CN108995128A

CN108995128A - A kind of preparation method of high stable metal material of the surface coated with resin

Info

Publication number: CN108995128A
Application number: CN201810661451.8A
Authority: CN
Inventors: 白林森; 梁莲芝
Original assignee: Wuxi City Hengli Hong Kong Ltd
Current assignee: Wuxi City Hengli Hong Kong Ltd
Priority date: 2018-06-25
Filing date: 2018-06-25
Publication date: 2018-12-14
Anticipated expiration: 2038-06-25
Also published as: CN108995128B

Abstract

The present invention provides the preparation methods that a kind of surface is coated with the high stable metal material of resin, mainly there are pretreatment, anodic oxidation, surface coating corrosion-resistant finishes, laser fluting, electrochemical corrosion, freeze-drying, chemical attack, heat treatment to remove moisture and coating in metal base, the porosity of the metal surface of acquisition is high, moisture is low, the binding force of nanometer casting resin and metal base is strong, stability is high, and fluctuation is small.

Description

A kind of preparation method of high stable metal material of the surface coated with resin

Technical field

The present invention relates to field of metal surface treatment, it is related to a kind of aluminium and aluminium alloy surface treatment method, to obtain one kind High density holes aluminum or aluminum alloy metal base, and the method in metal-surface nano injection molding.

Background technique

Japanese great achievement plastics (Taiseiplas) Co., Ltd. has invented nanometer forming technique (NMT), the skill in 2002 Art be by metal and the integrated nanometer forming technique of plastics, can by metal and resin integrated molding, be widely used in it is thin it is light, On the shell of portable mobile electronic product, such as computer terminal, cell phone.

Now in the art, the treatment process of NMT includes process as follows: the metal for needing to combine is carried out at lye Reason, sour processing, ester propylhomoserin weak acid treatment are dried after washing with water again completely, are molded.Metal surface after processing, just It can countless apertures be formed in metal surface be about 20nm micropore, that is to say, that may be considered by treated metal Many small concaveconvex structures are formd on surface, the resin of injection enters in these concaveconvex structures, generates anchoring effect.Wherein Acid processing and rouge propylhomoserin weak acid treatment step are two steps of most critical, wherein the main purpose of acid processing are as follows: (a) removes metal watch The extra lye in face；(b) a large amount of etch pits are formed on the metal surface, and the formation of the etch pit is mainly due to acid and metal Corrosion reaction, the formation in hole place one's entire reliance upon the composition phase and impurity phase of metal base, due to metal surface composition phase and Impurity phase is different to the corrosion rate of acid, directly results in the etch pit of metal surface, and corrosion pore size distribution is mixed and disorderly, unordered, and duct is deep Spend different, completely disordered state；Therefore will lead to causes the resin of metal surface at uneven, shakiness in nanometer injection moulding process Fixed, the big and deep local gumminess in hole is good, and the small and shallow local gumminess in hole is poor, eventually lead to its mechanical property, fatigue durability, There is more apparent defect in impact flexibility, good heat resistance and moulding processability, secondly, the hole after corrosion is nanometer Grade, not for naked eyes as it can be seen that in nanometer injection molding, resin hardly enters nano pore, and the binding force of metal and resin is caused to decline.

Secondly, such as the CN201711254332 patent of the applicant's Wuxi City Heng Lihong Industrial Co., Ltd., denomination of invention: A kind of method of high-bond aluminum or aluminum alloy nano surface injection molding can be changed using repeatedly corrosion, pre-etching in this method Kind surface state decides the density and distribution of etch pit, and direct current is powered and corrodes and can be formed in metal surface with a fixed length The micron-nanometer etch pit of degree and aperture；The further device to hole inner wall of direct current energization anticaustic is corroded, and unordered receive is formed Rice inner wall hole, repeatedly after corrosion, the duct naked eyes of formation are as it can be seen that duct penetrates through each other, and hole wall is connected, and etch pit is more, duct Aperture is more moderate, most important to binding force, but obtain micron order hole be completely it is unordered, eventually lead to its peel strength limit It is made as 250-290kgf/cm²In range, peel strength is to be improved, secondly CN201711256603A patent, denomination of invention one The method of kind metal-surface nano injection molding, prepare orderly micron order hole by preparing template: specific steps (1) use The natural oxide layer of one of polishing, polishing, tumbling, sandblasting or ball blast processing method removing metal-surface nano grade；(2) will Treated metal is soaked in alkali metal cleaning solution and cleans；(3) pure water is washed, and is dried；(4) in metallic substrate surface Covering W metal, Cr, Cu or its alloy corrosion resistant metal template, the metal form are divided into white space and metallic region；(5) to The substrate surface physical sputtering corrosion resistant metal of metal form in step (4)；(6) corrosion resistant metal template is removed, object will be passed through Metal substrate after managing sputter process immerses in acid corrosion liquid, is repeatedly corroded to substrate, corrodes equally distributed micron out Grade etch pit, pure water washing, wherein corrosion number >=1；(7) metal base after corrosion is soaked in and mainly contains rouge propylhomoserin In weak acid solution, equally distributed micron order corrosion inner surfaces of pores formed 20-80nm nano-pore, then pure water washing, It is dried；(8) nanometer injection molding is carried out to substrate, penetrates into resin in duct by injection molding.Although obtaining orderly micron Grade hole, but still face following problems: (1) corrosion-resistant splash-proofing sputtering metal can not effectively remove, and will affect binding force and the later period is steady It is qualitative；(2) template preparation difficulty is big, and equipment cost is higher；(3) process is tedious, limitation operation.

The patent of invention CN106363869 A of Bao Yuanjin Industrial Co., Ltd. of Shenzhen provides one kind in metal base The method of surface formation nano aperture, comprising the following steps: 1) by metal base titanium hanger；2) oil removing；3) it washes；4) sour Erosion；5) it washes；6) it neutralizes；7) it washes；8) first time electrolytic etching；9) it washes；10) adhesion is handled；11) it washes；12) second Electrolytic etching；13) it washes；14) chelation treatment；15) hot water wash；16) it dries.It is described to form nano aperture in metallic substrate surface Method in conjunction with nanometer plastic raw material of method and liquid metal, realize in the uniform nano grade pore of metallic substrate surface Hole is molded to realize metal base in conjunction with plastic cement nanosizing by nanometer plastic raw material (PPS, PBT), and binding force intensity reaches To 200KGF/CM²More than, due to electrolytic etching acquisition be unordered hole, the intensity of binding force is general, stability also can not with it is equal The duct of even distribution is identical to mention in the same breath, as the patent of invention CN105500600 (1) of Biyadi Co Ltd uses sulfuric acid, lemon Two or more mix acid liquor in lemon acid and phosphoric acid pre-processes metallic matrix, and forming surface has irregularly Corrode the metallic matrix of hole；(2) metallic matrix after pretreatment is put into alkaline solution and carries out electrochemical corrosion, there is corruption The width in borrosion hole hole, the corrosion hole is 100-50000nm, and depth 100-50000nm also faces identical problem.

In addition, the patent of invention CN104325597 A of Biyadi Co Ltd provides a kind of metal-resin composite Preparation method, method includes the following steps: (1) to metallic matrix carry out laser ablation, formed surface have micron order hole The metallic matrix in hole；(2) there is the metallic matrix of micron order hole to be put into acid solution the surface and carries out electrochemistry Corrosion；(3) metallic matrix obtained after step (2) processing is put into mold, is infused with thermoplastic resin composition Modeling, forms integrated metal-resin composite.Method system by the way that laser processing and electrochemical corrosion will be used to combine The excellent metal-resin composite of binding force is obtained, not only overcomes and is unable to roll in converted products using the processing of individual laser Rake angle is greater than the face of 180 degree, and overcomes using individual electrochemical corrosion process velocity relatively slow, corrosion depth not enough etc. Defect, although laser ablation can obtain equally distributed hole in substrate surface, duct inner wall surface is smooth, actually unfavorable In the fastening of nanometer casting resin and duct, that is, it is unfavorable for the raising of binding force.The binding force of such as patent of invention is inevitable not Such as the binding force that the preparation method of CN101607446 A obtains, this method enables aluminum alloy to surface and generates 1 μm of size or more, depth At least 1 μm of hole, this hole have staggering and multilayer, are conducive to thermoplastic resin and are attached on aluminium alloy.Work as melting Thermoplastic resin when batch overlaying on aluminum alloy surface, the thermoplastic resin of melting pours into these multi-layer intercrossed micron order holes, Thermoplastic resin cooling and solidifying to be melted, aluminium alloy and thermoplastic resin utilize these multi-layer intercrossed micron order holes tightly Clasp each other, and because of the staggered characteristic of hole, aluminium alloy will not remove with thermoplastic resin because of thermal expansion coefficient difference, production The aluminium alloy of a raw high bond strength and the combination of thermoplastic resin.

