CN104309054B - Preparation method of metal-resin composite, and metal-resin composite - Google Patents
Preparation method of metal-resin composite, and metal-resin composite Download PDFInfo
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- CN104309054B CN104309054B CN201310530988.8A CN201310530988A CN104309054B CN 104309054 B CN104309054 B CN 104309054B CN 201310530988 A CN201310530988 A CN 201310530988A CN 104309054 B CN104309054 B CN 104309054B
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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
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
- B29C45/14795—Porous or permeable material, e.g. foam
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/14—Etching locally
-
- 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
Abstract
The invention discloses a preparation method of a metal-resin composite. The method comprises the steps of carrying out electrochemical corrosion on a metal substrate in an acid solution containing chloride and oxide; and then carrying out injection molding on the electrochemically corroded metal substrate by using a thermoplastic resin composition to form an integrated metal-resin composite. The invention also provides the metal-resin composite prepared by the above method. With the above technical solution, a binding force between the metal substrate and the resin can be significantly enhanced. A fluoride-free technology is adopted by the method provided by the invention; a waste solution can be treated easily; the acid solution is in no need of heating; and volatility of the solution is low. The method has small pollution to environment and is energy-saving and environment-friendly.
Description
Technical field
The present invention relates to a kind of manufacture method of metal-resin composite, and it is multiple using the metal-resin of the method manufacture
It is fit.
Background technology
At present, by metal（Usually Titanium or titanium alloy）The method combined with resin mainly has three kinds, Yi Zhongshi
Using adhesive, acted on titanium alloy and molded resin respectively by chemical adhesive, so as to both be combined；Separately
One kind is to carry out chemical etching in titanium alloy surface, produces superminiature male and fomale(M＆F), then carries out injection combination；The third is to pass through
Anodised mode or electrochemical cathode are processed, and in titanium alloy surface nano level hole is produced, by this hole and modeling
Material injection is combined.
But using the method for adhesive, adhesion is poor, not acid and alkali-resistance, and adhesive has certain thickness, affects final
The size of product；It is to ensure adhesion by the way of chemical etching, needs with concentrated acid heating or using fluorine-containing corrosion
Liquid, time-consuming, high energy consumption for the mode of concentrated acid heating, and acid solution evaporative emission environment, using fluorine-containing corrosive liquid, due to the poison of fluorine
Property it is big, it is high to producing environmental requirement, belong to the high-risk material of high pollution；By the way of anodic oxidation or electrochemical cathode are processed,
Gained nano aperture is little, and oxide-film is very thin, causes nano aperture depth not enough, and gained injecting products adhesion is low, practicality
It is not high.
Therefore, exploitation is needed badly a kind of while taking into account the preparation of the metal-resin composite with reference to dynamics, environment and time
Method.
The content of the invention
The invention aims to provide the gold for realizing that adhesion is excellent, practicality is high and environmental pollution is little
The preparation method of category resin composite body.
To achieve these goals, on the one hand, the invention provides a kind of manufacture method of metal-resin composite, the party
Method includes：
（1）Electrochemical corrosion is carried out to metallic matrix in the acid solution containing chloride and oxidant；
（2）The metallic matrix through electrochemical corrosion is molded with thermoplastic resin composition, forms integration
Metal-resin composite.
On the other hand, the invention provides a kind of metal-resin composite prepared by above method.
By adopting above-mentioned technical proposal, metallic matrix is carried out in the acid solution containing chloride and oxidant electricity
Chemical attack, can metallic matrix injection-molding surfaces formed 1-200 microns hole, and do not form the part of hole being capable of shape
Into the oxide-film for thickening so that non-hole part can be protected well in corrosion process, and surface has this
The metallic matrix of structure and size is conducive to being combined with thermoplastic resin composition.Therefore, after to being processed using said method
Metallic matrix when being subsequently molded, the adhesion of metallic matrix and resin can be dramatically increased.And the method for the present invention is adopted
Floride-free technique is used, liquid waste processing, and the acid solution is easily carried out without the need for heating, the volatility of solution is low, to environment
Pollute little, energy-conserving and environment-protective.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the metallographic microscope picture of the titanium resin composite body prepared according to the method for embodiment 1.
