CN104562052A - Method for preparing ordered micropore structure on stainless steel surface - Google Patents
Method for preparing ordered micropore structure on stainless steel surface Download PDFInfo
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Abstract
The invention relates to a method for preparing an ordered micropore structure on a stainless steel surface, and belongs to the technical field of preparation of surface micro-structures. The method is an electrochemical etching method and comprises the following steps: placing stainless steel which is subjected to degreasing, electrochemical polishing and nitric acid passivation into a water base solution in which the concentration of phosphoric acid is 15 to 50g/L, and corroding for 30 to 120min under a process condition in which the current density is 5 to 50A/dm<2> and the temperature is 0 to 5 DEG C by a constant current method to obtain the ordered micropore structure which has a uniform pore diameter of 200 to 550nm and a pore depth of 1 to 3 microns. The micropore structure is generated in situ on the stainless steel surface, can avoid peeling problem and is smooth on surface; and the stainless steel can still keep the original glaring appearance; moreover, the micropore structure is prepared from amorphous Cr2O3 and Fe2O3 so as to have a better wear and corrosion resistance than the existing stainless steel material; and the electrochemical corrosion and the electrochemical polishing can be both carried out in an ordinary electrolytic bath, so that the device is simple, and the preparation cost is low, and the method is easy to popularize.
Description
Technical field
The present invention relates to a kind of preparation method of microvoid structure, be specifically related to a kind of preparation method of stainless steel surface ordered micro-cellular structure, belong to surface micro-structure preparing technical field.
Background technology
Stainless steel has attractive in appearance, corrosion-resistant, the premium properties such as ductility is good, easy processing, very extensive in field application such as building, medicine equipment, food-processing, household electrical appliance, as building and ornament materials, elevator & stairs handrail, railing, bio-medical material, embedded material, instruments, food processing machinery, dining car, food-shelf, tank, cabinet, kitchen cabinet, washing machine inner bag, shower, water tank, door handle etc.
In recent years, more and more investigator turns one's attention to the preparation of stainless steel surface microvoid structure, to widening its functional application further.As, stainless steel surface microvoid structure can increase the specific absorption to light, reduces its reflectivity, for solar energy collector, can improve the utilization ratio of sun power; For coronary artery bracket bracket for eluting medicament, medicine is inserted in stainless steel surface micropore, by release medicine in use procedure, can react by inflammation-inhibiting, control the generation of Vascular Restenosis after Balloom; For building surface, surface microporous structure can absorb microwave, infrared rays, sound wave, eliminates Contamination of Electromagnetic Wave, sound pollution, also has heat-insulating property simultaneously; Prepare microvoid structure on stainless steel tableware and cooking utensils surface, antiseptic elements is deposited in micropore, antibacterial layer can be prepared at surface of stainless steel product, thus anti-bacteria is multiplied.
At present, the method that stainless steel surface prepares micropore mainly contains chemical corrosion method and vacuum aluminum-coated+anodic oxidation composite algorithm.Chemical corrosion method is placed on by stainless steel in certain acid solution, utilize acid to form micro-hole of certain size and density to the corrosive nature of stainless steel surface, micro-hole is semisphere, opening diameter 0.5-2 μm, more shallow and the skewness of micro-hole degree of depth, undesirable for above-mentioned functions material result.Vacuum aluminum-coated+anonizing adopts physical vaporous deposition first to deposit skim aluminium at stainless steel surface, and then utilize anodic oxidation to prepare nano-porous alumina microvoid structure on aluminium coat surface, micro-pore diameter 25-100nm, hole density is up to 10
9/ cm
2, good for above-mentioned functions material result, but owing to there is sharp interface between aluminium coat and stainless steel substrate, aluminium coat is easily peeled off from substrate surface.
Chinese invention 2005100241969, tubular reducing stainlss steel micro porous film and preparation method thereof discloses a kind of tubular reducing stainlss steel micro porous film and preparation method thereof.The preparation method of this kind of film selects the Stainless Steel Powder powder material of different size to do supporting layer and key-course, by the slurry that the powder of stainless steel of two kinds of different sizes is made, synthesizes on forming mould, after high temperature sintering, obtain precision high, flux is large, the stainless steel microporous membrane containing reducing.This kind of film is particularly useful for the working order of extreme environment, and as high temperature, high pressure, high viscosity, high solid content, easily pollutes, and requires long-term operation continuously, needs the filtration condition that automatic backflushing and cleaning and regeneration etc. are strict.In industrial technical field such as chemical industry, environmental protection, nuclear power, medicine, food-processings, there is huge market potential.
Summary of the invention
The object of this invention is to provide a kind of processing method at stainless steel surface in-situ preparation ordered micro-cellular structure.Stainless steel surface micro-pore diameter prepared by the present invention is 200-550nm, and aperture is homogeneous, hole depth large (1-3 μm), and pore arrangement is orderly, and microvoid structure and matrix are an entirety, there is not spallation problems, and technique is simple, and preparation cost is low.Microvoid structure prepared by the present invention has larger hole depth/aperture ratio, is applicable to preparation above-mentioned functions material.
