CN106881813A - 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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- CN106881813A CN106881813A CN201510946787.5A CN201510946787A CN106881813A CN 106881813 A CN106881813 A CN 106881813A CN 201510946787 A CN201510946787 A CN 201510946787A CN 106881813 A CN106881813 A CN 106881813A
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- metallic
- metal
- metal base
- protective layer
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Classifications
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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
Abstract
The present invention relates to metallic composite field, a kind of metallic composite and preparation method thereof is disclosed.The preparation method of metallic composite of the invention is comprised 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 processed with chemical pretreatment solution；4) protective layer is removed, and the surface porous metal base material that will be obtained carries out integrated injection moulding with plastics.The bond strength of plastics and metal can be effectively improved by the preparation method of metallic composite provided by the present invention.
Description
Technical field
The present invention relates to a kind of metallic composite and preparation method thereof.
Background technology
In recent years, metal receives much concern with the seamless composite of plastics integrated injection molding, is enhancing
Adhesion between two kinds of materials, can form metallic substrate surface and not advise by chemically treated method
Then hole then carries out integrated injection moulding with plastics again.The method for forming hole in metal surface has two
Kind, one is the metal base of porous surface is formed by powder metallurgy sintered technology or anodic oxidation, then
Chemical pretreatment solution activating surface is carried out to metal base, so as to carry out strong combination with plastics；
And for the metal base of stainless steel series, one layer of densification can be formed in substrate surface during anodized
Oxide-film, it is impossible to form effective porous in metal surface.Traditional stainless steel and Plastic composite body
Preparation method, fixes with plastic products again generally by attachment 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 to metal
Base material carries out the method that chemical pretreatment solution activating surface prepares surface porous metal, is closed generally be directed to aluminium
Gold, and powder metallurgy sintered technology processing apparatus are complicated, it is relatively costly, it is not easy to realize.It is traditional
Stainless steel structure part increases the connection method that attachment structure is fixed with plastic products again, due to stainless steel processing
Efficiency is low, high cost, and cannot make the more complicated structure of shape, it is difficult to be widely used.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of new metallic composite
Preparation method and its metallic composite for preparing, can be effectively improved by the method for the present invention
The bond strength of plastics and metal.
To achieve these goals, the present invention provides a kind of preparation method of metallic composite, wherein,
The method is comprised 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 processed with chemical pretreatment solution；
4) protective layer is removed, and the surface porous metal base material that will be obtained carries out integrated injection moulding with plastics.
The present invention also provides a kind of metallic composite prepared by the above method.
According to the present invention, corrosion resistant protective layer is formed in metal surface by using Stripable paint, led to
The hole that laser-induced thermal etching etches micron dot matrix in metallic substrate surface is crossed, then by chemical pretreatment solution to micropore
Inside is widened, and the pore structure for preparing surface is the porous metal substrate of inverted " t " font, with powder
The metallurgy sintered technology in end, anodic oxidation and chemical etching are compared, and technique is simpler, it is easy to accomplish, and
And, due to that can form the pore structure of inverted " t " font on surface, carrying out injection to it can be effectively
Improve the bond strength of plastics and metal.In addition, the technology goes for the gold such as aluminium alloy, stainless steel
Category, it is applied widely.Due in preparation engineering, corrosion resistant protective layer being formed in metal surface, because
This, can also arbitrarily protect the non-processing face part of metal base from scuffing, corrosion in processed etc..
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation method of metallic composite, wherein, the method is comprised 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 processed with chemical pretreatment solution；
4) protective layer is removed, and the surface porous metal base material that will be obtained carries out integrated injection moulding with plastics.
According to the present invention, the material of the metal base is aluminium alloy or stainless steel.Preferably, the gold
The thickness for belonging to base material is more than 1mm, it is highly preferred that the thickness of the metal base is 1-10mm.
By the method for the present invention, it is to be applied to aluminium alloy, is also applied for stainless steel, and it uses scope
It is wider.
, according to the invention it is preferred in the case of, the method is additionally included in metallic substrate surface and forms peelable
Before protective layer, the step of cleaning to metal base.