In addition, in the prior art there is also using heat treatment to make a return journey the moisture in oxide film dissolving, to improve resin and receive Long-time stability between metre hole, the surface treated aluminum material as disclosed in UACJ Corporation's Hasegawa true one and its manufacturing method and Surface treated aluminum material/resin layer conjugant (CN106460221A), by heat treatment so that moisture contained by oxidation overlay film In 10 μ g/cm²(i.e. 100mg/m²) hereinafter, its heat treatment mode: since processing terminate for alternating current electrolysis, super until being exposed to Cross formed in 150 DEG C of atmosphere oxidation overlay film aluminium surface temperature reach 150 DEG C until time within 24 hours, The moisture in oxidation film can not be effectively removed, and the moisture in oxidation film is actually higher than 10 μ g/cm², i.e., described existing Method in technology by moisture in heat treatment removal oxidation duct is still to be improved, is based on the content, the present invention provides Heat treatment is improved, and is used for foramen magnum-mesoporous etch pit nanometer injection molding art.

Summary of the invention

Based on the above-mentioned problems of the prior art, the present invention provides a kind of aluminium and aluminium alloy surface treatment method, with A kind of high density holes aluminum or aluminum alloy metal base, and the method being molded in metal-surface nano are obtained, wherein the method Simply, conveniently the hole density of metal surface can be effectively improved, and improves the binding force (removing of nanometer casting resin and substrate Intensity), specific as follows:

A kind of aluminum or aluminum alloy metal surface treating method, the metal is by following processing: pretreatment-surface coating is corrosion-resistant Coating-laser fluting-electrochemical corrosion-freeze-drying-chemical attack-heat treatment removes moisture and painting in metal base Layer, wherein heat treatment step are as follows: the metal base Jing Guo chemical attack is placed in volume fraction as 2 ~ 5%H₂/N₂In mixed atmosphere, Temperature Programmed Processes are 15^oC/min rises to 160^oC, 0.5 ~ 2h of soaking time, then 5^oC/min rises to 365^oC, soaking time 2 ~ 3h, then 20^oC/min rises to 500^oC, 0.5 ~ 1h of soaking time, gaseous mixture purging are down to room temperature, the metal surface finally obtained Macropore and chemical attack containing electrochemical corrosion it is mesoporous, wherein the pore diameter range of macropore be 1-200 μm, the hole depth 10 of macropore ~ 90 μm, mesoporous pore diameter range is 2-40nm, and moisture is lower than 30mg/m²。

Further, the pore diameter range of the macropore is 50 ~ 60 μm, and mesoporous pore diameter range is 10-20nm.

Further, the pretreatment is that alkaline degreasing pre-processes, and alkaline degreaser is by 30g/L sodium carbonate, 30g/L phosphoric acid Trisodium, 15g/L sodium metasilicate and deionized water composition, treatment temperature 50^oC；Or acid deoiling pretreatment, acid deoiling agent by The sulfuric acid of the d of 100ml/L=1.84,25g/L OP emulsifier and deionized water composition, treatment temperature is room temperature；

It further, further include that one of polishing, polishing, tumbling, sandblasting or ball blast remove aluminium or aluminium conjunction before electrochemical deoiling Gold surface nanoscale natural oxide layer.

Further, coating corrosion-resistant finishes in the surface is thermoplastic resin coating, as polyvinyl chloride, polystyrene, One of polyethylene, polypropylene, polyamide, coating method be spraying, coating with a thickness of 5-20 μm.

Further, the groove obtained by laser is uniformly distributed containing well-regulated on cated metal base, recessed The aperture of slot is 1-200 μm, and the depth of groove is greater than or equal to the thickness of surface coating corrosion-resistant finishes, to expose substrate gold Belong to, for conduction, the parameter of laser fluting: electric current 5-10A, frequency 2-4KHz.

Further, the process of the electrochemical corrosion macropore are as follows: using the metal Jing Guo pre-etching as anode, graphite is made For cathode, while being soaked in hybrid corrosion liquid, connect DC power supply, the hybrid corrosion liquid include 1 ~ 3wt.% hydrochloric acid, 0.5 ~ 1wt.% sulfuric acid, 0.2 ~ 1wt.% oxalic acid and 0.1 ~ 0.15 wt.%AlCl₃Solution, auxiliary has ultrasound in direct current energization corrosion process Processing, 40 ~ 100KHz of supersonic frequency, temperature 30 ~ 40^oC, 3 ~ 5min of time, current density 50-200mA/cm², then pure water is washed It washs, the corrosion macropore of acquisition and groove aperture are in the same size, and the aperture of the macropore is 1-200 μm, and depth is 10-90 μm.

Further, the step of freeze-drying are as follows: the metal base after electrochemical corrosion is placed in temperature lower than 0^oC Freezer or refrigerator in 0.5 ~ 5h, be subsequently placed in freeze drier, vacuum degree be lower than 10 Pa, condenser temperature be -50^oC Under conditions of be freeze-dried 0.5 ~ 5 h, remove hole in moisture.

Further, the mesoporous process of the chemical attack is that will be put into T liquid to soak by the metallic matrix of freeze-drying Bubble forms the mesoporous of chemical attack by corrosion on macropore hole wall, and the main component of the T liquid is rouge propylhomoserin.

Then the aluminum or aluminum alloy substrate surface above method prepared carries out nanometer injection molding, the specific steps are as follows: (1) it mechanically polishes；(2) electrochemical deoiling；(3) surface coats corrosion-resistant finishes；(4) laser fluting exposes aluminum or aluminum alloy gold Belong to；(5) to the part for exposing aluminum or aluminum alloy metal, electrochemical corrosion is carried out, obtains macropore；(6) it is freeze-dried；(7) chemical Corrosion obtains mesoporous；(8) heat treatment removes the moisture and coating in metal base；(9) nanometer is molded, wherein the nanometer is molded Resin melt temperature be 200~300 DEG C, the temperature of nanometer injection molding is 70~90 DEG C, the pressure of the injection molding is 70 ~ The speed of 130Mpa, the nanometer injection molding are 400~900mm/s.

Further, wherein heat treatment step are as follows: it is 2 ~ 5% that the metal base Jing Guo chemical attack, which is placed in volume fraction, H₂/N₂Temperature programming, Temperature Programmed Processes 15 are carried out in mixed atmosphere^oC/min rises to 160^oC, 0.5 ~ 2h of soaking time, so Afterwards 5^oC/min rises to 365^oC, 2 ~ 3h of soaking time, then 20^oC/min rises to 500^oC, soaking time 0.51h, gaseous mixture purging It is down to room temperature.

Further, the mechanical polishing is selected from one of polishing, polishing, tumbling, sandblasting or ball blast, for removing aluminium Or aluminum alloy surface nanoscale natural oxide layer,

Further, the electrochemical deoiling includes alkaline degreasing or acid deoiling, wherein alkaline degreaser by 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L sodium metasilicate and deionized water composition, treatment temperature 50^oC；Acid deoiling agent by 100ml/L d= 1.84 sulfuric acid, 25g/L OP emulsifier and deionized water composition, treatment temperature is room temperature；

Further, the surface coating corrosion-resistant finishes is thermoplastic resin coating, such as polyvinyl chloride, polystyrene, poly- second One of alkene, polypropylene, polyamide, coating method be spraying, coating with a thickness of 5-20 μm.

Further, the metal base after electrochemical corrosion the freeze-drying: is placed in temperature lower than 0^oThe freezer of C or 0.5 ~ 5h in refrigerator, is subsequently placed in freeze drier, is lower than 10 Pa in vacuum degree, condenser temperature is -50^oUnder conditions of C It is freeze-dried 0.5 ~ 5 h, removes the moisture in hole.