Fig. 2 is the metallographic microscope picture of the titanium resin composite body prepared according to the method for comparative example 1.
Fig. 3 is the metallographic microscope picture of the titanium resin composite body prepared according to the method for comparative example 2.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of manufacture method of metal-resin composite, the method includes：
（1）Electrochemical corrosion is carried out to metallic matrix in the acid solution containing chloride and oxidant；
（2）The metallic matrix through electrochemical corrosion is molded with thermoplastic resin composition, forms integration
Metal-resin composite.
According to the present invention, in step（1）In, metallic matrix is carried out in the acid solution containing chloride and oxidant
Electrochemical corrosion, it is micron order that form surface can have aperture in the injection-molding surfaces of metallic matrix（For example, 1-200 microns）Hole
Metallic matrix；And described hole is in substrate surface dense distribution, while not forming one layer of thickening of hole portion branch generation
Nano-alumina film, can be effectively prevented non-hole part and be corroded, so that product size is stable.In the present invention, exist
The aperture of the hole formed on metallic matrix refers to the size of the maximum gauge of the hole.
In addition, in step（1）In, under preferable case, in order to further strengthen the adhesion of metallic matrix and resin, with institute
On the basis of stating the gross weight of acid solution, the muriatic content is 1-20 weight %, more preferably 5-15 weight %；The oxygen
The content of agent is 1-20 weight %, more preferably 5-15 weight %.
The present invention has no particular limits to the muriatic species, as long as not affecting the process of electrochemical corrosion i.e.
Can.In the case of preferred, the chloride is one or more in sodium chloride, potassium chloride, ferric trichloride and aluminium chloride.
The present invention also has no particular limits to the species of the oxidant, as long as not affecting the process of electrochemical corrosion i.e.
Can, and effectively can be corroded the metallic matrix.In order to improve the oxidisability of acid solution with to Metal Substrate
Body is preferably corroded, it is preferred in the case of, the oxidant is strong oxidizer.The strong oxidizer, for example, can be
One or more in hydrogen oxide, Na2Fe04, persulfate and hypochlorite.The persulfate can be sodium peroxydisulfate
And/or potassium peroxydisulfate；The hypochlorite can be sodium hypochlorite and/or postassium hypochlorite.
It was found by the inventors of the present invention that when also containing non-oxidizing sour in the acid solution, can be further
Realize the purpose of the present invention.Wherein, to it is described it is non-oxidizing acid species have no particular limits, for example, can for hydrochloric acid,
One or more in oxalic acid, phosphoric acid and acetic acid.
As long as in addition, the content of the non-oxidizing acid ensures that hydrionic concentration is in above-mentioned model in the acid solution
In enclosing, for example, the content of the non-oxidizing acid can be 0.1-20 weight %, preferably 0.5-5 weight %.At this
It is bright it is a kind of preferred embodiment in, it is described it is non-oxidizing acid be hydrochloric acid.
According to one kind of the invention preferred embodiment, in step（1）The electrochemical corrosion course in, with the gold
Category matrix makes the region to be molded of metallic matrix towards negative electrode as anode.The negative electrode can be in electrochemical corrosion course
Conventional various negative electrodes, in the present invention, negative electrode is preferably graphite.
According to the present invention, the operating condition of electrochemical corrosion course can be this area it is conventional for preparing metal-resin
The condition of complex, for example, the operating condition of the electrochemical corrosion course can include：Voltage is 2-18V, preferably 8-
12V, the time is 2-24min, preferably 10-12min.
According to the present invention, the metallic matrix is not particularly limited, what is can be known in the art is various for resin
The metallic matrix and its alloy substrate of injection.But it was found by the inventors of the present invention that method of the invention is particularly suitable for preparing titanium
The resin composite body of metal or titanium alloy.It is therefore preferred that the metallic matrix is titanium matrix or titanium alloy substrate.
