CN101642973B - Stainless composite material and preparation method thereof - Google Patents
Stainless composite material and preparation method thereof Download PDFInfo
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- CN101642973B CN101642973B CN 200810142274 CN200810142274A CN101642973B CN 101642973 B CN101642973 B CN 101642973B CN 200810142274 CN200810142274 CN 200810142274 CN 200810142274 A CN200810142274 A CN 200810142274A CN 101642973 B CN101642973 B CN 101642973B
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Abstract
The invention discloses a stainless composite material, which comprises a stainless base material as well as an aluminum-containing layer arranged on the surface of the stainless base material and an alumina layer arranged on the surface of the aluminum-containing layer. The invention also discloses a preparation method of the stainless composite material, which comprises the following steps of: forming the stainless composite material on the surface of the stainless base material; and forming the alumina layer on the surface of the aluminum-containing layer. In the stainless composite material and the preparation method thereof, the surface of the stainless composite material can be provided with various needed colors and has very good wear resistance. Preferentially, the preparation method provides the surface of the stainless composite material with various needed colors and an excellent decoration effect of the stainless base material by mixing and selecting dyeing pigments, thereby improving the value of products.
Description
Technical field
The present invention relates to a kind of stainless steel composite material, also relate to the preparation method of this stainless steel composite material.
Background technology
Traditional stainless steel surfaces is decorated methods such as adopting polishing, wire drawing, satin face and sandblast, and these class methods all can change stainless outward appearance to a certain extent, make stainless steel surfaces have certain aesthetic.Can also adopt the stainless steel coloring technology to make stainless steel surfaces have various colors; General stainless steel coloring technology can adopt spraying, silk-screen and oxide-film interference etc.; But adopt the wearability of the resulting stainless steel product of these methods relatively poor, color and aesthetic property are all undesirable.
Summary of the invention
The objective of the invention is to overcome the defective that wearability is relatively poor and color category is few of above-mentioned stainless steel product of the prior art, a kind of wearability colored stainless steel composite preferably is provided, the preparation method of this stainless steel composite material also is provided.
The invention provides a kind of stainless steel composite material, this composite comprises stainless steel substrate, and wherein, this composite also comprises containing metal aluminium lamination that is positioned at this stainless steel substrate surface and the alumina layer that is positioned at containing metal aluminium lamination surface.
The present invention also provides a kind of preparation method of stainless steel composite material, and this method is included in the stainless steel substrate surface and forms the containing metal aluminium lamination, forms alumina layer on said containing metal aluminium lamination surface.
According to stainless steel composite material provided by the invention and preparation method thereof, make the color of the various needs of stainless steel composite material surface acquisition, and wearability is fine.And through preparation method of the present invention; Under preferable case,, can make the stainless steel composite material surface obtain the color of various needs through the proportioning and the selection of dyeing pigment; Make stainless steel substrate can obtain better decorative effect, thereby can improve the value of product.
The specific embodiment
Stainless steel composite material provided by the invention comprises stainless steel substrate, and wherein, this composite also comprises containing metal aluminium lamination that is positioned at this stainless steel substrate surface and the alumina layer that is positioned at containing metal aluminium lamination surface.
According to stainless steel composite material provided by the invention, under the preferable case, the aluminum content on said containing metal aluminium lamination surface is at least 75%, and the aluminum content in 5 microns on the more preferably said containing metal aluminium lamination top layer is 80%.
According to stainless steel composite material provided by the invention, under the preferable case, the thickness of said containing metal aluminium lamination is the 50-120 micron, and the thickness of said alumina layer is the 5-25 micron.
The preparation method of stainless steel composite material provided by the invention comprises, forms the containing metal aluminium lamination on the stainless steel substrate surface, forms alumina layer on said containing metal aluminium lamination surface.
According to preparation method provided by the invention; Said containing metal aluminium lamination can adopt the whole bag of tricks to form; Under the preferable case; Said containing metal aluminium lamination adopts the ion implantation method to form, and the condition of ion implantation makes the aluminum content on said containing metal aluminium lamination surface be at least 75%, and the minimum aluminum content in 5 microns on the more preferably said containing metal aluminium lamination top layer is 80%.
According to preparation method provided by the invention, said ion implantation technique is for well known to a person skilled in the art, the condition of control ion implantation can obtain the containing metal aluminium lamination of the aluminum content at least 75% on surface.Under the preferable case, the condition of ion implantation comprises that voltage is that 100-1000 volt, temperature are that 300-600 ℃, gas pressure (argon gas, absolute pressure) are 3-8 hour for 10-1000Pa, time.Said ion implantation technique preferably adopts two brightness ion implantation techniques; The detailed process of this method and method of operating are for adopting the glow discharge of argon gas vacuum low-pressure; The metal fine aluminium is stimulated becomes ion and atom; Finally infiltrate stainless steel surfaces, make its surface alloying, and even form the aluminium alloy fine aluminium in the metal surface with certain speed.
