CN101376999A - Composite oxidation method for metallic products - Google Patents
Composite oxidation method for metallic products Download PDFInfo
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- CN101376999A CN101376999A CNA2008102235985A CN200810223598A CN101376999A CN 101376999 A CN101376999 A CN 101376999A CN A2008102235985 A CNA2008102235985 A CN A2008102235985A CN 200810223598 A CN200810223598 A CN 200810223598A CN 101376999 A CN101376999 A CN 101376999A
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Abstract
The invention provides a composite oxidization method of a metal product, which comprises the following steps: the metal product to be treated receives conductive oxidization treatment; an area on the metal product after conductive oxidization treatment to be conducted is shielded; the shielded metal product receives anode oxidization treatment; the shielding of the area is removed. The method can prepare the metal product with low cost and high yield according to the intention of the designer.
Description
Technical field
The present invention relates to the surface treatment method of metal products, the mode that particularly adopts electric conductive oxidation and anodic oxidation to combine is handled the method for metal products.
Background technology
Metal products can be made by pure metal or alloy.Some use under metal products situations, except that needs are used the performance that metal products self possesses, wish that also metal products possesses good specified property such as thermal diffusivity, electromagnetic compatibility, anti-vibrating and impact and erosion resistance or the like.In order to make metal products have these performances, can suitably handle metal products usually.In the practical application, treated metal products can guarantee to be subjected to object works better in abominable environment for use of its covering or protection.The metal products practical application is as being used to make the shell on military or the commercial power subset.
In the prior art, the process of surface treatment that metal products is carried out mainly contains following two kinds.
Paint application technology: with the surface of paint application at metal products; can form the continuous film of firm attachment at body surface; the protection object makes it not to be subjected to the erosion of corrosivess such as acid, alkali, salt in the environment; prolong the work-ing life of coated article body; beautifying and decorating coated article body makes it permanent and keeps beautiful, clean.
Oxidation processing technique: oxidation processing technique generally has two kinds, and electric conductive oxidation is handled and anodic oxidation treatment.Electric conductive oxidation is handled the metal products surface by chemical oxidation, and formed oxide film can make the metallic surface have lower contact resistance, and conductivity is good, and has erosion resistance preferably.Anodic oxidation is meant that in electrolyte solution the product with conductive surface places anode, under the effect of extrinsic current, forms the process of oxide film on the metal products surface.Have higher hardness, excellent corrosion resisting performance and good insulating property through the metal products surface of anodizing.If again with processing of dyeing such as oxalic acid, can have good surface appearance effect and higher heat emissivity coefficient through anodised metal products.
Current, surface treatment for electronic device shell, usually a kind of technology that adopts is electric conductive oxidation and paint application process combined, internal surface such as casing adopts electric conductive oxidation to handle, to guarantee to realize between each part that the successive conduction connects, outside surface is painted coating processes, so that the engineering design of outward appearance and the destruction of resisting outside atmosphere.But the shortcoming of this method is: the coating that is used in the paint application technology belongs to high thermal resistance material, is unfavorable for the integral heat sink of electronic module or electronics; Paint application technology is had relatively high expectations to the electronic device shell surfaceness, and is scratched easily in the assembling and setting process; The thermal expansion coefficient difference of employed coating of paint application technology and aluminium alloy is bigger, occurs crackle easily under envrionment temperature condition jumpy; Paint application technology only is suitable for producing in enormous quantities, and for separate unit or small serial production, cost is very high; Paint application technology belongs to the technology of strong pollution.
In addition, also having a kind of technology is exactly the technology that regional anodic oxide coating is removed in anodic oxidation treatment and machining, that is, casing integral body carried out anodic oxidation treatment after, with mach mode zone of oxidation is carried out on the surface of needs conduction and remove, to reach the effect that conduction connects between each part.The shortcoming of this method is: part is difficult to clamping, location when machining, or it is not enough and cause mismachining tolerance to increase local strength to occur; When the technological design of processing, must reserve the size surplus that anodized surface is removed; In mach process, be easy to destroy the part outward appearance when clamping, location; The cost height of machining process, operation easier height are unfavorable for producing in batches; Contact resistance with the metallic surface after the machining removal anodized surface will be far above the contact resistance on electric conductive oxidation surface.
Therefore, the process for treating surface of existing metal products exists as low, the difficult defective such as metal products of making according to the planner of cost height, yield rate.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of combined oxidation method of metal products, zone to metal products needs the surface of low contact resistance to carry out electric conductive oxidation, and anodic oxidation is carried out on the surface that needs high-heating radiation coefficient, high rigidity, high corrosion resistance, thereby can be easily according to planner's intention, low-cost, high rate of finished products is made metal products.
