CN106881813B - A kind of metallic composite and preparation method thereof - Google Patents
A kind of metallic composite and preparation method thereof Download PDFInfo
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- CN106881813B CN106881813B CN201510946787.5A CN201510946787A CN106881813B CN 106881813 B CN106881813 B CN 106881813B CN 201510946787 A CN201510946787 A CN 201510946787A CN 106881813 B CN106881813 B CN 106881813B
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/77—Measuring, controlling or regulating of velocity or pressure of moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/17—Component parts, details or accessories; Auxiliary operations
- B29C45/76—Measuring, controlling or regulating
- B29C45/78—Measuring, controlling or regulating of temperature
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76498—Pressure
-
- 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
- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
- B29C2945/76494—Controlled parameter
- B29C2945/76531—Temperature
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to metallic composite field, a kind of metallic composite and preparation method thereof is disclosed.1) preparation method of metallic composite of the invention is the following steps are included: form peelable protective layer in metallic substrate surface；2) micron order hole is etched in metallic surface with laser-induced thermal etching；3) metal surface is handled with chemical pretreatment solution；4) protective layer is removed, and obtained surface porous metal substrate and plastics are subjected to integrated injection moulding.The preparation method of provided metallic composite can effectively improve the bond strength of plastics and metal through the invention.
Description
Technical field
The present invention relates to a kind of metallic composites and preparation method thereof.
Background technique
In recent years, the seamless composite of metal and plastics integrated injection molding is concerned, to enhance two kinds of materials
Between binding force, can be made by chemically treated method metallic substrate surface formed irregular hole then again with plastics
Carry out integrated injection moulding.There are two ways to metal surface forms hole, one is passing through powder metallurgy sintered technology or sun
Pole aoxidizes the metal base to form porous surface, then carries out chemical pretreatment solution activating surface to metal base, so as to modeling
Material carries out strong combination；And for the metal base of stainless steel series, when anodized, can be formed in substrate surface
One layer of fine and close oxidation film can not be formed effective porous in metal surface.The preparation of traditional stainless steel and Plastic composite body
Method is fixed with plastic products again generally by connection structure is increased in stainless steel structure part.
The metal base of porous surface is formed by powder metallurgy sintered technology or anodic oxidation, then metal base is carried out
The method that chemical pretreatment solution activating surface prepares surface porous metal, generally be directed to aluminium alloy, and powder metallurgy sintered technology
Processing apparatus is complicated, and higher cost is not easy to realize.It is traditional stainless steel structure part increase connection structure again with plastic products
Fixed connection method, it is at high cost since processing efficiency is low for stainless steel, and the more complex structure of shape can not be made, it is difficult to
To being widely applied.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparation methods of new metallic composite
And its metallic composite being prepared, plastics can be effectively improved by means of the present invention and the combination of metal is strong
Degree.
To achieve the goals above, the present invention provides a kind of preparation method of metallic composite, wherein this method includes
Following steps:
1) peelable protective layer is formed in metallic substrate surface；
2) micron order hole is etched in metallic surface with laser-induced thermal etching；
3) metal surface is handled with chemical pretreatment solution；
4) protective layer is removed, and obtained surface porous metal substrate and plastics are subjected to integrated injection moulding.
The present invention also provides a kind of metallic composites being prepared by the above method.
According to the present invention, corrosion resistant protective layer is formed in metal surface by using Stripable paint, is lost by laser
It is engraved in the hole that metallic substrate surface etches micron dot matrix, then micropore inside is widened by chemical pretreatment solution, is prepared
The pore structure on surface is the porous metal substrate of inverted " t " font, with powder metallurgy sintered technology, anodic oxidation and chemical etching phase
Than technique is simpler, it is easy to accomplish, also, the pore structure due to being capable of forming inverted " t " font on surface, it is infused
Modeling can effectively improve the bond strength of plastics and metal.In addition, the technology can be adapted for the gold such as aluminium alloy, stainless steel
Belong to, it is applied widely.Due to corrosion resistant protective layer being formed in metal surface, and hence it is also possible to arbitrarily protect in preparation engineering
The non-processing face part of metal base is protected from scuffing, the corrosion etc. in processed.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of preparation method of metallic composite, wherein method includes the following steps:
1) peelable protective layer is formed in metallic substrate surface；
2) micron order hole is etched in metallic surface with laser-induced thermal etching；
3) metal surface is handled with chemical pretreatment solution；
4) protective layer is removed, and obtained surface porous metal substrate and plastics are subjected to integrated injection moulding.
