steps.
In this application, the metal substrate is preferably titanium or a titanium alloy (which may be collectively referred to as a titanium workpiece). The titanium alloy may be a titanium alloy such as TA5, TA6, TA7, TA10, TA11, TB2, TB3, TB4, TB5, TB6, TC1, TC2, TC3, TC4, or TC6, and the present application is not limited thereto.
It will be appreciated that the metal substrate may also be pre-treated (S0) prior to laser roughening the metal substrate. The pretreatment may include, but is not limited to, degreasing, pickling, water washing, and drying.
The degreasing of titanium workpieces (titanium metal or titanium alloy) can be performed using a more conventional alkaline degreasing process, and the degreasing agent can include: 80g/L of sodium hydroxide, 30g/L of sodium carbonate, 40g/L of sodium phosphate, 10g/L of sodium silicate and the like, the treatment temperature is 60-70 ℃, the treatment time is 5-10min, and ultrasonic waves can be adopted for auxiliary cleaning.
The titanium workpiece (titanium metal or titanium alloy) is generally formed by forging, CNC processing or heat treatment and other processes, so that the titanium workpiece is easy to generate thicker oxide layers and pollutants firmly adsorbed on the surface, the surface condition of the titanium workpiece is complex and uneven, the oxide layers and pollutants on the surface layer of the titanium workpiece can be effectively removed through acidic corrosive liquid, the uniform surface can be obtained, the surface can be formed to have certain roughness, the specific surface area of the titanium workpiece in the subsequent injection molding process is increased, and the bonding strength of the titanium-plastic bonding is increased. The acidic etchant may include: 60-100ml/L of hydrofluoric acid with the concentration of 40%, 250-350ml/L of phosphoric acid with the concentration of 85% and 10-20ml/L of ethylene glycol, and treating the titanium workpiece in the acidic corrosive liquid for 30s at normal temperature, wherein the titanium workpiece can slightly swing at the same time. Hydrofluoric acid is reacted with titanium metal in the pickling process, and acidic ammonium fluoride can be used for replacing the titanium metal in general; the phosphoric acid can improve the viscosity of the acidic corrosive liquid, effectively reduce the escape speed of the reaction gas, not only can enable hydrogen to stay on the surface of a titanium workpiece to play a role in corrosion inhibition, but also can reduce volatilization of hydrogen fluoride, so that the acidic corrosive liquid is more stable, and the pungent smell generated during treatment is weakened; the glycol plays a certain auxiliary role, can enhance the interfacial dispersibility in the acidic corrosive liquid, ensures that the surface of the titanium workpiece is corroded more uniformly, and has the function of improving viscosity.
After acid washing, the metal matrix can be washed by deionized water to remove residual acidic corrosive liquid, then dried, and subjected to the next laser roughening step (S1).
The titanium workpiece is subjected to laser roughening by a laser, and of course, other laser devices can be used for laser roughening, for example, a laser engraving machine and the like. The processing parameters of laser roughening can be: the speed is 100 mm/s-500 mm/s, the frequency is 60 KHz-80 KHz, the interval is 0.02 mm-0.04 mm, the angle is 45 degrees or 135 degrees, and the times can be 1 time or 2 times. The laser works under the processing parameters, and nanoscale holes can be formed after the titanium workpiece is etched.
In some embodiments, the nanoscale pores have a pore size of 70nm to 120nm, a depth of 40nm to 80nm, and a pitch of 0.02mm to 0.04mm. The distance refers to the distance between the circle centers of adjacent nanoscale holes. The formed nano-scale holes are beneficial to increasing the density of the holes due to smaller pore diameter, so that molten thermoplastic plastic is more fully filled into the nano-scale holes in the injection molding process, and the nano-scale holes are cooled and hardened, so that the mutually-gripped physical binding force formed between the metal matrix and the thermoplastic plastic is increased.
Further, the pore size of the nano-scale holes may be 100nm and the depth may be 50nm.
After laser roughening, the metal substrate is etched (S2). The metal substrate can be immersed in an acidic solution for acid etching treatment, or the surface of the metal substrate can be sprayed with the acidic solution. In some embodiments, the acidic solution comprises a 5% strength by mass hydrofluoric acid (HF) solution. The acid etching can further form micron-sized holes on the metal matrix, so that the surface of the metal matrix forms an uneven structure. The aperture size of the micron-sized holes can be 10-100 μm, and the depth can be 20-150 μm. It is understood that particles larger than the size of the nano-scale holes in the thermoplastic are difficult to embed into the nano-scale holes, which affects the bonding strength of the metal matrix and the thermoplastic. The micro-scale holes formed by acid etching can accommodate the thermoplastic plastics which cannot be embedded into the nano-scale holes, so that the bonding strength is further enhanced.
