CN104309056B - The manufacture method and metal-resin composite of metal-resin composite - Google Patents
The manufacture method and metal-resin composite of metal-resin composite Download PDFInfo
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- CN104309056B CN104309056B CN201310533719.7A CN201310533719A CN104309056B CN 104309056 B CN104309056 B CN 104309056B CN 201310533719 A CN201310533719 A CN 201310533719A CN 104309056 B CN104309056 B CN 104309056B
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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
-
- 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
- C25F3/08—Etching of refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C2045/1486—Details, accessories and auxiliary operations
- B29C2045/14868—Pretreatment of the insert, e.g. etching, cleaning
Abstract
The invention discloses a kind of manufacture method of metal-resin composite, this method includes：（1）Electrochemical corrosion is carried out to metallic matrix in the acid solution containing ferric trichloride；（2）The metallic matrix Jing Guo electrochemical corrosion is molded with thermoplastic resin composition, the metal-resin composite of integration is formed.Present invention also offers a kind of metal-resin composite prepared by above method.By using above-mentioned technical proposal, the adhesion of metallic matrix and resin can be significantly increased.And the method for the present invention is using floride-free technique, liquid waste processing, and the acid solution are easily carried out without heating, the volatility of solution is low, and the pollution to environment is small, energy-conserving and environment-protective.
Description
Technical field
The present invention relates to a kind of manufacture method of metal-resin composite, and the metal-resin manufactured using this method is answered
It is fit.
Background technology
At present, by metal（Usually Titanium or titanium alloy）The method being combined with resin mainly has three kinds, Yi Zhongshi
Using adhesive, acted on respectively with titanium alloy and molded resin by chemical adhesive, so that both be combined；Separately
One kind is to carry out chemical etching in titanium alloy surface, produces superminiature male and fomale(M＆F), then carry out injection combination；The third is to pass through
Mode or the electrochemical cathode processing of anodic oxidation, produce nano level hole in titanium alloy surface, pass through 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, and influence is final
The size of product；It is to ensure adhesion, it is necessary to which fluorine-containing corrosion is heated or used with concentrated acid by the way of chemical etching
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, high is required to production environment, belongs to the high-risk material of high pollution；By the way of anodic oxidation or electrochemical cathode processing,
Gained nano aperture is small, and oxide-film is very thin, causes nano aperture depth not enough, gained injecting products adhesion is low, practicality
It is not high.
Therefore, need badly and develop a kind of while taking into account the preparation with reference to dynamics, environment and the metal-resin composite of 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 small
Belong to the preparation method of 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 ferric trichloride；
（2）The metallic matrix Jing Guo electrochemical corrosion is molded with thermoplastic resin composition, integration is formed
Metal-resin composite.
On the other hand, the invention provides a kind of metal-resin composite prepared by above method.
By using above-mentioned technical proposal, metallic matrix is carried out to electrochemistry corruption in the acid solution containing ferric trichloride
Erosion, can form 1-200 microns of hole in the injection-molding surfaces of metallic matrix, and not form the part of hole to thicken to be formed
Nano-alumina film so that non-hole part can well be protected in corrosion process, and make surface have should
The metallic matrix of structure snd size is conducive to being combined with thermoplastic resin composition.Therefore, after to using above method processing
Metallic matrix when being subsequently molded, the adhesion of metallic matrix and resin can be significantly 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 heating, the volatility of solution is low, to environment
Pollute small, energy-conserving and environment-protective.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for 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.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of manufacture method of metal-resin composite, this method includes：
（1）Electrochemical corrosion is carried out to metallic matrix in the acid solution containing ferric trichloride；
（2）The metallic matrix Jing Guo electrochemical corrosion is molded with thermoplastic resin composition, integration is formed
Metal-resin composite.
According to the present invention, in step（1）In, electrochemistry is carried out to metallic matrix in the acid solution containing ferric trichloride
Corrosion, can have aperture to be micron order on the injection-molding surfaces formation surface of metallic matrix（For example, 1-200 microns）The metal of hole
Matrix；And described hole is in substrate surface dense distribution, while not forming the nano oxygen that hole portion branch generates one layer of thickening
Change film, can effectively prevent non-hole part to be corroded, so that product size is stable.In the present invention, in Metal Substrate
The aperture of the hole formed on body 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 the gross weight for stating acid solution, the content of ferric trichloride is 1-20 weight %, more preferably 5-15 weight %.