According to the present invention, the material of the metal base is aluminium alloy or stainless steel.Preferably, the thickness of the metal base
Degree be 1mm or more, it is highly preferred that the metal base with a thickness of 1-10mm.
By means of the present invention, that is, it is suitable for aluminium alloy, is also applied for stainless steel, use scope is wider.
In the case where, according to the invention it is preferred to, this method further include metallic substrate surface formed peelable protective layer it
Before, the step of cleaning to metal base.
The step of cleaning, for example can be with are as follows: carries out electrochemical deoiling processing to metal base with cleaning agent, removes metal
The greasy dirt on surface, wherein the temperature of oil removal treatment can be 60-80 DEG C, and the time of processing is 1-3min.With cleaning agent to gold
Belong to after substrate carries out electrochemical deoiling processing and washes with water 1-2min preferably to remove the cleaning agent of residual on metal base.
Above-mentioned cleaning agent can be commercially available, such as can be the degreaser of 504 model of Li Jie bodyguard company.
In accordance with the present invention it is preferred that forming the protective layer by coating coating and solidification in metallic substrate surface.
Preferably contain aliphatic anionic polyester type polyurethane dispersion and light-cured type polyurethane as the coating
The coating of acrylic acid dispersion.Coating of the invention is by by aliphatic anionic polyester type polyurethane dispersion and light-cured type
Polyurethane acroleic acid dispersion compounds according to a certain ratio, and rigid structure is thus introduced in polyurethane resin, again by
Photocuring forms the dense coating of high crosslinking, and film is not only able to strong alkali-acid resistance, and has stronger toughness, elasticity, machine
Tool intensity and temperature tolerance, thus, it is possible to prevent metallic substrate surface to be corroded and scratch in subsequent treatment process.
It is highly preferred that the ingredient and weight percent of above-mentioned coating are as follows: aliphatic anionic polyester type polyurethane dispersion:
30-60%；Light-cured type polyurethane acroleic acid dispersion: 30-60%；Cosolvent: 5-15%；Nanofiller: 3-12%；It helps
Agent: 1-5%；Photoinitiator: 1-3%；Water: 0-5%；It is further preferred that the ingredient and weight percent of above-mentioned coating are as follows: rouge
Fat race anionic polyester type polyurethane dispersion: 30-50%；Light-cured type polyurethane acroleic acid dispersion: 30-50%；Hydrotropy
Agent: 5-15%；Nanofiller: 3-7%；Auxiliary agent: 2-3%；Photoinitiator: 2-3%；Water: 3-4%.
Above-mentioned aliphatic anionic polyester type polyurethane dispersion can for example be purchased from the Bayhydrol UH of Beyer Co., Ltd
2342 models.
Above-mentioned light-cured type polyurethane acroleic acid dispersion can for example be purchased from the Bayhydrol UV XP of Beyer Co., Ltd
2690 models.
Above-mentioned cosolvent can be one of butyl glycol ether, propylene glycol monomethyl ether and dipropylene glycol methyl ether or a variety of.
Above-mentioned nanofiller can be Nano-meter SiO_22, Nano-meter CaCO33, nanometer Al2O3And nano-TiO2One of or it is a variety of.
Above-mentioned auxiliary agent can be one of thickener, defoaming agent and wetting dispersing agent etc. or a variety of.The thickener disappears
Infusion and wetting dispersing agent can be various thickeners, defoaming agent and wetting dispersing agent commonly used in the art.It is excellent in them
It is selected as thickener.The thickener for example can be TEGO ViscoPlus 3060, and TEGO ViscoPlus 3060 can be purchased
From three liters of Foshan trade Co., Ltd.