In addition, according to the invention it is preferred in the case of, in step（1）Afterwards and in step（2）Before, the method also includes
The step of metallic matrix after electrochemical corrosion is contacted with alkali, to further enhance the adhesion of metallic matrix and resin.Letter
Dan Di, the alkali is present in form of an aqueous solutions, by step（1）The metallic matrix obtained after process is immersed in alkaline solution,
Make alkaline solution that step is completely covered（1）The metallic matrix obtained after process.The alkali can be sour hydrogen sodium, saleratus, carbon
One or more in sour sodium, potassium carbonate, NaOH and potassium hydroxide.Under preferable case, the alkali is sodium carbonate.The table
The time that face is processed can be 1-30min；Preferably 5-20min.The concentration of the alkaline solution can be 1-10 weight %.
According to the present invention, in step（2）In, the thermoplastic resin composition can be containing the thermoplastic of 50-100 weight %
The fibrous material of property resin and 0-50 weight %.Under preferable case, the thermoplastic resin composition contains the heat of 70-95 weight %
The fibrous material of plastic resin and 5-30 weight %.
According to the present invention, various thermoplastic resins that the thermoplastic resin and fibrous material can be known in the art and
Fibrous material, for example, the thermoplastic resin can be polyphenylene sulfide, polybutylene terephthalate (PBT) resin, polyamides
One or more in amine, polycarbonate and polyolefin；The fibrous material can be ceramic fibre, glass fibre, alumina silicate
One or more in fiber and polyester fiber.
According to the present invention, in step（2）In, the consumption of the thermoplastic resin composition with through step（1）After process
The volume ratio of the consumption of the metallic matrix for obtaining can carry out accommodation according to the property of product.The method of the adjustment is this
Well known to art personnel, will not be described here.
According to the present invention, in step（1）In, before electrochemical corrosion is carried out to metallic matrix, can also be to Metal Substrate
Body carries out pre-treatment；The pretreatment process includes for metallic matrix being cut into the rectangle sheet of 15mm × 80mm, then respectively should
Metallic matrix is put into sanding and polishing in polishing machine, then, then carries out the processes such as oil removing, washing and drying successively.In the present invention
In, the polishing machine is not particularly limited, and can be the polishing machine that those skilled in the art often know, and to preparation of the invention
Method prepare metal-resin composite be polished, oil removing, washing and dry all be not particularly limited, can be this area
Technology known to technical staff.
On the other hand, present invention also offers the metal-resin composite prepared by above method.
According to the present invention, the metal-resin composite includes metallic matrix and the thermoplastic being combined as a whole with metallic matrix
Property resin combination.
According to the present invention, the surface of the metallic matrix has the micron order hole that aperture is 1-200 microns, the micron
Thermoplastic resin composition is filled with level hole.
According to the present invention, the metallic matrix is preferably titanium matrix or titanium alloy substrate.
Hereinafter the present invention will be described in detail by embodiment.
In following examples and comparative example,
Using universal testing machine（Purchased from Ying Site, model 3369）Characterize cutting for metallic matrix prepared by the present invention
Shear force；
Polishing machine is purchased from permanent safe, model 883；
Polyphenylene sulfide, polybutylene terephthalate (PBT) resin, polyamide, glass fibre, ceramic fibre and silicic acid
Aluminum fiber is purchased from and is purchased from Qi get engineering plastics Co., Ltd；
Metallic titanium plate and titanium alloy sheet belong to Materials Co., Ltd, model TA1 and TA2 purchased from port ancient sacrificial bronze ware.
Preparation example 1
Take TA1 titanium plates and TA2 titanium alloy sheets that thickness is 0.8mm each one piece, be cut into the rectangle sheet of 15mm × 80mm,
Respectively the TA1 titanium plates and TA2 titanium alloy sheets be put into into sanding and polishing in polishing machine again, then, then carry out successively oil removing, washing with
And drying etc. pretreatment process, finally, prepare TA1 Titanium bases and TA2 titanium alloy substrates.