Another object of the present invention is to provide a kind of metal products, can make the surface of metal products have the premium properties of electric conductive oxidation surface treatment and anodic oxidation treatment simultaneously.
To achieve these goals, the present invention relates to:
(1) a kind of combined oxidation method of metal products may further comprise the steps:
Pending metal products is carried out electric conductive oxidation to be handled;
The need conductive region that carried out the metal products that electric conductive oxidation handles is covered processing;
The metal products that carried out covering processing is carried out anodic oxidation treatment; And
Shaded areas is gone to cover processing.
According to the combined oxidation method of the metal products described in (1), it is characterized in that (2) described covering handled following carrying out: the need conductive region at metal products is coated with the masking material that is diluted by reactive thinner, is heating and curing then, forms and covers protective layer.
According to the combined oxidation method of the metal products described in (2), it is characterized in that (3) the metal products oil removing after before the coating masking material electric conductive oxidation being handled is also dried.
(4) according to the combined oxidation method of the metal products described in (2), it is characterized in that, metal products is put into 100 ℃～150 ℃ thermostat container toast 30min～60min and carry out described being heating and curing.
(5) according to the combined oxidation method of the metal products described in (2), it is characterized in that described masking material contains hydroxyethyl methylacrylate and Tetra hydro Phthalic anhydride.
(6) according to the combined oxidation method of the metal products described in (2), it is characterized in that described reactive thinner is an acrylic ester monomer.
(7) according to the combined oxidation method of the metal products described in (6), it is characterized in that described acrylic ester monomer comprises alkoxy acrylic ester and carbonic acid mono acrylic ester.
(8) according to the combined oxidation method of the metal products described in (1), it is characterized in that, described go to cover in the processing to remove with remover cover protective layer.
(9) according to the combined oxidation method of the metal products described in (8), it is characterized in that described remover is a chlorinated hydrocarbon.
(10) according to the combined oxidation method of the metal products described in (9), it is characterized in that described chlorinated hydrocarbon is a trieline.
(11) according to the combined oxidation method of the metal products described in (1), it is characterized in that described metal products is the aluminum or aluminum alloy goods.
(12) a kind of metal products handles to obtain by any described method in (1)～(10).
Combined oxidation method according to metal products of the present invention, can realize that the region surface of metal products has the good conductivity in electric conductive oxidation surface and the characteristic of corrosion resistance with mode low-cost, high rate of finished products, remaining surface has the characteristics such as high rigidity, high abrasion degree, high radiation coefficient and abundant colors effect of anodized surface simultaneously.
Description of drawings
Fig. 1 is the combined oxidation method flow diagram of metal products of the present invention;
Fig. 2 is the synoptic diagram that is used to illustrate certain Al-alloy products A of the present invention.
Embodiment
For making purpose of the present invention, technical scheme clearer, below with reference to the accompanying drawing embodiment that develops simultaneously, the present invention is described in further detail.
The present invention relates to a kind of combined oxidation method of metal products, may further comprise the steps: pending metal products is carried out electric conductive oxidation handle; The need conductive region that carried out the metal products that electric conductive oxidation handles is covered processing; The metal products that carried out covering processing is carried out anodic oxidation treatment; And shaded areas gone to cover processing.Like this, even baroque metal products also can be easily carry out the surface treatment of metal products according to planner's intention, and with low cost, yield rate is high.
The present invention relates to the metal products that obtains by above-mentioned combined oxidation method.
Fig. 1 is the combined oxidation method flow diagram of metal products of the present invention.As can be seen from Figure 1, this method comprises:
S101: the electric conductive oxidation treatment step, metal products is carried out electric conductive oxidation handle, form conductive oxide film;
S102: cover treatment step, processing is covered in the zone of needs conduction, the protection conductive region;
S103: the anodic oxidation treatment step, the metal products that the zone of needs conduction is covered processing carries out anodic oxidation treatment, forms anode oxide film in the zone of not covering processing; With
S104: remove and cover treatment step, the zone of covering processing is removed cover processing, the electric conductive oxidation zone is exposed.
Above-mentioned electric conductive oxidation is handled and above-mentioned anodic oxidation treatment can adopt existing electric conductive oxidation and anode oxidation process respectively.