The step of cleaning for example can be：Electrochemical deoiling treatment is carried out to metal base with cleaning agent,
The greasy dirt of metal surface is removed, wherein, the temperature of oil removal treatment can be 60-80 DEG C, the time for the treatment of
It is 1-3min.Preferably 1-2min is cleaned after electrochemical deoiling treatment is carried out to metal base with cleaning agent with water
To remove residual cleaning agent on metal base.
Above-mentioned cleaning agent can with commercially available, for example can the model of Shi Lijie bodyguards company 504 degreaser.
In accordance with the present invention it is preferred that, it is described by being formed in metallic substrate surface coating coating and solidification
Protective layer.
It is preferably as the coating and contains aliphatic anionic polyester type polyurethane dispersion and photocuring
The coating of type polyurethane acrylic acid dispersion.Coating of the invention gathers by by aliphatic anionic polyester type
Urethane dispersion and light-cured type polyurethane acroleic acid dispersion compound form according to a certain ratio, thus poly-
Rigid structure is introduced in urethane resin, the dense coating of crosslinking high is formed again by photocuring, film is not
But can strong alkali-acid resistance, and with stronger toughness, elasticity, mechanical strength and temperature tolerance, thus
Metallic substrate surface can be prevented to be corroded and scratch in follow-up processing procedure.
It is highly preferred that the composition and percentage by weight of above-mentioned coating are：The poly- ammonia of aliphatic anionic polyester type
Ester dispersion：30-60%；Light-cured type polyurethane acroleic acid dispersion：30-60%；Cosolvent：5-15%；
Nano filling：3-12%；Auxiliary agent：1-5%；Light trigger：1-3%；Water：0-5%；Further preferably
Ground, the composition and percentage by weight of above-mentioned coating are：Aliphatic anionic polyester type polyurethane dispersion：
30-50%；Light-cured type polyurethane acroleic acid dispersion：30-50%；Cosolvent：5-15%；Nanometer is filled out
Material：3-7%；Auxiliary agent：2-3%；Light trigger：2-3%；Water：3-4%.
Above-mentioned aliphatic anionic polyester type polyurethane dispersion can for example be purchased from Beyer Co., Ltd
The models of Bayhydrol UH 2342.
Above-mentioned light-cured type polyurethane acroleic acid dispersion can for example be purchased from the Bayhydrol of Beyer Co., Ltd
The models of UV XP 2690.
Above-mentioned cosolvent can be butyl glycol ether, propylene glycol monomethyl ether and dipropylene glycol methyl ether in one kind or
It is various.
Above-mentioned Nano filling can be Nano-meter SiO_22, Nano-meter CaCO33, nanometer Al2O3And nano-TiO2
In one or more.
Above-mentioned auxiliary agent can be one or more in thickener, defoamer and wetting dispersing agent etc..It is described
Thickener, defoamer and wetting dispersing agent can be various thickeners, defoamer commonly used in the art
And wetting dispersing agent.Thickener is preferably in them.The thickener for example can be TEGO
ViscoPlus 3060, TEGO ViscoPlus 3060 can be purchased from three liters of Foshan trade Co., Ltd.
Above-mentioned light trigger can be benzophenone, diphenylhydroxyethanone, benzil, 1- hydroxy cyclohexylphenyls
One or more of base Benzophenone (I184), monoacylphosphine oxides and double acylphosphine oxides, preferably two
Benzophenone.
By the protective layer formed using above-mentioned coating, protective layer can either be played a part of, additionally it is possible to
The method torn by hand in subsequent step simply removes protective layer.Above-mentioned protective layer is inventor through excessive
The preferred scheme found after amount experiment, those skilled in the art can also use other conventional protective layer materials
Material, the present invention is not specifically limited.
According to the present invention, the method that coating is coated on the metal base has no particular limits, can be with
It is various methods commonly used in the art, for example, can is dip-coating, showering or spraying etc., the present invention preferably makes
With spraying.
Thickness for coating is preferably 30-60 μm, more preferably 35-55 μm.