It is obtained in above-mentioned surface treatment and is equipped with chemical attack on equally distributed electrochemical corrosion macropore and macropore hole wall On the basis of mesoporous, further process of surface treatment is advanced optimized, obtains a kind of aluminum or aluminum alloy of high density holes Material, the high density holes metal base have the following structure, and the hole includes mesoporous and macropore, described mesoporous to be divided into anode It is mesoporous to aoxidize mesoporous and chemical attack, Anodic Oxidation is mesoporous to be distributed between macropore and macropore, the mesoporous distribution of chemical attack On the hole wall of macropore, the macropore, which is uniformly distributed in, to be obtained with aluminum or aluminum alloy surface, the macropore by electrochemical corrosion, Its Anodic Oxidation mesoporous pore size range is 10-90nm, and the mesoporous pore diameter range of chemical attack is 2-40nm, macropore diameter range It is 1-200 μm, 10 ~ 90 μm of the hole depth of macropore, the hole density on the aluminum or aluminum alloy surface is 10⁸-10¹⁰A/cm², aluminium or aluminium The moisture of alloy surface is lower than 30mg/m²。

Further, the mesoporous pore size range 30-50nm of the anodic oxidation, the mesoporous pore diameter range of chemical attack are 10-20nm, the pore diameter range of macropore are 50 ~ 60 μm.

Further, the mesoporous acquisition condition of the anodic oxidation are as follows: using aluminum or aluminum alloy as anode, inert metal or stone Ink is cathode, and anodizing solution is 10 ~ 20wt.% nitration mixture aqueous solution, and the nitration mixture is sulfuric acid and oxalic acid, the matter of sulfuric acid and oxalic acid Amount is than being (1 ~ 1.5): 1,10 ~ 30V of voltage is operated, temperature is 20 ~ 30^oC, time are 1 ~ 2h.

Further, the condition of the electrochemical corrosion macropore are as follows: make the aluminum or aluminum alloy obtained by anodic oxidation For anode, inert metal or graphite are cathode, while being soaked in hybrid corrosion liquid, connect DC power supply, the hybrid corrosion liquid Including 1 ~ 3wt.% hydrochloric acid, 0.5 ~ 1wt.% sulfuric acid, 0.2 ~ 1wt.% oxalic acid and 0.1 ~ 0.15 wt.%AlCl₃Solution, direct current are powered Corrosion auxiliary has ultrasonic treatment, 40 ~ 100KHz of supersonic frequency, temperature 30 ~ 40^oC, 3 ~ 5min of time, current density 50-200mA/ cm²。

Further, the mesoporous acquisition condition of the chemical attack are as follows: the aluminium or aluminium that will be obtained by electrochemical corrosion Alloy is put into T liquid and impregnates after freeze-drying, and the main component of the T liquid is rouge propylhomoserin, 0.5 ~ 2h of soaking time, leaching Steep temperature 20-50^oC。

Further, the aluminum or aluminum alloy passes through one of polishing, polishing, tumbling, sandblasting or ball blast processing method The natural oxide layer of aluminum or aluminum alloy nano surface grade is removed, then after acid or alkaline degreasing, is carrying out anodic oxidation operation.

Further, aluminum or aluminum alloy is heat-treated after the immersion of T liquid by temperature programming.

Further, the process of described program heating heat treatment are as follows: under normal temperature condition, with 15^oC/min rises to 160^oC is protected Warm 0.5 ~ 2h of time, then 5^oC/min rises to 365^oC, 2 ~ 3h of soaking time, then 20^oC/min rises to 500^oC, soaking time 0.5 ~ 1h, gaseous mixture purging are down to room temperature.

Further, the equally distributed macropore is obtained by template.

A kind of preparation method of the aluminum or aluminum alloy material of high density holes specifically comprises the following steps: that (1) is mechanical and throws Light；(2) electrochemical deoiling；(3) it is mesoporous to obtain anodic oxidation for anodic oxidation；(4) surface coats corrosion-resistant finishes；(5) laser incising is recessed Slot exposes aluminum or aluminum alloy metal；(6) to the part for exposing aluminum or aluminum alloy metal, electrochemical corrosion is carried out, obtains macropore； (7) it is freeze-dried；(8) it is mesoporous to obtain chemical attack for chemical attack；(7) heat treatment removes the moisture and coating in metal base； The hole density on the aluminum or aluminum alloy surface finally obtained is 10⁸-10¹⁰A/cm², the moisture on aluminum or aluminum alloy surface is lower than 30mg/m²。

Further, the mechanical polishing is that one of polishing, polishing, tumbling, sandblasting or ball blast processing method removes The natural oxide layer of aluminum or aluminum alloy nano surface grade, the electrochemical deoiling are acid or alkaline degreaser, the alkaline degreasing Agent is made of 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L sodium metasilicate and deionized water, treatment temperature 50^oC；Or acidity is removed Oil pretreatment, acid deoiling agent are made of the sulfuric acid of d=1.84,25g/L OP emulsifier and the deionized water of 100ml/L, processing temperature Degree is room temperature.

Further, the anodization step are as follows: using aluminum or aluminum alloy as anode, inert metal or graphite are cathode, Anodizing solution is 10 ~ 20wt.% nitration mixture aqueous solution, and the nitration mixture is sulfuric acid and oxalic acid, the mass ratio of sulfuric acid and oxalic acid be (1 ~ 1.5): 1,10 ~ 30V of voltage is operated, temperature is 20 ~ 30^oC, time are 1 ~ 2h, and the anodic oxidation is in aluminum or aluminum alloy surface shape At the mesoporous of 10-90nm.

Further, the corrosion-resistant finishes is in polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyamide It is a kind of.

Further, the groove obtained by laser ablation uniformly divides containing well-regulated on cated metal base Cloth, the aperture of groove are 1-200 μm, the depth of groove be greater than surface coating corrosion-resistant finishes and anodic oxide coating thickness it With, to expose substrate metal, for conductive, the parameter of laser fluting: electric current 5-10A, frequency 2-4KHz.

Further, using the aluminum or aluminum alloy obtained by laser ablation as anode, inert metal or graphite are cathode, It is soaked in hybrid corrosion liquid simultaneously, connects DC power supply, the hybrid corrosion liquid includes 1 ~ 3wt.% hydrochloric acid, 0.5 ~ 1wt.% sulphur Acid, 0.2 ~ 1wt.% oxalic acid and 0.1 ~ 0.15 wt.%AlCl₃Solution, direct current, which is powered to corroding, assists having ultrasonic treatment, supersonic frequency 40 ~ 100KHz, temperature 30 ~ 40^oC, 3 ~ 5min of time, current density 50-200mA/cm², the macropore diameter and laser incising of acquisition be recessed The pore size of slot is consistent, and range is 1-200 μm, 10 ~ 90 μm of the hole depth of macropore.

Further, the step of freeze-drying are as follows: the metal base after electrochemical corrosion is placed in temperature lower than 0^oC's is cold 0.5 ~ 5h in library or refrigerator, is subsequently placed in freeze drier, is lower than 10 Pa in vacuum degree, condenser temperature is -50^oThe item of C It is freeze-dried 0.5 ~ 5 h under part, removes the moisture in hole.

Further, the step of chemical attack are as follows: by the aluminum or aluminum alloy obtained by electrochemical corrosion through being subcooled Be lyophilized it is dry after, be put into T liquid and impregnate, the main component of the T liquid is rouge propylhomoserin, 0.5 ~ 2h of soaking time, soaking temperature 20- 50^oC, the mesoporous pore size range of chemical attack are 2-40nm.

Further, moisture and corrosion-resistant finishes can be removed simultaneously during the heat treatment.

Further, the process of the heat treatment are as follows: under normal temperature condition, with 15^oC/min rises to 160^oC, soaking time 0.5 ~ 2h, then 5^oC/min rises to 365^oC, 2 ~ 3h of soaking time, then 20^oC/min rises to 500^oC, 0.5 ~ 1h of soaking time are mixed Conjunction air-blowing, which is swept, is down to room temperature.

Then the high density holes aluminum or aluminum alloy substrate surface above method prepared carries out nanometer injection molding, obtains table Face is coated with the high stable metal material of resin, specific the preparation method is as follows: (1) mechanically polishes；(2) electrochemical deoiling；(3) anode It is mesoporous that oxidation obtains anodic oxidation；(4) surface coats corrosion-resistant finishes；(5) laser fluting exposes aluminum or aluminum alloy metal； (6) to the part for exposing aluminum or aluminum alloy metal, electrochemical corrosion is carried out, obtains macropore；(7) it is freeze-dried；(8) chemical attack It is mesoporous to obtain chemical attack；(9) heat treatment removes the moisture and coating in metal base；(10) nanometer is molded, wherein described receive The resin melt temperature of rice injection molding is 240~350 DEG C, and the temperature of the nanometer injection molding is 70~90 DEG C, the pressure of the injection molding For 70 ~ 130Mpa, the speed of the nanometer injection molding is 400~900mm/s, and the metal material is aluminum or aluminum alloy.