After the acid etching treatment, the metal matrix can be washed with water. Deionized water may be used for cleaning, and acidic or alkaline cleaning solutions may be used to remove corrosion residues on the surface of the metal substrate, such as metal residues, hydroxide precipitates, and the like. Among them, the acidic cleaning liquid preferably contains an aqueous solution of nitric acid, sulfuric acid, or the like, and the alkaline cleaning liquid preferably contains an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, sodium metasilicate, or the like. Besides the acidic or alkaline components, the cleaning liquid can also be added with a metal ion chelating agent and a surfactant to improve the effect of removing corrosion residues.
After the acid etching treatment and water washing, the metal substrate is put into an etching solution to be chemically etched (S3). In some embodiments, the etching solution includes an ammonium ion-containing compound, hydrogen peroxide (H) 2 O 2 ) And an alkaline compound, wherein the pH of the etching solution is 9-12. After the etching liquid is used for chemical etching, the depths of the nano-scale holes and the micro-scale holes formed on the surface of the metal matrix are further deepened, so that the bonding force between the metal matrix and the thermoplastic plastic is enhanced.
Further, the ammonium ion containing compound may be, but is not limited to, tetramethylammonium hydroxide, and the like. The basic compound may be, but is not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, and the like.
After chemical etching, the metal substrate may be rinsed with deionized water to remove residual etching solution.
After chemical etching and water washing, the metal substrate is immersed in a coating agent (S4). In some embodiments, the coating agent may be vinyltrimethoxysilane. The coating agent is dispersed into the nano-scale holes and the micro-scale holes of the metal matrix and is adsorbed on the inner walls of the holes; the film agent can also be chemically crosslinked with the functional groups of the thermoplastic plastics through the active groups in the injection molding process, so that the metal matrix and the thermoplastic plastics have better binding force and adhesion. Specifically, the alkoxy group bonded to the silicon atom in the coating agent is partially hydrolyzed to silanol (R (CH) 2 ) n -Si(OCH) 3 →R(CH 2 ) n -Si(OH) 3 +3CH 3 OH), the silanol still remains partially in the holes after washing with water, and a molecular film is formed after drying. In the subsequent injection molding step, silanol can undergo condensation reaction with hydroxyl groups of the thermoplastic to generate stable siloxane bonds; in addition, the organic group of the coating agent can form hydrogen bond or chemical bond with the thermoplastic plastic. Therefore, the coating agent can play a good role in connecting the metal matrix and the thermoplastic, and the combination effect of the metal matrix and the thermoplastic is enhanced.
After soaking, the metal matrix can be washed with deionized water and then dried.
And (5) placing the soaked, washed and dried metal matrix into a mold for injection molding (S5). The metal matrix is placed in the mould cavity, the thermoplastic plastics is fed into the charging barrel by means of hopper of injection moulding machine, heated and melted in the charging barrel, under the action of pushing high-speed rotating screw, the thermoplastic plastics is injected into the mould cavity by means of injection nozzle, filled with residual empty space in the mould cavity and contacted with surface of metal matrix, further injected into nano-level hole and micrometer-level hole of metal surface, cooled and hardened, opened and demoulded so as to obtain the invented metal-plastic composite body.
In order to increase the bonding force between the metal matrix and the thermoplastic, the metal matrix is preferably preheated prior to injection molding, and the metal matrix is preferably heated to a temperature close to the temperature of the mold during preheating. After injection molding is completed, the product can be optionally annealed according to the requirement, namely, the metal plastic composite is kept at a certain temperature for a period of time to eliminate residual stress. After injection molding, the metal plastic composite can be subjected to physical processing such as cutting, punching, drilling and the like, and chemical surface treatment such as chemical polishing, anodic oxidation, dyeing and the like.
In some embodiments, the thermoplastic described herein may be, but is not limited to, one or more of polybutylene terephthalate (PBT), polyphenylene sulfide resin (PPS), polyamide resin (PA), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), thermoplastic Polyimide (TPT), polymethyl methacrylate (PMMA).
The present application will be further described with reference to specific examples.
Example 1
Pretreatment: taking a TA5 titanium alloy plate with the thickness of 0.8mm, cutting the plate into rectangular slices with the thickness of 15mm multiplied by 80mm, and carrying out pretreatment steps such as degreasing, pickling, washing, drying and the like.
S1: laser coarsening is carried out on the surface of the TA5 titanium alloy matrix by adopting a laser, the speed is 100 mm/s-500 mm/s, the frequency is 60 KHz-80 KHz, the spacing is 0.02 mm-0.04 mm, and the angle is 45 degrees or 135 degrees so as to form nanoscale holes on the surface.