Additionally, the condition of the solidification includes：Baking temperature is 55-70 DEG C, baking time 20-30min,
UV energy is 1200-1500mj/m2。
According to the present invention, step 2) in, the aperture of the micron order hole that laser-induced thermal etching is formed is
20-200 μm, 50-200 μm of pitch of holes, 100-1000 μm of hole depth；Preferably, laser-induced thermal etching is formed
Micron order hole aperture be 50-150 μm, 50-200 μm of pitch of holes, 500-1000 μm of hole depth；
It is highly preferred that the aperture of the micron order hole of laser-induced thermal etching formation is 50-100 μm, pitch of holes
100-200 μm, 500-1000 μm of hole depth.
For step 2) used in laser equipment there is no particular limitation, as long as can be formed above-mentioned
Such hole.Preferably, using big nation's laser equipment EP-25S laser marking machines to Metal Substrate
Material is punched.
For the condition of laser-induced thermal etching, also there is no particular limitation, as long as hole as described above can be formed
.Preferably, the laser power is 15-25w.
In accordance with the present invention it is preferred that, step 3) in, metal surface is processed with chemical pretreatment solution
Metal surface is corroded using corrosive liquid specially.
It is highly preferred that step 3) in, carrying out treatment to metal surface with chemical pretreatment solution includes：
(1) corroded with sulfuric acid, wherein, sulfuric acid concentration is 180-220g/L, and the temperature of corrosion is
15-40 DEG C, etching time is 15-20min；
(2) base material is cleaned with water, removes the sulfuric acid remained on metal base；
(3) microcorrosion is carried out to aperture using methylamine, wherein, corrosion temperature is 15-40 DEG C, during corrosion
Between be 5-8min.
The inventors found that by first using sulfuric acid corrosion, then with the method for methylamine microcorrosion, can
Hole is widened, irregular inverted " t " font hole is formed, it is possible thereby to significantly improve what is obtained
The inter-layer bonding force of plastics and metal level in metallic composite.
According to the present invention, it is necessary to remove protective layer after being processed metal surface with chemical pretreatment solution.
Because protective layer used in the present invention is peelable protective layer, therefore when protective layer is removed, it is only necessary to use
Hand tears protective layer.
According to the present invention, step 4) in, the plastics can be various plastics commonly used in the art.
Such as described plastics be polyethylene, polypropylene, polymethyl methacrylate, polystyrene, makrolon,
In acrylonitrile-butadiene-phenylethylene, polyphenylene sulfide, polyamide, polyimides, polysulfones and polyether-ether-ketone
One or more.
In step 4 of the invention) in, during injection, the surface porous metal base material that will be obtained is put into one
Change in injection mold, the surface for then having hole to the base material carries out injection-moulded plastic.
The condition of above-mentioned injection can be various conditions commonly used in the art.Preferably, the injection
Condition include：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 composite prepared by the above method.
Below will the present invention will be described in detail by embodiment.
Embodiment 1
1) with cleaning agent (being purchased from the model of Li Jie bodyguards company 504) to metal base (aluminium alloy, thickness
It is 1mm) electrochemical deoiling treatment is carried out, the greasy dirt of metal surface is removed, wherein, the temperature of cleaning is
70 DEG C, the time is 2min；Then 2min is cleaned with running water；
2) peelable protective coating is sprayed to metallic substrate surface and peelable protective layer is formed after solidifying,
Wherein, the thickness of spraying is 35-45 μm；The condition of solidification is：60 DEG C of baking temperature, baking time
30min, UV energy 1300mj/m2；
The paint ingredient and percentage by weight for using be：Aliphatic anionic polyester type polyurethane dispersion
(being purchased from the models of Beyer Co., Ltd Bayhydrol UH 2342)：30%, light-cured type polyurethane acroleic acid point
A prose style free from parallelism (is purchased from the models of Beyer Co., Ltd Bayhydrol UV XP 2690)：50%, cosolvent (ethylene glycol
Butyl ether)：10%, Nano filling (nano silicon)：3%, auxiliary agent (thickener TEGO ViscoPlus
3060, three liters of Foshan trade Co., Ltd is purchased from, same as below)：2%, light trigger (benzophenone)：
2%, water：3%.