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, the non-oxidizing sour species is had 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 non-oxidizing sour content ensures that hydrionic concentration is in above-mentioned model in the acid solution
In enclosing, for example, the non-oxidizing sour content can be 0.1-20 weight %, preferably 1-15 weight %.In this hair
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）In described electrochemical corrosion course, with the gold
Belong to matrix as anode, make the region to be molded of metallic matrix towards negative electrode.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 for this area it is conventional be used for prepare 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 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 prepare titanium
The resin composite body of metal or titanium alloy metal.It is therefore preferred that the metallic matrix is titanium matrix or titanium alloy-based
Body.
In addition, according to the invention it is preferred in the case of, in step（1）Afterwards and in step（2）Before, this 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 exists in form of an aqueous solutions, by step（1）The metallic matrix obtained after processing is immersed in alkaline solution,
Make alkaline solution that step is completely covered（1）The metallic matrix obtained after processing.The alkali can be sour hydrogen sodium, saleratus, carbon
One or more in sour sodium, potassium carbonate, sodium hydroxide and potassium hydroxide.Under preferable case, the alkali is sodium carbonate.The table
The time of face processing 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 the thermoplastic containing 50-100 weight %
The fibrous material of property resin and 0-50 weight %.Under preferable case, the thermoplastic resin composition contains 70-95 weight % heat
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 is with passing through step（1）After processing
The volume ratio of the consumption of obtained metallic matrix can carry out accommodation according to the property of product.The method of the adjustment is this
Well known to art personnel, it will not be repeated here.
According to the present invention, in step（1）In, can also be to Metal Substrate before electrochemical corrosion is carried out to metallic matrix
Body carries out pre-treatment；The pretreatment process includes being cut into metallic matrix into 15mm × 80mm rectangle sheet, 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, the polishing machine that can often know for those skilled in the art, and the preparation to the present 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.
The present invention will be described in detail by embodiment below.
In following examples,
Use 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 and ceramic fibre are purchased from equal
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
The TA1 titanium plates and each one piece of TA2 titanium alloy sheets for taking thickness to be 0.8mm, are cut into 15mm × 80mm rectangle sheet,
The TA1 titanium plates and TA2 titanium alloy sheets are put into sanding and polishing in polishing machine respectively again, then, then successively carry out oil removing, wash with
And drying etc. pretreatment process, finally, prepare TA1 Titanium bases and TA2 titanium alloy substrates.
Embodiment 1
The present embodiment is used for illustrating the preparation method of the metal-resin composite of the present invention
（1）Electrochemical corrosion
The TA1 Titanium bases prepared in preparation example 1 are placed in ferric trichloride content for 10 weight %, the content of hydrochloric acid is 10 weights
In the acid solution for measuring %, using TA1 Titanium bases as anode, using graphite as negative electrode, and make the injection region direction of Titanium base cloudy
Pole plate.Be powered 12min under 10V voltages, then, takes out Titanium base, cleans drying, 5 weight % sodium carbonate liquor is put into afterwards
Middle immersion 10min；Titanium base is taken out again, drying is cleaned up.The aperture of the Titanium base is 1-150 microns.Its metallographic shows
Micro mirror picture is as shown in Figure 1.
（2）Injection
By it is above-mentioned after electrochemical corrosion course obtained by Titanium base be put into mould, with containing 20 weight % glass
The polyphenylene sulfide of fiber and 80 weight %（PPS）Thermoplastic resin composition be molded, and the thermoplastic resin group
The volume ratio of the consumption of compound and the consumption of the Titanium base is 1：1, obtain the Titanium base resin composite body S1 of integration.
Embodiment 2
The present embodiment is used for illustrating the preparation method of the metal-resin composite of the present invention
（1）Electrochemical corrosion
The TA1 Titanium bases prepared in preparation example 1 are placed in ferric trichloride content for 5 weight %, the content of phosphoric acid is 15 weights
In the acid solution for measuring %, using TA1 Titanium bases as anode, using graphite as negative electrode, and make the injection region direction of Titanium base cloudy
Pole plate.Be powered 10min under 8V voltages.Then, Titanium base is taken out, drying is cleaned, 10 weight % sodium carbonate liquor is put into afterwards
Middle immersion 5min；Titanium base is taken out again, drying is cleaned up.The aperture of the Titanium base is 1-100 microns.