Further, the groove obtained by laser ablation uniformly divides containing well-regulated on cated metal base Cloth, the aperture of groove are 1-200 μm, and the depth of groove is greater than or equal to the thickness of surface coating corrosion-resistant finishes, to expose base Material metal, for conduction, the parameter of laser fluting: electric current 5-10A, frequency 2-4KHz.

Further, the composite material is used for electric terminal shell field.

The present invention, which is surface-treated, obtains metal base or nanometer injecting products, has following excellent technical effect:

(1) metal surface is equipped with equally distributed electrochemical corrosion macropore, is conducive to the knot of nanometer casting resin and metal base Resultant force is stablized, i.e. the peel strength of nanometer injecting products is uniform, and fluctuation is small.

(2) hole wall of electrochemical corrosion macropore is equipped with the mesoporous of chemical attack, and anodic oxidation is equipped between macropore and is situated between The porosity in hole, i.e. metal surface is high, and the binding force for being conducive to nanometer casting resin and metal base improves.

(3) combination water or the Free water inside or outside metal duct are effectively eliminated by heat treatment, are conducive to receive Stability between rice casting resin and metal base improves.

(4) it is being heat-treated dewatered meanwhile, it is capable to simply and easily remove protective coating, is being protected without additional removal Sheath technique, i.e., entire metal surface treatment process it is high-efficient, cost performance is strong.

(5) mechanical property, fatigue durability, impact flexibility, heat resistance of nanometer injecting products and moulding processability are high In the product on similar market.

(6) simple process of metal-surface nano injection molding of the invention, safety, environmental protection are suitable for flowing water thread industrial Metaplasia produces.

Detailed description of the invention

Attached drawing 1:(a) in the prior art because moisture content is high and caused by casting resin remove；(b) present invention passes through heat Processing removes moisture, the stability combination schematic diagram of casting resin and substrate.

Attached drawing 2: in the prior art using template prepare equally distributed etch pit (with application No. is For CN201711256603A).

Attached drawing 3: nanometer prepared by the present invention is molded aluminium alloy schematic diagram.

Attached drawing 4: aluminum or aluminum alloy surface treatment of the present invention and nanometer are molded schematic diagram.

Attached drawing 5: aluminum or aluminum alloy Treatment of Metal Surface schematic diagram of the present invention.

Attached drawing 6: aluminum or aluminum alloy metal nano of the present invention is molded schematic diagram.

Attached drawing 7: surface of the present invention is coated with the preparation process schematic diagram of the high stable metal material of resin.

Attached drawing 8: the preparation process schematic diagram of the aluminum or aluminum alloy material of high density holes of the present invention.

Attached drawing 9: high density holes aluminum or aluminum alloy metal nano of the present invention is molded schematic diagram.

Detailed description of the invention: 1 aluminum or aluminum alloy substrate, 2 corrosion-resistant finishes, 3 grooves, 4 electrochemical corrosion macropores, 5 chemistry are rotten Lose mesoporous, 6 nanometers of casting resin layers, 7 anodic oxidations are mesoporous, 8 moisture.

Specific embodiment

As shown in attached drawing 1(a), in the prior art such as CN106363869 A, the direct nanometer note in the nano pore of corrosion Modeling, due to the bonding and sealing of polymeric resin, so that the moisture in nano pore can not effectively volatilize, by for a long time Use after, vapor can be generated, and then lead to casting resin and metal nano duct interface can generate peel stress, in turn The caking property and stability of product after nanometer is molded are influenced, in this regard, if UACJ Corporation's Hasegawa true one is by heat treatment, such as Attached drawing 1(b) shown in, after forming nano pore, substrate is heat-treated, effectively removes moisture, is finally molded and produces in nanometer Significantly reduce influence of the moisture to product in the use process of product, however " its since processing terminate for alternating current electrolysis, until exposure Formed in the atmosphere more than 150 DEG C oxidation overlay film aluminium surface temperature reach 150 DEG C until time at 24 hours Within " heat treatment can not effectively remove the moisture in oxidation film, and the moisture in oxidation film is actually higher than 10 μ g/cm², heat treatment is to be improved.

Based on above content, present invention improves the channel morphologies of substrate surface, and by heat treatment, effectively reduce Unavoidable moisture content in the forming process of duct, specific as follows:

Firstly, the selection about substrate, aluminium used in the present invention, can be used pure aluminum or aluminum alloy, al alloy component is simultaneously It is not particularly limited, if six systems, seven are the various aluminium alloys headed by alloy.And metal used in the present invention can also for Mg, Ti, Stainless steel etc. is suitable as the light metal of electric terminal metal-back, and to its shape, there is no particular restriction, to be formed from that can stablize It is suitable for using flat substance from the viewpoint of nanometer injection membrane.

Embodiment 1

Processing method about aluminum or aluminum alloy metal base mainly includes the following steps (as shown in attached drawing 4-5):

(1) it pre-processes: by mechanical treatment aluminum or aluminum alloy metal surface, to remove the nanoscale day on aluminum or aluminum alloy surface The binding force of right oxide layer, the oxide layer and substrate is lower, and physical and chemical performance is poor, thus the process of mechanical pretreatment can not or It lacks, the mechanical treatment includes one of polishing, polishing, tumbling, sandblasting or ball blast；Then using alkalinity or acid deoiling Agent, chemistry remove the grease of metal surface, due to inevitably adhering in metal surface in mechanical treatment metal base One layer of greasy dirt, in order to guarantee the firm connection of substrate and oxidation film or nanometer injected plastics material, it is necessary to remove the greasy dirt of metal surface.

Its chemical degreasing liquid mainly includes alkaline degreaser and acid deoiling agent, alkaline degreaser by 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L sodium metasilicate and deionized water composition, treatment temperature 50^oC；The alkaline degreaser is nontoxic, price Cheaply, by the saponification of solution and emulsification, to remove degreasing.Sodium carbonate has certain alkalinity, unobvious to aluminium Corrosiveness, and absorb air in CO2 can be changed into sodium bicarbonate, have good buffer function to alkaline degreaser； Tertiary sodium phosphate also has deoiling effect and buffering effect, and has certain emulsifying capacity；Sodium metasilicate itself has preferably Surface-active action and certain saponifying ability, and there is corrosion inhibiter effect.

Acid deoiling agent is made of the sulfuric acid of d=1.84,25g/L OP emulsifier and the deionized water of 100ml/L, processing temperature Degree is room temperature, the metal base processing that acid deoiling agent is suitable for containing corrosion in a small amount of surface.

(2) surface coats corrosion-resistant finishes；The surface coating corrosion-resistant finishes is thermoplastic resin coating, such as polychlorostyrene second One of alkene, polystyrene, polyethylene, polypropylene, polyamide, the thermoplastic resin coating is 500^oC can be in anaerobic Under the conditions of effectively decompose removal, therefore preferred polystyrene, coating method is spraying or electrophoresis plating, is preferably sprayed, coating With a thickness of 3 ~ 30 μm, preferably 5-20 μm, more preferable 5 ~ 8 μm, due to the main function of the corrosion-resistant finishes of surface coating For protective layer or template layer, it can be heat-treated removing in the technique needed after, therefore selected excellent with low cost, high rigidity, resistance toization It learns burn into good insulating, easily remove, relatively thin coating, i.e., the present invention is included in by the resinous coat that mentioned above principle is selected In the range of.

(3) laser fluting；The groove is blind hole, i.e., by programming, the object lens punching of short focus, so that laser The groove of etching is uniformly distributed containing well-regulated on cated metal base, and the aperture of groove is 1-200 μm, the depth of groove Degree is greater than or equal to the thickness of surface coating corrosion-resistant finishes, to expose substrate metal, for conduction, the ginseng of laser fluting Number: electric current 5-10A, frequency 2-4KHz can be conductive that is, near groove since the position in groove exposes metal base, lead to Later continue electrochemical corrosion processing, the groove location can corrode, generation and etched recesses groove of the same size, and exhausted Edge, the corrosion-resistant part not being etched will not corrode, and so, the recess coatings of the laser ablation can be used as mould Plate enables the hole of chemical attack to be uniformly distributed, and the punching range of the laser-beam drilling machine in currently available technology is as low as received Meter level, that is, only by the programming to laser macropore machine, can realize that distribution to groove, size are controllable, in turn It realizes and of the invention prepares micrometer-adjustable control, equally distributed macropore duct in metallic substrate surface.