3) it is etched into micron order hole in metallic surface with laser-induced thermal etching；
Design dot matrix, has peelable protection to surface using big nation's laser equipment EP-25S laser marking machines
The metal base of layer is punched, and aperture is 50 μm, and pitch of holes is 100 μm, 500-800 μm of hole depth,
Laser power 20w.
4) metal surface is processed with chemical pretreatment solution, forms irregular inverted " t " font hole,
Concretely comprise the following steps：
A) sulfuric acid corrosion is first used, sulfuric acid concentration is 200g/L, and temperature is 25 DEG C, and oxidization time is 18min,
Carry out widening intensification by sulfuric acid corrosion device to hole；
B) base material is cleaned with running water, removes base material residual sulfuric acid, cleaning temperature is 25 DEG C；
C) microcorrosion is carried out to aperture using methylamine, etching time is 8min, and temperature is 25 DEG C.
5) diaphragm is torn
Side is played with adhesive tape, peelable protective film is torn, the preparation of surface porous metal is completed.
6) prepared surface porous metal base material and plastics are carried out into integrated injection moulding, is concretely comprised the following steps：
Surface porous metal is put into integrated injection mold, then there is the surface of hole to the base material
Injection-moulded plastic is carried out, the metal metallic composite A1 integrated with plastics is obtained；Wherein, injection molding material
It is polyphenylene sulfide, injecting condition is：140-150 DEG C of mold temperature, 300 DEG C of melt adhesive temperature, injection pressure
Power 130bar.
Embodiment 2
1) with cleaning agent (being purchased from the model of Li Jie bodyguards company 504) to metal base (aluminium alloy, thickness
It is 1mm) electrochemical deoiling treatment is carried out, the greasy dirt of metal surface is removed, wherein, the temperature of cleaning is
70 DEG C, the time is 2min；Then 2min is cleaned with running water；
2) peelable protective coating is sprayed to metallic substrate surface and peelable protective layer is formed after solidifying,
Wherein, the thickness of spraying is 45-50 μm；The condition of solidification is：60 DEG C of baking temperature, baking time
30min, UV energy 1300mj/m2；
The paint ingredient and percentage by weight for using be：Aliphatic anionic polyester type polyurethane dispersion
(being purchased from the models of Beyer Co., Ltd Bayhydrol UH 2342)：50%, light-cured type polyurethane acroleic acid point
A prose style free from parallelism (is purchased from the models of Beyer Co., Ltd Bayhydrol UV XP 2690)：30%, cosolvent (ethylene glycol
Butyl ether)：6%, Nano filling (nano silicon)：5%, auxiliary agent (TEGO ViscoPlus 3060)：
3%, light trigger (benzophenone)：2%, water：4%.
3) it is etched into micron order hole in metallic surface with laser-induced thermal etching；
Design dot matrix, has peelable protection to surface using big nation's laser equipment EP-25S laser marking machines
The metal base of layer is punched, and aperture is 100 μm, and pitch of holes is 200 μm, hole depth
700-1000 μm, laser power 25w.
4) metal surface is processed with chemical pretreatment solution, forms irregular inverted " t " font hole,
Concretely comprise the following steps：
A) sulfuric acid corrosion is first used, sulfuric acid concentration is 220g/L, and temperature is 25 DEG C, and oxidization time is 20min,
Carry out widening intensification by sulfuric acid corrosion device to hole；
B) base material is cleaned with running water, removes base material residual 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) diaphragm is torn
Side is played with adhesive tape, peelable protective film is torn, the preparation of surface porous metal is completed.
6) prepared surface porous metal base material and plastics are carried out into integrated injection moulding, is concretely comprised the following steps：
Surface porous metal is put into integrated injection mold, then there is hole to the metal base
Surface carries out injection-moulded plastic, obtains the metal metallic composite A2 integrated with plastics；Wherein, note
Plastics are makrolon, and injecting condition is：140-150 DEG C of mold temperature, 300 DEG C of melt adhesive temperature, note
Injection pressure 120bar.