According to preparation method provided by the invention, said alumina layer can adopt the various methods that well known to a person skilled in the art to form, and preferably adopts anodised method to form, and anodised condition to make the thickness of said alumina layer be the 5-25 micron.
According to preparation method provided by the invention, the stainless steel substrate that will have the containing metal aluminium lamination carries out anodic oxidation, need make the aluminum content on containing metal aluminium lamination surface be at least 75%, just can carry out anodic oxidation and obtains alumina layer.Therefore need condition restriction with above-mentioned ion implantation in above-mentioned scope.
According to preparation method provided by the invention, said anodised condition is for well known to a person skilled in the art.Adopt dyeing to obtain having the product of different colours then,, thus can make stainless steel composite material of the present invention obtain various colors.
For example, anodised condition can comprise, the stainless steel substrate that forms the containing metal aluminium lamination is contacted with electrolyte as anode, and to be not negative electrode with fine aluminium or terne metal plate, voltage is the 12-22 volt, and current density is 0.5-2.5A/dm
2, the temperature of electrolyte is 13-26 ℃, the anodised time is 30-40 minute.Can control the thickness of alumina layer through the voltage in the above-mentioned condition of control, time, thereby can obtain the color of needs.
According to preparation method provided by the invention, the employed electrolyte of said anodic oxidation can be for well known to a person skilled in the art various acidic electrolysis baths, for example sulfuric acid, ethanedioic acid, chromic acid etc.In the present invention, preferably adopt sulfuric acid electrolyte, and said electrolyte is for containing the 160-200 grams per liter aqueous solution.
According to preparation method provided by the invention, obtain predetermined pattern if desired, can the mould with this pattern be covered on the stainless steel substrate, carry out the anodic oxidation of ion implantation then successively, can obtain needed pattern.
According to preparation method provided by the invention, under preferable case, preparation method of the present invention also comprises stainless steel substrate carried out pre-treatment, and the pre-treatment that stainless steel substrate carried out is generally included polishing and cleans or only clean.Polishing can be adopted and well known to a person skilled in the art and for example can adopt machine glazed finish, chemical polishing and electrobrightening by various finishing methods.Cleaning can be adopted and well known to a person skilled in the art the whole bag of tricks, and the cleaning fluid that also can directly select for use producer to prepare preferably can also cooperate ultrasonic vibration to clean.
Adopt the mode of embodiment that the present invention is described in further detail below.
Embodiment 1
Workpiece: stamping forming stainless steel (North America stainless steel company) phone housing
1, pre-treatment
(1) machine glazed finish
Adopting rough polishing ointment (SBT-600 type) in the yellow that polishing machine (JM-101 type) that the brilliant close plant equipment of Dongguan City Co., Ltd produces produces with the outstanding sharp letter rubbing down in Jiangmen Materials Co., Ltd is under 2840 rev/mins the condition workpiece slightly to be thrown 10 minutes at the rotating speed of polishing wheel, is under 2840 rev/mins the condition workpiece to be carried out essence throwing 10 minutes at the rotating speed of polishing wheel with the smart ointment (SBW-804 model) of throwing of white again.
(2) clean
Workpiece after the above-mentioned polishing is soaked successively in the solution of WX-1048F type antiscuffing paste cleaning agent (Shanghai Lufeng Promoter Co., Ltd.); In the normal temperature ultrasonic waves for cleaning; Scavenging period is 10 minutes, in pure water ultrasonic waves for cleaning 10-20 minute then, cleans the back oven dry that finishes.
2, ion implantation
Workpiece after the above-mentioned pre-treatment is put into ion metallizing device (multi-functional plasma surface modification equipment; Surface Engineering Co., Ltd runs initially in Wuhan; Model LDMC-15A/LD-15A) carry out the ion aluminising in, the voltage that is adopted is the 200-500 volt, and air pressure (argon gas, absolute pressure) is 20 ± 3 handkerchiefs; Temperature is 350 ± 20 ℃, and the aluminising time is 5 hours.Adopt the metallographic structure detection method to test out, obtaining thickness on the stainless steel substrate surface is 100 microns containing metal aluminium lamination, and adopts energy disperse spectroscopy to detect, and the aluminium content on containing metal aluminium lamination surface is 96%.
Then, adopt artificial mechanism slightly to throw, carry out acetone or alcohol (concentration 99.9%, Tianjin chemical reagent factory) ultrasonic waves for cleaning.