Above-mentioned electric conductive oxidation is handled except the chemical oxidation (S1014) on basis, can also comprise nitric acid bright dipping (S1013) process, and this nitric acid bright dipping is carried out in the formulated nitric acid bright dipping solution of nitric acid, chromic anhydride and water.Thereby, can guarantee the tack of the oxide film of process electric conductive oxidation to metal products.In addition, above-mentioned electric conductive oxidation is handled and can be comprised organic solution oil removing (S1011), alkali cleaning (S1012) and baking-curing steps such as (S1015) as required.
Cover in the processing above-mentioned, metal products oil removing after before the coating masking material electric conductive oxidation being handled is also dried (S1021), behind the coating masking material (S1022) metal products is put into 100 ℃～150 ℃ thermostat container and toasts 30min～60min be heating and curing (S1023).The masking material of coating contains hydroxyethyl methylacrylate and Tetra hydro Phthalic anhydride.This masking material is applied to the need conductive region of metal products afterwards with the reactive thinner dilution.The ratio of masking material and reactive thinner is not particularly limited, can be according to different coating processes, mix with certain proportion aptly according to required flowability, set time, solidification value, for example adopting when brushing technology is 1:3～1:4, is 1:8～1:10 when adopting spraying coating process.Reactive thinner is an acrylic ester monomer, as alkoxy acrylic ester, carbonic acid mono acrylic ester etc.Above-mentioned masking material coating process then can use any means so long as masking material evenly can be coated on the product surface, as brushing or spraying etc.Thereby, can protect the part that needs conduction fully, it is not destroyed by back anodic oxidation step.In addition, above-mentionedly cover processing and can comprise steps such as organic solution oil removing, flushing and baking-curing as required.
Above-mentioned anodic oxidation step is except in electrolytic solution, outside the anodic oxidation of carrying out under the effect of impressed voltage (S1032) process, can comprise organic solution oil removing (S1031) as required, flushing (S1033), dyeing, sealing of hole solidify (S1034) and steps such as (S1035) is dried in flushing.
Above-mentioned removal is covered step and is removed with remover dissolving removal masking material (S1041), outside the removal masking material process on the goods conductive oxide film till the no masking material, can comprise flushing steps such as (S1042) as required.Remover can use as chlorinated hydrocarbons such as trielines.
Employed metal products among the present invention is so long as can realize the combined oxidation on metal products surface by aforesaid method, then do not do special restriction, can be aluminum or aluminum alloy, magnesium or magnesium alloy, iron or copper etc., wherein, consider from aspects such as the adhesive ability of masking material and costs, be preferably the aluminum or aluminum alloy goods.
Be that aluminium alloy is an example with metal products below, with reference to Fig. 2 the present invention specifically implemented embodiment and be elaborated.
Fig. 2 is the synoptic diagram of certain Al-alloy products A.Surface 201 is the electric conductive oxidation zone, and surface 202 is the anodic oxidation zone.
At first, with the formulated organic solution of sodium phosphate 50～70g/L, water glass 25～35g/L, sodium laurylsulfonate 8～12g/L and water Al-alloy products A is carried out drying after the oil removing.Then, under 50～70 ℃ of temperature, soaked 0.5～2 minute,, rinse well afterwards until the Ex-all of workpiece surface greasy dirt with sodium hydroxide 20～35g/L, yellow soda ash 20～30g/L and the formulated soda-wash solution of water.Then, at room temperature, clean with nitric acid 300～500g/L, chromic anhydride 5～15g/L and the formulated solution of water, till the black film that forms because of the workpiece surface oxidation moves back only.Then, under 25～35 ℃ of temperature,, with hot water injection 0.5～1min of 40～50 ℃, dry naturally behind immersion 3～8min with chromic anhydride 3.5～4.0g/L, sodium dichromate 99 3.0～3.5g/L, Sodium Fluoride 1g/L and the formulated solution of water.In 40～50 ℃ of baking ovens of temperature, solidify 10～15min at last, formed all surface and carried out Al-alloy products A after electric conductive oxidation is handled.
Then, the Al-alloy products A after electric conductive oxidation handled dries after with above-mentioned organic solution oil removing, as 201 two dot chain line zones, the surface among Fig. 2, the product surface that promptly needs to conduct electricity on masking material after evenly coating is diluted with reactive thinner.The thermostat container of Al-alloy products A being put into 100 ℃～150 ℃ toasts 30min～60min again, makes the masking material completely solidified, forms the Al-alloy products A after the region surface crested is protected.