Above-mentioned photoinitiator can be benzophenone, diphenylhydroxyethanone, benzil, 1- hydroxy cyclohexyl phenylketone
(I184), monoacylphosphine oxides and double acylphosphine oxides is one or more, preferably benzophenone.
By using the protective layer that above-mentioned coating is formed, protective layer can either be played the role of, additionally it is possible in subsequent step
In protective layer simply removed by torn method.Above-mentioned protective layer is the preferred side that inventor has found after many experiments
Case, those skilled in the art can also use other common protective layer materials, and the present invention is not specifically limited.
According to the present invention, the method that coating is coated on the metal base is not particularly limited, and can be this field
Common various methods, such as can be dip-coating, showering or spraying etc., present invention preferably uses sprayings.
Film thickness for coating is preferably 30-60 μm, and more preferably 35-55 μm.
In addition, it is 55-70 DEG C that the cured condition, which includes: baking temperature, baking time 20-30min, UV energy is
1200-1500mj/m2。
According to the present invention, in step 2), the aperture for the micron order hole that laser-induced thermal etching is formed is 20-200 μm, pitch of holes
50-200 μm, 100-1000 μm of hole depth；Preferably, the aperture for the micron order hole that laser-induced thermal etching is formed is 50-150 μm, hole
50-200 μm of spacing, 500-1000 μm of hole depth；It is highly preferred that the aperture for the micron order hole that laser-induced thermal etching is formed is 50-100
μm, 100-200 μm of pitch of holes, 500-1000 μm of hole depth.
For the laser equipment used in step 2), there is no particular limitation, as long as being capable of forming hole as described above
?.Preferably, metal base is punched using big nation's laser equipment EP-25S laser marking machine.
For the condition of laser-induced thermal etching, also there is no particular limitation, as long as being capable of forming hole as described above.It is excellent
Selection of land, the laser power are 15-25w.
In accordance with the present invention it is preferred that being handled specially metal surface using corruption with chemical pretreatment solution in step 3)
Erosion liquid corrodes metal surface.
It is highly preferred that carrying out processing to metal surface with chemical pretreatment solution includes: in step 3)
(1) corroded with sulfuric acid, wherein sulfuric acid concentration 180-220g/L, the temperature of corrosion are 15-40 DEG C, corrosion
Time is 15-20min；
(2) substrate is cleaned with water, removes remaining sulfuric acid on metal base；
(3) microcorrosion is carried out to aperture using methylamine, wherein corrosion temperature is 15-40 DEG C, etching time 5-8min.
The inventors found that by first using sulfuric acid corrosion, then with the method for methylamine microcorrosion, can to hole into
Row is widened, and irregular inverted " t " font hole is formed, it is possible thereby to the plastics in the metallic composite significantly improved and gold
Belong to the inter-layer bonding force of layer.
According to the present invention, it after handling metal surface with chemical pretreatment solution, needs to remove protective layer.Due to this hair
Protective layer used in bright is peelable protective layer, therefore when removing protective layer, it is only necessary to fall protective layer with tearing.
According to the present invention, in step 4), the plastics can be various plastics commonly used in the art.Such as the modeling
Material is polyethylene, polypropylene, polymethyl methacrylate, polystyrene, polycarbonate, acrylonitrile-butadiene-phenylethylene, gathers
One of diphenyl sulfide, polyamide, polyimides, polysulfones and polyether-ether-ketone are a variety of.
In step 4) of the invention, when injection molding, obtained surface porous metal substrate is put into integrated injection mold
It is interior, then there is the surface of hole to carry out injection-moulded plastic the substrate.
The condition of above-mentioned injection molding can be various conditions commonly used in the art.Preferably, the condition packet of the injection molding
It includes: 120-150 DEG C of mold temperature, 280-350 DEG C of melt adhesive temperature, injection pressure 110-150bar.