（2）Injection
Above-mentioned resulting Titanium base after electrochemical corrosion course is put into mould, with containing, 5 weight % ceramics are fine
The thermoplastic resin composition of the weight % of peacekeeping 95 polybutylene terephthalate (PBT) resin is molded, and the thermoplasticity
The volume ratio of the consumption of resin combination and the consumption of the Titanium base is 1：1, obtain the Titanium base resin composite body of integration
S2。
Embodiment 3
The present embodiment is used for illustrating the preparation method of the metal-resin composite of the present invention
（1）Electrochemical corrosion
The TA2 titanium alloy substrates prepared in preparation example 1 are placed in ferric trichloride content for 15 weight %, the content of acetic acid is 1
In weight % acid solution, using TA2 titanium alloy substrates as anode, using graphite as negative electrode, and make the injection region of Titanium base
Towards minus plate.Be powered 12min under 12V voltages, then, takes out titanium alloy substrate, cleans drying, is put into 1 weight %'s afterwards
20min is soaked in sodium carbonate liquor；Titanium alloy substrate is taken out again, drying is cleaned up.The aperture of the Titanium base is 1-100
Micron.
（2）Injection
By it is above-mentioned after electrochemical corrosion course obtained by titanium alloy substrate be put into mould, with containing 30 weight % silicon
The thermoplastic resin composition of sour aluminum fiber and 70 weight % polyamide is molded to be molded with carrying out containing 70 weight %, and
The polyphenylene sulfide（PPS）The volume ratio of consumption of consumption and the titanium alloy substrate be 1：1, obtain the titanium of integration
Alloy substrate resin composite body S3.
Embodiment 4
Metallic matrix resin composite body S4 is prepared according to preparation method same as Example 1, the difference is that in electrochemistry
During, with the acid solution prepared（The mixed solution of ferric trichloride and hydrochloric acid）Gross weight on the basis of, ferric trichloride
Content is 1 weight %, and the content of hydrochloric acid is 20 weight %.The hole of gained Titanium base injection-molding surfaces is 1-200 microns.
Embodiment 5
Metallic matrix resin composite body S5 is prepared according to preparation method same as Example 1, the difference is that in electrochemistry
During, with the acid solution prepared（The mixed solution of ferric trichloride and hydrochloric acid）Gross weight on the basis of, ferric trichloride
Content is 20 weight %, and the content of hydrochloric acid is 0.1 weight %.The hole of gained Titanium base injection-molding surfaces is 1-100 microns.
Embodiment 6
Metallic matrix resin composite body S6 is prepared according to preparation method same as Example 1, unlike, the acidity
Non-oxidizing acid is not contained in solution, is only the solution of ferric trichloride.The hole of gained Titanium base injection-molding surfaces is that 1-100 is micro-
Rice.
Embodiment 7
Metallic matrix resin composite body S7 is prepared according to preparation method same as Example 1, unlike, the acidity
It is that a kind of non-oxidizing acid is 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 for illustrating the metal-resin composite of reference.
By the TA1 Titanium bases prepared in preparation example 1 directly polyphenyl of the injection containing 20 weight % glass fibres and 80 weight %
Sulfide resin（PPS）Thermoplastic resin composition, obtain integration Titanium base resin composite body DS1.The Titanium base note
Modeling face is without pore space structure.Its metallographic microscope picture is as shown in Figure 2.
Comparative example 2
This comparative example is used for the manufacture method for illustrating the metal-resin composite of reference.
Metallic matrix resin composite body DS2 is prepared according to preparation method same as Example 1, by TA1 Titanium bases with containing
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, with rough mat surface.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, unlike, in 500ml
Containing in 10 weight % phosphoric acid electrolytes to TA1 Titanium bases carry out anodic oxidation.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,
It is fixed on universal testing machine and carries out extension test, average shear force can regards titanium alloy-based as in test result
The size of adhesion between body 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 | 14.41 | S7 | 11.67 |
| S2 | 11.27 | ||
| S3 | 10.85 | ||
| S4 | 14.16 | DS1 | Come off |
| S5 | 11.69 | DS2 | 9.21 |
| S6 | 10.53 | DS3 | 7.63 |
The Titanium base that is prepared in embodiment 1-7 it can be seen from the data of table 1 or titanium alloy substrate resin S1-S7's is flat
Titanium base resin DS1-DS3 of the equal shearing force than being prepared in comparative example 1-3 average shear force is significantly improved, and illustrates the present invention's
Titanium base or the adhesion of titanium alloy substrate and resin prepared by method is excellent, 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 in the preparation process using the method for the present invention, institute
Acid solution is stated without heating, and the acid solution concentration is low, nontoxic, the pollution to environment is small, energy-conserving and environment-protective.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of 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 embodiment, in not lance
In the case of shield, it 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 no longer separately illustrates.