Then, handle and the Al-alloy products A that covers processing dries after cleaning oil removing through electric conductive oxidation above-mentioned with above-mentioned organic solution.In sulphuric acid soln, under 20～30 ℃ of temperature, the voltage 12V condition, handle 40～60min.Afterwards, the debris on the flushing goods.Put into then with buffalo black ATT20～30g/L, acid lake blue 2～3g/L and the formulated staining fluid of water, under 50～70 ℃ of temperature, pH3～3.5 or 4.5～5.5 conditions, soak time 10～15min finishes dyeing.Do not have the color requirement as fruit product, then do not need to dye.Under 40～60 ℃ of temperature, in baking oven, solidify 15～30min afterwards.Wash again afterwards and dry.Like this, formed, the surface 201 of regional crested material protection has been arranged on the goods A, the surface 202 that forms hard anodized film has also been arranged through the Al-alloy products A after the anodic oxidation treatment.
At last, it is removed, on the electric conductive oxidation face of goods, do not have masking material residual with remover dissolving masking material.After goods are washed, obtained the Al-alloy products A after the combined oxidation surface treatment.Remover can use as chlorinated hydrocarbons such as trielines.
For the flushing process among the present invention, unless otherwise noted, all water washes.
Embodiment
Take by weighing sodium phosphate (Na
3PO
412H
2O) 60g, water glass (Na
2SiO
3) 30g, sodium laurylsulfonate 10g be added to the water, the organic solution of preparation 1L.Al-alloy products A dries after putting into this organic solution oil removing as shown in Figure 2.Weighing sodium hydroxide 30g, yellow soda ash 25g are added to the water, the soda-wash solution of preparation 1L.Under 60 ℃ of temperature, in this soda-wash solution, will soak 1min through the above-mentioned Al-alloy products A after the organic solution oil removing, make the Ex-all of workpiece surface greasy dirt after, rinse well.Then, at room temperature the Al-alloy products A by above-mentioned organic solution deoiling step and alkali cleaning step is carried out nitric acid bright dipping step, till black film moves back only with the solution of nitric acid 400g, chromium 10g and water preparation 1L.Then at room temperature, chromic anhydride 4g, sodium dichromate 99 3g, Sodium Fluoride 1g and water be made into soak 8min in the solution of 1L after, the hot water injection 1min with 50 ℃ dries naturally.In 50 ℃ of baking ovens of temperature, solidify 15min at last, formed the Al-alloy products A behind all surface electric conductive oxidation.
Al-alloy products A behind the electric conductive oxidation is dried after with above-mentioned organic solution oil removing, with JFT5011 type reactive thinner and the JFT301 type printing ink (containing hydroxyethyl methylacrylate and Tetra hydro Phthalic anhydride) that mixed Shenzhen Jia Meide Science and Technology Ltd. of 10:1 produces, make masking material.Even this masking material of spraying on as Fig. 2 two dot chain line zone, the product surface that promptly needs to conduct electricity.The thermostat container of goods being put into 150 ℃ toasts 50min again, makes the masking material completely solidified, forms the Al-alloy products A after regional crested is protected.
Then, dry after the Al-alloy products A that the process said process is obtained cleans oil removing with above-mentioned organic solution.Under the condition of room temperature, impressed voltage 12V, in sulphuric acid soln, handle 60min.Afterwards, the residual solution on the flushing goods.The 1L solution that preparation is made by buffalo black ATT30g, acid lake 3g and water makes the pH value of this solution remain on 3～3.5, soaks goods 15min down for 50 ℃ in temperature, thereby obtains not having the zone of crested material protection to be blue Al-alloy products A.Under 50 ℃ of temperature, in baking oven, solidify 30min afterwards.Wash again afterwards and dry.
At last, remove masking material, no any residuals on Al-alloy products electric conductive oxidation face with the trieline dissolving.Al-alloy products is washed, formed the Al-alloy products A after the combined oxidation surface treatment.
By combined oxidation method of the present invention, can make the surface of metal products have all premium propertiess of electric conductive oxidation surface treatment and anodic oxidation treatment simultaneously, and can freely select treat surface, thereby be implemented in the performance requriements of the conductivity that Application Areas proposed, hardness, fastness to rubbing, erosion resistance, heat emissivity coefficient etc. of metal products to the metal products surface according to the design effect of metal products; Implementation cost is low, and process is simple and easy to control, the yield rate height.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1, a kind of combined oxidation method of metal products may further comprise the steps:
Pending metal products is carried out electric conductive oxidation to be handled;
The need conductive region that carried out the metal products that electric conductive oxidation handles is covered processing;
The metal products that carried out covering processing is carried out anodic oxidation treatment; And
Shaded areas is gone to cover processing.