Embodiment 1
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
（1）Electrochemical corrosion
It is 10 weights that the TA1 Titanium bases prepared in preparation example 1 are placed in into sodium chloride content for 10 weight %, sodium peroxydisulfate content
Amount %, the content of hydrochloric acid is in the acid solution of 1 weight %, using TA1 Titanium bases as anode, using graphite as negative electrode, and to make titanium
The injection region of matrix is towards minus plate.Be powered 12min under 10V voltages, subsequently, takes out Titanium base, cleans and dries up, Zhi Houfang
10min is soaked in the sodium carbonate liquor for entering 5 weight %；Titanium base is taken out again, is cleaned up and is dried up.The aperture of the Titanium base
For 1-150 microns.Its metallographic microscope picture is as shown in Figure 1.
（2）Injection
Above-mentioned resulting Titanium base after electrochemical process is put in mould, with containing 20 weight % glass fibres
With the polyphenylene sulfide of 80 weight %（PPS）Thermoplastic resin composition be molded, and the thermoplastic resin composition
Consumption and the consumption of the Titanium base volume ratio be 1：1, obtain the Titanium base resin composite body S1 of integration.
Embodiment 2
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
（1）Electrochemical corrosion
It is 5 weight % that the TA1 Titanium bases prepared in preparation example 1 are placed in into ferric trichloride content, and the content of sodium hypochlorite is 15
Weight %, the content of phosphoric acid is in the acid solution of 5 weight %, using TA1 Titanium bases as anode, using graphite as negative electrode, and to make
The injection region of Titanium base is towards minus plate.Be powered 10min under 8V voltages.Subsequently, Titanium base is taken out, cleans and dry up, afterwards
It is put in the sodium carbonate liquor of 10 weight % and soaks 5min；Titanium base is taken out again, is cleaned up and is dried up.The hole of the Titanium base
Footpath is 1-100 microns.
（2）Injection
Above-mentioned resulting Titanium base after electrochemical process is put in mould, with containing 5 weight % ceramic fibres and
The thermoplastic resin composition of the polybutylene terephthalate (PBT) resin of 95 weight % is molded, and the thermoplastic resin
The consumption of composition is 1 with the volume ratio of the consumption of the Titanium base：1, obtain the Titanium base resin composite body S2 of integration.
Embodiment 3
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
（1）Electrochemical corrosion
It is 5 that the TA2 titanium alloy substrates prepared in preparation example 1 are placed in into KCE content for 15 weight %, content of hydrogen peroxide
Weight %, the content of acetic acid is in the acid solution of 0.5 weight %, using TA2 titanium alloy substrates as anode, using graphite as the moon
Pole, and the injection region of titanium alloy substrate is made towards minus plate.Be powered 12min under 12V voltages, subsequently, takes out titanium alloy-based
Body, cleans and dries up, and is put into afterwards in the sodium carbonate liquor of 1 weight % and soaks 20min；Titanium alloy substrate is taken out again, is cleaned up
Dry up.The aperture of the Titanium base is 1-150 microns.
（2）Injection
Above-mentioned resulting titanium alloy substrate after electrochemical process is put in mould, with containing 30 weight % silicic acid
The thermoplastic resin composition of the polyamide of aluminum fiber and 70 weight % is molded to be molded with the carrying out containing 70 weight %, and institute
State polyphenylene sulfide（PPS）Consumption and the consumption of the titanium alloy substrate volume ratio be 1：1, the titanium for obtaining integration is closed
Auri body resin composite body S3.
Embodiment 4
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
Metallic matrix resin composite body S4 is prepared according to preparation method same as Example 1, except for the difference that in electrochemistry
During, on the basis of the gross weight of the acid solution prepared, sodium chloride content is 1 weight %, sodium peroxydisulfate content is 20 weights
Amount %, the content of hydrochloric acid is 10 weight %.The hole of gained Titanium base injection-molding surfaces is 1-200 microns.