The present invention also provides a kind of metallic composites being prepared by the above method.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) chemistry is carried out to metal base (aluminium alloy, with a thickness of 1mm) with cleaning agent (being purchased from 504 model of Li Jie bodyguard company)
Oil removal treatment removes the greasy dirt of metal surface, wherein the temperature of cleaning is 70 DEG C, time 2min；Then it is cleaned with tap water
2min；
2) peelable protective layer is formed after spraying peelable protective coating and solidification to metallic substrate surface, wherein spraying
Film thickness be 35-45 μm；Cured condition are as follows: 60 DEG C of baking temperature, baking time 30min, UV energy 1300mj/m2；
The paint ingredient and weight percent used are as follows: aliphatic anionic polyester type polyurethane dispersion (is purchased from Bayer
2342 model of company Bayhydrol UH): 30%, light-cured type polyurethane acroleic acid dispersion (is purchased from Beyer Co., Ltd
2690 model of Bayhydrol UV XP): 50%, cosolvent (butyl glycol ether): 10%, nanofiller (nanometer titanium dioxide
Silicon): 3%, auxiliary agent (thickener TEGO ViscoPlus 3060 is purchased from three liters of Foshan trade Co., Ltd, same as below):
2%, photoinitiator (benzophenone): 2%, water: 3%.
3) micron order hole is etched into metallic surface with laser-induced thermal etching；
Dot matrix is designed, there is the Metal Substrate of peelable protective layer to surface using big nation's laser equipment EP-25S laser marking machine
Material is punched, aperture be 50 μm, pitch of holes be 100 μm, 500-800 μm of hole depth, laser power 20w.
4) metal surface is handled with chemical pretreatment solution, forms irregular inverted " t " font hole, specific steps are as follows:
A) sulfuric acid corrosion, sulfuric acid concentration 200g/L are first used, temperature is 25 DEG C, oxidization time 18min, passes through sulfuric acid corruption
Erosion device to hole carries out widening intensification；
B) substrate is cleaned with tap water, removes substrate and remain sulfuric acid, cleaning temperature is 25 DEG C；
C) microcorrosion, etching time 8min are carried out to aperture using methylamine, temperature is 25 DEG C.
5) protective film is torn
Side is played with adhesive tape, tears peelable protective film, the preparation of surface porous metal is completed.
6) prepared surface porous metal substrate and plastics are subjected to integrated injection moulding, specific steps are as follows:
Surface porous metal is put into integrated injection mold, then there is the surface of hole to be molded the substrate
Plastics obtain metal and the integrated metallic composite A1 of plastics；Wherein, injection molding material is polyphenylene sulfide, injecting condition are as follows: mould
140-150 DEG C of temperature of tool, 300 DEG C of melt adhesive temperature, injection pressure 130bar.
Embodiment 2
1) chemistry is carried out to metal base (aluminium alloy, with a thickness of 1mm) with cleaning agent (being purchased from 504 model of Li Jie bodyguard company)
Oil removal treatment removes the greasy dirt of metal surface, wherein the temperature of cleaning is 70 DEG C, time 2min；Then it is cleaned with tap water
2min；
2) peelable protective layer is formed after spraying peelable protective coating and solidification to metallic substrate surface, wherein spraying
Film thickness be 45-50 μm；Cured condition are as follows: 60 DEG C of baking temperature, baking time 30min, UV energy 1300mj/m2；
The paint ingredient and weight percent used are as follows: aliphatic anionic polyester type polyurethane dispersion (is purchased from Bayer
2342 model of company Bayhydrol UH): 50%, light-cured type polyurethane acroleic acid dispersion (is purchased from Beyer Co., Ltd
2690 model of Bayhydrol UV XP): 30%, cosolvent (butyl glycol ether): 6%, nanofiller (nano silica):
5%, auxiliary agent (TEGO ViscoPlus 3060): 3%, photoinitiator (benzophenone): 2%, water: 4%.
3) micron order hole is etched into metallic surface with laser-induced thermal etching；
Dot matrix is designed, there is the Metal Substrate of peelable protective layer to surface using big nation's laser equipment EP-25S laser marking machine
Material is punched, aperture be 100 μm, pitch of holes be 200 μm, 700-1000 μm of hole depth, laser power 25w.