Embodiment 3
1) with cleaning agent (being purchased from the model of Li Jie bodyguards company 504) to metal base (stainless steel, thickness
It is 1mm) electrochemical deoiling treatment is carried out, the greasy dirt of metal surface is removed, wherein, the temperature of cleaning is
70 DEG C, the time is 2min；Then 2min is cleaned with tap water；
2) peelable protective coating is sprayed to metallic substrate surface and peelable protective layer is formed after solidifying,
Wherein, the thickness of spraying is 50-55 μm；The condition of solidification is：60 DEG C of baking temperature, baking time
30min, UV energy 1400mj/m2；
The paint ingredient and percentage by weight for using be：Aliphatic anionic polyester type polyurethane dispersion
(being purchased from the models of Beyer Co., Ltd Bayhydrol UH 2342)：40%, light-cured type polyurethane acroleic acid point
A prose style free from parallelism (is purchased from the models of Beyer Co., Ltd Bayhydrol UV XP 2690)：40%, cosolvent (ethylene glycol
Butyl ether)：5%, Nano filling (nano silicon)：7%, auxiliary agent (TEGO ViscoPlus 3060)：
2%, light trigger (benzophenone)：2%, water：4%.
3) it is etched into micron order hole in metallic surface with laser-induced thermal etching；
Design dot matrix, has peelable protection to surface using big nation's laser equipment EP-25S laser marking machines
The metal base of layer is punched, and aperture is 50 μm, and pitch of holes is 200 μm, 500-600 μm of hole depth,
Laser power 25w.
4) metal surface is processed with chemical pretreatment solution, forms irregular inverted " t " font hole,
Concretely comprise the following steps：
A) sulfuric acid corrosion is first used, sulfuric acid concentration is 220g/L, and temperature is 25 DEG C, and oxidization time is 20min,
Carry out widening intensification by sulfuric acid corrosion device to hole；
B) base material is cleaned with running water, removes base material residual 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) diaphragm is torn
Side is played with adhesive tape, peelable protective film is torn, the preparation of surface porous metal is completed.
6) prepared surface porous metal base material and plastics are carried out into integrated injection moulding, is concretely comprised the following steps：
Surface porous metal is put into integrated injection mold, then there is hole to the metal base
Surface carries out injection-moulded plastic, obtains the metal metallic composite A3 integrated with plastics；Wherein, note
Plastics are makrolon, and injecting condition is：140-150 DEG C of mold temperature, 300 DEG C of melt adhesive temperature, note
Injection pressure 120bar.
Embodiment 4
Method according to embodiment 1 is carried out, unlike, step 3) in punching aperture be 30 μm,
Similarly obtain metallic composite A4.
Embodiment 5
Method according to embodiment 1 is carried out, unlike, step 3) in punching aperture be 200 μm,
Similarly obtain metallic composite A5.
Test case 1
Using omnipotent pull-out test machine, according to the standard of GB/T228.1-2010 to metal obtained above
Composite board A1-A5 carries out pull strength test, and its 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 described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (12)
1. a kind of preparation method of metallic composite, it is characterised in that the method is comprised 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 processed with chemical pretreatment solution；
4) protective layer is removed, and the surface porous metal base material that will be obtained carries out integrated injection moulding with plastics.
2. method according to claim 1, wherein, step 1) in, by metal base table
Face coating coating and solidification forms the protective layer.
3. method according to claim 2, wherein, the coating contains aliphatic anion and gathers
Ester type dispersions of polyurethanes and light-cured type polyurethane acroleic acid dispersion.
4. method according to claim 3, wherein, the thickness of the coating is 30-60 μm；
The condition of the solidification includes：Baking temperature is 55-70 DEG C, baking time 20-30min, UV energy
It is 1200-1500mj/m2。
5. method according to claim 1, wherein, the material of the metal base is aluminium alloy
Or stainless steel；
Preferably, the thickness of the metal base is more than 1mm.
6. the method according to any one in claim 1-5, wherein, step 2) in, laser
The aperture for etching the micron order hole for being formed is 20-200 μm, 50-200 μm of pitch of holes, hole depth
100-1000μm；
Preferably, the aperture of the micron order hole that laser-induced thermal etching is formed is 50-150 μm, pitch of holes
50-200 μm, 500-1000 μm of hole depth.