S2: and (2) putting the TA5 titanium alloy matrix treated in the step (S1) into hydrofluoric acid (HF) solution with the mass concentration of 5% for acid etching so as to form micron-sized holes on the surface of the titanium alloy matrix, and then cleaning the titanium alloy matrix with deionized water.
S3: putting the TA5 titanium alloy substrate treated in the step S2 into etching solution (comprising tetramethyl ammonium hydroxide and H) 2 O 2 And sodium hydroxide, etc.), and then rinsed with deionized water.
S4: and (3) soaking the TA5 titanium alloy matrix treated in the step (S3) in vinyl trimethoxy silane (coating agent), washing with water and drying.
S5: and (3) placing the TA5 titanium alloy matrix treated in the step (S4) into a mold, and performing injection molding with polybutylene terephthalate (PBT) to obtain the metal plastic composite (namely the titanium plastic composite).
Example 2
The only difference from example 1 is that: the thermoplastic in this embodiment is polyphenylene sulfide resin (PPS). The remainder is the same as in example 1 and will not be described here again.
Example 3
The only difference from example 1 is that: the thermoplastic in this embodiment is a polyamide resin (PA). The remainder is the same as in example 1 and will not be described here again.
Comparative example 1
The TA5 titanium alloy plate in example 1 is subjected to a pretreatment step, and then is directly put into a mold to be subjected to injection molding with polybutylene terephthalate (PBT) to obtain a metal plastic composite (namely a titanium plastic composite).
The titanium plastic composites prepared in examples 1 to 3 and comparative example 1 were respectively fixed on a universal material tester for tensile test, and the average shear force in the test results can be regarded as the binding force between the TA5 titanium alloy substrate and the thermoplastic, and the test results are shown in Table 1.
TABLE 1
| Average shear force (MPa) | |
| Example 1 | 32.1 |
| Example 2 | 32.4 |
| Example 3 | 32.6 |
| Comparative example 1 | 27.0 |
As can be seen from the data in Table 1, the average shear force of the titanium plastic composites prepared in examples 1-3 is higher than that of the titanium plastic composite prepared in comparative example 1 by about 20%, indicating that the bonding force of the metal matrix prepared by the method of the present application is excellent. In addition, the preparation method of the metal plastic composite provided by the application has the advantages of higher yield, simple production process and energy conservation.
The foregoing description is of some embodiments of the present application, but is not limited to only those embodiments during actual application. Other variations and modifications of the present application, which are apparent to those of ordinary skill in the art, are intended to be within the scope of the present application.
Claims (10)
1. The preparation method of the metal plastic composite is characterized by comprising the following steps of:
coarsening by laser: providing a metal matrix, and carrying out laser roughening on the metal matrix so as to form nanoscale holes on the surface of the metal matrix;
acid etching: carrying out acid etching on the metal matrix subjected to laser roughening by using an acid solution so as to form micron-sized holes on the surface of the metal matrix;
chemical etching: carrying out chemical etching on the metal matrix subjected to acid etching by using etching liquid so as to corrode the nano-scale holes and the micro-scale holes;
soaking: soaking the metal matrix subjected to chemical etching with a coating agent; and
injection molding: and placing the soaked metal matrix into a mould, and performing injection molding by using thermoplastic plastics to form the integrated metal-plastic composite.
2. The method for preparing a metal plastic composite according to claim 1, wherein the nano-scale holes have a pore size of 70nm to 120nm, a depth of 40nm to 80nm, and a pitch of 0.02mm to 0.04mm.
3. The method of claim 2, wherein the nanoscale pores have a pore size of 100nm and a depth of 50nm.
4. The method for preparing a metal-plastic composite according to claim 1, wherein the micron-sized holes have a pore size of 10 μm to 100 μm and a depth of 20 μm to 150. Mu.m.
5. The method of claim 1, wherein the laser roughening parameters are: the speed is 100 mm/s-500 mm/s, the frequency is 60 KHz-80 KHz, the spacing is 0.02 mm-0.04 mm, and the angle is 45 degrees or 135 degrees.
6. The method of claim 1, wherein the acidic solution comprises a 5% strength by mass hydrofluoric acid solution.
7. The method of claim 1, wherein the etching solution comprises an ammonium ion-containing compound, hydrogen peroxide and an alkaline compound, and the etching solution has a pH of 9 to 12.
8. The method of claim 1, wherein the coating agent comprises vinyltrimethoxysilane.
9. The method of making a metal-plastic composite according to claim 1, wherein the metal matrix comprises titanium or a titanium alloy; the thermoplastic comprises at least one of polybutylene terephthalate, polyphenylene sulfide resin, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polyamide, thermoplastic polyimide and polymethyl methacrylate.
10. A metal-plastic composite, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9.
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