3, anodic oxidation
The above-mentioned stainless steel substrate that carries out after the pre-treatment is immersed in the electrolyte of electrolytic cell, is anode with the workpiece, is negative electrode with the pure aluminum plate plate, is 15-25V at voltage, and current density is 0.5-2.5A/dm
2, and be to carry out anodic oxidation under 25 ℃ the condition in the temperature of electrolyte, the anodised time is 45 minutes.
Electrolyte is for containing sulfuric acid 160-200 grams per liter, Al
3+Be the aqueous solution of 10 ± 3 grams per liters.
The taking-up workpiece cleaning is clean, with the organic dyestuff that will prepare color (purplish red) workpiece dyeed, and sealing of hole, cleaning then, and 75 ℃ of oven dry down, finally obtain the surface and be mauve stainless steel composite material.
Embodiment 2
The corrosion resistant plate of workpiece: 300 * 60 * 0.5mm (304, North America stainless steel company)
1, pre-treatment
Clean
Workpiece after the above-mentioned polishing is immersed in normal temperature successively removes La Shui, remove in the deionized water of oil-bound distemper solution and 70 ℃ and carry out ultrasonic waves for cleaning, scavenging period was followed successively by 5 minutes, 5 minutes, 10 minutes, and each all uses water washing between the step.Wherein remove La Shui and remove oil-bound distemper and be wheat dolantin Fine Chemical Co., Ltd product.Oven dry after cleaning finishes.
2, ion implantation
Workpiece after the above-mentioned pre-treatment is put into ion metallizing device (multi-functional plasma surface modification equipment; Surface Engineering Co., Ltd runs initially in Wuhan; Model LDMC-15A/LD-15A) carry out the aluminising of single face ion in, the voltage that is adopted is 800 volts, and air pressure (argon gas, absolute pressure) is 100 handkerchiefs; Temperature is 580 ℃, and the aluminising time is 6 hours.Adopt metallographic structure to detect (German ZEISS metallographic microscope; Model Axio Imager.A1m) tests out; Obtain thickness on stainless steel substrate surface and be 150 microns containing metal aluminium lamination; And adopt energy disperse spectroscopy (Japanese ULVAC-PHI company 1800 type photoelectron spectrographs) to test out, the aluminium content on containing metal aluminium lamination surface is 99%.
Then, directly the ultrasonic wave oil removing is cleaned, is dried.
3, anodic oxidation
The above-mentioned stainless steel substrate that carries out after the pre-treatment is immersed in the electrolyte of electrolytic cell, is anode with the workpiece, is negative electrode with stereotype not, is 40-50V at voltage, and current density is 1.5-2.8A/dm
2, and be to carry out anodic oxidation under 25 ℃ the condition in the temperature of electrolyte, the anodised time is 60 minutes.
Electrolyte is the ethanedioic acid aqueous solution of 1 grams per liter chromic anhydride, 40-50 grams per liter.Clean organic dyestuff (Prussian blue) dyeing, sealing of hole (low temperature pore sealing agent) then.
Take out the clean and oven dry under 80 ℃ of workpiece cleaning, oxide thickness is that 8-15 micron (metallographic structure detection) finally obtains the surperficial blue stainless steel composite material that is.
Comparative Examples
The corrosion resistant plate of 300 * 60 * 0.5mm (304, general stainless steel alloy), adopt with quadrat method smartly throw, clean, oven dry, adopt spraying then, solidify, spraying is solidified again again.Artificial spraying method is adopted in spraying, and be conventional spraying coating process: spray distance is that 20-25cm, spray gun diameter are that 1.1-1.5mm, spray pressure are that 0.1-0.3MPa, baking temperature are 130 ℃, solidifies the UV machine (Runao Electromechanical Co., Ltd., Shenzhen City) that adopts.At first primer spray (model: 3655-series), spray UV colored paint (model: 3600-70001) then.Coating all is products of Hong Kong card show brightness fort coating Co., Ltd.
Finally obtain the coating that thickness is the 5-25 micron on the stainless steel substrate surface.
Performance test
1, tack
Test institute accepted standard: ISO 2409.
Testing procedure:
Mark the grid of 100 1mm * 1mm at sample surfaces to be tested; The degree of depth of drawing lattice is to exposing the sample ground; The model of using Minnesota Mining and Manufacturing Company to produce is that 600 adhesive tape sticks on and draws on the good grid, and adhesive tape and grid are pasted fully, and phenomenons such as wrinkle bubble can not be arranged.Drag adhesive tape from adhesive tape is monolateral rapidly with 180 ° of horizontal directions then.
Evaluation criterion is:
The 5B cut edge is smooth fully, four jiaos of not distortion of grid;
There is little peeling off 4B overlay film inside, and the zone less than 5% is affected;
There is little peeling off at 3B overlay film edge with inner, and the zone of quadrille 5-15% is affected;
The edge of 2B overlay film and part plane have and come off, and the zone of influence accounts for the 15-30% of grid;
Peel off the cut edge of 1B overlay film, and have large-area band to separate with monoblock, and the influence area is at 35-65%;
0B comes off and surpasses the requirement of 1B level with separating.