Embodiment 5
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
Metallic matrix resin composite body S5 is prepared according to preparation method same as Example 1, except for the difference that in electrochemistry
During, on the basis of the gross weight of the acid solution prepared, sodium chloride content is 20 weight %, sodium peroxydisulfate content is 1 weight
Amount %, the content of hydrochloric acid is 0.1 weight %.The hole of gained Titanium base injection-molding surfaces is 1-100 microns.
Embodiment 6
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
Metallic matrix resin composite body S6, except for the difference that, the acidity are prepared according to preparation method same as Example 2
Non-oxidizing acid is not contained in solution, is only ferric trichloride and the solution of sodium hypochlorite.The hole of gained Titanium base injection-molding surfaces
For 1-100 microns.
Embodiment 7
The present embodiment is used for the preparation method of the metal-resin composite for illustrating the present invention
Metallic matrix resin composite body S7, except for the difference that, the acidity are prepared according to preparation method same as Example 1
It is a kind of non-oxidizing sour for phosphoric acid in solution.The hole of gained Titanium base injection-molding surfaces is 1-100 microns.
Comparative example 1
This comparative example is used for the manufacture method of the metal-resin composite for illustrating reference.
The TA1 Titanium bases prepared in preparation example 1 are directly molded into the polyphenyl containing 20 weight % glass fibres and 80 weight %
Sulfide resin（PPS）Thermoplastic resin composition, obtain the Titanium base resin composite body DS1 of integration, Titanium base note
Modeling face is without hole.Its metallographic microscope picture is as shown in Figure 2.
Comparative example 2
This comparative example is used for the manufacture method of the metal-resin composite for illustrating reference.
Prepare metallic matrix resin composite body DS2 according to preparation method same as Example 1, by TA1 Titanium bases with contain
The ammonium hydrogen fluoride solution for having 1 weight % carries out chemical attack, and chemical attack condition includes：Temperature is 25 DEG C, and the time is 12min.Institute
It is non-pore space structure to obtain Titanium base injection-molding surfaces, is rough matsurface.Its metallographic microscope picture is as shown in Figure 3.
Comparative example 3
Metallic matrix resin composite body DS3 is prepared according to preparation method same as Example 1, except for the difference that, in 500ml
Containing carrying out anodic oxidation to TA1 Titanium bases in 10 weight % phosphoric acid electrolytes.Anodic oxidation voltage is 20V, and the time is 10min.
The hole of gained Titanium base injection-molding surfaces is 10-100 nanometers.
Test case
After metallic matrix resin composite body resulting in above-described embodiment 1-7 and comparative example 1-3 is stood into 24 hours,
Being fixed on universal testing machine carries out extension test, and average shear force can regard titanium base as in test result
The size of the adhesion between body or titanium alloy substrate and resin.Test result is as shown in table 1.