The present invention prepares equally distributed microvoid structure mainly through electrochemical corrosive process at stainless steel surface: after stainless steel is carried out degreasing, electrochemical etching, Passivation Treatment, DC current regulator power supply is adopted to carry out galvanic corrosion to stainless steel sample, stainless steel sample is made anode, high purity graphite sheet makes negative electrode, and being placed in phosphoric acid concentration is that the aqueous solution of 15-50g/L carries out galvanic corrosion.Electrochemical corrosive process: negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, solution temperature 0-5 DEG C, adopt galvanostatic method to carry out galvanic corrosion, current density is 5-50A/dm
2, etching time 30-120min.The microvoid structure of certain pore size and thickness is obtained by controlling the processing parameters such as solution formula, solution temperature, corrosion electric current density, etching time;
Concrete steps are as follows:
(1) stainless steel pre-treatment:
1) stainless steel is put into cleaner for metal ultrasonic cleaning 15min, carry out skimming treatment;
2) adopt DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm2, polishing time 3min;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 15-50g/L, solution temperature 0-5 DEG C, adopts galvanostatic method, current density is 5-50A/dm2, etching time 30-120min;
According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth;
Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step.
Technical characterstic of the present invention: the phosphate aqueous solution that 1) galvanic corrosion employing corrodibility is more weak, the present invention also adopted the strong acid of different concns, if sulfuric acid, nitric acid are as corrosive fluid, but corrosion speed is too fast, the intergranular corrosion that easy generation is serious or general corrosion, be difficult to obtain equally distributed microvoid structure; 2) in corrosion process, solution temperature is strict controlled in 0-5 DEG C, and intergranular corrosion or general corrosion easily occur temperature drift, not easily obtains equally distributed microvoid structure; 3) before galvanic corrosion; first stainless steel is carried out Passivation Treatment in the salpeter solution of 50%; stainless steel surface is made to generate fine and close oxide film; find through lot of experiments; generate dense oxidation film in advance to contribute to protecting stainless steel, on galvanic corrosion initial stage surface, intergranular corrosion or general corrosion do not occur, be conducive to the generation of stainless steel surface ordered micro-cellular structure.
Microvoid structure formation mechenism of the present invention: electrochemical corrosion course initial stage, by the protection of surface compact oxide film, the general corrosion of stainless steel surface is suppressed.But because the resistance of dense oxidation film is comparatively large, under electric field action, there is random breakdown phenomenon in dense oxidation film surface, causes surface electric field distribution uneven, punctures place's strength of current high, accelerate the galvanic corrosion of dense oxidation film, start to form micropore.Because stainless steel is anode, still constantly formed bottom micropore new passive film (anodic reaction:
,
,
mfor
cr, Fedeng), therefore there is the working cycle of passivation-corrosion-passivation again-corrode again bottom micropore, cause hole constantly to develop to vertical-depth.Because power line mainly concentrates at the bottom of hole, so galvanic corrosion mainly occurs in bottom micropore, and hole wall mainly occur chemical corrosion (
,
mfor
cr, Fedeng), chemical corrosion is mainly by H in solution
+ionic concn controls, so by controlling phosphorus acid content in solution, can control the dissolution rate of hole wall, obtains the microvoid structure of different pore size.The homogenizing of micro-pore diameter is mainly by the effect of microporous layers internal stress, and the homogenizing reaching stress distribution causes.According to purposes and the requirement of Stainless Steel Products, prepare the microvoid structure of different pore size size and hole depth by controlling electrochemical corrosive process.
The present invention is compared with existing stainless steel surface microvoid structure technology of preparing, and advantage is:
(1) at stainless steel surface in-situ preparation microvoid structure, there is not spallation problems, and technique is simple.
(2) the microvoid structure aperture of preparing is homogeneous, and hole depth is large, and hole distribution is even.
(3) stainless steel after galvanic corrosion still keeps higher surface smoothness.
(4) surface microporous structure is primarily of amorphous Cr
2o
3, Fe
2o
3form, there is wear-resisting, the corrosion resistance nature that are better than stainless steel bulk material.
(5) galvanic corrosion and electrochemical etching all can carry out in plain electrolysers, and equipment is simple, and preparation cost is low, easily promotes.
Accompanying drawing explanation
Fig. 1 is electrochemical corrosion device schematic diagram prepared by stainless steel surface microvoid structure;
Fig. 2 is the stainless steel surface microvoid structure SEM photo of preparation in embodiment 1;
Fig. 3 is the stainless steel surface microvoid structure SEM photo of preparation in embodiment 2;
Fig. 4 is the stainless steel surface microvoid structure SEM photo of preparation in embodiment 6;
Number in the figure illustrates: 1, anode; 2, negative electrode; 3, oxidation solution; 4, frozen water mixing bath; 5, stirrer; 6, temperature display; 7, temperature control magnetic stirring apparatus; 8, constant voltage dc source.
Embodiment
Be described in further details the present invention below by example, these examples are only used for the present invention is described, do not limit the scope of the invention.