4) metal surface is handled with chemical pretreatment solution, forms irregular inverted " t " font hole, specific steps are as follows:
A) sulfuric acid corrosion, sulfuric acid concentration 220g/L are first used, temperature is 25 DEG C, oxidization time 20min, passes through sulfuric acid corruption
Erosion device to hole carries out widening intensification；
B) substrate is cleaned with tap water, removes substrate and remain sulfuric acid, temperature is 25 DEG C；
C) microcorrosion is carried out to aperture using methylamine, the time is 8min, and temperature is 25 DEG C.
5) protective film is torn
Side is played with adhesive tape, tears peelable protective film, the preparation of surface porous metal is completed.
6) prepared surface porous metal substrate and plastics are subjected to integrated injection moulding, specific steps are as follows:
Surface porous metal is put into integrated injection mold, then there is the surface of hole to carry out the metal base
Injection-moulded plastic obtains metal and the integrated metallic composite A2 of plastics；Wherein, injection molding material is polycarbonate, injecting condition
Are as follows: 140-150 DEG C of mold temperature, 300 DEG C of melt adhesive temperature, injection pressure 120bar.
Embodiment 3
1) chemistry is carried out to metal base (stainless steel, with a thickness of 1mm) with cleaning agent (being purchased from 504 model of Li Jie bodyguard company)
Oil removal treatment removes the greasy dirt of metal surface, wherein the temperature of cleaning is 70 DEG C, time 2min；Then clear with tap water
Wash 2min；
2) peelable protective layer is formed after spraying peelable protective coating and solidification to metallic substrate surface, wherein spraying
Film thickness be 50-55 μm；Cured condition are as follows: 60 DEG C of baking temperature, baking time 30min, UV energy 1400mj/m2；
The paint ingredient and weight percent used are as follows: aliphatic anionic polyester type polyurethane dispersion (is purchased from Bayer
2342 model of company Bayhydrol UH): 40%, light-cured type polyurethane acroleic acid dispersion (is purchased from Beyer Co., Ltd
2690 model of Bayhydrol UV XP): 40%, cosolvent (butyl glycol ether): 5%, nanofiller (nano silica):
7%, auxiliary agent (TEGO ViscoPlus 3060): 2%, photoinitiator (benzophenone): 2%, water: 4%.
3) micron order hole is etched into metallic surface with laser-induced thermal etching；
Dot matrix is designed, there is the Metal Substrate of peelable protective layer to surface using big nation's laser equipment EP-25S laser marking machine
Material is punched, aperture be 50 μm, pitch of holes be 200 μm, 500-600 μm of hole depth, laser power 25w.
4) metal surface is handled with chemical pretreatment solution, forms irregular inverted " t " font hole, specific steps are as follows:
A) sulfuric acid corrosion, sulfuric acid concentration 220g/L are first used, temperature is 25 DEG C, oxidization time 20min, passes through sulfuric acid corruption
Erosion device to hole carries out widening intensification；
B) substrate is cleaned with tap water, removes substrate and remain sulfuric acid, temperature is 25 DEG C；
C) microcorrosion is carried out to aperture using methylamine, the time is 8min, and temperature is 25 DEG C.
5) protective film is torn
Side is played with adhesive tape, tears peelable protective film, the preparation of surface porous metal is completed.
6) prepared surface porous metal substrate and plastics are subjected to integrated injection moulding, specific steps are as follows:
Surface porous metal is put into integrated injection mold, then there is the surface of hole to carry out the metal base
Injection-moulded plastic obtains metal and the integrated metallic composite A3 of plastics；Wherein, injection molding material is polycarbonate, injecting condition
Are as follows: 140-150 DEG C of mold temperature, 300 DEG C of melt adhesive temperature, injection pressure 120bar.
Embodiment 4
It carries out according to the method for embodiment 1, unlike, the aperture punched in step 3) is 30 μm, gets similarly gold
Belong to composite A 4.