(4) electrochemical corrosion；Using the metal Jing Guo pre-etching as anode, graphite is soaked in mixing as cathode Corrosive liquid, connects DC power supply, the hybrid corrosion liquid include 1 ~ 3wt.% hydrochloric acid, 0.5 ~ 1wt.% sulfuric acid, 0.2 ~ 1wt.% oxalic acid and 0.1~0.15 wt.%AlCl₃Solution, auxiliary has ultrasonic treatment, 40 ~ 100KHz of supersonic frequency, temperature in direct current energization corrosion process Degree 30 ~ 40^oC, 3 ~ 5min of time, current density 50-200mA/cm², then pure water, the corrosion macropore and recess hole of acquisition Diameter is in the same size, and the aperture of the macropore is 1-200 μm, and depth is 10-90 μm, preferably 50 ~ 60 μm of the aperture of the macropore, hole Diameter is too small or too shallow, is unfavorable for coming into full contact with for resin and substrate, be binding force is too small.On the other hand, aperture is too greatly or too It is deep, the binding force of electrochemical oxidation hole and substrate aluminium can be made to decline, be unfavorable for finally obtaining the binding force of product.

In addition, the metal Al of groove part can be aoxidized in direct current energization corrosion process, Al is generated³⁺Into solution, and Forming electrochemical corrosion groove in oxidation position can be effectively formed recessed with laser ablation by the adjusting of electrochemical parameter The consistent electrochemical corrosion groove of slot aperture, secondly about in electrolytic etching mixed liquor, chloride ion be it is necessary, chloride ion belongs to One of most strong ion of erosion performance in halogen family ion can penetrate oxidation layer film, corrode dissolution aluminum substrate and form etch pit.It is single The HCl corrosive liquid of ingredient is unfavorable for corroding in metal surface, in some instances it may even be possible to there is a phenomenon where heavy corrosion, it is therefore desirable to Oxidizing acid sulfuric acid and oxalic acid are added in corrosive liquid, wherein AlCl₃For improving Cl^-Concentration is conducive to vertical etches, mainly Vertical etches are carried out along { 100 } crystal face, guarantee to obtain good corrosive effect, wherein ultrasound is conducive to pre-etching generation Duct is further deepened, so that the Al after corrosion³⁺Duct is excluded, the micron openings which forms is in the majority.

(5) it is freeze-dried；Metal base after electrochemical corrosion is placed in temperature lower than 0^o0.5 in the freezer or refrigerator of C ~ 5h is subsequently placed in freeze drier, is lower than 10 Pa in vacuum degree, condenser temperature is -50^o0.5 is freeze-dried under conditions of C ~ 5 h remove the moisture in hole, and drying mode is also an option that other conventional drying modes, such as cold wind drying, are air-dried Case, noble gas drying box, vacuum oven etc., preferably freeze drying of the present invention are mainly based upon following consideration: (1) in closed loop In border, the included vacuum pump of condenser dryer can be effectively formed evacuated state, conducive to the moisture removed in duct；(2) water Be point directly gaseous state by solid state sublimation, by constantly freeze-distil-re-dry can effectively remove aerial moisture；(3) Conducive to the reaction of subsequent chemistry corrosion.

(6) chemical attack；Stating the mesoporous process of chemical attack is that will be put into T liquid to soak by the metallic matrix of freeze-drying Bubble forms the mesoporous of chemical attack by corrosion on macropore hole wall, and the main component of the T liquid is rouge propylhomoserin, at the T It manages liquid and selects commercial commercially available T treatment fluid, for forming mesoporous, the mesoporous hole of chemical attack on the macropore of electrochemical corrosion Diameter range is 2-40nm, and preferably mesoporous pore diameter range is 10-20nm.

(7) heat treatment removes the moisture and coating in metal base: wherein heat treatment step are as follows: will be by chemical attack It is 2 ~ 5%H that metal base, which is placed in volume fraction,₂/N₂In mixed atmosphere, Temperature Programmed Processes 15^oC/min rises to 160^oC, heat preservation 0.5 ~ 2h of time, then 5^oC/min rises to 365^oC, 2 ~ 3h of soaking time, then 20^oC/min rises to 500^oC, soaking time 0.5 ~ 1h, gaseous mixture purging are down to room temperature, and above-mentioned heat treatment mode is mainly analyzed according to TGA-DTA and obtained, in 100-160^oC is base The moisture of material surface or the absorption of macropore surface physics or weak chemisorption, secondly selects 365^oC handles 2 ~ 3h, is mainly used for removing The hydrone inside hole and the hydrone of extensive chemical absorption are removed, the moisture of the position is due to originals such as capillary (surface) tension Thus more difficult desorption, high temperature 500^oC is mainly used for removing the protective coating on surface, at such a temperature, as polystyrene can be direct It decomposes, gasification, and on substrate duct without influence.

The metallic substrate surface that finally obtains contains the macropore of electrochemical corrosion and mesoporous, the wherein macropore of chemical attack Pore diameter range is 1-200 μm, 10 ~ 90 μm of the hole depth of macropore, and mesoporous pore diameter range is 2-40nm, and moisture is lower than 30mg/m²

Furthermore, it is necessary to it is clear that, use the electrochemical corrosion macropore of metallic substrate surface prepared by the present invention and chemical attack It is mesoporous be disordered state, as described in attached drawing 3.Heretofore described macropore, which is uniformly distributed, to be referred to and is protected by laser ablation Coating obtains the macropore being evenly distributed, and by homogeneous corrosion, the hole depth of realization macropore as far as possible is consistent, but in order to remove, it is concise Illustrate macropore, the mesoporous state in metal base, by the more regular of macropore and mesoporous design in schematic diagram attached drawing 5-6 With it is orderly, the schematic diagram do not represent surface substrate of the present invention macropore and mesoporous end-state.

Embodiment 2

It has been observed that the present inventor CN201711256603A patent prepares orderly micron order hole by preparing template: specific step Suddenly (1) removes the natural oxygen of metal-surface nano grade using one of polishing, polishing, tumbling, sandblasting or ball blast processing method Change layer；(2) treated metal is soaked in alkali metal cleaning solution and is cleaned；(3) pure water is washed, and is dried；(4) in gold Belong to substrate surface covering W metal, Cr, Cu or its alloy corrosion resistant metal template, the metal form and is divided into white space and metal Region；(5) in step (4) metal form substrate surface physical sputtering corrosion resistant metal；(6) corrosion resistant metal mould is removed Plate will immerse in acid corrosion liquid by physical sputtering treated metal substrate, repeatedly be corroded to substrate, corrode uniform out The micron order etch pit of distribution, pure water washing, wherein corrosion number >=1；(7) metal base after corrosion is soaked in and is mainly contained In the weak acid solution for having rouge propylhomoserin, the nano-pore of 20-80nm is formed in equally distributed micron order corrosion inner surfaces of pores, then Pure water washing is dried；(8) nanometer injection molding is carried out to substrate, penetrates into resin in duct by injection molding.Although being had The micron order hole of sequence, but still face a distinct issues: corrosion-resistant splash-proofing sputtering metal can not be removed effectively, will affect combination Power and stability at later stage.As shown in Fig. 2, the corrosion resisting alloy template of physical sputtering can not be removed effectively, finally be clipped in note Mould between resin and substrate, since the corrosion resisting alloy template surface of physical sputtering does not contain any duct, make its substrate with The binding force of resin is not high, and the moisture in substrate does not also remove effectively, and problem above can be to the nanometer finally obtained Being molded mobile terminal product and generating significantly influences, i.e., the porosity of above-mentioned prior art metallic substrate surface, the moisture in hole It is to be improved, following improvement is made based on the problem.