2, the combined oxidation method of metal products according to claim 1 is characterized in that, described covering handled following carrying out: the need conductive region at metal products is coated with the masking material that is diluted by reactive thinner, is heating and curing then, forms and covers protective layer.
3, the combined oxidation method of metal products according to claim 2 is characterized in that, the metal products oil removing after before the coating masking material electric conductive oxidation being handled is also dried.
4, the combined oxidation method of metal products according to claim 2 is characterized in that, metal products is put into 100 ℃～150 ℃ thermostat container toast 30min～60min and carry out described being heating and curing.
5, the combined oxidation method of metal products according to claim 2 is characterized in that, described masking material contains hydroxyethyl methylacrylate and Tetra hydro Phthalic anhydride.
6, the combined oxidation method of metal products according to claim 2 is characterized in that, described reactive thinner is an acrylic ester monomer.
7, the combined oxidation method of metal products according to claim 6 is characterized in that, described acrylic ester monomer comprises alkoxy acrylic ester and carbonic acid mono acrylic ester.
8, the combined oxidation method of metal products according to claim 1 is characterized in that, described go to cover in the processing to remove with remover cover protective layer.
9, the combined oxidation method of metal products according to claim 8 is characterized in that, described remover is a chlorinated hydrocarbon.
10, the combined oxidation method of metal products according to claim 9 is characterized in that, described chlorinated hydrocarbon is a trieline.
11, the combined oxidation method of metal products according to claim 1 is characterized in that, described metal products is the aluminum or aluminum alloy goods.
12, a kind of metal products handles to obtain by any described method in the claim 1～11.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102235985A CN101376999B (en) | 2008-10-08 | 2008-10-08 | Composite oxidation method for metallic products |
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|---|---|---|---|
| CN2008102235985A CN101376999B (en) | 2008-10-08 | 2008-10-08 | Composite oxidation method for metallic products |
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| CN101376999A true CN101376999A (en) | 2009-03-04 |
| CN101376999B CN101376999B (en) | 2011-09-07 |
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| CN2008102235985A Expired - Fee Related CN101376999B (en) | 2008-10-08 | 2008-10-08 | Composite oxidation method for metallic products |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453933A (en) * | 2010-10-25 | 2012-05-16 | 深圳市国人射频通信有限公司 | Selective plating method for aluminum material |
| CN104498932A (en) * | 2014-12-21 | 2015-04-08 | 天津七六四通信导航技术有限公司 | Surface treatment method for structural components of satellite navigation receiver |
| CN104741787A (en) * | 2015-03-20 | 2015-07-01 | 大族激光科技产业集团股份有限公司 | Metal product forming method and metal product |
| CN105695928A (en) * | 2016-01-27 | 2016-06-22 | 太仓捷公精密金属材料有限公司 | Oxidizing method for metal product |
| CN114481111A (en) * | 2022-01-18 | 2022-05-13 | 深圳市飞航精工科技有限公司 | Rainbow color conductive oxidation method and oxidation liquid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8902584D0 (en) * | 1989-02-06 | 1989-03-22 | Taubmans Ind Ltd | Coating process |
| JP2923434B2 (en) * | 1994-07-20 | 1999-07-26 | 株式会社フジクラ | Piston for internal combustion engine and method of manufacturing the same |
-
2008
- 2008-10-08 CN CN2008102235985A patent/CN101376999B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453933A (en) * | 2010-10-25 | 2012-05-16 | 深圳市国人射频通信有限公司 | Selective plating method for aluminum material |
| CN102453933B (en) * | 2010-10-25 | 2016-05-04 | 深圳市国人射频通信有限公司 | Selective plating method for aluminum material |
| CN104498932A (en) * | 2014-12-21 | 2015-04-08 | 天津七六四通信导航技术有限公司 | Surface treatment method for structural components of satellite navigation receiver |
| CN104741787A (en) * | 2015-03-20 | 2015-07-01 | 大族激光科技产业集团股份有限公司 | Metal product forming method and metal product |
| CN105695928A (en) * | 2016-01-27 | 2016-06-22 | 太仓捷公精密金属材料有限公司 | Oxidizing method for metal product |
| CN114481111A (en) * | 2022-01-18 | 2022-05-13 | 深圳市飞航精工科技有限公司 | Rainbow color conductive oxidation method and oxidation liquid |
| CN114481111B (en) * | 2022-01-18 | 2023-09-29 | 深圳市飞航精工科技有限公司 | Iridescent conductive oxidation method and oxidation liquid |
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