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 equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of manufacture method of metal-resin composite, this method includes：
(1) electrochemical corrosion is carried out to metallic matrix in the acid solution containing ferric trichloride, with the injection of metallic matrix
Face forms micron-sized hole, and does not form in the injection-molding surfaces of metallic matrix the nano-alumina film that the part of hole is formed；
(2) metallic matrix Jing Guo electrochemical corrosion is molded with thermoplastic resin composition, forms the metal of integration
Resin composite body；
Wherein, in step (1), in the acid solution also contain non-oxidizing acid, using the gross weight of the acid solution as
Benchmark, the non-oxidizing sour content is 0.1-20 weight %；
Wherein, the metallic matrix is titanium matrix or titanium alloy substrate；
Wherein, after the step (1) and before step (2), this method also include by the metallic matrix after electrochemical corrosion with
The step of alkali is contacted.
2. according to the method described in claim 1, wherein, in step (1), on the basis of the gross weight of the acid solution, three
The content of iron chloride is 1-20 weight %.
3. according to the method described in claim 1, wherein, it is described it is non-oxidizing acid be hydrochloric acid, oxalic acid, phosphoric acid and acetic acid in
It is one or more.
4. the method according to any one in claim 1-3, wherein, in the electrochemical corrosion course described in step (1)
In, using the metallic matrix as anode, make the region to be molded of metallic matrix towards negative electrode, and the electrochemical corrosion course
Operating condition include：Voltage is 2-18V, and the time is 2-24min.
5. according to the method described in claim 1, wherein, the alkali exists in the form of aqueous slkali, the concentration of the aqueous slkali
For 1-10 weight %；The time contacted with alkali is 1-30min.
6. method according to claim 1 or 5, wherein, the alkali is sodium acid carbonate, saleratus, sodium carbonate, carbonic acid
One or more in potassium, sodium hydroxide and potassium hydroxide.
7. according to the method described in claim 1, wherein, in step (2), the thermoplastic resin composition contain 50-100 weight
Measure % thermoplastic resin and 0-50 weight % fibrous material.
8. method according to claim 7, 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.
9. metal-resin composite 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, which has in the micron order hole that aperture is 1-200 microns, the micron order hole, to be filled with
Thermoplastic resin composition；
The metallic matrix is titanium matrix or titanium alloy substrate.
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| CN108501306A (en) * | 2018-04-04 | 2018-09-07 | 广州凯腾新材料科技有限公司 | The method of metal and resin-bonded |
| CN116463028A (en) * | 2023-04-06 | 2023-07-21 | 郑州艾洁环保设备科技有限公司 | Preparation method of metal surface anti-corrosion coating |
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|---|---|---|---|---|
| CN1113969A (en) * | 1994-05-31 | 1995-12-27 | 中国科学院大连化学物理研究所 | Surface treatment method for titanium matrix metal electrode |
| CN102229266A (en) * | 2010-06-10 | 2011-11-02 | 鸿富锦精密工业（深圳）有限公司 | Compound of aluminum or aluminum alloy and plastics and manufacturing method thereof |
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| CN85102762B (en) * | 1985-04-01 | 1987-03-04 | 大连工学院 | Electrochemical method for producing thermal-conducting elements with porous surfaces |
| CN101422947A (en) * | 2007-10-30 | 2009-05-06 | 光宝科技股份有限公司 | Heterogeneous combination structure of aluminum alloy and plastics and treatment method thereof |
| CN102345125A (en) * | 2010-07-28 | 2012-02-08 | 比亚迪股份有限公司 | Method for forming multilayer patterns on surface of metal base material |
| CN102672878A (en) * | 2011-03-14 | 2012-09-19 | 鸿富锦精密工业（深圳）有限公司 | Stainless steel and resin compound and manufacturing method thereof |
| CN103895161A (en) * | 2012-12-28 | 2014-07-02 | 比亚迪股份有限公司 | Preparation method of stainless steel-resin composite and stainless steel-resin composite prepared by same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113969A (en) * | 1994-05-31 | 1995-12-27 | 中国科学院大连化学物理研究所 | Surface treatment method for titanium matrix metal electrode |
| CN102229266A (en) * | 2010-06-10 | 2011-11-02 | 鸿富锦精密工业（深圳）有限公司 | Compound of aluminum or aluminum alloy and plastics and manufacturing method thereof |
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