Table 1
| Metal-resin composite | Average shear force（MPa） | Metal-resin composite | Average shear force（MPa） |
| S1 | 12.89 | S7 | 12.09 |
| S2 | 11.48 | ||
| S3 | 11.26 | DS1 | Come off |
| S4 | 12.44 | DS2 | 9.21 |
| S5 | 10.28 | DS3 | 7.63 |
| S6 | 10.08 |
The flat of the Titanium base for preparing in embodiment 1-7 or titanium alloy substrate resin S1-S7 is can be seen that by the data of table 1
The average shear force of Titanium base resin DS1-DS3 of the shearing force than preparing in comparative example 1-3 is significantly improved, and illustrates the present invention's
Titanium base or titanium alloy substrate prepared by method is excellent with the adhesion of resin, that is to say, that prepared using the method for the present invention
Titanium base or titanium alloy substrate resin composite body adhesion it is excellent；And using in the preparation process of the method for the present invention, institute
Acid solution is stated without the need for heating, and the acid solution concentration is low, nontoxic, the pollution to environment is little, energy-conserving and environment-protective.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, the present invention range of the technology design in, various simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as it is without prejudice to this
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of manufacture method of metal-resin composite, the method includes：
(1) electrochemical corrosion is carried out to metallic matrix in the acid solution containing chloride and oxidant；So that electrochemistry is rotten
The metal base surface of erosion has the micron order hole that aperture is 1-200 microns；
(2) metallic matrix through electrochemical corrosion is molded with thermoplastic resin composition, forms the metal of integration
Resin composite body；
Wherein, after step (1) and before step (2), the method also include by the metallic matrix after electrochemical corrosion with
The step of alkali is contacted；
Wherein, in step (1), the one kind or many of the chloride in sodium chloride, potassium chloride, ferric trichloride and aluminium chloride
Kind；The oxidant is selected from one or more in hydrogen peroxide, Na2Fe04, persulfate and hypochlorite；
Wherein, in step (1), on the basis of the gross weight of the acid solution, the muriatic content is 1-20 weight %；
The content of the oxidant is 1-20 weight %；Also contain non-oxidizing acid in the acid solution, with the acid solution
Gross weight on the basis of, it is described it is non-oxidizing acid content be 0.1-20 weight %.
2. method according to claim 1, wherein, the non-oxidizing acid is in hydrochloric acid, oxalic acid, phosphoric acid and acetic acid
One or more.
3. method according to claim 1 and 2, wherein, in step (1) electrochemical corrosion course, with the gold
Category matrix makes the region to be molded of metallic matrix towards negative electrode as anode, and the operating condition of the electrochemical corrosion course
Including：Voltage is 2-18V, and the time is 2-24min.
4. method according to claim 1, wherein, the alkali in the form of aqueous slkali, the concentration of the aqueous slkali
For 1-10 weight %；The time contacted with alkali is 1-30min.
5. the method according to claim 1 or 4, wherein, the alkali is sodium acid carbonate, saleratus, sodium carbonate, carbonic acid
One or more in potassium, NaOH and potassium hydroxide.
6. method according to claim 1, wherein, in step (2), the thermoplastic resin composition contains 50-100 weights
The thermoplastic resin of amount % and the fibrous material of 0-50 weight %.
7. method according to claim 6, wherein, the thermoplastic resin is polyphenylene sulfide, poly terephthalic acid
One or more in butanediol ester resin, polyamide, polycarbonate and polyolefin；The fibrous material is ceramic fibre, glass
One or more in glass fiber, aluminium silicate fiber peacekeeping polyester fiber.
8. method according to claim 1, wherein, the metallic matrix is titanium matrix or titanium alloy substrate.
9. the metal-resin composite that prepared by the method according to any one in claim 1-8.
10. metal-resin composite according to claim 9, wherein,
The metal-resin composite includes metallic matrix and the thermoplastic resin composition being combined as a whole with metallic matrix；
The surface of the metallic matrix has the micron order hole that aperture is 1-200 microns, is filled with the micron order hole
Thermoplastic resin composition；
The metallic matrix is titanium matrix or titanium alloy substrate.
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| CN106894010B (en) * | 2015-12-17 | 2019-10-11 | 比亚迪股份有限公司 | Metal surface treating composition, metal-resin complex and preparation method thereof |
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| CN106917129B (en) * | 2017-01-16 | 2019-01-04 | 歌尔股份有限公司 | The engaging member and its processing method of stainless steel and plastics |
| JP6967953B2 (en) * | 2017-11-30 | 2021-11-17 | 日本パーカライジング株式会社 | Etching agent for roughening the surface of a base material whose surface is at least all or part of aluminum or an aluminum alloy, a method for producing a roughened base material, a roughened base material, a base material-a cured resin product. Manufacturing method of the bonded body and the bonded body of the base material-resin cured product |
| CN112342604A (en) * | 2020-09-25 | 2021-02-09 | 深圳市裕展精密科技有限公司 | Metal product and preparation method thereof, and metal composite and preparation method thereof |
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