7. method according to claim 1, wherein, step 3) in, with chemical pretreatment solution to gold
Metal surface is processed specially to be corroded using corrosive liquid to metal surface.
8. the method according to any one in claim 1-5 and 7, wherein, step 3) in,
Carrying out treatment to metal surface with chemical pretreatment solution includes：
(1) corroded with sulfuric acid, wherein, sulfuric acid concentration is 180-220g/L, and the temperature of corrosion is
15-40 DEG C, etching time is 15-20min；
(2) base material is cleaned with water, removes the sulfuric acid remained on metal base；
(3) microcorrosion is carried out to aperture using methylamine, wherein, corrosion temperature is 15-40 DEG C, during corrosion
Between be 5-8min.
9. the method according to any one in claim 1-5, wherein, step 4) in, it is described
Plastics are fine polyethylene, polypropylene, polymethyl methacrylate, polystyrene, makrolon, propylene
One kind in-butadiene-styrene, polyphenylene sulfide, polyamide, polyimides, polysulfones and polyether-ether-ketone
Or it is various.
10. method according to claim 9, wherein, step 4) in, the condition of the injection
Including：120-150 DEG C of mold temperature, 280-350 DEG C of melt adhesive temperature, injection pressure 110-150bar.
11. method according to any one in claim 1-5, wherein, the method is additionally included in
Before metallic substrate surface forms peelable protective layer, the step of cleaning to metal base.
12. a kind of metallic composites, it is characterised in that by any one in claim 1-11
Described method is prepared.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108499826A (en) * | 2018-04-22 | 2018-09-07 | 湖州吉复新型材料科技有限公司 | A kind of waterborne UV coating spraying curing process |
| 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 |
| CN112209334A (en) * | 2020-10-13 | 2021-01-12 | 深圳迪致科技术有限公司 | Micropore preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516598A (en) * | 2006-09-19 | 2009-08-26 | 诺基亚公司 | Plastic-acceptor hybrid components |
| CN101634018A (en) * | 2008-07-27 | 2010-01-27 | 比亚迪股份有限公司 | Selective chemical plating method for plastic base material |
| CN102442028A (en) * | 2010-10-13 | 2012-05-09 | 鸿富锦精密工业（深圳）有限公司 | Manufacturing method for compound of metal and resin |
| CN103507203A (en) * | 2012-06-25 | 2014-01-15 | 比亚迪股份有限公司 | Metal-resin composite and preparation method thereof |
| CN103582329A (en) * | 2012-07-24 | 2014-02-12 | 富泰华工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN104325597A (en) * | 2013-10-31 | 2015-02-04 | 比亚迪股份有限公司 | Metal-resin complex and preparation method thereof |
-
2015
- 2015-12-16 CN CN201510946787.5A patent/CN106881813B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101516598A (en) * | 2006-09-19 | 2009-08-26 | 诺基亚公司 | Plastic-acceptor hybrid components |
| CN101634018A (en) * | 2008-07-27 | 2010-01-27 | 比亚迪股份有限公司 | Selective chemical plating method for plastic base material |
| CN102442028A (en) * | 2010-10-13 | 2012-05-09 | 鸿富锦精密工业（深圳）有限公司 | Manufacturing method for compound of metal and resin |
| CN103507203A (en) * | 2012-06-25 | 2014-01-15 | 比亚迪股份有限公司 | Metal-resin composite and preparation method thereof |
| CN103582329A (en) * | 2012-07-24 | 2014-02-12 | 富泰华工业（深圳）有限公司 | Shell and manufacturing method thereof |
| CN104325597A (en) * | 2013-10-31 | 2015-02-04 | 比亚迪股份有限公司 | Metal-resin complex and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108499826A (en) * | 2018-04-22 | 2018-09-07 | 湖州吉复新型材料科技有限公司 | A kind of waterborne UV coating spraying curing process |
| CN112209334A (en) * | 2020-10-13 | 2021-01-12 | 深圳迪致科技术有限公司 | Micropore preparation method |
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| CN106881813B (en) | 2019-05-14 |
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