Secondly, although effectively eliminating coating template by heat treatment, being not present as documented by embodiment 1 The corrosion resisting alloy template of physical sputtering can not be removed effectively in CN201711256603A patent, finally be clipped in casting resin The problem between substrate, but smooth metal base is still below coating template (i.e. in the lower section of coating template Without any duct on metal base), when nanometer injection molding, casting resin can be with the macropore of electrochemical corrosion and chemical attack It is mesoporous to be effectively combined or fasten, (the Metal Substrate of the lower section of coating template can not be combined with the smooth metal base in surface Material), eventually the bond strength of nanometer casting resin and metal base is impacted.Based on content, the embodiment of the present invention 2 exists Continue to improve on the basis of embodiment 1, prepare a kind of aluminum or aluminum alloy material of high density holes, the convenient nanometer that is used as is molded base Material.

Firstly, the selection of substrate, as the relevant portion of embodiment 1 is recorded.

Secondly, the metal base that the present invention improves has the following structure: a kind of aluminum or aluminum alloy material of high density holes (1), the hole includes mesoporous and macropore (4), it is described it is mesoporous be divided into anodic oxidation mesoporous (7) and chemical attack is mesoporous (8), Anodic Oxidation mesoporous (7) is distributed between macropore (4) and macropore (4), and chemical attack mesoporous (8) is distributed in the hole of macropore (4) On wall, the macropore, which is uniformly distributed in, to be obtained with aluminum or aluminum alloy (1) surface, the macropore by electrochemical corrosion, middle-jiao yang, function of the spleen and stomach It is 10-90nm that pole, which aoxidizes mesoporous (7) pore diameter range, and the pore diameter range of chemical attack mesoporous (8) is 2-40nm, the hole of macropore (4) Diameter range is 1-200 μm, 10 ~ 90 μm of the hole depth of macropore, and the hole density on the aluminum or aluminum alloy surface is 10⁸-10¹⁰A/cm², The moisture on aluminum or aluminum alloy surface is lower than 30mg/m²。

Further, the preferred 30-50nm of mesoporous pore size range of the anodic oxidation, the mesoporous aperture model of chemical attack It enclosing for preferred 10-20nm, the pore diameter range of macropore is 50 ~ 60 μm, if the aperture of anodic oxidation or chemical attack is less than 10nm, Similar capillary effect can be led to the problem of, the resin of nanometer injection molding can not effectively enter nano pore, and then cause to contact Area is insufficient, so that sufficient binding force can not be obtained, if the pore size of anodic oxidation is greater than 50nm, receives although can improve The binding force of rice casting resin and duct, but the binding force of duct and substrate can be reduced, and then reduce the performance of final products.

Further, the mesoporous acquisition condition of anodic oxidation are as follows: using aluminum or aluminum alloy as anode, inert metal or graphite are Cathode, anodizing solution are 10 ~ 20wt.% nitration mixture aqueous solution, and the nitration mixture is sulfuric acid and oxalic acid, the mass ratio of sulfuric acid and oxalic acid For (1 ~ 1.5): 1,10 ~ 30V of voltage is operated, temperature is 20 ~ 30^oC, time are 1 ~ 2h.

Further, the condition of electrochemical corrosion macropore are as follows: using the aluminum or aluminum alloy obtained by anodic oxidation as sun Pole, inert metal or graphite are cathode, while being soaked in hybrid corrosion liquid, and DC power supply is connect, and the hybrid corrosion liquid includes 1 ~ 3wt.% hydrochloric acid, 0.5 ~ 1wt.% sulfuric acid, 0.2 ~ 1wt.% oxalic acid and 0.1 ~ 0.15 wt.%AlCl₃Solution, direct current energization corrosion are auxiliary Ultrasonic treatment, 40 ~ 100KHz of supersonic frequency, temperature 30 ~ 40 are helped^oC, 3 ~ 5min of time, current density 50-200mA/cm², directly It circulates in electrical corrosion, the metal Al of groove part can be aoxidized, and generate Al³⁺It is formed into solution, and in oxidation position Electrochemical corrosion groove can be effectively formed and the consistent electricity in laser ablation groove aperture by the adjusting of electrochemical parameter Chemical attack groove, secondly about in electrolytic etching mixed liquor, chloride ion be it is necessary, chloride ion, which belongs in halogen family ion, to be corroded One of most strong ion of performance can penetrate oxidation layer film, corrode dissolution aluminum substrate and form etch pit.The HCl of single component corrodes Liquid is unfavorable for corroding in metal surface, in some instances it may even be possible to there is a phenomenon where heavy corrosion, it is therefore desirable to be added in corrosive liquid Oxidizing acid sulfuric acid and oxalic acid, wherein AlCl₃For improving Cl^-Concentration is conducive to vertical etches, mainly along { 100 } crystal face Vertical etches are carried out, guarantee to obtain good corrosive effect, wherein ultrasound is conducive to further add the duct that pre-etching generates It is deep, so that the Al after corrosion³⁺Duct is excluded, the micron openings which forms is in the majority.

Further, the mesoporous acquisition condition of chemical attack are as follows: the aluminum or aluminum alloy that will be obtained by electrochemical corrosion It after freeze-drying, is put into T liquid and impregnates, the main component of the T liquid is rouge propylhomoserin, and 0.5 ~ 2h of soaking time impregnates temperature Spend 20-50^oC。

Further, aluminum or aluminum alloy is removed by one of polishing, polishing, tumbling, sandblasting or ball blast processing method The natural oxide layer of aluminum or aluminum alloy nano surface grade then after acid or alkaline degreasing, is carrying out anodic oxidation operation, specifically Referring to the related content in embodiment 1.

Further, aluminum or aluminum alloy is heat-treated after the immersion of T liquid by temperature programming, temperature programming heat treatment Process are as follows: under normal temperature condition, with 15^oC/min rises to 160^oC, 0.5 ~ 2h of soaking time, then 5^oC/min rises to 365^oC, heat preservation 2 ~ 3h of time, then 20^oC/min rises to 500^oC, 0.5 ~ 1h of soaking time, gaseous mixture purging are down to room temperature.

That is, the surface of the aluminum or aluminum alloy material of the high density holes is evenly distributed with through template electrochemical corrosion Macropore, it is mesoporous equipped with anodic oxidation between macropore and macropore, and chemistry is distributed in the big hole surface of electrochemical corrosion Mesoporous, the range 10 of the hole density on the aluminum or aluminum alloy surface finally obtained of corrosion⁸-10¹⁰A/cm², have and received higher than same type The hole density range (usually 10 of rice injection molding substrate⁶-10⁸A/cm²).

Based on a kind of above-mentioned aluminum or aluminum alloy material description of high density holes, the aluminum or aluminum alloy material of the high density holes The preparation method is as follows: (1) mechanically polish；(2) electrochemical deoiling；(3) it is mesoporous to obtain anodic oxidation for anodic oxidation；(4) surface applies Cover corrosion-resistant finishes；(5) laser fluting exposes aluminum or aluminum alloy metal；(6) to expose aluminum or aluminum alloy metal part, Electrochemical corrosion is carried out, macropore is obtained；(7) it is freeze-dried；(8) it is mesoporous to obtain chemical attack for chemical attack；(9) heat treatment removes Moisture and coating in metal base；The hole density on the aluminum or aluminum alloy surface finally obtained is 10⁸-10¹⁰A/cm², aluminium Or the moisture of aluminum alloy surface is lower than 30mg/m²。

Further, the groove obtained by laser ablation uniformly divides containing well-regulated on cated metal base Cloth, the aperture of groove are 1-200 μm, the depth of groove be greater than surface coating corrosion-resistant finishes and anodic oxide coating thickness it With, to expose substrate metal, for conductive, the parameter of laser fluting: electric current 5-10A, frequency 2-4KHz, due to anodic oxidation It is mesoporous be aluminium oxide, weak inductive material, such as into embodiment 1 only be used only laser remove coating, without except deoxygenate Change film, electrochemical corrosion macropore just can not be effectively obtained by electrochemical corrosion, therefore the depth of the groove of radium-shine etching must It must be greater than, or be convenient at least equal to surface coating the sum of corrosion-resistant finishes and the thickness of anodic oxide coating with exposing substrate metal Subsequent calls corrosion treatment.

Embodiment 3

PPS nanometers of injection moldings are carried out to the metal base that embodiment 1 obtains.