Embodiment 5
It carries out according to the method for embodiment 1, unlike, the aperture punched in step 3) is 200 μm, gets similarly gold
Belong to composite A 5.
Test case 1
Using omnipotent pull-out test machine, according to the standard of GB/T228.1-2010 to metallic composite panel obtained above
A1-A5 carries out pull strength test, and result is shown in Table 1 below.
Table 1
| Pull strength (Mpa) | |
| A1 | 25 |
| A2 | 25.5 |
| A3 | 23.5 |
| A4 | 18 |
| A5 | 20 |
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of preparation method of metallic composite, which is characterized in that method includes the following steps:
1) peelable protective layer is formed in metallic substrate surface；
2) micron order hole is etched in metallic surface with laser-induced thermal etching；
3) metal surface is handled with chemical pretreatment solution；
4) protective layer is removed, and obtained surface porous metal substrate and plastics are subjected to integrated injection moulding,
Wherein, in step 3), carrying out processing to metal surface with chemical pretreatment solution includes:
(1) corroded with sulfuric acid, wherein sulfuric acid concentration 180-220g/L, the temperature of corrosion are 15-40 DEG C, etching time
For 15-20min；
(2) substrate is cleaned with water, removes remaining sulfuric acid on metal base；
(3) microcorrosion is carried out to aperture using methylamine, wherein corrosion temperature is 15-40 DEG C, etching time 5-8min.
2. according to the method described in claim 1, wherein, in step 1), by coating coating in metallic substrate surface and solidifying
To form the protective layer.
3. according to the method described in claim 2, wherein, the coating contains aliphatic anionic polyester type polyurethane dispersion
With light-cured type polyurethane acroleic acid dispersion.
4. according to the method described in claim 3, wherein, the film thickness of the coating is 30-60 μm；The cured condition packet
Include: baking temperature is 55-70 DEG C, and baking time 20-30min, UV energy is 1200-1500mj/m2。
5. according to the method described in claim 1, wherein, the material of the metal base is aluminium alloy or stainless steel.
6. according to the method described in claim 5, wherein, the metal base with a thickness of 1mm or more.
7. method described in any one of -6 according to claim 1, wherein in step 2), the micron order of laser-induced thermal etching formation
The aperture of hole is 20-200 μm, 50-200 μm of pitch of holes, 100-1000 μm of hole depth.
8. the aperture for the micron order hole that laser-induced thermal etching is formed is 50-150 μm according to the method described in claim 7, wherein,
50-200 μm of pitch of holes, 500-1000 μm of hole depth.
9. method described in any one of -6 according to claim 1, wherein in step 4), the plastics are polyethylene, poly- third
Alkene, polystyrene, polycarbonate, acrylonitrile-butadiene-phenylethylene, polyphenylene sulfide, polyamide, gathers polymethyl methacrylate
One of acid imide, polysulfones and polyether-ether-ketone are a variety of.
10. according to the method described in claim 9, wherein, in step 4), the condition of the injection molding includes: mold temperature 120-
150 DEG C, 280-350 DEG C of melt adhesive temperature, injection pressure 110-150bar.
11. method described in any one of -6 according to claim 1, wherein this method further includes in metallic substrate surface shape
Before peelable protective layer, the step of cleaning to metal base.
12. a kind of metallic composite, which is characterized in that prepared by method described in any one of claim 1-11
It obtains.
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| CN107599299A (en) * | 2017-08-31 | 2018-01-19 | 歌尔股份有限公司 | A kind of stainless steel of high-bond and the engaging member of plastics and its processing method |
| CN107650325A (en) * | 2017-08-31 | 2018-02-02 | 歌尔股份有限公司 | A kind of complex of stainless steel and plastics and preparation method thereof |
| CN109468047A (en) * | 2017-09-07 | 2019-03-15 | 比亚迪股份有限公司 | A kind of preparation method of peelable protective coating, coating and coating |
| CN108499826B (en) * | 2018-04-22 | 2021-05-04 | 湖州吉复新型材料科技有限公司 | Spraying and curing process of water-based UV (ultraviolet) coating |
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