2, wearability
Use the RCA paper tape wear resistant instrument of model as F350008, friction sample surfaces under 175 gram forces is milled to when show-through the number of turns that the record rubber wheel rotates to sample surfaces.
Adopt above-mentioned method of testing that embodiment 1-2 and Comparative Examples 1 resulting stainless steel composite material are carried out performance test, gained is the result list in the table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative Examples 1 | |
| Tack | 5B | 5B | 3B |
| Wearability | 78 | 84 | 51 |
Can find out that from the data of table 1 adopt the stainless steel material of gained of the present invention all good than spraying on adhesive force and wearability, stainless steel has great application prospect in decorating and protecting in modern times.
Claims (7)
1. stainless steel composite material, this composite comprises stainless steel substrate, it is characterized in that, this composite also comprises containing metal aluminium lamination that is positioned at this stainless steel substrate surface and the alumina layer that is positioned at containing metal aluminium lamination surface; Said containing metal aluminium lamination is the ion aluminized coating; The aluminum content on said containing metal aluminium lamination surface is at least 75%; Said alumina layer is an anode oxidation membrane, and the thickness of said alumina layer is the 5-25 micron.
2. composite according to claim 1, wherein, the thickness of said containing metal aluminium lamination is the 30-200 micron.
3. composite according to claim 1 and 2, wherein, the minimum aluminum content in 5 microns on the said containing metal aluminium lamination top layer is 80%.
4. the preparation method of the described stainless steel composite material of claim 1 is characterized in that, this method is included in the stainless steel substrate surface and forms the containing metal aluminium lamination, forms alumina layer on said containing metal aluminium lamination surface; Said containing metal aluminium lamination adopts the ion implantation method to form, and the condition of ion implantation makes the aluminum content on said containing metal aluminium lamination surface be at least 75%; Said alumina layer adopts anodised method to form, and anodised condition to make the thickness of said alumina layer be the 5-25 micron.
5. method according to claim 4, wherein, the condition of said ion implantation comprises that voltage is that 100-1000 volt, temperature are that 300-600 ℃, gas pressure are that 10-1000Pa, time are 3-8 hour.
6. method according to claim 4, wherein, said anodised condition comprises; The stainless steel substrate that forms the containing metal aluminium lamination is contacted with electrolyte as anode; To be not negative electrode with the conductive material of electrolyte reaction, voltage is the 10-50 volt, and current density is 0.5-10A/dm
2And even the temperature of electrolyte is 50-70 ℃ or normal temperature low temperature, and the anodised time is 20-50 minute.
7. method according to claim 6, wherein, said electrolyte is for containing H
2SO
4: 160-200 grams per liter, Al
3+Less than 20 grams per liters; Perhaps ethanedioic acid: the aqueous solution of 50-70 grams per liter.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103451662B (en) * | 2012-06-01 | 2016-05-04 | 广东欧珀移动通信有限公司 | A kind of stainless surface treatment method |
| CN104309192B (en) * | 2013-11-14 | 2017-05-31 | 比亚迪股份有限公司 | A kind of complex of stainless steel and resin and preparation method thereof |
| CN110484949A (en) * | 2019-08-14 | 2019-11-22 | 江苏苏扬包装股份有限公司 | The method that using plasma liquid phase electrolytic deposition prepares piston ring surface ceramic membrane |
| CN111497375B (en) * | 2020-03-17 | 2022-10-18 | 富联裕展科技(深圳)有限公司 | Metal composite part and method for producing the same |
| CN111676501B (en) * | 2020-07-22 | 2021-05-18 | 中山市三美高新材料技术有限公司 | Anodic oxidation coloring process with characteristic spectrum reflection enhancement |
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| CN1415783A (en) * | 2002-10-10 | 2003-05-07 | 上海大学 | Method for preparing layer for guarding against pervasion of hydrogen on surface of stainless steel |
| CN200940160Y (en) * | 2006-07-18 | 2007-08-29 | 大连海事大学 | Abrasion-resistant, corrosion-proof and antioxidation treatment layer on steel surface |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415783A (en) * | 2002-10-10 | 2003-05-07 | 上海大学 | Method for preparing layer for guarding against pervasion of hydrogen on surface of stainless steel |
| CN200940160Y (en) * | 2006-07-18 | 2007-08-29 | 大连海事大学 | Abrasion-resistant, corrosion-proof and antioxidation treatment layer on steel surface |
Non-Patent Citations (1)
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| 沈嘉年等.不锈钢表面渗铝并热氧化处理对氢渗透的影响.《腐蚀科学与防护技术》.2005,第17卷(第1期),15-19. * |
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