Specific step is as follows:

(1) it mechanically polishes；(2) electrochemical deoiling；(3) surface coats corrosion-resistant finishes；(4) laser fluting, exposes aluminium or aluminium closes Metal；(5) to the part for exposing aluminum or aluminum alloy metal, electrochemical corrosion is carried out, obtains macropore；(6) it is freeze-dried；(7) Chemical attack obtains mesoporous；(8) heat treatment removes the moisture and coating in metal base；(9) nanometer is molded, wherein the nanometer The resin melt temperature of injection molding is 200~300 DEG C, and the temperature of the nanometer injection molding is 70~90 DEG C, and the pressure of the injection molding is The speed of 70 ~ 130Mpa, the nanometer injection molding are 400~900mm/s.

Wherein, mechanical polishing removes the natural oxide layer of aluminum or aluminum alloy nano surface grade selected from polishing.

Alkaline degreaser oil removing is wherein used, degreaser is by 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L sodium metasilicate It is formed with deionized water, treatment temperature 50^oC handles time 0.5h.

Further, surface coat corrosion-resistant finishes polystyrene, coating method be spraying, coating with a thickness of 10 μm.

Further, the groove obtained by laser is uniformly distributed containing well-regulated on cated metal base, recessed The aperture of slot is 50 μm, and the depth of groove is greater than or equal to 10 μm, to expose substrate metal, for conductive, laser fluting Parameter: electric current 5-10A, frequency 2-4KHz.

Further, the process of electrochemical corrosion macropore are as follows: using the metal Jing Guo pre-etching as anode, graphite is as yin Pole, while being soaked in hybrid corrosion liquid, connects DC power supply, the hybrid corrosion liquid include 2wt.% hydrochloric acid, 0.75wt.% sulfuric acid, 0.5wt.% oxalic acid and 0.12 wt.%AlCl₃Solution, auxiliary has ultrasonic treatment, supersonic frequency in direct current energization corrosion process 60KHz, temperature 35^oC, time 4min, current density 100mA/cm², then pure water, the corrosion macropore and recess hole of acquisition Diameter is in the same size, and the aperture of the macropore is 50 μm, and depth is 10-90 μm.

Further, it is freeze-dried: the metal base after electrochemical corrosion is placed in temperature lower than 0^oThe freezer or refrigerator of C Middle 3h, is subsequently placed in freeze drier, is lower than 10 Pa in vacuum degree, condenser temperature is -50^o3 are freeze-dried under conditions of C H removes the moisture in hole.

Further, the mesoporous process of chemical attack is that will be put into T liquid to impregnate by the metallic matrix of freeze-drying, is led to Excessive erosion, forms the mesoporous of chemical attack on macropore hole wall, and the main component of the T liquid is rouge propylhomoserin, soaking time 1h, leaching Steep temperature 35^oC, the mesoporous pore size range of chemical attack are 2-40nm.

Further, heat treatment step are as follows: it is 3%H that the metal base Jing Guo chemical attack, which is placed in volume fraction,₂/N₂It is mixed It closes in atmosphere and carries out temperature programming, Temperature Programmed Processes 15^oC/min rises to 160^oC, soaking time 1h, then 5^oC/min liter To 365^oC, soaking time 2h, then 20^oC/min rises to 500^oC, soaking time 0.5h, gaseous mixture purging are down to room temperature.

The nanometer injecting products finally obtained are named as S-3.

Embodiment 4

PPS nanometers of injection moldings are carried out to the high density holes metal base that embodiment 2 obtains.

Specific step is as follows, as shown in attached drawing 7-9:

(1) it mechanically polishes；(2) electrochemical deoiling；(3) it is mesoporous to obtain anodic oxidation for anodic oxidation；(4) surface coats corrosion-resistant painting Layer；(5) laser fluting exposes aluminum or aluminum alloy metal；(6) to the part for exposing aluminum or aluminum alloy metal, electrochemistry is carried out Corrosion obtains macropore；(7) it is freeze-dried；(8) it is mesoporous to obtain chemical attack for chemical attack；(9) heat treatment removes in metal base Moisture and coating；(10) nanometer is molded, wherein the resin melt temperature of nanometer injection molding is 200~300 DEG C, the nanometer The temperature of injection molding is 70~90 DEG C, and the pressure of the injection molding is 70 ~ 130Mpa, the speed of the nanometer injection molding is 400~ 900mm/s。

Further, the natural oxide layer that aluminum or aluminum alloy nano surface grade is removed for polishing method is mechanically polished.

Further, using alkaline degreaser oil removing, degreaser is by 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L silicon Sour sodium and deionized water composition, treatment temperature 50^oC handles time 0.5h；

Further, anodization step are as follows: using aluminum or aluminum alloy as anode, inert metal or graphite are cathode, anodic oxidation Liquid is 15wt.% nitration mixture aqueous solution, and the nitration mixture is sulfuric acid and oxalic acid, and the mass ratio of sulfuric acid and oxalic acid is (1.2): 1, operation electricity Press 20V, temperature 25^oC, time 1.5h, the anodic oxidation form the mesoporous of 10-90nm on aluminum or aluminum alloy surface.

Further, the groove obtained by laser is uniformly distributed containing well-regulated on cated metal base, recessed The aperture of slot is 50 μm, and the depth of groove is greater than 10 μm, to expose substrate metal, for conduction, the parameter of laser fluting: electricity Flow 5-10A, frequency 2-4KHz.

The nanometer injecting products finally obtained are named as S-4.

Comparative example 1

Specific step is as follows:

(1) it mechanically polishes；(2) electrochemical deoiling；(3) electrochemical corrosion obtains macropore；(4) it is freeze-dried；(5) chemical attack obtains It obtains mesoporous；(6) it is heat-treated；(9) nanometer is molded PPS, wherein the resin melt temperature of nanometer injection molding is 200~300 DEG C, institute The temperature for stating nanometer injection molding is 70~90 DEG C, and the pressure of the injection molding is 70 ~ 130Mpa, and the speed of the nanometer injection molding is 400 ~900mm/s.

Further, heat treatment step are as follows: the metal base Jing Guo chemical attack is placed in air drying cabinet and carries out journey Sequence heating, Temperature Programmed Processes 15^oC/min rises to 150^oC, soaking time 4h, cooled to room temperature.

Further, mechanical polishing removes the natural oxide layer of aluminum or aluminum alloy nano surface grade selected from polishing.

Further, using alkaline degreaser oil removing, degreaser is by 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L silicon Sour sodium and deionized water composition, treatment temperature 50^oC handles time 0.5h.

Further, the process of electrochemical corrosion macropore are as follows: using the metal Jing Guo pre-etching as anode, graphite is as yin Pole, while being soaked in hybrid corrosion liquid, connects DC power supply, the hybrid corrosion liquid include 2wt.% hydrochloric acid, 0.75wt.% sulfuric acid, 0.5wt.% oxalic acid and 0.12 wt.%AlCl₃Solution, auxiliary has ultrasonic treatment, supersonic frequency in direct current energization corrosion process 60KHz, temperature 35^oC, time 4min, current density 100mA/cm², then pure water.

Further, the mesoporous process of chemical attack is that will be put into T liquid to impregnate by the metallic matrix of freeze-drying, is led to Excessive erosion, forms the mesoporous of chemical attack on macropore hole wall, and the main component of the T liquid is rouge propylhomoserin, soaking time 1h, leaching Steep temperature 35^oC。

The nanometer injecting products finally obtained are named as D-1.

Comparative example 2

Specific step is as follows:

(1) it mechanically polishes；(2) electrochemical deoiling；(3) surface coats corrosion-resistant finishes；(4) laser fluting, exposes aluminium or aluminium closes Metal；(5) to the part for exposing aluminum or aluminum alloy metal, electrochemical corrosion is carried out, obtains macropore；(6) it is freeze-dried；(7) Chemical attack obtains mesoporous；(8) it is heat-treated；(9) nanometer be molded, wherein the nanometer injection molding resin melt temperature be 200~ 300 DEG C, the temperature of the nanometer injection molding is 70~90 DEG C, and the pressure of the injection molding is 70 ~ 130Mpa, the speed of the nanometer injection molding Degree is 400~900mm/s.

The nanometer injecting products finally obtained are named as D-2.

Comparative example 3

Specific step is as follows:

(1) it mechanically polishes；(2) electrochemical deoiling；(3) electrochemical corrosion；(4) it is freeze-dried；(5) chemical attack obtains mesoporous；(7) Heat treatment removes the moisture and coating in metal base；(8) nanometer is molded, wherein the resin melt temperature of nanometer injection molding is 200~300 DEG C, the temperature of the nanometer injection molding is 70~90 DEG C, and the pressure of the injection molding is 70 ~ 130Mpa, the nanometer note The speed of modeling is 400~900mm/s.