The stainless steel that the present invention adopts is SUS304 type stainless steel, and the chemical reagent of employing is analytical pure, and the water of obtain solution is deionized water.Electrochemical etching and electrochemical corrosion apparatus all adopt WYK-15010K DC current regulator power supply (voltage 0-150V, electric current 0-10A), in electrochemical corrosion course, in order to keep solution temperature to be 0-5 DEG C, adopt the equipment with refrigeration plant.Meanwhile, adopt magnetic agitation that solution temperature is kept evenly.
Embodiment 1
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 min, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 15g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 5A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 2
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 15g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 12.5A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 3
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 15g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 25A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 4
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 15g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 37.5A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 5
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 15g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 50A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 6
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 30g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 5A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 7
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 30g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 12.5A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
Embodiment 8
The preparation method of stainless steel surface ordered micro-cellular structure mainly comprises the following steps:
(1) stainless steel pre-treatment:
1) thick for 1mm stainless steel plate Linear cut is become the sample of 30mm × 20mm;
2) stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
3) adopt WYK-15010K DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface; Electrochemical polishing process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, and electrolytic polishing liquid is for being 300ml/L H by concentration
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C, adopts constant flow method, current density 50A/dm
2, polishing time 3min; Between each step, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step;
(2) passivation for stainless steel process: the salpeter solution polished stainless steel being put into 50% carries out Passivation Treatment, obtains fine and close oxide film; Passivation technology: passivation time is 20 minutes, temperature is room temperature.Totally put into deionized water rinsing the phosphoric acid solution prepared again after passivation and carry out galvanic corrosion;
(3) stainless steel electrochemical corrosion: adopt WYK-15010K DC current regulator power supply to carry out galvanic corrosion to the stainless steel sample after Passivation Treatment, obtain ordered micro-cellular structure; Electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, negative electrode and positive electrode area ratio 3:1, cathode anode spacing 50mm, the aqueous solution of electrochemical corrosive liquid to be phosphoric acid concentration be 50g/L, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 5A/dm
2, etching time 120min; According to purposes and the requirement of Stainless Steel Products, control micro-pore diameter by the phosphoric acid concentration size adjusting electrochemical corrosive liquid, the adjustment galvanic corrosion time controling micropore degree of depth.
The electrochemical corrosive process condition of the embodiment of the present invention is as shown in table 1, and the microvoid structure parameter prepared under different process is as shown in table 2:
table 1 electrochemical corrosive process parameter
table 2 microvoid structure parameter
Above-described embodiment is used for explaining this explanation, instead of limits the invention, and in the protection domain of spirit of the present invention and claim, any amendment make the present invention and change, all fall into protection scope of the present invention.
Claims (9)
1. a preparation method for stainless steel surface ordered micro-cellular structure, is characterized in that: comprise the steps:
(1) stainless steel pre-treatment:
1) stainless steel degreasing process: stainless steel is put into 836 shaped metal scavenging solution ultrasonic cleaning 15min, carry out skimming treatment;
2) stainless steel electrochemical polishing: adopt DC current regulator power supply to carry out electrochemical etching to the stainless steel after degreasing, obtain specular surface, electrochemical polishing process: adopt constant flow method, anode made by stainless steel, high purity graphite sheet makes negative electrode, and electrolytic polishing liquid is concentration is 300ml/L H
2sO
4, 600ml/L H
3pO
4, the aqueous solution that 30ml/L glycerol is formed, polishing fluid temperature 85 DEG C;
(2) passivation for stainless steel process: the stainless steel crossed by electrochemical etching is put into salpeter solution and carried out Passivation Treatment, obtain fine and close oxide film, passivation technology: passivation time is 20 min, temperature is room temperature;
(3) stainless steel electrochemical corrosion: clean with deionized water rinsing after passivation, DC current regulator power supply is adopted to carry out galvanic corrosion, obtain ordered micro-cellular structure, electrochemical corrosive process: anode made by stainless steel sample, high purity graphite sheet makes negative electrode, electrochemical corrosive liquid phosphate aqueous solution, solution temperature 0-5 DEG C, adopt galvanostatic method, current density is 5-50A/dm
2, etching time 30-120min.
2. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: the area ratio 3:1 of step (1) and the negative electrode and positive electrode described in step (3).
3. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: step (1) is 50mm with the cathode anode spacing described in step (3).
4. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: the current density 50A/dm of the constant flow method described in step (1)
2, polishing time 3min.
5. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: the DC current regulator power supply voltage 0-150V described in step (1), electric current 0-10A.
6. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: the passivation technology described in step (2) is: the volumetric concentration of salpeter solution is 50%, passivation time 20min, and temperature is room temperature.
7. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: the mass concentration of the phosphate aqueous solution described in step (3) is 15-50g/L.
8. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, it is characterized in that: described microvoid structure is according to the purposes of Stainless Steel Products and requirement, phosphoric acid concentration size by adjusting electrochemical corrosive liquid controls micro-pore diameter, the adjustment galvanic corrosion time controling micropore degree of depth.
9. the preparation method of a kind of stainless steel surface ordered micro-cellular structure according to claim 1, is characterized in that: between each step described in the method, stainless steel sample all need clean by washed with de-ionized water after, then carry out next step.
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