Further, the process of electrochemical corrosion macropore are as follows: using the metal Jing Guo pre-etching as anode, graphite is as yin Pole, while being soaked in hybrid corrosion liquid, connects DC power supply, the hybrid corrosion liquid include 2wt.% hydrochloric acid, 0.75wt.% sulfuric acid, 0.5wt.% oxalic acid and 0.12 wt.%AlCl₃Solution, auxiliary has ultrasonic treatment, supersonic frequency in direct current energization corrosion process 60KHz, temperature 35^oC, time 4min, current density 100mA/cm²。

The nanometer injecting products finally obtained are named as D-3.

In addition, by influence of the stability test moisture to nanometer injected plastics material, but water is only tested under normal conditions Influence of the steam to nanometer injected plastics material or nanometer injection molding electric terminal, test period are likely larger than 5 years or more, are unfavorable for returning Receive influence of the moisture content to nanometer injected plastics material, therefore the present invention improves testing of materials condition.First to above-mentioned system Nanometer the injected plastics material S-3, S-4, D-1 got ready, D-2, D-3 carry out peel strength test, as shown in table 1, then by S-3, S- 4, D-1, D-2, D-3 aluminium alloy are placed in air drying cabinet, and the temperature of drying box is 70 ~ 80^oC, relative humidity 10 ~ 20% are placed Time 30 days, near room temperature is taken out, tests peel strength, as shown in table 2.

1 nanometer of injection molding PPS resin peel strength table of table.

2 nanometers of injection molding PPS stability analysis tables of table.

By upper table it can be concluded that following conclusion.

(1) and it is mesoporous due to introducing anodic oxidation below coating, so that PPS comes into full contact with substrate, i.e., in Gao Kongmi It spends on metal material and is molded peel strength of the peel strength higher than lower well densities S-3 of PPS S-4, and since hole density obviously mentions Rise, be its standard deviation and fluctuation it is smaller, i.e. the metal base of high density holes is more advantageous to the consistent nanometer of processability There is the chance decline of defect ware in injected plastics material.

(2) due to introducing uniform macropore, so that PPS and substrate contact surface (i.e. PPS and duct contact position) are uniform, i.e., The fluctuation of product is small, if being not suitable for uniform template prepares equally distributed macropore, nanometer is molded the fluctuation of metal base Property is larger, if S-3 is compared with D-1, D-3.

(3) if free moisture or combination moisture extra in duct cannot be removed effectively, (moisture can reduce note Mould the contact area of resin and duct), binding force and fluctuation are larger, if S-3 is compared with D-1, D-2.

(4) by being placed in air drying cabinet, the temperature of drying box is 70 ~ 80^oC, relative humidity 10 ~ 20%, standing time After 30 days, the binding force of all samples has decline, and caused by can summing up the aging of PPS, but main cause should be attributed to duct The evaporation of interior moisture, so that peel strength is remarkably decreased, but if can be significantly reduced using suitable heat treatment Influence of the moisture to nanometer injected plastics material, such as the S-3 of table 1, the S-3 of S-4, D-3 and table 2, S-4, D-3 is compared, if only removing The moisture in part free water or macropore is removed, binding force can be not only reduced, also will affect the permanent stabilization of nanometer injected plastics material Property, such as the D-1 of table 1, the D-1 of D-2 and table 2, D-2 is compared.

More than, although having carried out illustrative explanation to this practical invention by preferred embodiment, this practical invention It is not limited to this specific embodiment, change appropriate can be implemented in the scope for being recorded in protection scope of the present invention More.

Claims

1. a kind of surface is coated with the preparation method of the high stable metal material of resin, feature is the method includes walking as follows It is rapid: (1) to mechanically polish；(2) electrochemical deoiling；(3) it is mesoporous to obtain anodic oxidation for anodic oxidation；(4) surface coats corrosion-resistant finishes； (5) laser fluting exposes aluminum or aluminum alloy metal；(6) to the part for exposing aluminum or aluminum alloy metal, it is rotten to carry out electrochemistry Erosion obtains macropore；(7) it is freeze-dried；(8) it is mesoporous to obtain chemical attack for chemical attack；(9) heat treatment removes in metal base Moisture and coating；(10) nanometer is molded, wherein the resin melt temperature of nanometer injection molding is 200~300 DEG C, the nanometer note The temperature of modeling is 70~90 DEG C, and the pressure of the injection molding is 70 ~ 130Mpa, and the speed of the nanometer injection molding is 400~900mm/ S, the metal material are aluminum or aluminum alloy.

2. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists It is that one of polishing, polishing, tumbling, sandblasting or ball blast processing method removing aluminum or aluminum alloy surface is received in the mechanical polishing The natural oxide layer of meter level, the electrochemical deoiling are acid or alkaline degreaser, the alkaline degreaser by 30g/L sodium carbonate, 30g/L tertiary sodium phosphate, 15g/L sodium metasilicate and deionized water composition, treatment temperature 50^oC；Or acid deoiling pretreatment, acidity are removed Finish is made of the sulfuric acid of d=1.84,25g/L OP emulsifier and the deionized water of 100ml/L, and treatment temperature is room temperature.

3. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists In the anodization step are as follows: using aluminum or aluminum alloy as anode, inert metal or graphite are cathode, anodizing solution is 10 ~ 20wt.% nitration mixture aqueous solution, the nitration mixture are sulfuric acid and oxalic acid, and the mass ratio of sulfuric acid and oxalic acid is (1 ~ 1.5): 1, operate voltage 10 ~ 30V, temperature are 20 ~ 30^oC, time are 1 ~ 2h, and the anodic oxidation forms Jie of 10-90nm on aluminum or aluminum alloy surface Hole.

4. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists One of polyvinyl chloride, polystyrene, polyethylene, polypropylene, polyamide are selected from the corrosion-resistant finishes.

5. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists It is uniformly distributed in the groove obtained by laser ablation containing well-regulated on cated metal base, the aperture of groove is 1- 200 μm, the depth of groove is greater than or equal to the thickness of surface coating corrosion-resistant finishes, to expose substrate metal, for conduction, swashs The parameter of photoetching groove: electric current 5-10A, frequency 2-4KHz.

6. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists In that will pass through the aluminum or aluminum alloy of laser ablation acquisition as anode, inert metal or graphite are cathode, while being soaked in mixing In corrosive liquid, DC power supply is connect, the hybrid corrosion liquid includes 1 ~ 3wt.% hydrochloric acid, 0.5 ~ 1wt.% sulfuric acid, 0.2 ~ 1wt.% oxalic acid With 0.1 ~ 0.15 wt.%AlCl₃Solution, direct current, which is powered to corroding, assists having ultrasonic treatment, 40 ~ 100KHz of supersonic frequency, and temperature 30 ~ 40^oC, 3 ~ 5min of time, current density 50-200mA/cm², the macropore diameter of acquisition is consistent with the pore size of laser fluting, Range is 1-200 μm, 10 ~ 90 μm of the hole depth of macropore.

7. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists In the step of being freeze-dried are as follows: the metal base after electrochemical corrosion is placed in temperature lower than 0^o0.5 in the freezer or refrigerator of C ~ 5h is subsequently placed in freeze drier, is lower than 10 Pa in vacuum degree, condenser temperature is -50^o0.5 is freeze-dried under conditions of C ~ 5 h remove the moisture in hole.

8. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists In the chemical attack the step of are as follows: T liquid will be put by the aluminum or aluminum alloy that electrochemical corrosion obtains after freeze-drying Middle immersion, the main component of the T liquid are rouge propylhomoserin, 0.5 ~ 2h of soaking time, soaking temperature 20-50^oC, Jie of chemical attack Hole pore diameter range is 2-40nm.

9. a kind of surface as described in claim 1 is coated with the preparation method of the high stable metal material of resin, feature exists In the process of the heat treatment are as follows: under normal temperature condition, with 15^oC/min rises to 160^oC, 0.5 ~ 2h of soaking time, then 5^oC/min Rise to 365^oC, 2 ~ 3h of soaking time, then 20^oC/min rises to 500^oC, 0.5 ~ 1h of soaking time, gaseous mixture purging are down to room Temperature.

10. a kind of metal resin composite material obtained such as claim 1 ~ 9 preparation method, it is characterised in that described compound Material is used for electric terminal shell field.